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WO2000069933A1 - Method for producing inherently microbicidal polymer surfaces - Google Patents

Method for producing inherently microbicidal polymer surfaces Download PDF

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Publication number
WO2000069933A1
WO2000069933A1 PCT/EP2000/002780 EP0002780W WO0069933A1 WO 2000069933 A1 WO2000069933 A1 WO 2000069933A1 EP 0002780 W EP0002780 W EP 0002780W WO 0069933 A1 WO0069933 A1 WO 0069933A1
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WIPO (PCT)
Prior art keywords
film
radiation
antimicrobial
substrate
minutes
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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.)
Ceased
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PCT/EP2000/002780
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German (de)
French (fr)
Inventor
Peter Ottersbach
Beate Kossmann
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
Priority to JP2000618348A priority Critical patent/JP2002544346A/en
Priority to AU37901/00A priority patent/AU3790100A/en
Priority to EP00920619A priority patent/EP1183289A1/en
Publication of WO2000069933A1 publication Critical patent/WO2000069933A1/en
Priority to NO20015530A priority patent/NO20015530L/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • 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 preparation of antimicrobial polymers by polymerizing amino-functionalized monomers and the use of the antimicrobial polymers thus produced
  • the invention relates to a process for the preparation 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 in 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 made with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients that 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" 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 aliphatic unsaturated monomers which are functionalized at least simply by a secondary amino group are polymerized
  • the aliphatic unsaturated monomers functionalized at least simply by a secondary 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 substituents of the amino group can have aliphatic or vinyl hydrocarbon radicals such as methyl, Have ethyl, propyl or acrylic radicals or cyclic hydrocarbon radicals such as substituted or unsubstituted phenyl or cyclohexyl radicals having up to 25 carbon atoms.
  • the amino group can also be substituted by keto or aldehyde groups such as acryloyl or oxo 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 secondary amino group are functionalized simply by a secondary amino group
  • R Branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms and R 2 branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 25 C. Atoms which can be substituted by O, N or S atoms, be used
  • all aliphatic unsaturated monomers which have at least one secondary amino function are suitable as monomer units - ethyl butenate, 3-methylamino-2-butenoate, 3-methylamino-1-phenyl-2-propen-1-one, 2-methyl-N-4-methylamino-1-anthraquinoyl-acrylamide, N-9, 10-dihydro -4- (4-methylphenylamino) -9,10-dioxo-l-anthrachinyl-2-methyl-propenamide, 2-hydroxy-3- (3-triethoxysilylpropylamino) -2-propenoic acid propyl ester, l- (l-methylethylamino) -3 - (2
  • the method according to the invention can also be carried out by polymerizing the monomers functionalized at least simply by a secondary amino group on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate
  • Suitable substrate materials are above all all all polymeric plastics, such as polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), corresponding copolymers and Blends as well as natural and synthetic rubbers, with or without radiation-sensitive groups.
  • the method according to the invention can also be applied to surfaces of lacquered or otherwise plastic, metal, glass or wood bodies
  • the antimicrobial polymers can be obtained by graft-polymerizing a substrate with an aliphatically unsaturated monomer functionalized at least simply by a secondary amino group.
  • the grafting of the substrate enables covalent attachment of the antimicrobial polymers on the substrate All polymeric materials, such as the plastics already mentioned, can be used as substrates
  • the surfaces of the substrates can be activated before the graft copolymerization using a number of methods. All standard methods for activating polymeric surfaces can be used here.
  • the activation of the substrate before the graft polymerization is carried out by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge of ⁇ -radiation, methods used
  • the surfaces are expediently freed of oils, fats or other contaminants 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 activation can also be achieved by plasma treatment by means of 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 in particular those with a barrier flame front, can be built in a simple manner or, for example, can be obtained from ARCOTEC, 71297 Monsheim, Germany
  • Exposure times generally range from 0.1 seconds to 1 minute, preferably
  • the substrate surfaces activated in this way are coated by known methods, such as dipping, spraying or brushing, with aliphatic unsaturated monomers which are at least simply functionalized by a secondary amino group, if appropriate in solution.
  • Water and water / ethanol mixtures have retained as solvents, however other solvents can also be used, provided 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 approximately 5% by weight, have been found to be effective in practice and generally give, in one pass, Coatings covering substrate surface 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 range or in the long-wave segment of the UV range of the electromagnetic radiation.
  • the 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
  • graft copolymerization can also be achieved by a process which is described in 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 secondary amino group.
  • An aliphatic unsaturated monomer functionalized at least simply by a secondary amine group with acrylates or methacrylates, for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, can be used as the monomer mixture.
  • 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 secondary amino group, produced by the process according to the invention show a microbicidal or antimicrobial behavior even without grafting onto a substrate surface
  • customary 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, for example Use acetophenones, ⁇ -hydroxy ketones, dimethyl ketals and 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 can contain or consist of modified polymer substrates according to the invention.
  • Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or -imides, PVC, polyolefins, 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 handset, handrails of stairs, door and window handles, and holding straps and handles in public transport.
  • Medical technology items include catheters, tubes, cover foils or surgical cutlery
  • the polymers, copolymers or graft polymers produced by the process according to the invention can be used wherever bacterial-free, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of uses for microbicidal polymers or graft polymers produced by the process 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 equipment, 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 2-acrylamido-2-methoxyacetic acid methyl ester (Fa Aldrich) and 97 g of methanol are coated.
  • the radiation chamber is closed and placed 10 cm below one another Excimer irradiation unit made by 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 rinsed with 30 ml of methanol.
  • the film is then dried in a vacuum at 50 ° C. for 12 hours the film is extracted in water 5 times 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 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 countercurrently flowed with 20 ml of a mixture of 3 g of 2-acetamidoacrylic acid methyl ester (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 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
  • Example 2a 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 the bacterial count decreased from 10 7 to 10 4
  • 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 mixture is determined dropped from 10 7 to 10 4
  • EXAMPLE 3 A polyamide 12 film is exposed to 172 nm radiation from an excimer radiation source from Heraeus for 2 minutes at a pressure of 1 mbar.
  • the film activated in this way is placed in a radiation reactor under a protective gas and fixed thereupon Mixture of 3 g of acrylic acid-tert-butylamide (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 30 ml Methanol is unwound.
  • the film is then dried under vacuum at 50 ° C. for 12 hours.
  • the film is then extracted 5 times for 6 hours at 30 ° C. in water, then dried at 50 ° C. 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 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 countercurrently flowed with 20 ml of a mixture of 3 g of 2-acrylamido-2-methoxyacetic acid methyl ester (from Aldrich), 2 g of methyl methacrylate (from 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 the The wavelength is 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 extracted in water 5 times 6 hours at 30 ° C., 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
  • Example 4b A coated piece of film from example 4 (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 the bacterial count decreased 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 countercurrently flowed with 20 ml of a mixture of 3 g of 2-acetamidoacrylic acid methyl ester (from Aldrich), 2 g of methyl methacrylate (from 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 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 12 Dried in vacuo at 50 ° C for hours.
  • the film is then extracted in water 5 times 6 hours at 30 ° C., then dried at 50 ° C. for 12 hours.
  • the back of the film is then treated in the same way, so that a polyamide film coated on both sides with grafted polymer is finally obtained.
  • a coated piece of film from Example 5 (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 microbial suspension is removed and the number of microbes in the test mixture is determined. After this time, no Staphylococcus aureus germs can be detected.
  • Example 5b A coated piece of film from Example 5 (5 ⁇ 4 cm) is placed in 30 ml of a test germ 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 microbes in the test mixture is determined. After this time the number of germs has dropped from 10 7 to 10 4 .

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Abstract

The invention relates to a method for producing antimicrobial polymers by the polymerisation of aliphatic unsaturated monomers which are at least simply functionalised by a secondary amino group. The antimicrobial polymers which are produced by the inventive method can be used as a microbicidal coating, among others, on hygiene articles or in the medical field and also in lacquers or protective paints.

Description

Verfahren zur Herstellung inhärent mikrobizider PolymeroberflächenProcess for the production of inherently microbicidal polymer surfaces

Die Erfindung betrifft ein Verfahren zur Herstellung antimikrobieller Polymere durch Polymerisation von aminofünktionalisierten Monomeren und die Verwendung der so hergestellten antimikrobiellen PolymereThe invention relates to a process for the preparation of antimicrobial polymers by polymerizing amino-functionalized monomers and the use of the antimicrobial polymers thus produced

Desweiteren betrifft die Erfindung ein Verfahren zur Herstellung antimikrobieller Polymere durch Pfrop olymerisation von aminofünktionalisierten Monomeren auf einem Substrat und die Verwendung der so hergestellten antimikrobiellen SubstrateFurthermore, the invention relates to a process for the preparation of antimicrobial polymers by graft polymerization of amino-functionalized monomers on a substrate and the use of the antimicrobial substrates thus produced

Besiedlungen und Ausbreitungen von Bakterien auf Oberflachen von Rohrleitungen, Behaltern oder Verpackungen sind im hohen Maße unerwünscht Es bilden sich häufig Schleimschichten, die -Mikrobenpopulationen extrem ansteigen lassen, die Wasser-, Getränke- und Lebensmittelqualitaten nachhaltig beeinträchtigen und sogar zum Verderben der Ware sowie zur gesundheitlichen Schädigung der Verbraucher fuhren könnenColonization and spreading of bacteria on the surfaces of pipelines, containers or packaging are highly undesirable.There are often layers of mucus which cause microbial populations to rise extremely, which have a lasting impact on the quality of water, beverages and food, and even spoil the goods and affect health Can cause harm to consumers

Aus allen Lebensbereichen, in denen Hygiene von Bedeutung ist, sind Bakterien fernzuhalten Davon betroffen sind Textilien für den direkten Korperkontakt, insbesondere für den Intimbereich und für die Kranken- und Altenpflege Außerdem sind Bakterien fernzuhalten von Möbel- und Gerateoberflachen in Pflegestationen, insbesondere im Bereich der Intensivpflege und der Kleinstkinder-Pflege, in Krankenhausern, insbesondere in Räumen für medizinische Eingriffe und in Isolierstationen für kritische Infektionsfalle sowie in ToilettenBacteria 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

Gegenwartig werden Gerate, Oberflachen von Mobein und Textilien gegen Bakterien im Bedarfsfall oder auch vorsorglich mit Chemikalien oder deren Losungen sowie Mischungen behandelt, die als Desinfektionsmittel mehr oder weniger breit und massiv antimikrobiell wirken Solche chemischen Mittel wirken unspezifisch, sind häufig selbst toxisch oder reizend oder bilden gesundheitlich bedenkliche Abbauprodukte Häufig zeigen sich auch Unverträglichkeiten bei entsprechend sensibilisierten PersonenAt present devices, surfaces of mobeine and textiles against bacteria are treated if necessary or as a precautionary measure with chemicals or their solutions as well as mixtures which act as a disinfectant to a greater or lesser extent and have a massive antimicrobial effect.These chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products that are harmful to health There are often also intolerances in appropriately sensitized people

Eine weitere Vorgehensweise gegen oberflachige Bakterienausbreitungen stellt die Einarbeitung antimikrobiell wirkender Substanzen in eine Matrix dar Tert -Butylaminoethylmethacrylat ist ein handelsübliches Monomer der Methacrylatchemie und wird insbesondere als hydrophiler Bestandteil in Copolymerisationen eingesetzt So wird in EP -PS 0 290 676 der Einsatz verschiedener Polyacrylate und Polymethacrylate als Matrix für die Immobilisierung von bakteriziden quaternaren Ammoniumverbindungen beschriebenAnother way of preventing surface bacteria from spreading is to incorporate antimicrobial substances into a matrix Tert-butylaminoethyl methacrylate is a commercially available monomer in 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

Aus einem anderen technischen Bereich offenbart US-PS 4 532 269 ein Terpolymer aus Butylmethacrylat, Tributylzinnmethacrylat und tert -Butylaminoethylmethacrylat Dieses Polymer wird als antimikrobieller Schiffsanstrich verwendet, wobei das hydrophile tert - Butylaminoethylmethacrylat die langsame Erosion des Polymers fordert und so das hochtoxische Tributylzinnmethacrylat als antimikrobiellen Wirkstoff freisetztFrom another technical field, 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

In diesen Anwendungen ist das mit Aminomethacrylaten hergestellte Copolymer nur Matrix oder Tragersubstanz für zugesetzte mikrobizide Wirkstoffe, die aus dem Tragerstoff diffundieren oder migrieren können Polymere dieser Art verlieren mehr oder weniger schnell ihre Wirkung, wenn an der Oberflache die notwendige „minimale inhibitorische Konzentration,, (MIK) nicht mehr erreicht wirdIn these applications, the copolymer made with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients that 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" on the surface ( MIK) is no longer achieved

Aus den europaischen Patentanmeldungen 0 862 858 und 0 862 859 ist bekannt, daß Homo- und Copolymere von tert -Butylaminoethylmethacrylat, einem Methacrylsaureester mit sekundärer Aminofünktion, inhärent mikrobizide Eigenschaften besitzen Um unerwünschten Anpassungsvorgangen der mikrobiellen Lebensformen, gerade auch in Anbetracht der aus der Antibiotikaforschung bekannten Resistenzentwicklungen von Keimen, wirksam entgegenzutreten, müssen auch zukunftig Systeme auf Basis neuartiger Zusammensetzungen und verbesserter Wirksamkeit entwickelt werdenFrom European patent applications 0 862 858 and 0 862 859 it is known that homo- and copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with secondary amino function, have inherent microbicidal properties in order to undesirably adapt the microbial life forms, especially in view of those known from antibiotic research Resistance developments of germs to counteract effectively must also be developed in the future systems based on new compositions and improved effectiveness

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, neuartige, antimikrobiell wirksame Polymere zu entwickeln Diese sollen ggf als Beschichtung die Ansiedelung und Verbreitung von Bakterien auf Oberflachen verhindernThe 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

Es wurde nun überraschend gefunden, daß durch Polymerisation von aliphatisch ungesättigten Monomeren, die mindestens einfach durch eine sekundäre Aminogruppe fünktionalisiert sind, Polymere mit einer Oberflache erhalten werden, die dauerhaft mikrobizid ist, durch Losemittel und physikalische Beanspruchung nicht angegriffen wird und keine Migration zeigt Dabei ist es nicht notig, weitere biozide Wirkstoffe einzusetzenIt has now surprisingly been found that by polymerizing aliphatic unsaturated monomers which are functionalized at least simply by a secondary amino group, polymers having a surface which is permanently microbicidal are obtained by means of solvents and physical stress is not attacked and shows no migration. It is not necessary to use other biocidal agents

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von antimikrobiellen Polymeren, dadurch gekennzeichnet, daß aliphatisch ungesättigte Monomere, die mindestens einfach durch eine sekundäre Aminogruppe fünktionalisiert sind, polymerisiert werdenThe present invention relates to a process for the preparation of antimicrobial polymers, characterized in that aliphatic unsaturated monomers which are functionalized at least simply by a secondary amino group are polymerized

Die im erfindungsgemaßen Verfahren eingesetzten, mindestens einfach durch eine sekundäre Aminogruppe fünktionalisierten, aliphatisch ungesättigten Monomeren können einen Kohlenwasserstoffrest von bis zu 50, bevorzugt bis zu 30, besonders bevorzugt bis zu 22 Kohlenstoffatomen aufweisen Die Substituenten der Aminogruppe können aliphatische oder vinylische Kohlenwasserstoffreste wie Methyl-, Ethyl-, Propyl- oder Acrylreste oder cyclische Kohlenwasserstoffreste wie substituierte oder unsubstituierte Phenyl- oder Cyclohexylreste mit bis zu 25 Kohlenstoffatomen aufweisen Weiterhin kann die Aminogruppe auch durch Keto- oder Aldehydgruppen wie Acryloyl- oder Oxogruppen substituiert seinThe aliphatic unsaturated monomers functionalized at least simply by a secondary 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 substituents of the amino group can have aliphatic or vinyl hydrocarbon radicals such as methyl, Have ethyl, propyl or acrylic radicals or cyclic hydrocarbon radicals such as substituted or unsubstituted phenyl or cyclohexyl radicals having up to 25 carbon atoms. The amino group can also be substituted by keto or aldehyde groups such as acryloyl or oxo groups

Um eine ausreichende Polymerisationsgeschwindigkeit zu erreichen, sollten die erfindungsgemaß eingesetzten Monomere eine Molmasse von unter 900, bevorzugt unter 550 g/mol aufweisenIn order to achieve a sufficient polymerization rate, the monomers used according to the invention should have a molar mass of less than 900, preferably less than 550 g / mol

In einer besonderen Ausführungsform der vorliegenden Erfindung können einfach durch eine sekundäre Aminogruppe fünktionalisierte, aliphatische ungesättigte Monomere der allgemeinen FormelIn a particular embodiment of the present invention, aliphatic unsaturated monomers of the general formula which are functionalized simply by a secondary amino group

Figure imgf000005_0001
Figure imgf000005_0001

mit R! Verzweigter, unverzweigter oder cyclischer, gesättigter oder ungesättigter Kohlenwasserstoffrest mit bis zu 50 C- Atomen, die durch O-, N- oder S-Atome substituiert sein können und R2 Verzweigter, unverzweigter oder cyclischer, gesättigter oder ungesättigter Kohlenwasserstoffrest mit bis zu 25 C-Atomen, die durch O-, N- oder S-Atome substituiert sein können, eingesetzt werdenwith R! Branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms and R 2 branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 25 C. Atoms which can be substituted by O, N or S atoms, be used

Als Monomerbausteine eignen neben den in den europaischen Anmeldungen 0 862 858 und 0 862 859 beschriebenen sekundaraminofünktionalisierten Acryl- bzw Methacrylsaureestern alle aliphatisch ungesättigten Monomere, die zumindest eine sekundäre Aminofünktion besitzen, wie z B 3-Phenylmethylamino-2-butensaureethylester, 3-Ethylamino-2- butensaureethylester, 3 -Methylamino-2-butensaureethylester, 3 -Methylamino- 1 -phenyl-2- propen- 1 -on, 2-Methyl-N-4-methylamino- 1 -anthrachinoyl-acrylamid, N-9, 10-Dihydro-4-(4- methylphenylamino)-9,10-dioxo-l-anthrachinyl-2-methyl-propenamid, 2-Hydroxy-3-(3- triethoxysilylpropylamino)-2-propensaurepropylester, l-(l-Methylethylamino)-3-(2-(2- propenyl)-phenoxy)-2-propanolhydrochlorid, 3 -Phenylamino-3 -methyl-2-butensaure- ethylester, 1 -( 1 -Methylethylamino)-3 -(2-(2-propenyloxy)-phenoxy)-2-propanolhydrochlorid, 2-Acrylamido-2-methoxyessigsauremethylester, 2-Acetamidoacrylsauremethylester,In addition to the secondary amino-functionalized acrylic or methacrylic acid esters described in European applications 0 862 858 and 0 862 859, all aliphatic unsaturated monomers which have at least one secondary amino function, such as ethyl 3-phenylmethylamino-2-butenoate, 3-ethylamino-2, are suitable as monomer units - ethyl butenate, 3-methylamino-2-butenoate, 3-methylamino-1-phenyl-2-propen-1-one, 2-methyl-N-4-methylamino-1-anthraquinoyl-acrylamide, N-9, 10-dihydro -4- (4-methylphenylamino) -9,10-dioxo-l-anthrachinyl-2-methyl-propenamide, 2-hydroxy-3- (3-triethoxysilylpropylamino) -2-propenoic acid propyl ester, l- (l-methylethylamino) -3 - (2- (2-propenyl) phenoxy) -2-propanol hydrochloride, 3-phenylamino-3-methyl-2-butenoic acid, ethyl ester, 1 - (1-methylethylamino) -3 - (2- (2-propenyloxy) - phenoxy) -2-propanol hydrochloride, 2-acrylamido-2-methoxyacetic acid methyl ester, 2-acetamidoacrylic acid methyl ester,

Acrylsaure-tert -butylamid, 2-Hydroxy-N-2-propenyl-benzamid, N-Methyl-2-propenamidAcrylic acid tert -butylamide, 2-hydroxy-N-2-propenyl-benzamide, N-methyl-2-propenamide

Das erfindungsgemaße Verfahren kann auch durch Polymerisation der mindestens einfach durch eine sekundäre Aminogruppe fünktionalisierten Monomere auf einem Substrat durchgeführt werden Es wird eine physisorbierte Beschichtung aus dem antimikrobiellen Copolymer auf dem Substrat erhaltenThe method according to the invention can also be carried out by polymerizing the monomers functionalized at least simply by a secondary amino group on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate

Als Substratmaterialien eigenen sich vor allem alle polymeren Kunststoffe, wie z B Polyurethane, Polyamide, Polyester und -ether, Polyetherblockamide, Polystyrol, Polyvinylchlorid, Polycarbonate, Polyorganosiloxane, Polyolefine, Polysulfone, Polyisopren, Poly- Chloropren, Polytetrafluorethylen (PTFE), entsprechende Copolymere und Blends sowie naturliche und synthetische Kautschuke, mit oder ohne strahlungssensitive Gruppen Das erfindungsgemaße Verfahren laßt sich auch auf Oberflachen von lackierten oder anderweitig mit Kunststoffbeschichteten Metall-, Glas- oder Holzkorpern anwendenSuitable substrate materials are above all all polymeric plastics, such as polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), corresponding copolymers and Blends as well as natural and synthetic rubbers, with or without radiation-sensitive groups. The method according to the invention can also be applied to surfaces of lacquered or otherwise plastic, metal, glass or wood bodies

In einer weiteren Ausführungsform der vorliegenden Erfindung können die antimikrobiellen Polymere durch Pfropfpolymerisation eines Substrats mit einem mindestens einfach durch eine sekundäre Aminogruppe fünktionalisierten, aliphatisch ungesättigten Monomeren erhalten werden Die Pfropfung des Substrats ermöglicht eine kovalente Anbindung des antimikrobiellen Polymers an das Substrat Als Substrate können alle polymeren Materialien, wie die bereits genannten Kunststoffe eingesetzt werdenIn a further embodiment of the present invention, the antimicrobial polymers can be obtained by graft-polymerizing a substrate with an aliphatically unsaturated monomer functionalized at least simply by a secondary amino group. The grafting of the substrate enables covalent attachment of the antimicrobial polymers on the substrate All polymeric materials, such as the plastics already mentioned, can be used as substrates

Die Oberflachen der Substrate können vor der Pfropfcopolymerisation nach einer Reihe von Methoden aktiviert werden Hier können alle Standardmethoden zur Aktivierung von polymeren Oberflachen zum Einsatz kommen, Beispielsweise ist die Aktivierung des Substrats vor der Pfropfpolymerisation durch UV-Strahlung, Plasmabehandlung, Coronabehandlung, Beflammung, Ozonisierung, elektrische Entladung der γ-Strahlung, eingesetzte Methoden Zweckmäßig werden die Oberflachen zuvor in bekannter Weise mittels eines Losemittels von Ölen, Fetten oder anderen Verunreinigungen befreitThe surfaces of the substrates can be activated before the graft copolymerization using a number of methods. All standard methods for activating polymeric surfaces can be used here. For example, the activation of the substrate before the graft polymerization is carried out by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge of γ-radiation, methods used The surfaces are expediently freed of oils, fats or other contaminants beforehand in a known manner by means of a solvent

Die Aktivierung der Substrate kann durch UV-Strahlung im Wellenlangenbereich 170- 400 nm, bevorzugt 170-250 nm erfolgen Eine geeignete Strahlenquelle ist z B ein UV-Excimer-Gerat HERAEUS Noblelight, Hanau, Deutschland Aber auch Quecksilberdampflampen eignen sich zur Substrataktivierung, sofern sie erhebliche Strahlungsanteile in den genannten Bereichen emittieren Die Expositionszeit betragt im allgemeinen 0 1 Sekunden bis 20 Minuten, vorzugsweise 1 Sekunde bis 10 MinutenThe 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. However, 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

Die Aktivierung der Standardpolymeren mit UV-Strahlung kann weiterhin mit einem zusatzlichen Photosensibilisator erfolgen Hierzu wird der Photosensibilisator, wie z. B Benzophenon auf die Substratoberflache aufgebracht und bestrahlt Dies kann ebenfalls mit einer Quecksilberdampflampe mit Expositionszeiten von 0 1 Sekunden bis 20 Minuten, vorzugsweise 1 Sekunde bis 10 Minuten, erfolgenThe activation of the standard polymers with UV radiation can also be carried out with an additional photosensitizer. B Benzophenone applied to the substrate surface and irradiated. This can also be done with a mercury vapor lamp with exposure times of 0.1 seconds to 20 minutes, preferably 1 second to 10 minutes

Die Aktivierung kann erfindungsgemaß auch durch Plasmabehandlung mittels eines RF- oder Mikrowellenplasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Deutschland) in Luft, Stickstoff- oder Argon- Atmosphäre erreicht werden Die Expositionszeiten betragen im allgemeinen 2 Sekunden bis 30 Minuten, vorzugsweise 5 Sekunden bis 10 Minuten Der Energieeintrag liegt bei Laborgeraten zwischen 100 und 500 W, vorzugsweise zwischen 200 und 300 W Weiterhin lassen sich auch Corona-Gerate (Fa SOFTAL, Hamburg, Deutschland) zur Aktivierung verwenden Die Expositionszeiten betragen in diesem Falle in der Regel 1 bis 10 Minuten, vorzugsweise 1 bis 60 SekundenAccording to the invention, the activation can also be achieved by plasma treatment by means of 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) can also be used for activation. The exposure times in this case are generally 1 to 10 minutes, preferably 1 to 60 seconds

Die Aktivierung durch elektrische Entladung, Elektronen- oder γ-Strahlen (z B aus einer Kobalt-60-Quelle) sowie die Ozonisierung ermöglicht kurze Expositionszeiten, die im allgemeinen 0 1 bis 60 Sekunden betragenActivation by electrical discharge, electron or γ-rays (e.g. from a cobalt 60 source) and ozonization enable short exposure times, which are generally 0 1 to 60 seconds

Eine Beflammung von Substrat-Oberflachen führt ebenfalls zu deren Aktivierung Geeignete Gerate, insbesondere solche mit einer Barriere-Flammfront, lassen sich auf einfache Weise bauen oder beispielsweise beziehen von der Fa ARCOTEC, 71297 Monsheim, DeutschlandFlaming substrate surfaces also leads to their activation. Suitable devices, in particular those with a barrier flame front, can be built in a simple manner or, for example, can be obtained from ARCOTEC, 71297 Monsheim, Germany

Sie können mit Kohlenwasserstoffen oder Wasserstoff als Brenngas betrieben werden In jedem Fall muß eine schädliche Uberhitzung des Substrats vermieden werden, was durch innigen Kontakt mit einer gekühlten Metallflache auf der von der Beflammungsseite abgewandten Substratoberflache leicht erreicht wird Die Aktivierung durch Beflammung ist dementsprechend auf verhältnismäßig dünne, flachige Substrate beschrankt DieThey can be operated with hydrocarbons or hydrogen as fuel gas. 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 substrate surface facing away from the flame side. Activation by flame treatment is accordingly on relatively thin, flat substrates limited Die

Expositionszeiten belaufen sich im allgemeinen auf 0 1 Sekunde bis 1 Minute, vorzugsweiseExposure times generally range from 0.1 seconds to 1 minute, preferably

0 5 bis 2 Sekunden, wobei es sich ausnahmslos um nicht leuchtende Flammen behandelt und die Abstände der Substratoberflachen zur äußeren Flammenfront 0 2 bis 5 cm, vorzugsweise 0 5 bis 2 cm betragen0 5 to 2 seconds, all of which deal with 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

Die so aktivierten Substratoberflachen werden nach bekannten Methoden, wie Tauchen, Sprühen oder Streichen, mit aliphatisch ungesättigten Monomeren, die mindestens einfach durch eine sekundäre Aminogruppe fünktionalisiert sind, gegebenenfalls in Losung, beschichtet Als Losemittel haben sich Wasser und Wasser-Ethanol-Gemische bewahrt, doch sind auch andere Losemittel verwendbar, sofern sie ein ausreichendes Losevermogen für die Monomeren aufweisen und die Substratoberflachen gut benetzen Weitere Losungsmittel sind beispielsweise Ethanol, Methanol, Methylethylketon, Diethylether, Dioxan, Hexan, Heptan, Benzol, Toluol, Chloroform, Dichlormethan, Tetrahydrofüran und Acetonitril Losungen mit Monomerengehalten von 1 bis 10 Gew -%, beispielsweise mit etwa 5 Gew -% haben sich in der Praxis bewahrt und ergeben im allgemeinen in einem Durchgang zusammenhangende, die Substratoberflache bedeckende Beschichtungen mit Schichtdicken, die mehr als 0 1 μm betragen könnenThe substrate surfaces activated in this way are coated by known methods, such as dipping, spraying or brushing, with aliphatic unsaturated monomers which are at least simply functionalized by a secondary amino group, if appropriate in solution. Water and water / ethanol mixtures have retained as solvents, however other solvents can also be used, provided 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 approximately 5% by weight, have been found to be effective in practice and generally give, in one pass, Coatings covering substrate surface with layer thicknesses that can be more than 0 1 μm

Die Propfcopolymerisation der auf die aktivierten Oberflächen aufgebrachten Monomeren kann zweckmäßig durch Strahlen im kurzwelligen Segment des sichtbaren Bereiches oder im langwelligen Segment des UV-Bereiches der elektromagnetischen Strahlung initiiert werden Gut geeignet ist z B die Strahlung eines UV-Excimers der Wellenlangen 250 bis 500 nm, vorzugsweise von 290 bis 320 nm Auch hier sind Quecksilberdampflampen geeignet, sofern sie erhebliche Strahlungsanteile in den genannten Bereichen emittieren Die Expositionszeiten betragen im allgemeinen 10 Sekunden bis 30 Minuten, vorzugsweise 2 bis 15 MinutenThe graft copolymerization of the monomers applied to the activated surfaces can expediently be initiated by radiation in the short-wave segment of the visible range or in the long-wave segment of the UV range of the electromagnetic radiation. For example, the radiation from a UV excimer of the wavelengths 250 to 500 nm is very suitable. preferably from 290 to 320 nm Here too, 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

Weiterhin laßt sich eine Pfropfcopolymerisation auch durch ein Verfahren erreichen, das in der europaischen Patentanmeldung 0 872 512 beschrieben ist, und auf einer Pfropfpolymerisation von eingequollenen Monomer- und Initiatormolekulen beruhtFurthermore, graft copolymerization can also be achieved by a process which is described in European patent application 0 872 512 and is based on a graft polymerization of swollen monomer and initiator molecules

Im erfindungsgemaßen Verfahren können weitere aliphatisch ungesättigte Monomere, neben den durch eine sekundäre Aminogruppe fünktionalisierten Monomeren, verwendet werden So kann als Monomerenmischung ein mindestens einfach durch eine sekundäre Amingruppe fünktionalisiertes aliphatisch ungesättigtes Monomer mit Acrylaten oder Methacrylate, z B Acrylsaure, tert -Butylmethacrylat oder Methylmethacrylat, Styrol, Vinylchlorid, Vinylether, Acrylamide, Acrylnitrile, Olefine (Ethylen, Propylen, Butylen, Isobutylen), Allylverbindungen, Vinylketone, Vinylessigsaure, Vinylacetat oder Vinylester eingesetzt werdenIn the process according to the invention, further aliphatic unsaturated monomers can be used, in addition to the monomers functionalized by a secondary amino group. An aliphatic unsaturated monomer functionalized at least simply by a secondary amine group with acrylates or methacrylates, for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, can be used as the monomer mixture. 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

Die nach den erfindungsgemaßen Verfahren hergestellten antimikrobiellen Polymere aus aliphatisch ungesättigten Monomeren, die mindestens einfach durch eine sekundäre Aminogruppe fünktionalisiert sind, zeigen auch ohne Pfropfung auf eine Substratoberflache ein mikrobizides oder antimikrobielles VerhaltenThe antimicrobial polymers made from aliphatic unsaturated monomers, which are functionalized at least simply by a secondary amino group, produced by the process according to the invention show a microbicidal or antimicrobial behavior even without grafting onto a substrate surface

Wird das erfindungsgemaße Verfahren ohne Pfropfung direkt auf der Substratoberflache angewendet, so können übliche Radikalinitiatoren zugesetzt werden Als Initiatoren lassen sich u a Azonitrile, Alkylperoxide, Hydroperoxide, Acylperoxide, Peroxoketone, Perester, Peroxocarbonate, Peroxodisulfat, Persulfat und alle üblichen Photoinitiatoren wie z B Acetophenone, α-Hydroxyketone, Dimethylketale und Benzophenon verwenden Die Polymerisationsinitiierung kann weiterhin auch thermisch oder wie bereits ausgeführt, durch elektromagnetische Strahlung, wie z B UV-Licht oder γ-Strahlung erfolgenIf the process according to the invention is used directly on the substrate surface without grafting, customary radical initiators can be added. Among the initiators are azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as, for example Use acetophenones, α-hydroxy ketones, dimethyl ketals and benzophenone. The polymerization can also be initiated thermally or, as already stated, by electromagnetic radiation, such as UV light or γ radiation

Verwendung der modifizierten PolymersubstrateUse of the modified polymer substrates

Weitere Gegenstande der vorliegenden Erfindung sind die Verwendung der erfindungsgemaß hergestellten antimikrobiellen Polymere zur Herstellung von antimikrobiell wirksamen Erzeugnissen und die so hergestellten Erzeugnisse als solche Die Erzeugnisse können erfindungsgemaß modifizierte Polymersubstrate enthalten oder aus diesen bestehen Solche Erzeugnisse basieren vorzugsweise auf Polyamiden, Polyurethanen, Polyetherblockamiden, Polyesteramiden oder -imiden, PVC, Polyolefinen, Silikonen, Polysiloxanen, Polymethacrylat oder Polyterephthalaten, die mit erfindungsgemaß hergestellten Polymeren modifizierte Oberflachen aufweisenThe 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 can contain or consist of modified polymer substrates according to the invention. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or -imides, PVC, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, which have surfaces modified with the polymers produced according to the invention

Antimikrobiell wirksame Erzeugnisse dieser Art sind beispielsweise und insbesondere Maschinenteile für die Lebensmittelverarbeitung, Bauteile von Klimaanlagen, Bedachungen, Badezimmer- und Toilettenartikel, Kuchenartikel, Komponenten von Sanitareinrichtungen, Komponenten von Tierkafigen und -behausungen, Spielwaren, Komponenten in Wassersystemen, Lebensmittelverpackungen, Bedienelemente (Touch Panel) von Geraten und KontaktlinsenAntimicrobial 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

Außerdem sind Gegenstande der vorliegenden Erfindung die Verwendung der mit erfindungsgemaß hergestellten antimikrobiellen Polymeren an der Oberflache modifizierten Polymersubstrate zur Herstellung von Hygieneerzeugnissen oder medizintechnischen Artikeln Die obigen Ausführungen über bevorzugte Materialien gelten entsprechend Solche Hygieneerzeugnisse sind beispielsweise Zahnbürsten, Toilettensitze, Kamme und Verpackungsmaterialien Unter die Bezeichnung Hygieneartikel fallen auch andere Gegenstande, die u U mit vielen Menschen in Berührung kommen, wie Telefonhorer, Handlaufe von Treppen, Tur- und Fenstergriffe sowie Haltegurte und -griffe in öffentlichen Verkehrsmitteln Medizintechnische Artikeln sind z B Katheter, Schlauche, Abdeckfolien oder auch chirurgische Bestecke Die durch das erfindungsgemaße Verfahren hergestellten Polymere, Copolymere oder Pfropfpolymere können überall verwendet werden, wo es auf möglichst bakterienfreie d h mikrobizide Oberflachen oder Oberflachen mit Antihafteigenschaften ankommt Verwendungsbeispiele für nach dem erfindungsgemaßen Verfahren hergestellte mikrobizide Polymere oder Pfropfpolymere sind insbesondere Lacke, Schutzanstriche oder Beschichtungen in den folgenden BereichenThe 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. The above statements regarding preferred materials apply accordingly. Such 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 handset, handrails of stairs, door and window handles, and holding straps and handles in public transport. Medical technology items include catheters, tubes, cover foils or surgical cutlery The polymers, copolymers or graft polymers produced by the process according to the invention can be used wherever bacterial-free, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of uses for microbicidal polymers or graft polymers produced by the process according to the invention are, in particular, paints, protective coatings or coatings in the following Areas

Marine Schiffsrumpfe, Hafenanlagen, Bojen, Bohrplattformen, Ballastwassertanks, Haus Bedachungen, Keller, Wände, Fassaden, Gewächshäuser, Sonnenschutz, Gartenzaune, HolzschutzMarine hull, port facilities, buoys, drilling platforms, ballast water tanks, house roofing, cellars, walls, facades, greenhouses, sun protection, garden fences, wood protection

Sanitär Öffentliche Toiletten, Badezimmer, Duschvorhange, Toilettenartikel, Schwimmbad, Sauna, Fugen, DichtmassenSanitary Public toilets, bathrooms, shower curtains, toiletries, swimming pools, saunas, joints, sealing compounds

Lebensmittel Maschinen, Küche, Kuchenartikel, Schwämme, Spielwaren, Lebensmittelverpackungen, Milchverarbeitung, Trinkwassersysteme, Kosmetik - Maschinenteile Klimaanlagen, Ionentauscher, Brauchwasser, Solaranlagen,Food machines, kitchen, cake items, sponges, toys, food packaging, milk processing, drinking water systems, cosmetics - machine parts air conditioning, ion exchangers, process water, solar systems,

Wärmetauscher, Bioreaktoren, Membranen Medizintechnik Kontaktlinsen, Windeln, Membranen, Implantate Gebrauchsgegenstande Autositze, Kleidung (Strumpfe, Sportbekleidung), -Krankenhauseinrichtungen, Türgriffe, Telefonhorer, Öffentliche Verkehrsmittel, Tierkafige, Registrierkassen, Teppichboden, TapetenHeat exchangers, bioreactors, membranes, medical technology, contact lenses, diapers, membranes, implants, utensils, car seats, clothing (stockings, sportswear), hospital equipment, door handles, telephone receivers, public transport, animal cages, cash registers, carpets, wallpapers

Zur weiteren Beschreibung der vorliegenden Erfindung werden die folgenden Beispiele gegeben, die die Erfindung weiter erläutern, nicht aber ihren Umfang begrenzen sollen, wie er in den Patentansprüchen dargelegt istTo further describe the present invention, the following examples are given, which further illustrate the invention but are not intended to limit its scope as set out in the claims

Beispiel 1example 1

Eine Polyamid 12-Folie wird 2 Minuten bei einem Druck von 1 mbar der 172 nm-Strahlung einer Excimerstrahlungsquelle der Fa Heraeus ausgesetzt Die so aktivierte Folie wird unter Schutzgas in einen Bestrahlungsreaktor gelegt und fixiert Daraufhin wird die Folie im Schutzgasgegenstrom mit 20 ml einer Mischung von 3 g 2-Acrylamido-2- methoxyessigsauremethylester (Fa Aldrich) und 97 g Methanol uberschichtet Die Bestrahlungskammer wird verschlossen und im Abstand von 10 cm unter eine Excimerbestrahlungseinheit der Fa Heraeus gestellt, die eine Emission der Wellenlange 308 nm aufweist Die Bestrahlung wird gestartet, die Belichtungsdauer betragt 15 Minuten Die Folie wird anschließend entnommen und mit 30 ml Methanol abgespult Die Folie wird dann 12 Stunden bei 50° C im Vakuum getrocknet Anschließend wird die Folie in Wasser 5 mal 6 Stunden bei 30° C extrahiert, dann bei 50° C 12 Stunden getrocknetA 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 2-acrylamido-2-methoxyacetic acid methyl ester (Fa Aldrich) and 97 g of methanol are coated. The radiation chamber is closed and placed 10 cm below one another Excimer irradiation unit made by 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 rinsed with 30 ml of methanol. The film is then dried in a vacuum at 50 ° C. for 12 hours the film is extracted in water 5 times 6 hours at 30 ° C, then dried at 50 ° C for 12 hours

Im Anschluß wird die Ruckseite der Folie in gleicher Weise behandelt, so daß man abschließend eine beidseitig mit gepfropftem Polymer beschichtete Polyamidfolie erhaltThe back of the film is then treated in the same way, so that finally a polyamide film coated on both sides with grafted polymer is obtained

Beispiel laExample la

Eine beschichtetes Folienstuck aus Beispiel 1 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Staphylococcus aureus eingelegt und geschüttelt Nach einer Kontaktzeit von 15 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbarA 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

Beispiel lbExample lb

Eine beschichtetes Folienstuck aus Beispiel 1 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Pseudomonas aeruginosa eingelegt und geschüttelt Nach einer Kontaktzeit von 60 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit ist die Keimzahl von 107 auf 104 abgefallenA 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 4

Beispiel 2Example 2

Eine Polyamid 12-Folie wird 2 Minuten bei einem Druck von 1 mbar der 172 nm-Strahlung einer Excimerstrahlungsquelle der Fa Heraeus ausgesetzt Die so aktivierte Folie wird unter Schutzgas in einen Bestrahlungsreaktor gelegt und fixiert Daraufhin wird die Folie im Schutzgasgegenstrom mit 20 ml einer Mischung von 3 g 2-Acetamidoacrylsauremethylester (Fa Aldrich) und 97 g Methanol uberschichtet Die Bestrahlungskammer wird verschlossen und im Abstand von 10 cm unter eine Excimerbestrahlungseinheit der Fa Heraeus gestellt, die eine Emission der Wellenlange 308 nm aufweist Die Bestrahlung wird gestartet, die Belichtungsdauer betragt 15 Minuten Die Folie wird anschließend entnommen und mit 30 ml Methanol abgespult Die Folie wird dann 12 Stunden bei 50° C im Vakuum getrocknet Anschließend wird die Folie in Wasser 5 mal 6 Stunden bei 30° C extrahiert, dann bei 50° C 12 Stunden getrocknetA 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 2-acetamidoacrylic acid methyl ester (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 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

Im Anschluß wird die Ruckseite der Folie in gleicher Weise behandelt, so daß man abschließend eine beidseitig mit gepfropftem Polymer beschichtete Polyamidfolie erhaltThe back of the film is then treated in the same way, so that finally a polyamide film coated on both sides with grafted polymer is obtained

Beispiel 2a Eine beschichtetes Folienstuck aus Beispiel 2 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Staphylococcus aureus eingelegt und geschüttelt Nach einer Kontaktzeit von 15 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit ist die Keimzahl von 107 auf 104 abgefallenExample 2a 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 the bacterial count decreased from 10 7 to 10 4

Beispiel 2bExample 2b

Eine beschichtetes Folienstuck aus Beispiel 2 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Pseudomonas aeruginosa eingelegt und geschüttelt Nach einer Kontaktzeit von 60 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit ist die Keimzahl von 107 auf 104 abgefallenA 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 mixture is determined dropped from 10 7 to 10 4

Beispiel 3 Eine Polyamid 12-Folie wird 2 Minuten bei einem Druck von 1 mbar der 172 nm-Strahlung einer Excimerstrahlungsquelle der Fa Heraeus ausgesetzt Die so aktivierte Folie wird unter Schutzgas in einen Bestrahlungsreaktor gelegt und fixiert Daraufhin wird die Folie im Schutzgasgegenstrom mit 20 ml einer Mischung von 3 g Acrylsaure-tert -butylamid (Fa Aldrich) und 97 g Methanol uberschichtet Die Bestrahlungskammer wird verschlossen und im Abstand von 10 cm unter eine Excimerbestrahlungseinheit der Fa Heraeus gestellt, die eine Emission der Wellenlange 308 nm aufweist Die Bestrahlung wird gestartet, die Belichtungsdauer betragt 15 Minuten Die Folie wird anschließend entnommen und mit 30 ml Methanol abgespult Die Folie wird dann 12 Stunden bei 50° C im Vakuum getrocknet Anschließend wird die Folie in Wasser 5 mal 6 Stunden bei 30° C extrahiert, dann bei 50° C 12 Stunden getrocknetEXAMPLE 3 A polyamide 12 film is exposed to 172 nm radiation from an excimer radiation source from Heraeus for 2 minutes at a pressure of 1 mbar. The film activated in this way is placed in a radiation reactor under a protective gas and fixed thereupon Mixture of 3 g of acrylic acid-tert-butylamide (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 30 ml Methanol is unwound. The film is then dried under vacuum at 50 ° C. for 12 hours. The film is then extracted 5 times for 6 hours at 30 ° C. in water, then dried at 50 ° C. for 12 hours

Im Anschluß wird die Ruckseite der Folie in gleicher Weise behandelt, so daß man abschließend eine beidseitig mit gepfropftem Polymer beschichtete Polyamidfolie erhaltThe back of the film is then treated in the same way, so that finally a polyamide film coated on both sides with grafted polymer is obtained

Beispiel 3aExample 3a

Eine beschichtetes Folienstuck aus Beispiel 3 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Staphylococcus aureus eingelegt und geschüttelt Nach einer Kontaktzeit von 15 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbarA 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

Beispiel 3bExample 3b

Eine beschichtetes Folienstuck aus Beispiel 3 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Pseudomonas aeruginosa eingelegt und geschüttelt Nach einer Kontaktzeit von 60 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit ist die Keimzahl von 107 auf 104 abgefallenA 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 4

Beispiel 4Example 4

Eine Polyamid 12-Folie wird 2 Minuten bei einem Druck von 1 mbar der 172 nm-Strahlung einer Excimerstrahlungsquelle der Fa Heraeus ausgesetzt Die so aktivierte Folie wird unter Schutzgas in einen Bestrahlungsreaktor gelegt und fixiert Daraufhin wird die Folie im Schutzgasgegenstrom mit 20 ml einer Mischung von 3 g 2-Acrylamido-2-methoxyessigsaure- methylester (Fa Aldrich), 2 g Methylmethacrylat (Fa Aldrich) und 95 g Methanol uberschichtet Die Bestrahlungskammer wird verschlossen und im Abstand von 10 cm unter eine Excimerbestrahlungseinheit der Fa Heraeus gestellt, die eine Emission der Wellenlange 308 nm aufweist Die Bestrahlung wird gestartet, die Belichtungsdauer betragt 15 Minuten Die Folie wird anschließend entnommen und mit 30 ml Methanol abgespult Die Folie wird dann 12 Stunden bei 50° C im Vakuum getrocknet Anschließend wird die Folie in Wasser 5 mal 6 Stunden bei 30° C extrahiert, dann bei 50° C 12 Stunden getrocknetA 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 2-acrylamido-2-methoxyacetic acid methyl ester (from Aldrich), 2 g of methyl methacrylate (from 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 the The wavelength is 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 extracted in water 5 times 6 hours at 30 ° C., then dried at 50 ° C. for 12 hours

Im Anschluß wird die Ruckseite der Folie in gleicher Weise behandelt, so daß man abschließend eine beidseitig mit gepfropftem Polymer beschichtete Polyamidfolie erhaltThe back of the film is then treated in the same way, so that finally a polyamide film coated on both sides with grafted polymer is obtained

Beispiel 4aExample 4a

Eine beschichtetes Folienstuck aus Beispiel 4 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Staphylococcus aureus eingelegt und geschüttelt Nach einer Kontaktzeit von 15 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbarA 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

Beispiel 4b Eine beschichtetes Folienstuck aus Beispiel 4 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Pseudomonas aeruginosa eingelegt und geschüttelt Nach einer Kontaktzeit von 60 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit ist die Keimzahl von 107 auf 104 abgefallenExample 4b A coated piece of film from example 4 (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 the bacterial count decreased from 10 7 to 10 4

Beispiel 5Example 5

Eine Polyamid 12-Folie wird 2 Minuten bei einem Druck von 1 mbar der 172 nm-Strahlung einer Excimerstrahlungsquelle der Fa Heraeus ausgesetzt Die so aktivierte Folie wird unter Schutzgas in einen Bestrahlungsreaktor gelegt und fixiert Daraufhin wird die Folie im Schutzgasgegenstrom mit 20 ml einer Mischung von 3 g 2-Acetamidoacrylsauremethylester (Fa Aldrich), 2 g Methylmethacrylat (Fa Aldrich) und 95 g Methanol uberschichtet Die Bestrahlungskammer wird verschlossen und im Abstand von 10 cm unter eine Excimerbestrahlungseinheit der Fa Heraeus gestellt, die eine Emission der Wellenlange 308 nm aufweist Die Bestrahlung wird gestartet, die Belichtungsdauer betragt 15 Minuten Die Folie wird anschließend entnommen und mit 30 ml Methanol abgespult Die Folie wird dann 12 Stunden bei 50° C im Vakuum getrocknet. Anschließend wird die Folie in Wasser 5 mal 6 Stunden bei 30° C extrahiert, dann bei 50° C 12 Stunden getrocknet.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 2-acetamidoacrylic acid methyl ester (from Aldrich), 2 g of methyl methacrylate (from 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 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 12 Dried in vacuo at 50 ° C for hours. The film is then extracted in water 5 times 6 hours at 30 ° C., then dried at 50 ° C. for 12 hours.

Im Anschluß wird die Rückseite der Folie in gleicher Weise behandelt, so daß man abschließend eine beidseitig mit gepfropftem Polymer beschichtete Polyamidfolie erhält.The back of the film is then treated in the same way, so that a polyamide film coated on both sides with grafted polymer is finally obtained.

Beispiel 5a:Example 5a

Eine beschichtetes Folienstück aus Beispiel 5 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Staphylococcus aureus eingelegt und geschüttelt. Nach einer Kontaktzeit von 15 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt. Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbar.A coated piece of film from Example 5 (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 microbial suspension is removed and the number of microbes in the test mixture is determined. After this time, no Staphylococcus aureus germs can be detected.

Beispiel 5b: Eine beschichtetes Folienstück aus Beispiel 5 (5 mal 4 cm) wird in 30 ml einer Testkeimsuspension von Pseudomonas aeruginosa eingelegt und geschüttelt. Nach einer Kontaktzeit von 60 Minuten wird 1 ml der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt. Nach Ablauf dieser Zeit ist die Keimzahl von 107 auf 104 abgefallen.Example 5b: A coated piece of film from Example 5 (5 × 4 cm) is placed in 30 ml of a test germ 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 microbes in the test mixture is determined. After this time the number of germs has dropped from 10 7 to 10 4 .

Zusätzlich zur oben beschriebenen mikrobiziden Wirksamkeit gegenüber Zellen von Pseudomonas aeruginosa und Staphylococcus aureus zeigten alle Proben ebenfalls eine mikrobizide Wirkung gegenüber Zellen von Klebsieila pneumoniae, Escherichia coli, Rhizopus oryzae, Candida tropicalis und Tetrahymena pyriformis. In addition to the microbicidal activity against cells of Pseudomonas aeruginosa and Staphylococcus aureus described above, all samples also showed a microbicidal activity against cells of Klebsieila pneumoniae, Escherichia coli, Rhizopus oryzae, Candida tropicalis and Tetrahymena pyriformis.

Claims

Patentansprüche:Claims: 1 Verfahren zur Herstellung von antimikrobiellen Polymeren, dadurch gekennzeichnet, daß aliphatisch ungesättigte Monomere, die mindestens einfach durch eine sekundäre1 Process for the preparation of antimicrobial polymers, characterized in that aliphatic unsaturated monomers, which are at least simply by a secondary Aminogruppe fünktionalisiert sind, polymerisiert werdenAmino group are functionalized, are polymerized 2 Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß aliphatisch ungesättigte, durch eine sekundäre Aminogruppe fünktionalisierte2 The method according to claim 1, characterized in that aliphatically unsaturated, functionalized by a secondary amino group Monomere der allgemeinen FormelMonomers of the general formula
Figure imgf000017_0001
Figure imgf000017_0001
 mit Ri Verzweigter, unverzweigter oder cyclischer, gesättigter oder ungesättigter Kohlenwasserstoffrest mit bis zu 50 C- Atomen, die durch O-, N- oder S-Atome substituiert sein können und R2 Verzweigter, unverzweigteroder cyclischer, gesättigter oder ungesättigter Kohlenwasserstoffrest mit bis zu 25 C-Atomen, die durch O-, N- oder S-Atome substituiert sein können, eingesetzt werdenwith Ri branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 C atoms, which can be substituted by O, N or S atoms and R 2 branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 25 C atoms, which can be substituted by O, N or S atoms, are used 3 Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Polymerisation mit weiteren aliphatisch ungesättigten Monomeren durchgeführt wird3 The method according to claim 1 or 2, characterized in that the polymerization is carried out with further aliphatic unsaturated monomers 4 Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Polymerisation auf einem Substrat durchgeführt wird4 The method according to any one of claims 1 to 3, characterized in that the polymerization is carried out on a substrate 5 Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Polymerisation als Pfropfpolymerisation eines Substrats durchgeführt wird.5 Method according to one of claims 1 to 4, characterized in that the polymerization is carried out as a graft polymerization of a substrate. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Substrat vor der Pfropfpolymerisation durch UV-Strahlung, Plasmabehandlung, Koronabehandlung, Beflammung, Ozonisierung, elektrische Entladung oder γ-Strahlung aktiviert wird.6. The method according to claim 5, characterized in that the substrate is activated before the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or γ-radiation. 7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Substrat vor der Pfropfpolymerisation durch UV-Strahlung mit einem Photosensibilisator aktiviert wird.7. The method according to claim 5, characterized in that the substrate is activated before the graft polymerization by UV radiation with a photosensitizer. 8. Verwendung der nach einem der Ansprüche 1 bis 7 hergestellten antimikrobiellen Polymeren zur Herstellung von Erzeugnissen mit einer antimikrobiellen Beschichtung aus dem Polymer.8. Use of the antimicrobial polymers produced according to one of claims 1 to 7 for the production of products with an antimicrobial coating from the polymer. 9. Verwendung der nach einem der Ansprüche 1 bis 7 hergestellten antimikrobiellen Polymeren zur Herstellung von medizintechnischen Artikeln mit einer antimikrobiellen9. Use of the antimicrobial polymers produced according to one of claims 1 to 7 for the production of medical articles with an antimicrobial Beschichtung aus dem Polymer.Polymer coating. 10. Verwendung der nach einem der Ansprüche 1 bis 7 hergestellten antimikrobiellen Polymeren zur Herstellung von Hygieneartikeln mit einer antimikrobiellen Beschichtung aus dem Polymer.10. Use of the antimicrobial polymers produced according to one of claims 1 to 7 for the production of hygiene articles with an antimicrobial coating made of the polymer. 11. Verwendung der nach einem der Ansprüche 1 bis 7 hergestellten antimikrobiellen Polymeren in Lacken, Schutzanstrichen oder Beschichtungen. 11. Use of the antimicrobial polymers produced according to one of claims 1 to 7 in lacquers, protective coatings or coatings.
PCT/EP2000/002780 1999-05-12 2000-03-30 Method for producing inherently microbicidal polymer surfaces Ceased WO2000069933A1 (en)

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EP00920619A EP1183289A1 (en) 1999-05-12 2000-03-30 Method for producing inherently microbicidal polymer surfaces
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