WO2000069936A1 - Copolymeres antimicrobiens - Google Patents

Copolymeres antimicrobiens Download PDF

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Publication number
WO2000069936A1
WO2000069936A1 PCT/EP2000/002799 EP0002799W WO0069936A1 WO 2000069936 A1 WO2000069936 A1 WO 2000069936A1 EP 0002799 W EP0002799 W EP 0002799W WO 0069936 A1 WO0069936 A1 WO 0069936A1
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Prior art keywords
component
antimicrobial
functionalized
amino group
aliphatic unsaturated
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PCT/EP2000/002799
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German (de)
English (en)
Inventor
Peter Ottersbach
Beate Kossmann
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Application filed by Creavis Gesellschaft Für Technologie Und Innovation Mbh filed Critical Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority to AU72365/00A priority Critical patent/AU7236500A/en
Priority to JP2000618351A priority patent/JP2002544348A/ja
Priority to EP00926777A priority patent/EP1183291A1/fr
Publication of WO2000069936A1 publication Critical patent/WO2000069936A1/fr

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    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium 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
    • 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
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • 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
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • A61L2300/45—Mixtures of two or more drugs, e.g. synergistic mixtures

Definitions

  • the invention relates to antimicrobial polymers, obtainable by copolymerization of aliphatic unsaturated monomers with amino and ester functionalities, with one or more aliphatic unsaturated amino functionalized monomers, a process for the preparation of the copolymers and their use
  • the invention further relates to antimicrobial polymers obtainable by graft copolymerization of ester- and amino-functionalized, aliphatic unsaturated monomers, a process for the preparation of the graft polymers and their use
  • 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, especially in rooms for medical interventions and in isolation stations for critical infection cases and in toilets. Devices, surfaces of mobeine and textiles against bacteria are treated as needed or as a precaution with chemicals or their solutions and mixtures, which act as a disinfectant more or less broadly and massively antimicrobial Such chemical agents have a non-specific effect, are often themselves toxic or irritant or form degradation products which are harmful to health genuinely sensitized people
  • 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 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 therefore relates to antimicrobial polymers which, by copolymerization of aliphatic, unsaturated monomers which are functionalized by an ester group and at least simply by a tertiary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by an amino group is (component 4 II), component I and component II being different from one another, are obtained
  • the present invention also relates to a process for the preparation of antimicrobial polymers which are functionalized by graft copolymerization of aliphatic unsaturated monomers which are functionalized by an ester group and at least simply by a tertiary amino group (component I), with a further aliphatic unsaturated monomer which is at least simple by an amino group is functionalized (component II), component I and component II being different from one another, are obtained
  • Component I can consist of aliphatic unsaturated monomers which are functionalized at least once in their ester group, preferably by a tertiary amino group.
  • Particularly preferred monomers for component I are acrylic acid esters or metacrylic acid esters which are functionalized at least simply by a tertiary amino group. The preferred position of the amino group is also here in the ester function
  • the aliphatically unsaturated monomers of components I or II which are functionalized at least once by a tertiary amino group and used 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 contain aliphatic or vinyl hydrocarbon radicals such as methyl, ethyl, propyl or acrylic radicals or cyclic hydrocarbon radicals such as substituted or unsubstituted phenyl or cyclohexyl radicals have 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 of component I contain an ester group
  • the monomers of components I or II 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 by a tertiary amino group can simply be used for components I or II
  • Ri branched, unbranched or cyclic, saturated or unsaturated hydrocarbon radical with up to 50 carbon atoms, which can be substituted by O, N or S atoms and R 2 , R 3 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, where R 2 and R 3 are identical or different,
  • Ri contains an ester group for monomers of component I.
  • Suitable comonomer building blocks for component I are, for example, 2-diethylaminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropylamide methacrylate, 2-diethylaminoethyl ester, 2-dimethylaminoethyl acrylate, 3-dimethylaminoethyl acrylate, 3-dimethylaminoethyl acrylate -2,2-dimethylpropyl ester
  • All aliphatic unsaturated monomers which have at least one amino function are suitable for component II.
  • This amino function can be primary, secondary, tertiary or quaternary
  • Suitable aliphatic unsaturated monomers with at least one primary amino function are, for example, l-amino-2-propene, N-6-aminohexyl-2-propenamide, N-3-
  • Suitable comonomer units with at least one secondary amino function are, in addition to the secondary amino-functionalized acrylic or methacrylic acid esters described in European applications 0 862 858 and 0 862 859, for example 3-
  • Methylamino-2-butenoic acid ethyl ester 3-methylamino-1-phenyl-2-propen-1-one, 2-methyl-N-4-methylamino-1-anthraquinoyl-acrylamide, N-9, 10-dihydro-4- (4th -methylphenylamino) -9, 10- dioxo-l-anthrachinyl-2-methyl-propenamide, 2-hydroxy-3- (3-triethoxysilylpropylamino) -2-propenoic acid propyl ester, 1 - (1-methylethylamino) -3 - (2- ( 2-propenyl) phenoxy) -2-propanol hydrochloride, 3-phenylamino-3-methyl-2-butenoic acid ethyl ester, 1 - (1 -
  • Aliphatic unsaturated monomers having at least one tertiary amino function are, for example, 2-diethylaminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropylamide methacrylate, 2-diethylaminoethyl acrylate, 3-dimethylaminoethyl acrylate, 3-dimethylaminoethyl acrylate, acrylate - dimethylamino-2,2-dimethylpropyl ester
  • aliphatic unsaturated monomers which have at least one quaternary amino function such as, for example, 3-methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammoniummethosulfate, 3-acrylamidopropyltrimethylchloromethylchloride-ammoni
  • Suitable monomers are, for example, 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
  • the antimicrobial copolymers according to the invention can also be produced by copolymerizing components I and II or I, II and III on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate
  • All polymeric plastics are particularly suitable as substrate materials, 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.
  • substrate materials 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
  • the antimicrobial polymers can be obtained by graft polymerization of a substrate with components I and II or I, II and III.
  • the grafting of the substrate enables the antimicrobial polymer to be covalently bound to the substrate.
  • 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, for example the activation of the substrate before the graft polymerization by UN 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 UN radiation in the wavelength range 170-400 nm, preferably 170-250 nm.
  • a suitable radiation source is, for example, a UV excimer device HERAEUS ⁇ oblelight, Hanau, Germany.
  • mercury vapor lamps are also suitable for substrate activation if they are emit significant amounts of radiation in the above-mentioned areas.
  • the exposure time is in general from 0.1 seconds to 20 minutes, preferably from 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, for example, benzophenone
  • the substrate surface is irradiated.
  • This can also be done with a mercury vapor lamp with exposure times of from 0 seconds to 20 minutes, preferably from 1 second to 10 minutes
  • the activation can also be carried out by plasma treatment using an RF or microwave plasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany) in air.
  • RF or microwave plasma Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany
  • Nitrogen or argon atmosphere can be reached.
  • the exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes
  • energy input 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 easily built or, for example, obtained from ARCOTEC, 71297 Monsheim, Germany. They 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 surface of the substrate facing away from the flame side.
  • Activation by flame is accordingly limited to relatively thin, flat substrates.
  • the exposure times generally amount to 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 coated with components I and II or I, II and III, if appropriate in solution, by known methods, such as dipping, spraying or brushing.
  • solvents water and water / ethanol mixtures have been preserved, but there are also others Solvents can be used, provided they have sufficient bulk for the monomers and wet the substrate surfaces well.
  • solvents include ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile solutions
  • Monomer contents of 1 to 10% by weight, for example about 5% by weight have proven themselves in practice and generally result in coherent coats which cover the substrate surface and have layer thicknesses which can be more than 0.1 ⁇ m
  • the graft copolymerization of the monomers (components) 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 UN range of electromagnetic radiation.
  • the radiation from a UV excimer of wavelengths 250 to 250 is well suited 500 nm, preferably from 290 to 320 nm.
  • Mercury vapor lamps are also suitable here, 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
  • antimicrobial copolymers made from components I and II or I, II and III produced by the process according to the invention exhibit microbicidal or antimicrobial behavior even without grafting onto a substrate surface
  • customary radical initiators can be added.
  • initiators among other things, azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as, for example, ⁇ -acetophenones -Using 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 copolymers according to the invention for the production of antimicrobial 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, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, which with Polymers produced according to the invention have modified surfaces
  • 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 antimicrobial copolymers 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
  • copolymers or graft polymers 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 according to the invention are, in particular, paints, protective coatings or coatings in the following areas
  • Marine hull, port facilities, buoys, drilling platforms, ballast water tanks House roofing, basement, walls, facades, greenhouses, sun protection,
  • Machine parts air conditioning systems ion exchangers, process water, solar systems,
  • Example 1 0.05 g of the product from Example 1 is placed in 20 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. After this time, no Staphylococcus aureus bacteria are found more detectable
  • Example 2 0.05 g of the product from Example 1 are placed in 20 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. After this time, the number of bacteria is 10 7 dropped to 10 3
  • Example 2 8 ml of methacrylic acid-3-dimethylaminopropylamide (Aldrich), 8 ml of methacrylic acid-2-dimethylaminoethyl ester (from Adrich) and 80 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.2 g of azobisisobutyronitrile is dissolved slowly added dropwise in 6 ml of ethyl methyl ketone with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours.
  • reaction mixture is stirred into 0.8 1 n-hexane, the polymeric product precipitating after filtering off the product the filter residue is rinsed with 150 ml of n-hexane in order to remove any remaining monomers.
  • the product is then dried in vacuo at 50 ° C. for 24 hours
  • Example 2b 0.05 g of the product from Example 2 are placed in 20 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. After this time the number of bacteria is 10 7 dropped to 10 2 Example 2b
  • Example 2 0.05 g of the product from Example 2 are placed in 20 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. After this time, the number of bacteria is 10 7 dropped to 10 4
  • Example 3 a 0.05 g of the product from Example 3 is placed in 20 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
  • Example 4 0.05 g of the product from Example 3 are placed in 20 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. After this time, the number of bacteria is 10 7 dropped to 10 3 Example 4
  • 0.05 g of the product from Example 4 are placed in 20 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. After this time the number of bacteria is 10 7 dropped to 10 2
  • 0.05 g of the product from Example 4 are placed in 20 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. After this time, the number of bacteria is 10 7 dropped to 10 4
  • reaction mixture is stirred into 0.5 1 n-hexane
  • the polymer Product fails after filtering off the product, the filter residue rinsed with 100 ml of n-hexane to remove remaining monomers.
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • Example 5a 0.05 g of the product from Example 5 are placed in 20 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 the number of germs has dropped from 10 7 to 10 2 .
  • 0.05 g of the product from Example 5 are placed in 20 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 microbes in the test mixture is determined. After this time, the number of germs has dropped from 10 7 to 10 3 .
  • reaction mixture is stirred into 0.5 l of n-hexane, the polymeric product precipitating; after filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present.
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • Example 6b 0.05 g of the product from Example 6 are placed in 20 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 6b
  • 0.05 g of the product from Example 6 are placed in 20 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 3 .

Abstract

L'invention concerne des copolymères antimicrobiens obtenus par copolymérisation de monomères aliphatiquement insaturés qui sont fonctionnalisés par un groupe ester et au moins une fois par un groupe amino tertiaire (composant I), avec un autre monomère aliphatiquement insaturé qui est fonctionnalisé au moins une fois par un groupe amino (composant II), les composants I et II étant différents. D'autres monomères aliphatiquement insaturés peuvent être employés comme composant III pour la copolymérisation. Ces copolymères antimicrobiens 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.
PCT/EP2000/002799 1999-05-12 2000-03-30 Copolymeres antimicrobiens WO2000069936A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU72365/00A AU7236500A (en) 1999-05-12 2000-03-30 Antimicrobial copolymers
JP2000618351A JP2002544348A (ja) 1999-05-12 2000-03-30 抗微生物性コポリマー
EP00926777A EP1183291A1 (fr) 1999-05-12 2000-03-30 Copolymeres antimicrobiens

Applications Claiming Priority (2)

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DE19921895.1 1999-05-12
DE19921895A DE19921895A1 (de) 1999-05-12 1999-05-12 Antimikrobielle Copolymere

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WO2001085813A2 (fr) * 2000-05-09 2001-11-15 Creavis Gesellschaft Für Technologie Und Innovation Mbh Copolymeres antimicrobiens aminofonctionnalises
WO2002069709A1 (fr) * 2001-03-08 2002-09-12 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de fluides microbicides contenant des polymeres antimicrobiens
WO2002080674A1 (fr) * 2001-04-06 2002-10-17 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de conservation antimicrobiens pour produits alimentaires
EP1293123A1 (fr) * 2001-09-14 2003-03-19 Creavis Gesellschaft für Technologie und Innovation mbH Formulations biocides à effet retardé

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DE10062201A1 (de) * 2000-12-13 2002-06-20 Creavis Tech & Innovation Gmbh Verfahren zum Einsatz antimikrobieller Polymere im Bauten- und Denkmalschutz
DE10110885A1 (de) * 2001-03-07 2002-09-12 Creavis Tech & Innovation Gmbh Mokrobizide Trennsysteme
DE10122149A1 (de) * 2001-05-08 2002-11-14 Creavis Tech & Innovation Gmbh Verfahren zur antimikrobiellen Ausrüstung poröser Materialien
CA2620175C (fr) * 2005-08-22 2013-04-30 Quick-Med Technologies, Inc. Desinfectant a activite durable a base de polymeres et de copolymeres d'ammonium quaternaire solubles dans l'alcool
JP2016017130A (ja) * 2014-07-08 2016-02-01 互応化学工業株式会社 細菌付着抑制性樹脂
CN104774522B (zh) * 2015-05-01 2017-01-11 温州市欧霖涂料有限公司 一种隔热涂料的制备方法

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US5208016A (en) * 1988-03-03 1993-05-04 Sumitomo Chemical Co., Ltd. Antimicrobial substance and antimicrobial resin composition containing ethylene copolymer
EP0862858A1 (fr) * 1997-03-06 1998-09-09 Hüls Aktiengesellschaft Procédé de préparation matières plastiques antimicrobiennes
EP0872512A2 (fr) * 1997-04-14 1998-10-21 Hüls Aktiengesellschaft Procédé pour modifier la surface d'un substrat polymère par polymérisation de greffage

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US5208016A (en) * 1988-03-03 1993-05-04 Sumitomo Chemical Co., Ltd. Antimicrobial substance and antimicrobial resin composition containing ethylene copolymer
EP0862858A1 (fr) * 1997-03-06 1998-09-09 Hüls Aktiengesellschaft Procédé de préparation matières plastiques antimicrobiennes
EP0872512A2 (fr) * 1997-04-14 1998-10-21 Hüls Aktiengesellschaft Procédé pour modifier la surface d'un substrat polymère par polymérisation de greffage

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001085813A2 (fr) * 2000-05-09 2001-11-15 Creavis Gesellschaft Für Technologie Und Innovation Mbh Copolymeres antimicrobiens aminofonctionnalises
WO2001085813A3 (fr) * 2000-05-09 2002-08-15 Creavis Tech & Innovation Gmbh Copolymeres antimicrobiens aminofonctionnalises
WO2002069709A1 (fr) * 2001-03-08 2002-09-12 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de fluides microbicides contenant des polymeres antimicrobiens
WO2002080674A1 (fr) * 2001-04-06 2002-10-17 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de conservation antimicrobiens pour produits alimentaires
EP1293123A1 (fr) * 2001-09-14 2003-03-19 Creavis Gesellschaft für Technologie und Innovation mbH Formulations biocides à effet retardé

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EP1183291A1 (fr) 2002-03-06
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JP2002544348A (ja) 2002-12-24

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