EP1183293A1 - Copolymeres microbicides - Google Patents

Copolymeres microbicides

Info

Publication number
EP1183293A1
EP1183293A1 EP00929329A EP00929329A EP1183293A1 EP 1183293 A1 EP1183293 A1 EP 1183293A1 EP 00929329 A EP00929329 A EP 00929329A EP 00929329 A EP00929329 A EP 00929329A EP 1183293 A1 EP1183293 A1 EP 1183293A1
Authority
EP
European Patent Office
Prior art keywords
component
substrate
antimicrobial polymers
antimicrobial
copolymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00929329A
Other languages
German (de)
English (en)
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
Publication of EP1183293A1 publication Critical patent/EP1183293A1/fr
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • 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 which are obtained by copolymerization of a plurality of aliphatic unsaturated monomers which are functionalized at least simply by a secondary amino group.
  • the invention further relates to a method for producing and using the antimicrobial polymers.
  • the invention relates to antimicrobial polymers which are obtained on a substrate by graft copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a secondary amino group, to a process for their preparation and their use.
  • Mucus layers often form, which cause microbial populations to rise extremely, which have a lasting impact on the quality of water, beverages and food, and which can even spoil the goods and damage the health of consumers.
  • Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially 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, in particular 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 infections and in toilets.
  • Tert-butylaminoethyl methacrylate is a commercially available monomer of methacrylate chemistry and is used in particular as a hydrophilic component in copolymerizations.
  • EP-PS 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for the immobilization of bactericidal quaternary ammonium compounds
  • US Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate.
  • This polymer is used as an antimicrobial marine paint, the hydrophilic tert-butylaminoethyl methacrylate requiring the slow erosion of the polymer and thus the highly toxic tributyltin microbial methacrylate releases
  • the copolymer 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 It has now surprisingly been found that by copolymerizing several components of aliphatic, unsaturated monomers which are at least simply functionalized by a secondary amino group, or by graft copolymerizing these components on a substrate, polymers having a surface which is permanently microbicidal are obtained by solvents and physical stresses are not attacked and no migration shows. It is not necessary to use other biocidal agents
  • the present invention therefore relates to antimicrobial polymers which, by copolymerization of aliphatic, unsaturated monomers which are at least simply functionalized by a secondary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a secondary amino group (component 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 at least simply functionalized by a secondary amino group (component I) with a further aliphatic unsaturated monomer which is at least simple by a secondary amino group is functionalized (component II), component I and component II being different from one another, are obtained
  • Suitable comonomer building blocks are, in addition to the secondary amino-functionalized acrylic or .alpha. Described in European applications 0 862 858 and 0 862 859
  • Methacrylic acid esters all aliphatic unsaturated monomers which have at least one secondary amino function, such as, for example, 3-phenylmethylamino-2-butenoic acid ethyl ester, 3-ethylamino-2-butenoic acid ethyl ester, 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- (4- methylphenylamino) -9, 10-dioxo-1-anthrachinyl-2-methyl-propenamide, 2-hydroxy-3 - (3 - triethoxysilylpropylamino) -2-propenoic acid propyl ester, 1 - (1-methylethylamino) -3 - (2- (2nd - propenyl) phenoxy) -2-propan
  • the aliphatic unsaturated monomers of components I or II functionalized according to the invention and functionalized at least once by a secondary amino group 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, 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 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 simply by a secondary amino group for components I or II are functionalized simply by a secondary amino group for components I or II
  • R x 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 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
  • the monomers of components I and II must be different. A molecular weight difference of at least 23 g / mol can exist between these monomers. Exemplary combinations of monomers of components I, II and possibly III are described in the examples
  • the antimicrobial copolymers according to the invention can also be carried out 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, for example, polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefms, 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 copolymers can be prepared by graft-polymerizing a substrate with components I and II or components I, II and III.
  • the grafting of the substrate enables the antimicrobial copolymer to be covalently bonded to the substrate.
  • All polymeric materials can be used as substrates how the plastics already mentioned are used
  • 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 emit significant amounts of radiation in the areas mentioned
  • the exposure time is generally 0 1 seconds to 20 minutes, preferably 1 second to 10 minutes
  • the activation of the standard polymers with UV radiation can also be carried out with an additional photosensitizer.
  • the photosensitizer such as benzophenone
  • the substrate surface is irradiated. This can also be done with a mercury vapor lamp with exposure times of 0.1 seconds to 20 minutes, preferably 1 second up to 10 minutes
  • the activation can also be achieved by plasma treatment using an RF or microwave plasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen or argon atmosphere.
  • the exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds up to 10 minutes
  • the energy input for laboratory devices is between 100 and 500 W, preferably between 200 and 300 W.
  • Corona devices SOFTAL, Hamburg, Germany
  • the exposure times in this case are generally 1 to 10 minutes, preferably 1 to 60 seconds
  • Activation by electrical discharge, electron or ⁇ -rays (e.g. from a cobalt 60 source) and ozonization enable short exposure times, which are generally 0 1 to 60 seconds
  • Flaming substrate surfaces also leads to their activation.
  • Suitable devices especially those with a barrier flame front, can be easily built or, for example, obtained from ARCOTEC, 71297 Monsheim, Germany. They can be operated with hydrocarbons or hydrogen as fuel gas In In any case, damaging overheating of the substrate must be avoided, which is easily achieved by intimate contact with a cooled metal surface on the surface of the substrate facing away from the flame side.
  • Activation by flame treatment is accordingly limited to relatively thin, flat substrates.
  • the exposure times are generally 0 1 second to 1 minute, preferably 0 5 to 2 seconds, all of which deal with non-luminous flames and the distances between the substrates 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, according to known methods, such as dipping, spraying or brushing, with aliphatic unsaturated monomers which are at least simply functionalized by a secondary amino group (component I), with one or more aliphatic unsaturated monomers, at least one of which is by a secondary amino group is functionalized (component II), component I and component II being different from one another, if appropriate in solution, coated Water and water / ethanol mixtures have proven to be suitable as solvents, but other solvents can also be used, provided they have a sufficient capacity for the monomers and the substrate surfaces wet well solutions with monomer contents of 1 to 10% by weight, for example about 5% by weight, have been found to be effective in practice and generally result in coherent coatings covering the substrate surface with layer thicknesses of more than 0Can be 1 ⁇ m
  • the graft copolymerization of the monomers applied to the activated surfaces can expediently be initiated by radiation in the short-wave segment of the visible region or in the long-wave segment of the UV region of the electromagnetic radiation.
  • radiation from a UV excimer of the wavelengths 250 to 500 nm is very suitable. preferably from 290 to 320 nm
  • mercury vapor lamps are suitable, provided they emit considerable amounts of radiation in the areas mentioned.
  • the exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes
  • a graft copolymerization of the comonomer compositions according to the invention can also be achieved by a process which is known in Europe Patent application 0 872 512 is described, and is based on a graft polymerization of swollen monomer and initiator molecules.
  • the monomer used for swelling can be component III
  • antimicrobial copolymers of aliphatic unsaturated monomers according to the invention which are functionalized at least simply by a secondary amino group (component I and II), and optionally a further aliphatic unsaturated monomer (component III), component I and component II being different from one another, also show microbicidal or antimicrobial behavior without grafting onto a substrate surface
  • a further embodiment of the present invention consists in that the copolymerization of components I and II or I, II and II, component I and component II being different from one another, is carried out on a substrate
  • Components I, II and III can be applied to the substrate in solution.
  • suitable solvents are water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile
  • Component III can also serve for components I and II
  • component III All aliphatic unsaturated monomers which undergo copolymerization with components I and II can be used as component III. Further aliphatic unsaturated monomers which are functionalized at least simply by a secondary amino group can also be used as component III, in which case components I , II and III are all different from one another.
  • component III can be 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 are used.
  • the antimicrobial copolymers according to the invention can also be used directly, ie not by polymerizing the components on a substrate, but rather as an antimicrobial coating. Suitable coating methods are the application of the copolymers in solution or as a melt
  • the solution of the polymers according to the invention can be applied to the substrates, for example by dipping, spraying or painting
  • the initiators that can be used include azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all the usual photoinitiators such as acetophenones, ⁇ -hydroxyketones, dimethyl ketals and and benzophenone
  • the polymerization can also be initiated thermally or, as already stated, by electromagnetic radiation, such as UV light or ⁇ radiation
  • antimicrobial polymers according to the invention can also be used as components for the formulation of paints and varnishes
  • Modified Polymer Substrates Further objects of the present invention are the use of the antimicrobial polymers 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 polymers 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 polymers or processes 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 bacterial-free, ie microbicidal surfaces or surfaces with non-stick properties are important.
  • examples of uses for the copolymers or graft polymers according to the invention are, in particular, paints, protective coatings or coatings in the following areas
  • Air conditioning systems ion exchangers, process water, solar systems, heat exchangers, bioreactors, membranes, medical technology, contact lenses, diapers, membranes, implants, utensils, car seats, clothing (stockings, sportswear), hospital facilities, door handles, telephone receiver, public transport,
  • reaction mixture is stirred into 0.5 1 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 remaining monomers.
  • the product is then dried in vacuo at 50 ° C. for 24 hours
  • Example la 0.05 g of the product from Example 1 is placed in 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 30 minutes, 1 ml of the test germ suspension is removed, and the number of bacteria in the test mixture is determined 10 7 dropped to 10 3
  • Example 1 0.05 g of the product from Example 1 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 bacterial count in the test mixture is determined. After this time, the bacterial count has dropped from 10 7 to 10 4
  • reaction mixture is stirred into 0.5 1 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 remaining monomers.
  • the product is then dried in vacuo at 50 ° C. for 24 hours
  • Example 2 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 30 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
  • 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 3
  • Example 3 4 g of methyl 2-acetamidoacrylate (Aldrich), 5 g of tert-butyl acrylate (Aldrich) and 65 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.15 g of azobisisobutyronitrile is dissolved in 5 ml Ethyl methyl ketone was slowly added dropwise with stirring. The mixture was heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture was stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue became rinsed with 100 ml of n-hexane to remove any residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours
  • Example 3 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. After this time, no Staphylococcus aureus bacteria are found more detectable
  • Example 3b 0.05 g of the product from Example 3 is 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 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, no Staphylococcus aureus bacteria are found more detectable
  • 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 2
  • reaction mixture is stirred into 0.5 1 n-hexane, during which time the polymeric product precipitates 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 5b 0.05 g of the product from Example 5 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, no Staphylococcus aureus bacteria are found more detectable Example 5b
  • 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 bacteria in the test mixture is determined. After this time, the number of bacteria is 10 7 dropped to 10 2
  • reaction mixture is stirred into 0.5 l of n-hexane , whereby the polymeric product precipitates.
  • the filter residue is rinsed with 100 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 6a 0.05 g of the product from Example 6 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 10 7 dropped to 10 3
  • 0.05 g of the product from Example 6 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

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Abstract

L'invention concerne des polymères antimicrobiens, obtenus par copolymérisation de monomères insaturés aliphatiquement, fonctionnalisés au moins une fois par un groupe amino secondaire (constituant I), avec un autre monomère insaturé aliphatiquement, fonctionnalisé au moins une fois par un groupe amino secondaire (constituant II), les constituants I et II étant différents l'un de l'autre. On peut utiliser pour la copolymérisation d'autres monomères insaturés aliphatiquement comme constituant III. Les polymères antimicrobiens selon l'invention peuvent servir de revêtement microbicide, entre autres sur des articles d'hygiène ou dans le domaine médical ainsi que dans des peintures, protectrices ou non.
EP00929329A 1999-05-12 2000-03-30 Copolymeres microbicides Withdrawn EP1183293A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19921899A DE19921899A1 (de) 1999-05-12 1999-05-12 Mikrobizide Copolymere
DE19921899 1999-05-12
PCT/EP2000/002781 WO2000069934A1 (fr) 1999-05-12 2000-03-30 Copolymeres microbicides

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EP1183293A1 true EP1183293A1 (fr) 2002-03-06

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EP (1) EP1183293A1 (fr)
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CN (1) CN1361797A (fr)
AU (1) AU7236300A (fr)
DE (1) DE19921899A1 (fr)
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DE10061250A1 (de) * 2000-12-09 2002-06-13 Creavis Tech & Innovation Gmbh Verfahren zur thermisch unterstützten antimikrobiellen Oberflächenausrüstung
DE10110885A1 (de) * 2001-03-07 2002-09-12 Creavis Tech & Innovation Gmbh Mokrobizide Trennsysteme
DE10117106A1 (de) * 2001-04-06 2002-10-17 Creavis Tech & Innovation Gmbh Antimikrobielle Konservierungssysteme für Lebensmittel
EP2036930A1 (fr) * 2007-09-12 2009-03-18 Institut National De La Recherche Agronomique (Inra) Substrat de polyoléfine copolymère greffée doté de propriétés antimicrobiennes et procédé de greffage
CN102325446B (zh) * 2008-12-29 2014-07-09 3M创新有限公司 通过乙烯胺-乙烯醇共聚物的衍生化获得的涂层表面抗微生物共聚物
JP6809776B2 (ja) * 2014-03-28 2021-01-06 株式会社日本触媒 重合体、樹脂組成物、樹脂成形体、および重合体の製造方法
JP6809777B2 (ja) * 2015-03-27 2021-01-06 株式会社日本触媒 熱可塑性重合体、樹脂組成物、樹脂成形体、光学部材、および熱可塑性重合体の製造方法
JP6846105B2 (ja) * 2015-08-20 2021-03-24 株式会社日本触媒 重合体、樹脂組成物および樹脂成形体ならびに重合体の製造方法

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DE19709075A1 (de) * 1997-03-06 1998-09-10 Huels Chemische Werke Ag Verfahren zur Herstellung antimikrobieller Kunststoffe
ATE201031T1 (de) * 1997-04-14 2001-05-15 Degussa Verfahren zur modifizierung der oberfläche von polymersubstraten durch pfropfpolymerisation

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See references of WO0069934A1 *

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AU7236300A (en) 2000-12-05
CN1361797A (zh) 2002-07-31
JP2002544347A (ja) 2002-12-24
NO20015531D0 (no) 2001-11-12
WO2000069934A1 (fr) 2000-11-23
DE19921899A1 (de) 2000-11-16

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