EP1228112A1 - Copolym res de compos s acryloylaminoalkyl - Google Patents

Copolym res de compos s acryloylaminoalkyl

Info

Publication number
EP1228112A1
EP1228112A1 EP00954450A EP00954450A EP1228112A1 EP 1228112 A1 EP1228112 A1 EP 1228112A1 EP 00954450 A EP00954450 A EP 00954450A EP 00954450 A EP00954450 A EP 00954450A EP 1228112 A1 EP1228112 A1 EP 1228112A1
Authority
EP
European Patent Office
Prior art keywords
antimicrobial
butyl
methacrylic acid
substrate
acrylic acid
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Withdrawn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
EP00954450A
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
Priority claimed from DE19943344A external-priority patent/DE19943344A1/de
Priority claimed from DE1999152222 external-priority patent/DE19952222A1/de
Application filed by Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical Creavis Gesellschaft fuer Technologie und Innovation mbH
Publication of EP1228112A1 publication Critical patent/EP1228112A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/20—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • 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
    • A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/26—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • 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
    • A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • 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
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials

Definitions

  • the invention relates to antimicrobial polymers which are obtained by copolymerizing acryloylaminoalkyl compounds with further monomers.
  • the invention further relates to a process for the preparation and use of these antimicrobial polymers
  • the invention relates to antimicrobial polymers which are obtained by graft copolymerization of acryloylaminoalkyl compounds with further monomers on a substrate, to a process for their preparation and their use
  • Acryloylaminoalkyl compounds for the purposes of the present invention are, in particular, dialkylaminoalkyl acrylates and acryloylaminoalkylammonium salts
  • 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
  • Another way of preventing surface bacteria from spreading is to incorporate antimicrobial substances into a matrix
  • US 4,532,269 discloses a terpolymer composed 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 methacrylate active ingredient as antisettable tin methacrylate
  • the copolymer produced 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, , (MIK) is no longer reached
  • Tert-butylaminoethyl methacrylate is a commercially available monomer in methacrylate chemistry and is used in particular as a hydrophilic component in copolymerizations.
  • EP 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for the immobilization of bactericidal quaternary ammonium compounds
  • Dialkylaminoalkyl methacrylamides are found as a comonomer component, in particular as a constituent of dispersing and viscosity improvements for lubricants wide application, for example EP 0 750 031 describes a terpolymer of two alkyl acrylates, each with alkyl chains of different lengths and a nitrogen-containing monomer, including dimethylamino-acrylamides US Pat. No. 5,821,313 describes analog systems with an amino-containing monomer weight fraction of up to 45% by weight
  • Dimethylaminopropyl methacrylamide is also used as a terpolymer component in cationic electrocoating compositions, as described in EP 0 416 762
  • the object of the present invention is therefore to develop novel, antimicrobial polymers which prevent the settlement and spread of bacteria on surfaces
  • the present invention therefore relates to antimicrobial copolymers which are obtained by copolymerizing a monomer of the formula I.
  • R 2 branched or unbranched aliphatic hydrocarbon radical
  • the present invention furthermore relates to a process for the preparation of antimicrobial copolymers, a copolymerization of monomers of the formula I
  • R 2 branched or unbranched aliphatic hydrocarbon radical
  • the monomers of the formula I which can be used to prepare the copolymers according to the invention can therefore also be described by the formulas II (dialkylaminoacrylamides) and III (acryloylaminoalkylammonium salts)
  • the proportion of monomers of the formula I in the reaction mixture in the preparation of the antimicrobial copolymers or in the process according to the invention should, in order to obtain a sufficient antimicrobial effect of the copolymer or graft polymer, between 5 and 98 mol%, preferably between 30 and 98 mol%, particularly preferably between 40 and 98 mol%, based on the sum of the monomers
  • All monomers which undergo copolymerization with the monomers of the formula I can be used as aliphatic unsaturated monomers.
  • suitable acrylates or methacrylates such as 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, in particular, for example, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid tert-butyl ester, acrylic acid methyl ester,
  • the aliphatic unsaturated monomers are preferably acrylic acid or methacrylic acid compounds, particularly preferred are acrylic acid or methacrylic acid esters
  • Dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide or acrylic acid-3-dimethylaminopropylamide are preferably used as the monomer according to formula II
  • Preferred monomers according to formula III are methacryloylaminoalkyltrialkylammonium salts or acryloylaminoalkyltrialkylammonium salts, particularly preferably 3-methacryloylaminopropyltrimethylammonium salts or 3-
  • Acryloylaminopropyltrimethylammonium salts especially the corresponding chlorides or methosulfates (2-methacryloylaminopropyltrimethylammonium methosulfate or 3-acryloylaminopropyltrimethylammonium chloride) are used
  • the antimicrobial copolymers according to the invention can be obtained by copolymerizing monomers of the formula I or II or III with one or more aliphatically unsaturated Monomers are obtained.
  • the polymerization is expediently carried out by means of a free radical initiator or by radiation-induced typical procedures are described in the examples
  • the antimicrobial copolymers according to the invention can also be obtained by copolymerizing monomers of the formula I or II or III with at least one aliphatic unsaturated monomer on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate
  • All polymeric plastics such as polyurethanes, polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), are suitable as substrate materials 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 metal, glass or wood bodies coated with plastic
  • the copolymers can be obtained by graft polymerization of a substrate with monomers of the formula I or II or III and at least one aliphatic unsaturated monomer.
  • the grafting of the substrate enables the antimicrobial copolymer to be covalently bound to the substrate. All polymers can be used as substrates Materials such as the plastics already mentioned can be 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, for example the activation of the substrate before the graft polymerization can be activated by UV radiation, plasma treatment, corona treatment, flame treatment, Ozonization, electrical discharge, ⁇ -radiation are carried out.
  • 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 substrate before the graft polymerization with UV radiation can also be carried out with an additional photosensitizer.
  • the photosensitizer such as, for example, benzophenone
  • the photosensitizer is applied to the surface of the substrate and irradiated. This can also be done with a mercury vapor lamp with exposure times of from 0 seconds to 20 minutes, preferably 1 second 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 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 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 treatment is accordingly based on relatively thin, flat substrates limited
  • the exposure times generally range from 0 1 second to 1 minute, preferably 0 5 to 2 seconds, all of which deal with non-illuminating flames and the distances from the substrate surfaces to the outer flame front 0 2 to 5 cm, preferably 0 5 up to 2 cm
  • the substrate surfaces activated in this way are coated by known methods, such as dipping, spraying or brushing, with monomers of the formula I or II or III (component I) and one or more aliphatic unsaturated monomers (component II), if appropriate in solution, as solvents Water and water-ethanol mixtures are preserved, but other solvents can also be used, provided they have a sufficient bulk ratio for the monomers and the substrate surfaces are well wetted. Solutions with monomer contents of 1 to 10% by weight, for example about 5% by weight. have proven themselves in practice and generally result in coherent coherent coatings covering the substrate surface with layer thicknesses which can be more than 0.1 ⁇ m
  • the graft copolymerization of the monomers applied to the activated surfaces can expediently be initiated by radiation in the short-wave segment of the visible region or in the long-wave segment of the UV region of the electromagnetic radiation.
  • radiation from a UV excimer of the wavelengths 250 to 500 nm is very suitable. preferably from 290 to 320 nm
  • mercury vapor lamps are suitable, provided they emit considerable amounts of radiation in the areas mentioned.
  • the exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes
  • graft copolymerization of the comonomer compositions according to the invention 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.
  • the monomer used for swelling can be component II
  • the antimicrobial copolymers of monomers according to formula I or II or III (component I) and at least one further aliphatic unsaturated monomer (component II) according to the invention exhibit a microbicidal or antimicrobial behavior even without grafting onto a substrate surface.
  • a further embodiment of the present invention consists in that the copolymerization of components I and II is carried out on a substrate
  • the components 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 I can also be a component II serve
  • 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 which can be used in the preparation of the copolymers according to the invention include azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as acetophenones, ⁇ -hydroxyketones, dimethyl ketals and benzophenone.
  • the polymerization can also be initiated thermally or, as already stated, by electromagnetic radiation, such as For example, UV light or ⁇ radiation
  • the present invention furthermore relates to the use of the antimicrobial copolymers 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, machine parts for food processing, air conditioning components, 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) from Devices and contact lenses
  • copolymers or graft copolymers according to the invention can be used wherever bacteria-free, ie microbicidal surfaces or surfaces with non-stick properties are important.
  • examples of uses for the copolymers or graft polymers according to the invention are, in particular, paints, protective coatings or coatings in the following areas
  • Machine parts air conditioning systems ion exchangers, process water, solar systems, heating exchangers, bioreactors, membranes
  • Medical technology contact lenses, diapers, membranes, implants, everyday items, car seats, clothing (stockings, sportswear), hospital facilities, door handles, telephone receiver, public transport, animal cages, cash registers, carpets, wallpaper
  • copolymers or coatings of these copolymers according to the invention are also used as components for the formulation of paints and varnishes, for example as an additive or as a coating of an additive or pigment
  • the present invention also relates to the use of the polymer substrates modified according to the invention with the inventive polymers or processes on the surface for the production of hygiene products or medical articles.
  • hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials
  • hygiene articles also include other objects that may come into contact with many people, such as telephone receivers, handrails of stairs, door and window handles as well as holding straps and handles in public transport.
  • Medical technology articles include catheters, tubes, cover foils or surgical items Cutlery
  • Example la 0.05 g of the product from Example 1 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 microbes in the test mixture is determined the bacterial count decreased from 10 7 to 10 4
  • 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 10 7 dropped to 10 4
  • 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 15 minutes, 1 ml of the test microbial suspension is removed and the number of bacteria in the test mixture is determined 10 dropped to 10 3
  • Example 2b 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 microbes in the test mixture is determined the bacterial count dropped from 10 7 to 10 4
  • reaction mixture is stirred into 0.5 l of deionized water, the polymeric product precipitates After filtering off the product, the filter residue is rinsed with 100 ml of deionized water to remove any residual monomers that are 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 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 product from Example 3 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 product from Example 3 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
  • Example 3 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 10 7 dropped to 10 4
  • Example 4 0.05 g of the product from Example 4 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 10 7 dropped to 10 3
  • 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 microbes in the test mixture is determined by After this time, the number of bacteria has dropped from 10 to 10
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50% strength by weight solution in water) (Aldrich company), 9 g of butyl methacrylate (Aldrich company) and 60 g of ethanol are coated.
  • the radiation chamber is closed and at a distance of 10 cm from one 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 ethanol.
  • the film is then dried in vacuo 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 5 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 7 to 10 4
  • a coated piece of film from Example 5 (5 ⁇ 4 cm) is placed in 30 ml of a test germ suspension from Pseudomonas aeruginosa and shaken after a contact time of
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 12 g of 3-acrylamidopropyltrimethylammonium chloride (75% by weight solution in water) (Aldrich company), 9 g of tert-butyl methacrylate (Aldrich company) and 60 g of ethanol are coated.
  • the radiation chamber is closed and at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of the wavelength 308 nm.
  • the irradiation is started, the exposure time is 15 minutes.
  • the film is then removed and rinsed with 30 ml of ethanol.
  • the film is then dried in vacuo at 50 ° C. for 12 hours Film 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 6 (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 bacteria in the test mixture is determined dropped from 10 7 to 10 4
  • a coated piece of film from example 6 (5 ⁇ 4 cm) is placed in 30 ml of a test germ suspension from Pseudomonas aeruginosa and shaken after a contact time of
  • Example 1 0.05 g of the product from Example 1 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 Staphylococcus aureus 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 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 10 dropped to 10 3
  • 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 9 14 g of dimethylaminopropyl methacrylamide (Aldrich), 10 g of tert-butyl methacrylic acid (Aldrich) and 120 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.3 g of azobisisobutyronitrile is dissolved in 8 ml Ethyl methyl ketone slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.6 l of demineralized water, the polymer product precipitating. After filtering off the product, the Filter residue rinsed with 100 ml of n-hexane Remove any residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours
  • Example 9a 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 the bacterial count dropped from 10 7 to 10 3
  • 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 10a 0.05 g of the product from Example 4 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 removed, and the number of bacteria in the test batch determined After this time, the number of bacteria has dropped from 10 7 to 10 3
  • Example 10b 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 dropped from 10 7 to 10 4

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Abstract

L'invention concerne des polymères antimicrobiens, obtenus par copolymérisation d'un monomère de formule (I) avec d'autres monomères insaturés aliphatiquement, et leur procédé de fabrication. Dans la formule (I), R1 représente -H ou -CH¿3, R?2 représente un reste hydrocarbure aliphatique ramifié ou non ayant 1 à 5 atomes de carbone, Y représente NR?3R4, N+R3R4R5 X-, R3, R4 et R5¿ représentent H, un reste hydrocarbure aliphatique ramifié ou non ayant 1 à 5 atomes de carbone, R?3, R4 et R5¿ pouvant être identiques ou différents, et X- représente CH¿3SO?-4, NO-3, F?-, Cl-, Br-, I-, CH¿3CH2-, NO2?-, NO-, CN-, SCN-, CNO-, ClO-, ClO¿2-, ClO3-, ClO4-. Les polymères selon l'invention peuvent également être obtenus par copolymérisation par greffage d'un substrat, un revêtement lié par covalence étant obtenu sur la surface du substrat. Les polymères antimicrobiens selon l'invention peuvent être utilisés comme revêtement microbicide, par exemple sur des articles d'hygiène ou dans le domaine médical, ainsi que dans des peintures ou des peintures de protection.
EP00954450A 1999-09-10 2000-07-08 Copolym res de compos s acryloylaminoalkyl Withdrawn EP1228112A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19943344A DE19943344A1 (de) 1999-09-10 1999-09-10 Copolymere von Dialkylaminoalkylacrylamiden
DE19943344 1999-09-10
DE19952222 1999-10-29
DE1999152222 DE19952222A1 (de) 1999-10-29 1999-10-29 Copolymere von Acryloylaminoalkylammoniumsalzen
PCT/EP2000/006487 WO2001019878A1 (fr) 1999-09-10 2000-07-08 Copolymères de composés acryloylaminoalkyl

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EP1228112A1 true EP1228112A1 (fr) 2002-08-07

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AU (1) AU6690300A (fr)
CA (1) CA2384427A1 (fr)
WO (1) WO2001019878A1 (fr)

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DE10022406A1 (de) * 2000-05-09 2001-11-15 Creavis Tech & Innovation Gmbh Antimikrobielle, Aminofunktionalisierte Copolymere
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
JP2006522174A (ja) * 2003-04-07 2006-09-28 ライモン セラピューティックス エルティーディー． 古代防御ポリマー
WO2005026224A1 (fr) * 2003-09-17 2005-03-24 Gambro Lundia Ab Materiau de separation
EP1518870B1 (fr) * 2003-09-17 2018-11-28 Gambro Lundia AB Matière de séparation
JP2007327008A (ja) * 2006-06-09 2007-12-20 Nippon Shokubai Co Ltd 抗菌性吸水性樹脂の製造方法
FR2976485B1 (fr) * 2011-06-20 2013-10-11 Oreal Utilisation comme agent anti-transpirant d'un polymere hydrodispersible floculant comportant des groupements amines non quaternises
WO2016008824A1 (fr) * 2014-07-15 2016-01-21 Akzo Nobel Coatings International B.V. Composition de revêtement antisalissure comprenant au moins deux copolymères contenant du sel
JP6329229B2 (ja) * 2015-09-30 2018-05-23 株式会社日本触媒 抗菌剤
JP6755014B2 (ja) 2015-12-14 2020-09-16 Jsr株式会社 重合体、抗菌剤、殺菌剤、抗菌材料、殺菌材料、抗菌方法及び殺菌方法
WO2018074334A1 (fr) * 2016-10-17 2018-04-26 株式会社日本触媒 Copolymère destiné à un détergent
JP7161856B2 (ja) * 2017-09-29 2022-10-27 株式会社日本触媒 繊維処理剤

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US4237218A (en) * 1979-02-09 1980-12-02 Bio-Rad Laboratories, Inc. Micro-carrier cell culture
JP2661241B2 (ja) * 1988-03-03 1997-10-08 住友化学工業株式会社 エチレン共重合体を有効成分とする殺菌剤および殺菌性樹脂組成物
DE19646965C2 (de) * 1996-11-14 1999-08-12 Roehm Gmbh Biophobe Polymere auf Acrylatbasis, Verfahren zu ihrer Herstellung und ihre Verwendung
FR2757866B1 (fr) * 1996-12-30 2004-12-17 Catalyse Polymeres comportant des groupes ammoniums quaternaires, leur utilisation pour la fabrication d'un materiau a propretes antibacteriennes et leurs procedes de preparation
DE19709076A1 (de) * 1997-03-06 1998-09-10 Huels Chemische Werke Ag Verfahren zur Herstellung antimikrobieller Kunststoffe

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See references of WO0119878A1 *

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CA2384427A1 (fr) 2001-03-22

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