EP1218425A1 - Additifs microbicides - Google Patents

Additifs microbicides

Info

Publication number
EP1218425A1
EP1218425A1 EP00944020A EP00944020A EP1218425A1 EP 1218425 A1 EP1218425 A1 EP 1218425A1 EP 00944020 A EP00944020 A EP 00944020A EP 00944020 A EP00944020 A EP 00944020A EP 1218425 A1 EP1218425 A1 EP 1218425A1
Authority
EP
European Patent Office
Prior art keywords
antimicrobial
hours
test
product
branched
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Withdrawn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
EP00944020A
Other languages
German (de)
English (en)
Inventor
Friedrich Sosna
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 DE10022453A external-priority patent/DE10022453A1/de
Application filed by Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical Creavis Gesellschaft fuer Technologie und Innovation mbH
Publication of EP1218425A1 publication Critical patent/EP1218425A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • A01N37/12—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, 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
    • A01N37/14—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; 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
    • A01N37/20—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/60—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
    • 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
    • C08F20/10—Esters
    • C08F20/34—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the invention relates to antimicrobial polymers which are obtained by polymerizing acryloxyalkylamines.
  • the invention further relates to a process for the preparation and use of these antimicrobial polymers
  • 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 intimate area and for nursing and elderly care. Bacteria must also be kept away from furniture and device surfaces in care stations, especially in the Area of intensive care and young child care, in hospitals, especially 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 Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate.
  • This copolymer is used as an antimicrobial marine paint, the hydrophilic tert-butylaminoethyl methacrylate being the long same erosion of the polymer and thus releases the highly toxic tributyltin methacrylate as an antimicrobial agent
  • 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, antimicrobially active polymers which, as a coating or coating material, are intended to prevent the settlement and spread of bacteria on surfaces
  • the present invention therefore relates to antimicrobial polymers which are obtained by polymerizing a monomer of the formula I.
  • Rl -H or -CH 3 R2 - branched or unbranched ahphatic hydrocarbon residue with 1 to 5
  • R3 H, branched or unbranched aliphatic hydrocarbon radical with 1 to 7
  • Carbon atoms and R4 H, branched or unbranched aliphatic hydrocarbon radical having 1 to 7 carbon atoms,
  • R5 H, branched or unbranched aliphatic hydrocarbon with 1 to 7
  • R3 and R4 can have the same or different meanings. If R3 and / or R4 denote hydrocarbon groups, these can in particular be methyl, ethyl, i-propyl, n-propyl or tert-butyl groups
  • Preferred monomers of the formula I are methacrylic acid-2-tert-butylaminoethyl ester, methacrylic acid-2-diethylaminoethyl ester, methacrylic acid-2-dimethylaminomethyl ester, acrylic acid-2-tert-butylaminoethyl ester, acrylic acid-3-dimethylaminopropyl ester, acrylic acid 2-diethylaminoethylester -dimethylaminoethyl ester, methacrylic acid-3-dimethylaminopropylamide, methacrylic acid-3-diethylaminopropylamide, acrylic acid-3-dimethylaminopropylamide or acrylic acid-3-diethylaminopropylamide
  • the antimicrobial polymers according to the invention can be obtained by homopolymerizing monomers of the formula I.
  • the free-radical polymerization is expediently carried out chemically by means of a free-radical initiator
  • the present invention furthermore relates to antimicrobial polymer blends which can be obtained by mixing one or more antimicrobial polymers, in each case by polymerizing monomers of the formula I, where R 1, R 2, R 3, R 4, R 5 and X have the meanings already mentioned, with at least one other polymers can be produced
  • the proportion of the antimicrobial polymer according to the invention should be 0.2 to 90, preferably 40-90% by weight
  • the production of the antimicrobially active polymer blends can in principle be carried out by all processes known in the art, such as are described in detail in, for example, "HG Elias, Macromolecules, Vol. 2, 5th Edition, S 620 ff" Schemlzmischen two pre-formed polymers the granular or powder polymers on roller mills, in kneaders or with extruders mixed. For thermoplastics, this is heated above the glass or melting temperatures. Solution mixing is based on independently prepared solutions of the two polymers in the same solvent
  • the proportion of the one or more antimicrobial polymers according to the invention in a blend is less than 40-90% by weight, such as 0 2-70, preferably 0.2 to 30, particularly preferably 0 , 2 to 15, very particularly preferably 0.2-10% by weight
  • a preferred method for producing the antimicrobial polymers according to the invention or polymer blends is the radical polymerization of monomers of the formula I in solution with a radical initiator.
  • the antimicrobial polymers obtained in this way can, if necessary, be mixed on a surface by mixing with other polymers by known methods, such as dipping, spraying or brushing.
  • Methanol, water-alcohol mixtures, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile are preserved, but other solvents can also be used, provided that they have a sufficient bulk ratio for the polymers and the substrate surfaces wet well solutions with polymer contents of 3 to 20% by weight, for example about 5% by weight, have been found to be effective in practice and generally give coherent coatings covering the substrate surface with layer thicknesses of more than 0.1 ⁇ m can be
  • antimicrobial polymers or polymer blends according to the invention can also be applied to the substrates as a melt, for example by coextrusion, by dipping, spraying or painting
  • antimicrobial polymers or polymer blends according to the invention can also be used as additives and components for the formulation of polymer blends, paints, varnishes and biocides
  • polymers or polymer blends according to the invention are used as an additive or component in paints, lacquers or biocides, far lower concentrations, for example in the lower percent or per mille range, may be sufficient
  • the present invention further relates to the use of the antimicrobial polymers or polymer blends according to the invention for the production of antimicrobially active products and the products thus produced as such.
  • the products May contain or consist of antimicrobial polymers 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 coated with polymers according to the invention or with polymers according to the invention in the form of a polymer blend were processed
  • Antimicrobial products of this type are, for example, 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
  • polymers or polymer blends 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 polymers or polymer blends according to the invention are, in particular, paints, protective coatings or coatings in the following areas
  • the antimicrobial polymers or polymer blends according to the invention can be used as additives in the formulation of cosmetic products, for example for pastes and ointments.
  • the proportion of polymers or polymer blends according to the invention can be up to the lower percentages. or alcohol range can be lowered
  • the polymers or polymer blends according to the invention are used as biofouling inhibitors in cooling circuits.
  • they In order to avoid damage to cooling circuits caused by algae or bacteria, they often have to be cleaned or built accordingly oversized.
  • microbicidal substances such as formalin is in open cooling systems, such as in power plants or chemical Plants are common, not possible.
  • Other microbicidal substances are often highly corrosive or foam-forming, which prevents use in such systems
  • the present invention therefore furthermore relates to processes for the disinfection of cooling water streams, in which antimicrobial polymers or their polymer blends are added in dispersed form to the cooling water.
  • Cooling water in the sense of the present invention is all process water streams which are used for heating or cooling purposes in closed or open circulation systems
  • the dispersed form of the copolymers or their blends can be obtained in the production process itself, for example by emulsion polymerization, precipitation or suspension polymerization or subsequently by grinding, for example in a jet mill.
  • the particles obtained in this way are preferred in a size distribution of 0.001 to 3 mm (as a spherical diameter) used so that, on the one hand, a large surface is available for killing the bacteria or algae, on the other hand, where necessary, separation from the cooling water is easily possible, e.g. by filtering.
  • the process can, for example, be carried out in such a way that a part (5- 10%) of the copolymers / blends used are removed from the system and replaced by an appropriate amount of fresh material.
  • further antimicrobial copolymer / blend can be added if required.
  • the amount used - depending on the water quality - is 0.1 -100 g antimicrobial copolyme r or their blends per ITT cooling water
  • the present invention also relates to the use of the polymer substrates modified on the surface with polymers or polymer blends 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
  • 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 hand straps and handles in public transport.
  • Medical technology articles include catheters, tubes, cover foils or surgical cutlery
  • Example 1 60 ml of 2-diethylaminoethyl methacrylate (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.74 g of azobisisobutyrometril dissolved in 20 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of demineralized water, the polymer product precipitating. After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water. to remove residual monomers that are still present. The product is then dried in vacuo at 50 ° C. for 24 hours
  • 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 10 7 dropped to 10 "
  • 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 Staphylococcus aureus more detectable
  • 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 10 7 dropped to 10 2
  • Example 3 0.05 g of the product from Example 3 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
  • 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 microbes in the test mixture is determined by After this time, the number of bacteria has dropped from 10 7 to 10 J.
  • Example 4a 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 microbes in the test mixture is determined Germ count decreased from 10 to 10 J.
  • 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 10 7 dropped to 10 4
  • the product is then dried in vacuo for 24 hours at 50 ° C. 5 g of the product are dissolved in 32 g of di-isononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture and the mixture is thoroughly stirred until it becomes pasty 20 g of the paste obtained are knife-coated spread on a metal plate so that a layer thickness of 0.7 mm is obtained. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, the paste gelling and a soft PVC film being formed
  • a 3 by 3 cm piece of the soft PVC film from Example 5 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected
  • a 3 x 3 cm piece of the soft PVC film from Example 5 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time no more Pseudomonas aeruginosa germs can be detected
  • Example 6 90 ml of methacrylic acid-2-tert-butylaminoethyl ester (from Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyrometrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is added heated to 70 ° C and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 liter of demineralized water, whereby the polymeric product precipitates.
  • the filter residue is washed with 100 ml of a 10% solution of ethanol in Rinsed water to remove any residual monomers still present.
  • the product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 32 g of di-isononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture and the mixture is thoroughly stirred until she will be pasty 20 g of the paste obtained with a squeegee so on a meta Spread the plate so that a layer thickness of 0.7 mm is obtained. The plate with the paste on it is then heated to 200 ° C. for 2 minutes, the Gelled paste and a soft PVC film is created
  • a 3 by 3 cm piece of the soft PVC film from Example 6 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected
  • a 3 x 3 cm piece of the soft PVC film from Example 6 is placed on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, the number of bacteria has dropped from 10 7 to 10 3
  • Example 7a Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 7 and then dried in a drying cabinet at 35 ° C. for a period of 24 hours.
  • This coated aluminum plate is coated placed upwards on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed and the number of germs in the test mixture is determined After this time no more Staphylococcus aureus germs are left detectable
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 7 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no Pseudomonas aeruginosa germs are detectable
  • the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water
  • the product is subsequently dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are stirred into 98 g of an acrylic lacquer called Rowacryl G-31293 from ROWA
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 8 and then dried in a drying cabinet at 35 ° C. for a period of 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension was removed, and the number of bacteria in the test mixture was determined. After this time, no bacteria from Staphylococcus aureus can be detected
  • Example 8b Using a brush, a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 8 and then dried in a drying cabinet at 35 ° C. for a period of 24 hours.
  • This aluminum plate is coated with the coated side upwards on the floor placed in a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 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 has dropped from 10 to 10 3
  • the product is then dried in vacuo for 24 hours at 50 ° C. 5 g of the product are stirred into 95 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic ester / acrylic acid ester copolymer
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 9 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the bacterial count in the test mixture is determined after After this time, no Staphylococcus aureus germs can be detected
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 9 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 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 has dropped from 10 to 10
  • the product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are stirred into 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic ester / acrylic acid ester copolymer
  • Example 10b Using a brush, a 5 x 5 cm aluminum plate is coated with the dispersion from Example 10 treated in this way and then dried in a drying cabinet at 35 ° C. for a period of 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test microbial suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no bacteria of Staphylococcus aureus are detectable
  • Example 10b Example 10b
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 10 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 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 has dropped from 10 7 to 10 2
  • the product is then dried in vacuo for 24 hours at 50 ° C. 1 g of the product is dissolved in 99 g of ethanol. Six cotton pads, each with a diameter of 3 cm, are immersed in this solution for 1 second, removed and 24 Dried for hours at room temperature
  • Example 1 1 a In each case a coated cotton pad from Example 11 is inoculated with Chlorella sp, Trentepohlia sp, Gloeocapsa sp Calothrix sp and Aspergilus niger. These samples are then placed in an incubator for 3 weeks. In contrast to accompanying control samples, none of the coated cotton pads fouling is noticeable
  • the filter residue is washed with 100 ml of a 10% solution Solution of ethanol rinsed in water to remove any residual monomers still present.
  • the product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm with a 100 micron doctor blade thick and 2 x 2 cm large aluminum plate applied The plate is then dried at 50 ° C for 24 hours
  • Example 12 The aluminum plate from Example 12 is placed with its coated side upward on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined according to After this time, no Staphylococcus aureus germs can be detected
  • the aluminum plate from Example 12 is placed with its coated side upward on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the bacterial count in the test mixture is determined according to No more Pseudomonas aeruginosa germs can be detected after this time
  • Example 13 90 ml of methacrylic acid-2-tert-butylaminoethyl ester (Aldrich) and 180 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.745 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is added heated to 70 ° C and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1 liter of demineralized water, whereby the polymeric product precipitates.
  • the filter residue is washed with 100 ml of a 10% solution of ethanol in Water rinsed to remove residual monomers still present.
  • the product is then left for 24 hours Dried in vacuo at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 ⁇ 2 cm aluminum plate using a 100 micrometer doctor blade. The plate is then dried at 50 ° C. for 24 hours
  • Example 13 The coated aluminum side of Example 13 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected
  • Example 13 The coated aluminum side of Example 13 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to No more Pseudomonas aeruginosa germs can be detected after this time
  • Example 14 20 ml of 3-dimethylaminopropyl acrylate (Aldrich) and 70 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 dissolved in 5 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred for 72 hours at this temperature.
  • the reaction mixture is stirred into 0.5 l of demineralized water, the polymeric product precipitates After filtering off the product, the filter residue is rinsed with 100 ml of a 10% solution of ethanol in water in order to remove any remaining monomers.
  • the product is then dried in vacuo at 50 ° C. for 24 hours, and 2 g of the product are dried dissolved in 10 g of tetrahydrofuran and applied with a 100 micrometer doctor blade to a 0.5 cm thick and 2 by 2 cm large aluminum plate. The plate is then dried at 50 ° C. for 24 hours
  • Example 14a The coated aluminum side of Example 14 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected
  • Example 14 The coated aluminum side of Example 14 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to No more Pseudomonas aeruginosa germs can be detected after this time
  • Example 15 10 g of the polymer from Example 1 are heated to 165 ° C. This heated polymer is then mixed with 3 g of polymethyl methacrylate (Aldrich), which was also previously heated to 165 ° C. The two polymers are mixed thoroughly on an aluminum plate 0.5 cm thick and 2 x 2 cm in size and cooled at a rate of 20 ° C per hour to room temperature
  • Example 15 The coated aluminum side of Example 15 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected
  • the aluminum plate from Example 15 is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of the
  • Test microbial suspension removed, and the number of microbes in the test batch determined after expiration During this time, Pseudomonas aeruginosa germs can no longer be detected
  • the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried in vacuo for 24 hours at 50 ° C.
  • 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 ⁇ 2 cm aluminum plate using a 100 micrometer doctor blade ° C dried for 24 hours
  • Example 16 The coated aluminum side of Example 16 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected
  • Example 16 The coated aluminum side of Example 16 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to Over this time, the number of germs has decreased from 10 7 to 10 3 germs per ml
  • the product is then dried in vacuo for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and with a 100 micron doctor blade on a 0.5 cm thick and 2 x 2 cm large aluminum plate applied The plate is then dried at 50 ° C for 24 hours
  • Example 17 The coated aluminum side of Example 17 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected
  • Example 17 The coated aluminum side of Example 17 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of microbes in the test batch is determined according to Over this time, the number of bacteria has decreased from 10 to 10 bacteria per ml
  • the filter residue is rinsed with 100 ml of n-hexane in order to add residual monomers still present Then remove the Product dried in a vacuum for 24 hours at 50 ° C. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 ⁇ 2 cm aluminum plate using a 100 micrometer doctor blade. The plate is then at 50 ° C dried for 24 hours
  • Example 18 The coated aluminum side of Example 18 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected
  • Example 18 The coated aluminum side of Example 18 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to Over this time the number of germs has decreased from 10 7 to 10 4 germs per ml
  • Example 19b The coated aluminum side of Example 19 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 1 ml of the test microbial suspension is removed and the number of bacteria in the test batch is determined according to After this time, no Staphylococcus aureus germs can be detected.
  • Example 19b
  • Example 19 The coated aluminum side of Example 19 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined according to Over this time, the number of germs has decreased from 10 7 to 10 germs per ml
  • Example 20 50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is brought to 70 ° C. heated and stirred for 72 hours at this temperature. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating.
  • 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 for 24 hours at 50 ° C. 6 g of the product are dissolved in 32 g of diisononyl phthalate. Then 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty 20 g of the paste obtained are spread with a squeegee on a metal plate so that they are one layer thick n Sets the thickness to 0.7 mm. The plate with the paste on it is then heated to 200 ° C for 2 minutes, the paste gelling and a soft PVC film being produced
  • Example 20a A 3 by 3 cm piece of the soft PVC film from Example 20 is placed on the bottom of a
  • a 3 by 3 cm piece of the soft PVC film from Example 20 is placed on the bottom of a Beaker placed containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 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 has decreased from 10 to 10 bacteria per ml
  • the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried for 24 hours at 50 ° C. in vacuo.
  • 2 g of the product are dissolved in 32 g of diisononyl phthalate.
  • 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty.
  • 20 g of the paste obtained are mixed with a Spread the squeegee onto a metal plate so that it is 0.7 mm thick The plate with the paste on it is then heated to 200 ° C for 2 minutes, during which the paste gels and a soft PVC film is created
  • a 3 by 3 cm piece of the soft PVC film from Example 21 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected
  • a 3 x 3 cm piece of the soft PVC film from Example 21 is placed on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time the Germ count decreased from 10 7 to 10 "
  • the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried for 24 hours at 50 ° C. in vacuo.
  • 2 g of the product are dissolved in 32 g of diisononyl phthalate.
  • 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty.
  • 20 g of the paste obtained are mixed with a Spread the squeegee onto a metal plate so that it is 0.7 mm thick The plate with the paste on it is then heated to 200 ° C for 2 minutes, during which the paste gels and a soft PVC film is created
  • a 3 x 3 cm piece of the soft PVC film from Example 22 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed and the Number of bacteria determined in the test batch After this time, no bacteria from Staphylococcus aureus can be detected
  • a 3 x 3 cm piece of the soft PVC film from Example 22 is placed on the bottom of a beaker containing 20 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 4 hours, 1 ml of the test germ suspension is removed, and the Number of bacteria determined in the test batch After this time, the number of bacteria has dropped from 10 7 to 10 1
  • Example 23 50 ml of dimethylaminopropyl methacrylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then slowly added dropwise with stirring. The mixture is heated to 70 ° C. and 72 Stirred at this temperature for h hours. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymer product precipitating.
  • the filter residue is rinsed with 100 ml of n-hexane in order to remove residual monomers still present the product dried in vacuo for 24 hours at 50 ° C. 5 g of the product are stirred into 95 g of an acrylic varnish called Rowacryl G-31293 from ROWA
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 23 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up that contains 20 ml of a test microbial suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no bacteria of Staphylococcus aureus are detectable
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 23 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 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 has dropped from 10 7 to 10 4
  • Example 24 45 ml of acrylic acid-3-dimethylaminopropylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone are then 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 1.5 l of cyclohexane, the polymer product precipitating.
  • the filter residue is rinsed with 100 ml of n-hexane In order to remove any residual monomers still present, the product is subsequently dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are stirred into 98 g of an acrylic lacquer called Rowacryl G-31293 from ROWA
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 24 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined
  • Example 24 Brush acrylic paint from Example 24 and then dry in a drying cabinet at 35 ° C for 24 hours.
  • This coated aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken
  • the contact time of 2 hours is taken from 1 ml of the test microbial suspension, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria has dropped from 10 to 10 3
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 25 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined. After this time, no germs of Staphylococcus aureus are detectable
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 25 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 2 hours, 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 has dropped from 10 7 to 10 4
  • Example 26 45 ml of acrylic acid-3-dimethylaminopropylamide (Aldrich) and 250 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.6 g of azobisisobutyronitrile dissolved in 20 ml of ethyl methyl ketone is slowly added dropwise with stirring. The mixture is added heated to 70 ° C and stirred for 72 h at this temperature. After this time, the reaction mixture is stirred into 1.5 l of cyclohexane, the polymeric product precipitating.
  • the filter residue is rinsed with 100 ml of n-hexane to still Remove existing residual monomers.
  • the product is subsequently dried in vacuo at 50 ° C. for 24 hours. 2 g of the product are dissolved in 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic acid ester. / Acrylic acid ester copolymers, stirred in
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 26 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed on the bottom of a beaker with its coated side up placed, which contains 20 ml of a test germ suspension of Staphylococcus aureus and shaken After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined
  • Example 26 Spread the dispersion from Example 26 and then dry in a drying cabinet at 35 ° C. for 24 hours.
  • This coated aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken Contact time of 2 hours, 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 has dropped from 10 7 to 10 3

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Abstract

L'invention concerne des polymères et des mélanges de polymères microbicides obtenus par polymérisation d'un monomère de formule (I), éventuellement en mélangeant ultérieurement le produit formé avec au moins un autre polymère, formule dans laquelle R1 = -H ou -CH3, R2 désigne un reste hydrocarbure aliphatique ramifié ou non ramifié de 1 à 5 atomes de carbone, R3 désigne un H ou un reste hydrocarbure aliphatique ramifié ou non ramifié de 1 à 7 atomes de carbone, et R4 désigne un H ou un reste hydrocarbure aliphatique ramifié ou non ramifié de 1 à 7 atomes de carbone, R5 désigne un H ou un reste hydrocarbure aliphatique ramifié ou non ramifié de 1 à 7 atomes de carbone, X désigne O, NH, NR5. Les polymères ou mélanges de polymères microbicides peuvent être utilisés pour la fabrication d'articles hygiéniques ou d'articles médicaux, par exemple, comme revêtements, ainsi que dans des vernis ou dans des peintures protectrices. Par ailleurs, ils peuvent être utilisés dans un procédé destiné à éviter et à réduire le fouling biologique dans des systèmes aqueux.
EP00944020A 1999-09-09 2000-07-08 Additifs microbicides Withdrawn EP1218425A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19943182 1999-09-09
DE19943182 1999-09-09
DE10022453 2000-05-09
DE10022453A DE10022453A1 (de) 1999-09-09 2000-05-09 Antimikrobielle Zusatzstoffe
PCT/EP2000/006501 WO2001018077A1 (fr) 1999-09-09 2000-07-08 Additifs microbicides

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EP1218425A1 true EP1218425A1 (fr) 2002-07-03

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EP00944020A Withdrawn EP1218425A1 (fr) 1999-09-09 2000-07-08 Additifs microbicides

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US (1) US6790910B1 (fr)
EP (1) EP1218425A1 (fr)
JP (1) JP2003508604A (fr)
CN (1) CN1387542A (fr)
AU (1) AU5826600A (fr)
CA (1) CA2384531A1 (fr)
NO (1) NO20021183L (fr)
WO (1) WO2001018077A1 (fr)

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* Cited by examiner, † Cited by third party
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DE10111144A1 (de) * 2001-03-08 2002-09-19 Creavis Tech & Innovation Gmbh Mikrobizide Fluidsysteme
DE10117106A1 (de) * 2001-04-06 2002-10-17 Creavis Tech & Innovation Gmbh Antimikrobielle Konservierungssysteme für Lebensmittel
DE10117805A1 (de) * 2001-04-10 2002-10-17 Creavis Tech & Innovation Gmbh Antimikrobielle Reaktivformulierungen mit Aminoalkoholen
DE10122753A1 (de) * 2001-05-12 2002-11-14 Creavis Tech & Innovation Gmbh Antimikrobielle Fasern und Gewebe
DE10139574A1 (de) * 2001-08-10 2003-02-20 Creavis Tech & Innovation Gmbh Erhalt des Lotus-Effektes durch Verhinderung des Mikrobenwachstums auf selbstreinigenden Oberflächen
DE10139572A1 (de) * 2001-08-10 2003-03-13 Creavis Tech & Innovation Gmbh Erhalt des Lotus-Effektes durch Verhinderung des Mikrobenwachstums nach Beschädigung der selbstreinigenden Oberfläche
DE10160054A1 (de) * 2001-12-06 2003-06-18 Degussa Lichtstreuende Werkstoffe die selbstreinigende Oberflächen aufweisen
DE10160055A1 (de) * 2001-12-06 2003-06-18 Degussa Diffus reflektierende Oberflächen zu deren Herstellung
GB0319933D0 (en) * 2003-08-19 2003-09-24 Syngenta Ltd Fungicidal method
GB0319506D0 (en) * 2003-08-19 2003-09-17 Syngenta Ltd Fungicidal method
US7598299B2 (en) * 2004-02-03 2009-10-06 Akzo Nobel Coatings International B.V. Anti-fouling compositions comprising a polymer with salt groups
JP5027659B2 (ja) * 2004-07-23 2012-09-19 ザ トラスティーズ オブ ザ ユニバーシティ オブ ペンシルバニア 抗菌コポリマーおよびその使用
JP2008534714A (ja) * 2005-03-22 2008-08-28 バイオセーフ インク． 優れた持続性の抗菌特性を有する、無溶媒のシリコン含有第４級アンモニウムを含むポリマー抗菌剤の作製法
US7563734B2 (en) * 2005-04-11 2009-07-21 Massachusetts Institute Of Technology Chemical vapor deposition of antimicrobial polymer coatings
KR100636023B1 (ko) 2005-08-02 2006-10-18 삼성전자주식회사 유기금속 전구체 및 이를 이용한 박막 제조방법
US7618697B2 (en) * 2005-09-26 2009-11-17 Ciba Specialty Chemicals Corporation Carboxylic acid esters of zosteric acid for prevention of biofouling
AT502765B1 (de) 2005-10-17 2008-05-15 Ke Kelit Kunststoffwerk Gesmbh Biozide polymere
TW200901890A (en) * 2007-04-03 2009-01-16 Sure Internat Ventures B V New compostions and methods for cell killing
EP2146581A2 (fr) * 2007-05-01 2010-01-27 Oplon B.V. Compositions et methodes pour detruire les cellules
BRPI0810339A2 (pt) * 2007-05-01 2014-10-07 Oplon Bv "biocidic packaging for cosmetics and foodstuffs"
EP4249001A3 (fr) 2009-08-21 2023-11-29 Novan, Inc. Gels topiques
CA2771389C (fr) 2009-08-21 2019-04-09 Novan, Inc. Pansements, procedes d'utilisation de ceux-ci et procedes de formation de ceux-ci
GB201015492D0 (en) * 2010-09-16 2010-10-27 Univ Edinburgh Binding and non-binding polymers
CN103619359A (zh) * 2011-06-23 2014-03-05 巴斯夫欧洲公司 作为广谱抗微生物剂的烷基氨基烷基低聚物
JP6074686B2 (ja) * 2011-09-15 2017-02-08 和歌山県 ペプチド含有ポリマー、及び繊維へのペプチド固定化方法
US20150257383A1 (en) 2012-10-12 2015-09-17 Basf Se Method for combating phytopathogenic harmful microbes on cultivated plants or plant propagation material
US20160150778A1 (en) 2013-04-22 2016-06-02 Jansen Ag Plastic having a biocidal surface and method for producing said plastic
EP2824139A1 (fr) 2013-07-12 2015-01-14 Jansen AG Matière synthétique ayant une surface biocide et son procédé de fabrication
CN103483478A (zh) * 2013-09-30 2014-01-01 浙江华峰氨纶股份有限公司 一种氨纶染色助剂的制作方法
CN105199490B (zh) * 2015-10-24 2017-08-25 山东寿光健元春有限公司 一种抗菌涂膜母料、抗菌涂膜编织袋及其生产方法
US20180326391A1 (en) * 2017-05-15 2018-11-15 Powdermet, Inc. Evaporation-Resistant Coating
PL428604A1 (pl) * 2019-01-16 2020-07-27 Bolix Spółka Akcyjna Sposób zabezpieczenia nowo wykonanej elewacji przed wystąpieniem skażenia mikrobiologicznego oraz sposób renowacji elewacji budynku dotkniętej skażeniem mikrobiologicznym

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3220866A1 (de) 1982-06-03 1983-12-08 Dynamit Nobel Ag, 5210 Troisdorf Vernetzbare harzmischungen
DE19709075A1 (de) 1997-03-06 1998-09-10 Huels Chemische Werke Ag Verfahren zur Herstellung antimikrobieller Kunststoffe
DE19624972C2 (de) 1996-06-22 1998-06-04 Herberts Gmbh Wäßrige Dispersion von silanfunktionellen Polyurethanharzen, deren Herstellung und 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
DE19715426A1 (de) 1997-04-14 1998-10-15 Bayer Ag Blockierte Isocyanatgruppen aufweisende kolloidale Metalloxide
US6057415A (en) 1998-04-09 2000-05-02 Bayer Corporation Water dispersible polyisocyanates containing alkoxysilane groups

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0118077A1 *

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AU5826600A (en) 2001-04-10
JP2003508604A (ja) 2003-03-04
US6790910B1 (en) 2004-09-14
CN1387542A (zh) 2002-12-25
WO2001018077A1 (fr) 2001-03-15

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