EP1367890A1 - Microbicidal fluid systems using antimicrobial polymers - Google Patents

Microbicidal fluid systems using antimicrobial polymers

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Publication number
EP1367890A1
EP1367890A1 EP02712830A EP02712830A EP1367890A1 EP 1367890 A1 EP1367890 A1 EP 1367890A1 EP 02712830 A EP02712830 A EP 02712830A EP 02712830 A EP02712830 A EP 02712830A EP 1367890 A1 EP1367890 A1 EP 1367890A1
Authority
EP
European Patent Office
Prior art keywords
microbicidal
emulsions
methacrylate
polymers
emulsion
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Withdrawn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
EP02712830A
Other languages
German (de)
French (fr)
Inventor
Peter Ottersbach
Beate Kossmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
CREAVIS GESELLSCHAFT fur TECHNOLOGIEUND INNOVATION MBH
CREAVIS GES fur TECHNOLOGIEUN
Creavis Gesellschaft fuer Technologie und Innovation mbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CREAVIS GESELLSCHAFT fur TECHNOLOGIEUND INNOVATION MBH, CREAVIS GES fur TECHNOLOGIEUN, Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical CREAVIS GESELLSCHAFT fur TECHNOLOGIEUND INNOVATION MBH
Publication of EP1367890A1 publication Critical patent/EP1367890A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • 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
    • A01N37/22—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 the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A01N37/24—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 the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof

Definitions

  • the invention relates to microbicidal fluid systems using antimicrobial polymers.
  • Mucus layers often form, which cause microbial populations to rise extremely, which have a lasting impact on the quality of water, beverages and food, and can even lead to product spoilage and consumer health damage.
  • Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially for the genital area and for nursing and elderly care. In addition, bacteria must be kept away from furniture and device surfaces in care stations, in particular in the area of intensive care and the care of small children, in hospitals, in particular in rooms for medical interventions and in isolation stations for critical infections and in toilets.
  • 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 requiring the slow erosion of the polymer and thus the highly toxic tributyltimicrobial agent as the active ingredient
  • the copolymer produced with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients which 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” is found on the surface. (MIK) is no longer achieved
  • the described antimicrobial systems are solids that are used in powder form or as a coating.
  • Fluid products have the great advantage that precipitation, drying and grinding processes can be completely bypassed, which also avoids the problematic handling of pulmonary dust.
  • fluid products can be easily requested and stored using pump and tank systems, and dosed efficiently.
  • solvent-free formulation so that fluid water-based products have a great competitive advantage. If required, corresponding products can also be directly and precisely related to water systems, e.g. udosieren
  • the present invention therefore relates to microbicidal emulsions containing microbicidal polymers
  • the emulsions according to the invention can be mixed with water in any ratio and can therefore be used for the disinfection of aqueous systems such as drinking water, cooling water, Dispersion paints or varnishes can be used
  • Another object of the invention is a process for the preparation of microbicidal emulsions, microbicidal polymers being produced by emulsion polymerization of corresponding monomers
  • the microbicidal polymers can contain nitrogen and / or phosphorus groups.
  • the emulsion polymerization to give the microbicidal polymers is carried out in a known manner, ie an emulsion of water, an emulsifier, at least one monomer and a thermal or photochemical radical initiator is reacted in such a way that a Emulsion is obtained It is possible to add further, possibly another monomer or one of the comonomers mentioned below to the reaction
  • Preferred monomers for the preparation of the microbicidal polymers are methacrylic acid 2-tert-butylaminoethyl ester, methacrylic acid 2-diethylaminoethyl ester, methacrylic acid 2-diethylaminomethyl ester, acrylic acid 2-tert-butylaminoethyl ester, acrylic acid 3-dimethylaminopropyl ester, acrylic acid ethyl 2-diet acrylic acid 2-dimethylaminoethyl,
  • Methacryloyloxyethyltrimethylammonium chloride 2-acryloyloxyethyl-4-benzoyl-dimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammonium bromide,
  • microbicidal polymers can be prepared by copolymerization from the monomers mentioned and at least one further comonomer
  • the other comonomers can be acrylates or methacrylates, for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene or its derivatives, vinyl chloride, vinyl ethers,
  • Ionic or non-ionic emulsifiers such as polyethylene glycol olates, polyethylene glycol ethers, in particular 4-octylphenol polyethoxylate (also known under the brand name Triton), alkylbenzenesulfonates, alkyl sulfates, alkyl sulfonates, ie ethoxylated fatty alcohols, alkylphenols or fatty acids, can be used as emulsifiers
  • Corresponding antimicrobial coatings can be obtained, for example, directly by painting or varnishing the antimicrobially active emulsion on surfaces or prior metering into further coating formulations.
  • Emulsion polymers generally have higher molecular weights than polymers which are produced, for example, by solution or bulk polymerization, it is high In this way it is also possible to produce very high molecular weight antimicrobial polymers.
  • Emulsions of this type are also suitable for antimicrobial finishing or preservation of other technically used emulsions, since such a combination generally leads to very homogeneous products.
  • the direct addition of antimicrobial emulsions to aqueous systems, e.g. B for the disinfection of cooling water circuits is possible without any problems
  • the present invention furthermore relates to the use of the antimicrobial emulsions produced according to the invention for the production of antimicrobially active products and the products thus produced as such.
  • Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or - imides, PVC, polyolefins, silicones, polysiloxanes, Polymethacrylate, polyacrylates or polyterephthalates, metals, wood, stones, concrete, glasses and ceramics which have surfaces coated with emulsions according to the invention or which are obtained in the form of a paint or varnish
  • Antimicrobial products of this type are, for example, and especially Machine parts for food processing, components of air conditioning systems, coated pipes, semi-finished products, 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, building materials, building and garden wood
  • the emulsions according to the invention can be used wherever bacteria-free, algae and fungus-free surfaces, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of uses for the emulsions according to the invention can be found in the following areas
  • 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
  • the present invention also relates to the use of the hygiene products or medical technology articles produced according to the emulsions or processes according to the invention.
  • Such hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials.
  • hygiene articles also includes other objects which may also be associated with many people come into contact, such as telephone listeners, handrails of stairs, door and window handles as well as holding belts and handles in public places Transport.
  • Medical technology articles are e.g. B. catheters, tubes, cover sheets or surgical cutlery.
  • microbicidal emulsions are preferably used as an emulsifier or as an additive to other emulsions such as latexes, emulsion paints, cooling lubricants, water-based paints or cosmetic formulations and for the disinfection of cooling water circuits.
  • the present invention further provides microbicidal dispersions prepared from the microbicidal emulsions according to the invention by drying and subsequent redispersion.
  • microbicidal emulsions according to the invention can be used to produce microbicidal coatings or as an adhesive or as an additive to an adhesive.
  • microbicidal dispersions according to the invention produced from the emulsions according to the invention, can also be used for the production of microbicidal coatings and as or in adhesives.
  • the emulsions are freed of water in a known manner, vacuum evaporators are preferred.
  • the solid obtained in this way can now simply be packaged and transported. Redispersion in water gives a dispersion which has almost the same microbicidal properties as the original emulsion and has sufficient stability.
  • 0.02 mL of the emulsion from Example 1 are mixed with 20 mL of a test microbial suspension of Pseudomonas aeruginosa, which has a bacterial count of 10 7 per mL, and shaken. After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the bacterial count in the experiment determined After this time no germs of Pseudomonas aeruginosa are detectable
  • Example Ib 0.02 mL of the emulsion from Example 1 are mixed with 20 mL of a test germ suspension of Staphylococcus aureus, which has a germ count of 10 7 per mL, and shaken. After a contact time of 2 hours, 1 mL of the test germ suspension is removed, and the germ count determined in the test batch After this time, no Staphylococcus aureus germs can be detected
  • 0.02 ml of the emulsion from example 2 are mixed with 20 ml of a test germ suspension of Pseudomonas aeruginosa, which has a germ count of 10 7 per ml, and Shaken After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After this time, no Pseudomonas aeruginosa germs can be detected
  • Example 2 0.02 mL of the emulsion from Example 2 are mixed with 20 mL of a test germ suspension of Staphylococcus aureus, which has a bacterial count of 10 7 per mL, and shaken. After a contact time of 2 hours, 1 mL of the test germ suspension is removed, and the bacterial count in the experiment determined After this time no more germs from Staphylococcus aureus are detectable
  • An aluminum sheet the size of 2 by 2 cm is immersed in 5 ml of the emulsion from Example 2 for 5 seconds.
  • the water is then removed from the coating by drying at 70 ° C. for a period of 24 hours.
  • the dried sheet is placed on the floor placed in a beaker, mixed with 20 mL of a test microbial suspension of Pseudomonas aeruginosa, which has a bacterial count of 10 7 per mL, and shaken After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the number of microbes in the test mixture is determined Pseudomonas aeruginosa no longer detectable
  • 0.02 mL of the emulsion from Example 3 are mixed with 20 mL of a test microbial suspension of Pseudomonas aeruginosa, which has a bacterial count of 10 7 per mL, and shaken. After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the bacterial count in the experiment determined After this time the number of bacteria has dropped to 10 7 per mL
  • Example 3b 0.02 ml of the emulsion from example 2 are mixed with 20 ml of a test germ suspension of Staphylococcus aureus, which has a germ count of 10 7 per ml, and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the germ count determined in the test batch After this time, no Staphylococcus aureus germs can be detected

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to microbicidal fluid systems using antimicrobal polymers, to a method for the production of fluid systems by means of emulsion polymerization and to the use of microbicidal emulsions. The invention also relates to a method for producing microbicidal emulsions, wherein microcrobicidal polymers are produced by emulsion polymerization of corresponding monomers. Generally, emulsion polymers have higher molecular weights than polymers which are produced, for example by solution or substance polymerization.Consequently, it is also possible to produce extremely high-molecular antimicrobial polymers. The microbial polymers can contain nitrogen and/or phosphorous groups. Emulsion polymerization to form microbicidal polymers is carried out in a way known per se i.e. water, an emulsifier, at least one monomer and one thermal or photochemical radical starter are made to react in such a way as to obtain an emulsion. It is possible to add more monomer or optionally another monomer or one of the comonomers mentioned hereafter. Ionic or non-ionic emulsifiers such as polyethylene glycol derivatives, polyethylene glycol ether, especially 4-octylphenol polyethoxylate (also known under the brand name Triton) alkylbenzol sulfonates, alkylsulfates, alkyl sulfonates i.e. ethoxylated fatty alcohols, alkyl phenols or fatty acids can be used as emulsifiers.

Description

MIKROBIZIDE FLUIDSYSTEME UNTER VERWENDUNG ANTIMIKROBIELLER POLYMERE MICROBICIDAL FLUID SYSTEMS USING ANTIMICROBIAL POLYMERS
Die Erfindung betrifft mikrobizide Fluidsysteme unter Verwendung antimikrobieller Polymere.The invention relates to microbicidal fluid systems using antimicrobial polymers.
Besiedlungen und Ausbreitungen von Bakterien auf Oberflächen von Rohrleitungen, Behältern oder Verpackungen sind im hohen Maße unerwünscht. Es bilden sich häufig Schleimschichten, die Mikrobenpopulationen extrem ansteigen lassen, die Wasser-, Getränke- und Lebensmittelqualitäten nachhaltig beeinträchtigen und sogar zum Verderben der Ware sowie zur gesundheitlichen Schädigung der Verbraucher fuhren können.Colonization and spreading of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Mucus layers often form, which cause microbial populations to rise extremely, which have a lasting impact on the quality of water, beverages and food, and can even lead to product spoilage and consumer health damage.
Aus allen Lebensbereichen, in denen Hygiene von Bedeutung ist, sind Bakterien fernzuhalten. Davon betroffen sind Textilien für den direkten Körperkontakt, insbesondere für den Intimbereich und für die Kranken- und Altenpflege. Außerdem sind Bakterien fernzuhalten von Möbel- und Geräteoberflächen in Pflegestationen, insbesondere im Bereich der Intensivpflege und der Kleinstkinder-Pflege, in Krankenhäusern, insbesondere in Räumen für medizinische Eingriffe und in Isolierstationen für kritische Infektionsfälle sowie in Toiletten.Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially for the genital area and for nursing and elderly care. In addition, bacteria must be kept away from furniture and device surfaces in care stations, in particular in the area of intensive care and the care of small children, in hospitals, in particular in rooms for medical interventions and in isolation stations for critical infections and in toilets.
Gegenwärtig werden Geräte, Oberflächen von Möbeln und Textilien gegen Bakterien im Bedarfsfall oder auch vorsorglich mit Chemikalien oder deren Lösungen sowie Mischungen behandelt, die als Desinfektionsmittel mehr oder weniger breit und massiv antimikrobiell wirken. Solche chemischen Mittel wirken unspezifisch, sind häufig selbst toxisch oder reizend oder bilden gesundheitlich bedenkliche Abbauprodukte. Häufig zeigen sich auch Unverträglichkeiten bei entsprechend sensibilisierten Personen.Devices, surfaces of furniture and textiles against bacteria are currently being treated as necessary or as a precautionary measure with chemicals or their solutions as well as mixtures that act as a disinfectant, more or less broadly and massively antimicrobially. Such chemical agents have a non-specific effect, are often themselves toxic or irritating or form degradation products which are harmful to health. Often, intolerances also appear in people who are appropriately sensitized.
Eine weitere Vorgehensweise gegen oberflächige Bakterienausbreitungen stellt die Einarbeitung antimikrobiell wirkender Substanzen in eine Matrix dar.Another way of preventing surface bacteria from spreading is to incorporate antimicrobial substances into a matrix.
Daneben stellt auch die Vermeidung von Algenbewuchs auf Oberflächen eine immer bedeutsamere Herausforderung dar, da inzwischen viele Aussenflächen von Gebäuden mit Kunststoffverkleidungen ausgestattet sind, die besonders leicht veraigen. Neben dem unerwünschten optischen Eindruck kann unter Umständen auch die Funktion entsprechender Bauteile vermindert werden. In diesem Zusammenhang ist z. B. an eine Veralgung von photovoltaisch funktionalen Flachen zu denkenIn addition, the prevention of algae growth on surfaces is becoming an increasingly important challenge, since many exterior surfaces of buildings are now equipped with plastic cladding that is particularly easy to handle. In addition to the undesirable visual impression, the function of corresponding components can also be reduced under certain circumstances. In this context, e.g. B. an algae from to think of photovoltaic functional areas
Eine weitere Form der mikrobiellen Verunreinigung, für die es bis heute ebenfalls keine technisch zufriedenstellende Losung gibt, ist der Befall von Oberflachen mit Pilzen So stellt z B der Befall von Fugen und Wanden in Feuchtraumen mit Aspergillus niger neben dem beeinträchtigten optischen auch einen ernstzunehmenden gesundheitsrelevanten Aspekt dar, da viele Menschen auf die von den Pilzen abgegebenen Stoffe allergisch reagieren, was bis hin zu schweren chronischen Atemwegserkrankungen führen kannAnother form of microbial contamination, for which there is still no technically satisfactory solution, is the infestation of surfaces with fungi.For example, the infestation of joints and walls in wet rooms with Aspergillus niger, in addition to the impaired visual appearance, also represents a serious health-related aspect because many people are allergic to the substances released by the fungi, which can lead to serious chronic respiratory diseases
Im Bereich der Seefahrt stellt das Fouling der Schiffsrumpfe eine ökonomisch relevante Einflußgroße dar, da mit dem Bewuchs verbundenen erhöhten Stromungswiderstand der Schiffe ein deutlicher Mehrverbrauch an Kraftstoff verbunden ist Bis heute begegnet man solchen Problemen allgemein mit der Einarbeitung giftiger Schwermetalle oder anderer niedermolekularer Biozide in Antifoulingbeschichtungen, um die beschriebenen Probleme abzumildern Zu diesem Zweck nimmt man die schädlichen Nebenwirkungen solcher Beschichtungen in Kauf, was sich aber angesichts der gestiegenen ökologischen Sensibilität der Gesellschaft als zunehmend problematisch herausstelltIn the field of seafaring, fouling of the ship's hull is an economically relevant factor, since the increased flow resistance of the ships associated with the vegetation means a significant increase in fuel consumption. To date, such problems are generally encountered with the incorporation of toxic heavy metals or other low-molecular biocides in antifouling coatings, To mitigate the problems described For this purpose, the harmful side effects of such coatings are accepted, which, however, is becoming increasingly problematic in view of the increased ecological sensitivity of society
So offenbart z B die US-PS 4 532 269 ein Terpolymer aus Butylmethacrylat, Tributylzinnmethacrylat und tert -Butylaminoethylmethacrylat Dieses Copolymer wird als antimikrobieller Schiffsanstrich verwendet, wobei das hydrophile tert - Butylaminoethylmethacrylat die langsame Erosion des Polymers fordert und so das hochtoxische Tributylzinnmethacrylat als antimikrobiellen Wirkstoff freisetztFor example, 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 requiring the slow erosion of the polymer and thus the highly toxic tributyltimicrobial agent as the active ingredient
In diesen Anwendungen ist das mit Aminomethacrylaten hergestellte Copolymer nur Matrix oder Trager Substanz für zugesetzte mikrobizide Wirkstoffe, die aus dem Tragerstoff diffundieren oder migrieren können Polymere dieser Art verlieren mehr oder weniger schnell ihre Wirkung, wenn an der Oberflache die notwendige „minimale inhibitorische Konzentration,, (MIK) nicht mehr erreicht wirdIn these applications, the copolymer produced with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients which 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” is found on the surface. (MIK) is no longer achieved
Aus der europaischen Patentanmeldungen 0 862 858 ist weiterhin bekannt, dass Copolymere von tert -Butylaminoethylmethacrylat, einem Methacrylsaureester mit sekundärer Aminofünktion, inhärent mikrobizide Eigenschaften besitzen Um unerwünschten Anpassungsvorgangen der mikrobiellen Lebensformen, gerade auch in Anbetracht der aus der Antibiotikaforschung bekannten Resistenzentwicklungen von Keimen, wirksam entgegenzutreten, müssen auch zukunftig Systeme auf Basis neuartiger Zusammensetzungen und verbesserter Wirksamkeit entwickelt werdenFrom European patent applications 0 862 858 it is also known that copolymers of tert-butylaminoethyl methacrylate, a methacrylic acid ester with secondary Amino function, inherently possessing microbicidal properties In order to effectively counteract undesired adaptation processes of microbial life forms, especially in view of the development of resistance to germs known from antibiotic research, systems based on novel compositions and improved effectiveness must also be developed in the future
Bei den beschriebenen antimikrobiellen Systemen handelt es sich um Feststoffe, die in Pulverform oder als Beschichtung verwendet werden Oftmals ist es aus ökonomischen Gründen und Arbeitsschutzuberlegungen aber wünschenswert, bei der Produktion von Beschichtungssystemen den Umweg über die Herstellung eines Feststoffes zu vermeiden und unmittelbar ein fluides Produkt zu erhalten Fluide Produkte besitzen den großen Vorteil, dass Fallungs-, Trocknung- und Vermahlprozesse komplett umgangen werden können, was auch den problematischen Umgang mit lungengangigen Stauben vermeidet Weiterhin lassen sich fluide Produkte in einfacher Weise mittels Pump- und Tanksystemen befordern und lagern, sowie effizient dosieren Daneben wünscht man sich aus okotoxikologischen Gründen zunehmend eine losemittelfreie Formulierung, so dass fluide Produkte auf Wasserbasis einen großen Wettbewerbsvorteil besitzen Entsprechende Produkte lassen sich bei Bedarf auch unmittelbar und präzise zu Wassersystemen zudosierenThe described antimicrobial systems are solids that are used in powder form or as a coating. For economic reasons and occupational safety considerations, however, it is often desirable to avoid the detour in the production of coating systems via the production of a solid and to immediately add a fluid product Fluid products have the great advantage that precipitation, drying and grinding processes can be completely bypassed, which also avoids the problematic handling of pulmonary dust. Furthermore, fluid products can be easily requested and stored using pump and tank systems, and dosed efficiently In addition, for ecotoxicological reasons, there is an increasing desire for a solvent-free formulation, so that fluid water-based products have a great competitive advantage. If required, corresponding products can also be directly and precisely related to water systems, e.g. udosieren
Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, antimikrobieller Polymere als fluides System zu entwickeln, welche die beschriebenen Vorteile fluider Systeme mit den Vorzügen inhärent antimikrobieller Polymere vereintThe present invention is therefore based on the object of developing antimicrobial polymers as a fluid system which combines the described advantages of fluid systems with the advantages of inherently antimicrobial polymers
Es wurde nun überraschend gefunden, dass durch Verwendung von Emulgatoren im Herstellprozess der antimikrobiellen Polymere fluide antimikrobielle Produkte erhalten werden, die den beschriebenen Anforderungen in nahezu idealer Weise entsprechenIt has now surprisingly been found that by using emulsifiers in the production process of the antimicrobial polymers, fluid antimicrobial products are obtained which correspond to the described requirements in an almost ideal manner
Gegenstand der vorliegenden Erfindung sind daher mikrobizide Emulsionen, enthaltend mikrobizide PolymereThe present invention therefore relates to microbicidal emulsions containing microbicidal polymers
Die erfmdungsgemaßen Emulsionen sind in jedem Verhältnis mit Wasser mischbar und können daher zur Entkeimung von wassrigen Systemen wie Trinkwasser, Kuhlwassern, Dispersionsfarben oder Lacken verwendet werdenThe emulsions according to the invention can be mixed with water in any ratio and can therefore be used for the disinfection of aqueous systems such as drinking water, cooling water, Dispersion paints or varnishes can be used
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung von mikrobiziden Emulsionen, wobei mikrobizide Polymere durch Emulsionspolymerisation von entsprechenden Monomeren hergestellt werdenAnother object of the invention is a process for the preparation of microbicidal emulsions, microbicidal polymers being produced by emulsion polymerization of corresponding monomers
Die mikrobiziden Polymere können Stickstoff- und/oder Phosphorgruppen enthalten Die Emulsionspolymerisation zu den mikrobiziden Polymeren wird in bekannter Weise durchgeführt, d h es wird eine Emulsion aus Wasser, einem Emulgator, mindestens einem Monomeren und einem thermischen oder photochemischen Radikalstarter so zur Reaktion gebracht, dass eine Emulsion erhalten wird Es ist möglich, der Reaktion weiteres, ggf anderes Monomer oder eines der im Folgenden genannten Comonomere zuzusetzenThe microbicidal polymers can contain nitrogen and / or phosphorus groups. The emulsion polymerization to give the microbicidal polymers is carried out in a known manner, ie an emulsion of water, an emulsifier, at least one monomer and a thermal or photochemical radical initiator is reacted in such a way that a Emulsion is obtained It is possible to add further, possibly another monomer or one of the comonomers mentioned below to the reaction
Bevorzugte Monomere zur Herstellung der mikrobiziden Polymere sind Methacrylsaure-2- tert -butylaminoethylester, Methacrylsaure-2-diethylaminoethylester, Methacrylsaure-2- diethylaminomethylester, Acrylsaure-2-tert -butylaminoethylester, Acrylsaure-3-dimethyl- aminopropylester, Acrylsaure-2-diethylaminoethylester, Acrylsaure-2-dimethylaminoethylester,Preferred monomers for the preparation of the microbicidal polymers are methacrylic acid 2-tert-butylaminoethyl ester, methacrylic acid 2-diethylaminoethyl ester, methacrylic acid 2-diethylaminomethyl ester, acrylic acid 2-tert-butylaminoethyl ester, acrylic acid 3-dimethylaminopropyl ester, acrylic acid ethyl 2-diet acrylic acid 2-dimethylaminoethyl,
Dimethylaminopropylmethacrylamid, Diethylaminopropylmethacrylamid, Acrylsaure-3 -dime- thylaminopropylamid, 2-Methacryloyloxyethyltrimethylammoniummethosulfat, Methacrylsaure-2-diethylaminoethylester, 2-Methacryloyloxyethyltrimethylammoniumchlorid,Dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, acrylic acid-3-dimethylaminopropylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate, methacrylic acid-2-diethylaminoethyl ester, 2-methacryloyloxyethyltrimethylammonium chloride,
3 -Methacryloylaminopropyltrimethylammonium-chlorid, 2-3-methacryloylaminopropyltrimethylammonium chloride, 2-
Methacryloyloxyethyltrimethylammoniumchlorid, 2- Acryloyloxyethyl-4-benzoyl- dimethylammoniumbromid, 2- Methacryloyloxyethyl-4-benzoyldimethylammoniumbromid,Methacryloyloxyethyltrimethylammonium chloride, 2-acryloyloxyethyl-4-benzoyl-dimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammonium bromide,
Allyltriphenylphosphoniumbromid, Allyltriphenylphosphoniumchlorid, 2-Acrylamido-2-methyl- 1-propansulfonsaure, 2-Diethylaminoethylvinylether und/oder 3-AminopropylvinyletherAllyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-diethylaminoethyl vinyl ether and / or 3-aminopropyl vinyl ether
Die mikrobiziden Polymere können durch Copolymerisation aus den genannten Monomeren und mindestens einem weiteren Comonomeren hergestellt werdenThe microbicidal polymers can be prepared by copolymerization from the monomers mentioned and at least one further comonomer
Die weiteren Comonomere können Acrylate oder Methacrylate, z B Acrylsaure, tert -Butyl- methacrylat oder Methylmethacrylat, Styrol oder seinen Derivaten, Vinylchlorid, Vinylethern,The other comonomers can be acrylates or methacrylates, for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene or its derivatives, vinyl chloride, vinyl ethers,
Acrylamiden, Acrylnitrilen, Olefinen (Ethylen, Propylen, Butylen, Isobutylen), Allylverbindun- gen, Vinylketonen, Vinylessigsaure, Vinylacetat oder Vinylester, insbesondere z B Methacryl- sauremethylester, Methacrylsaureethylester, Methacrylsaurebutylester, Methacrylsaure-tert - butylester, Acrylsauremethylester, Acrylsaureethylester, Acrylsaurebutylester, Acrylsaure-tert - butylester, tert -Butylaminoethylester seinAcrylamides, 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, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid tert-butyl ester, tert-butylamino ethyl ester
Als Emulgator können ionische oder nicht-ionische Emulgatoren wie Polyethylenglycoldenvate, Polyethylenglykolether, insbesondere 4-Octylphenolpolyethoxylat (auch bekannt unter dem Markennamen Triton) Alkylbenzolsulfonate, Alkylsulfate, Alkylsulfonate, d h ethoxylierte Fettalkohole, Alkylphenole oder Fettsauren eingesetzt werdenIonic or non-ionic emulsifiers such as polyethylene glycol olates, polyethylene glycol ethers, in particular 4-octylphenol polyethoxylate (also known under the brand name Triton), alkylbenzenesulfonates, alkyl sulfates, alkyl sulfonates, ie ethoxylated fatty alcohols, alkylphenols or fatty acids, can be used as emulsifiers
Entsprechende antimikrobielle Beschichtungen können z B unmittelbar durch Aufstreichen oder Lackieren der antimikrobiell wirksamen Emulsion auf Oberflachen oder aber vorherige Zudosierung in weitere Beschichtungsformulierungen erhalten werden Da Emulsionspolymerisate im Allgemeinen höhere Molekulargewichte besitzen als Polymerisate, welche z B durch Losungs- oder Substanzpolymerisation hergestellt werden, ist es auf diesem Wege auch möglich, sehr hochmolekulare antimikrobielle Polymere herzustellen Weiterhin bieten sich solche Emulsionen zur antimikrobiellen Ausrüstung bzw Konservierung anderer technisch genutzer Emulsionen an, da man bei einer solchen Kombination im Regelfall zu sehr homogenen Produkten gelangt Auch die unmittelbare Zugabe antimikrobieller Emulsionen zu wassrigen Systemen, z B zur Entkeimung von Kühlwasserkreisläufen, ist problemlos möglichCorresponding antimicrobial coatings can be obtained, for example, directly by painting or varnishing the antimicrobially active emulsion on surfaces or prior metering into further coating formulations. Emulsion polymers generally have higher molecular weights than polymers which are produced, for example, by solution or bulk polymerization, it is high In this way it is also possible to produce very high molecular weight antimicrobial polymers. Emulsions of this type are also suitable for antimicrobial finishing or preservation of other technically used emulsions, since such a combination generally leads to very homogeneous products. The direct addition of antimicrobial emulsions to aqueous systems, e.g. B for the disinfection of cooling water circuits is possible without any problems
Verwendung der modifizierten PolymersubstrateUse of the modified polymer substrates
Weitere Gegenstande der vorliegenden Erfindung sind die Verwendung der erfindungsgemaß hergestellten antimikrobiellen Emulsionen zur Herstellung von antimikrobiell wirksamen Erzeugnissen und die so hergestellten Erzeugnisse als solche Solche Erzeugnisse basieren vorzugsweise auf Polyamiden, Polyurethanen, Polyetherblockamiden, Polyesteramiden oder - imiden, PVC, Polyolefinen, Silikonen, Polysiloxanen, Polymethacrylat, Polyacrylaten oder Polyterephthalaten, Metallen, Holzern, Steinen, Beton, Glasern und Keramiken, die mit erfindungsgemaßen Emulsionen beschichtete Oberflachen aufweisen oder aber in Form einer Farbe oder eines Lackes erhalten werdenThe present invention furthermore relates to the use of the antimicrobial emulsions produced according to the invention for the production of antimicrobially active products and the products thus produced as such. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or - imides, PVC, polyolefins, silicones, polysiloxanes, Polymethacrylate, polyacrylates or polyterephthalates, metals, wood, stones, concrete, glasses and ceramics which have surfaces coated with emulsions according to the invention or which are obtained in the form of a paint or varnish
Antimikrobiell wirksame Erzeugnisse dieser Art sind beispielsweise und insbesondere Ma- schinenteile für die Lebensmittelverarbeitung, Bauteile von Klimaanlagen, beschichtete Rohre, Halbzeuge, Bedachungen, Badezimmer- und Toilettenartikel, Kuchenartikel, Komponenten von Sanitareinrichtungen, Komponenten von Tierkafigen - und behausungen, Spielwaren, Komponenten in Wassersystemen, Lebensmittelverpackungen, Bedienelemente (Touch Panel) von Geraten und Kontaktlinsen, Baustoffe, Bau- und GartenholzerAntimicrobial products of this type are, for example, and especially Machine parts for food processing, components of air conditioning systems, coated pipes, semi-finished products, 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, building materials, building and garden wood
Die erfindungsgemaßen Emulsionen können überall verwendet werden, wo es auf möglichst bakterienfreie, algen- und pilzfreie, d h mikrobizide Oberflachen oder Oberflachen mit Antihafteigenschaften ankommt Verwendungsbeispiele für die erfindungsgemaßen Emulsionen finden sich in den folgenden BereichenThe emulsions according to the invention can be used wherever bacteria-free, algae and fungus-free surfaces, ie microbicidal surfaces or surfaces with non-stick properties are important. Examples of uses for the emulsions according to the invention can be found in the following areas
Marine Schiffsrumpfe, Hafenanlagen, Bojen, Bohrplattformen, Ballastwassertanks Haus Bedachungen, Keller, Wände, Fassaden, Gewächshäuser, Sonnenschutz, Gartenzaune, Holzschutz - Sanitär Öffentliche Toiletten, Badezimmer, Duschvorhange, Toilettenartikel,Marine hull, port facilities, buoys, drilling platforms, ballast water tanks, house roofs, basements, walls, facades, greenhouses, sun protection, garden fences, wood protection - sanitary Public toilets, bathrooms, shower curtains, toiletries,
Schwimmbad, Sauna, Fugen, DichtmassenSwimming pool, sauna, joints, sealing compounds
Lebensmittel Maschinen, Küche, Kuchenartikel, Schwämme, Spielwaren, Lebensmittelverpackungen, Milchverarbeitung, Trinkwassersysteme, Kosmetik Maschinenteile Klimaanlagen, Ionentauscher, Brauchwasser, Solaranlagen, Warme- tauscher, Bioreaktoren, MembranenFood machinery, kitchen, cake items, sponges, toys, food packaging, milk processing, drinking water systems, cosmetics, machine parts, air conditioners, ion exchangers, process water, solar systems, heat exchangers, bioreactors, membranes
Medizintechnik Kontaktlinsen, Windeln, Membranen, Implantate Gebrauchsgegenstande Autositze, Kleidung (Strumpfe, Sportbekleidung) , Krankenhauseinrichtungen, Türgriffe, Telefonhorer, Öffentliche Verkehrsmittel, Tierkafige, Registrierkassen, Teppichboden, TapetenMedical 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
Außerdem sind Gegenstande der vorliegenden Erfindung die Verwendung der erfindungsgemaßen Emulsionen oder Verfahren hergestellten Hygieneerzeugnisse oder medizintechnische Artikel Die obigen Ausführungen über bevorzugte Materialien gelten entsprechend Solche Hygieneerzeugnisse sind beispielsweise Zahnbürsten, Toilettensitze, Kamme und Verpackungsmaterialien Unter die Bezeichnung Hygieneartikel fallen auch andere Gegenstande, die u U mit vielen Menschen in Berührung kommen, wie Telefonhorer, Handlaufe von Treppen, Tur- und Fenstergriffe sowie Haltegurte und -griffe in öffentlichen Verkehrsmitteln. Medizintechnische Artikeln sind z. B. Katheter, Schläuche, Abdeckfolien oder auch chirurgische Bestecke.The present invention also relates to the use of the hygiene products or medical technology articles produced according to the emulsions or processes according to the invention. The above statements regarding preferred materials apply accordingly. Such hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials. The term hygiene articles also includes other objects which may also be associated with many people come into contact, such as telephone listeners, handrails of stairs, door and window handles as well as holding belts and handles in public places Transport. Medical technology articles are e.g. B. catheters, tubes, cover sheets or surgical cutlery.
Bevorzugt werden die mikrobiziden Emulsionen als Emulgator oder Zusatz zu anderen Emulsionen wie Latices, Dispersionsfarben, Kühlschmierstoffe, Lacke auf Wasserbasis oder kosmetische Formulierungen und zur Entkeimung von Kühlwasserkreisläufen verwendet.The microbicidal emulsions are preferably used as an emulsifier or as an additive to other emulsions such as latexes, emulsion paints, cooling lubricants, water-based paints or cosmetic formulations and for the disinfection of cooling water circuits.
Ein weiterer Gegenstand der vorliegenden Erfindung sind mikrobizide Dispersionen, hergestellt aus den erfindungsgemäßen mikrobiziden Emulsionen durch Trocknen und anschließender Redispergierung.The present invention further provides microbicidal dispersions prepared from the microbicidal emulsions according to the invention by drying and subsequent redispersion.
Weiterhin können die erfindungsgemäßen mikrobiziden Emulsionen zur Herstellung von mikrobiziden Beschichtungen oder als Klebstoff bzw. als Zusatz zu einem Klebstoff verwendet werden.Furthermore, the microbicidal emulsions according to the invention can be used to produce microbicidal coatings or as an adhesive or as an additive to an adhesive.
Die erfindungsgemäßen mikrobiziden Dispersionen, hergestellt aus den Emulsionen gemäß der Erfindung können ebenfalls zur Herstellung von mikrobiziden Beschichtungen sowie als oder in Klebstoffen verwendet werden.The microbicidal dispersions according to the invention, produced from the emulsions according to the invention, can also be used for the production of microbicidal coatings and as or in adhesives.
Die Emulsionen werden auf bekannte Weise vom Wasser befreit, bevorzugt sind Vakuumverdampfer. Der so erhaltene Feststoff kann nun einfach abgepackt und transportiert werden. Durch Redispergierung in Wasser wird eine Dispersion erhalten, die nahezu die gleichen mikrobiziden Eigenschaften wie die ursprüngliche Emulsion aufweist und eine ausreichende Stabilität besitzt.The emulsions are freed of water in a known manner, vacuum evaporators are preferred. The solid obtained in this way can now simply be packaged and transported. Redispersion in water gives a dispersion which has almost the same microbicidal properties as the original emulsion and has sufficient stability.
Zur weiteren Beschreibung der vorliegenden Erfindung werden die folgenden Beispiele gegeben, die die Erfindung weiter erläutern, nicht aber ihren Umfang begrenzen sollen, wie er in den Patentansprüchen dargelegt ist.To further describe the present invention, the following examples are given, which further illustrate the invention but are not intended to limit its scope as set out in the claims.
Beispiel 1:Example 1:
3 mL Dimethylaminopropylmethacrylamid (Fa. Aldrich), 4,4 g Triton X 405 (Fa. Aldrich), 25 mL VE-Wasser und 0, 1 g Kaliumperoxodisulfat (Fa Aldrich) werden in einem Dreihalskolben vorgelegt und unter Argonzustrom auf 60 °C erhitzt Danach werden über einen Zeitraum von 4 Stunden weitere 23 mL Dimethylaminopropylmethacrylamid zugetropft Anschließend rührt man die Mischung noch weitere 2 Stunden bei 60 °C, danach laßt man die entstandene Emulsion auf Raumtemperatur abkühlen3 mL dimethylaminopropyl methacrylamide (Aldrich), 4.4 g Triton X 405 (Aldrich), 25 ml of deionized water and 0.1 g of potassium peroxodisulfate (from Aldrich) are placed in a three-necked flask and heated to 60 ° C. under a stream of argon. A further 23 ml of dimethylaminopropyl methacrylamide are then added dropwise over a period of 4 hours. The mixture is then stirred for a further 2 hours at 60 ° C, then the resulting emulsion is allowed to cool to room temperature
Beispiel laExample la
0,02 mL der Emulsion aus Beispiel 1 werden mit 20 mL einer Testkeimsuspension von Pseudomonas aeruginosa, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 24 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Pseudomonas aeruginosa mehr nachweisbar0.02 mL of the emulsion from Example 1 are mixed with 20 mL of a test microbial suspension of Pseudomonas aeruginosa, which has a bacterial count of 10 7 per mL, and shaken. After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the bacterial count in the experiment determined After this time no germs of Pseudomonas aeruginosa are detectable
Beispiel lb 0,02 mL der Emulsion aus Beispiel 1 werden mit 20 mL einer Testkeimsuspension von Staphylococcus aureus, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 2 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbarExample Ib 0.02 mL of the emulsion from Example 1 are mixed with 20 mL of a test germ suspension of Staphylococcus aureus, which has a germ count of 10 7 per mL, and shaken. After a contact time of 2 hours, 1 mL of the test germ suspension is removed, and the germ count determined in the test batch After this time, no Staphylococcus aureus germs can be detected
Beispiel 2:Example 2:
2 mL tert -Butylaminoethylmethacrylat (Fa Aldrich), 5,7 g Triton X 405 (Fa Aldrich), 25 mL VE-Wasser und 0,08 g Kaliumperoxodisulfat (Fa Aldrich) werden in einem Dreihalskolben vorgelegt und unter Argonzustrom auf 60 °C erhitzt Danach werden über einen Zeitraum von 4 Stunden weitere 23 mL tert -Butylaminoethylmethacrylat zugetropft Anschließend rührt man die Mischung noch weitere 2 Stunden bei 60 °C, danach laßt man die entstandene Emulsion auf Raumtemperatur abkühlen2 mL tert-butylaminoethyl methacrylate (Aldrich), 5.7 g Triton X 405 (Aldrich), 25 mL deionized water and 0.08 g potassium peroxodisulfate (Aldrich) are placed in a three-necked flask and heated to 60 ° C under a stream of argon A further 23 ml of tert-butylaminoethyl methacrylate are then added dropwise over a period of 4 hours. The mixture is then stirred for a further 2 hours at 60 ° C., after which the resulting emulsion is allowed to cool to room temperature
Beispiel 2aExample 2a
0,02 mL der Emulsion aus Beispiel 2 werden mit 20 mL einer Testkeimsuspension von Pseudomonas aeruginosa, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 24 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Pseudomonas aeruginosa mehr nachweisbar0.02 ml of the emulsion from example 2 are mixed with 20 ml of a test germ suspension of Pseudomonas aeruginosa, which has a germ count of 10 7 per ml, and Shaken After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After this time, no Pseudomonas aeruginosa germs can be detected
Beispiel 2bExample 2b
0,02 mL der Emulsion aus Beispiel 2 werden mit 20 mL einer Testkeimsuspension von Staphylococcus aureus, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 2 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbar0.02 mL of the emulsion from Example 2 are mixed with 20 mL of a test germ suspension of Staphylococcus aureus, which has a bacterial count of 10 7 per mL, and shaken. After a contact time of 2 hours, 1 mL of the test germ suspension is removed, and the bacterial count in the experiment determined After this time no more germs from Staphylococcus aureus are detectable
Beispiel 2cExample 2c
5 mL der Emulsion aus Beispiel 2 werden in eine Petrischale gegeben, und anschließend wird dem Produkt durch Trocknung bei 70 °C über einen Zeitraum von 24 Stunden das Wasser entzogen 0,1 g des getrockneten Produktes werden dann mit 20 mL einer Testkeimsuspension von Pseudomonas aeruginosa, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 24 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Pseudomonas aeruginosa mehr nachweisbar5 ml of the emulsion from example 2 are placed in a petri dish, and then the water is removed from the product by drying at 70 ° C. over a period of 24 hours. 0.1 g of the dried product is then mixed with 20 ml of a test germ suspension from Pseudomonas aeruginosa , which has a bacterial count of 10 7 per mL, added and shaken After a contact time of 24 hours, 1 mL of the test microbial suspension is removed and the bacterial count is determined in the test mixture. After this time, no Pseudomonas aeruginosa germs can be detected
Beispiel 2dExample 2d
In 5 mL der Emulsion aus Beispiel 2 wird für die Dauer von 5 Sekunden ein Aluminiumblech der Grosse 2 mal 2 cm getaucht Anschließend wird der Beschichtung durch Trocknung bei 70 °C über einen Zeitraum von 24 Stunden das Wasser entzogen Das getrocknete Blech wird auf den Boden eines Becherglases gelegt, mit 20 mL einer Testkeimsuspension von Pseudomonas aeruginosa, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 24 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Pseudomonas aeruginosa mehr nachweisbarAn aluminum sheet the size of 2 by 2 cm is immersed in 5 ml of the emulsion from Example 2 for 5 seconds. The water is then removed from the coating by drying at 70 ° C. for a period of 24 hours. The dried sheet is placed on the floor placed in a beaker, mixed with 20 mL of a test microbial suspension of Pseudomonas aeruginosa, which has a bacterial count of 10 7 per mL, and shaken After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the number of microbes in the test mixture is determined Pseudomonas aeruginosa no longer detectable
Beispiel 3:Example 3:
2 mL tert -Butylaminoethylmethacrylat (Fa Aldrich), 5,5 g Triton X 405 (Fa Aldrich), 25 mL VE-Wasser und 0,08 g Kaliumperoxodisulfat (Fa Aldrich) werden in einem Dreihalskolben vorgelegt und unter Argonzustrom auf 60 °C erhitzt Danach werden über einen Zeitraum von 4 Stunden eine Mischung aus 13 mL tert -Butylaminoethylmethacrylat und 10 mL Methacrylsauremethylester zugetropft Anschließend rührt man die Mischung noch weitere 2 Stunden bei 60 °C, danach laßt man die entstandene Emulsion auf Raumtemperatur abkühlen2 mL tert-butylaminoethyl methacrylate (Aldrich), 5.5 g Triton X 405 (Aldrich), 25 mL Demineralized water and 0.08 g of potassium peroxodisulfate (from Aldrich) are placed in a three-necked flask and heated to 60 ° C. under a stream of argon. A mixture of 13 ml of tert-butylaminoethyl methacrylate and 10 ml of methyl methacrylate are then added dropwise over a period of 4 hours the mixture for a further 2 hours at 60 ° C, after which the resulting emulsion is allowed to cool to room temperature
Beispiel 3 aExample 3 a
0,02 mL der Emulsion aus Beispiel 3 werden mit 20 mL einer Testkeimsuspension von Pseudomonas aeruginosa, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 24 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit ist die Keimzahl auf 107 pro mL gesunken0.02 mL of the emulsion from Example 3 are mixed with 20 mL of a test microbial suspension of Pseudomonas aeruginosa, which has a bacterial count of 10 7 per mL, and shaken. After a contact time of 24 hours, 1 mL of the test microbial suspension is removed, and the bacterial count in the experiment determined After this time the number of bacteria has dropped to 10 7 per mL
Beispiel 3b 0,02 mL der Emulsion aus Beispiel 2 werden mit 20 mL einer Testkeimsuspension von Staphylococcus aureus, welche eine Keimzahl von 107 pro mL besitzt, versetzt und geschüttelt Nach einer Kontaktzeit von 2 Stunden wird 1 mL der Testkeimsuspension entnommen, und die Keimzahl im Versuchsansatz bestimmt Nach Ablauf dieser Zeit sind keine Keime von Staphylococcus aureus mehr nachweisbar Example 3b 0.02 ml of the emulsion from example 2 are mixed with 20 ml of a test germ suspension of Staphylococcus aureus, which has a germ count of 10 7 per ml, and shaken. After a contact time of 2 hours, 1 ml of the test germ suspension is removed, and the germ count determined in the test batch After this time, no Staphylococcus aureus germs can be detected

Claims

Patentansprüche:claims:
1 Mikrobizide Emulsionen, enthaltend mikrobizide Polymere1 Microbicidal emulsions containing microbicidal polymers
2 Mikrobizide Emulsion nach Anspruch 1, dadurch gekennzeichnet, dass die mikrobizid wirksamen Polymere Stickstoffgruppen enthalten2 microbicidal emulsion according to claim 1, characterized in that the microbicidal polymers contain nitrogen groups
3 Mikrobizide Emulsion nach Anspruch 1, dadurch gekennzeichnet, dass die mikrobizid wirksamen Polymere Phosphorgruppen enthalten3 microbicidal emulsion according to claim 1, characterized in that the microbicidal polymers contain phosphorus groups
4 Mikrobizide Emulsion nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Emulsion nichtionische Emulgatoren enthalt4 microbicidal emulsion according to one of claims 1 to 3, characterized in that the emulsion contains nonionic emulsifiers
5 Mikrobizide Emulsion nach Anspruch 4, dadurch gekennzeichnet, dass die nichtionischen Emulgatoren Polyethylenglykolderivate sind5 microbicidal emulsion according to claim 4, characterized in that the nonionic emulsifiers are polyethylene glycol derivatives
6 Mikrobizide Emulsion nach Anspruch 5, dadurch gekennzeichnet, dass es sich bei dem nichtionischen Emulgator um 4-Octylphenolpolyethoxylat handelt6 microbicidal emulsion according to claim 5, characterized in that it is 4-octylphenol polyethoxylate in the nonionic emulsifier
7 Mikrobizide Emulsion nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die mikrobizid wirksamen Polymere aus mindestens einem der folgenden Monomere hergestellt wurden7 microbicidal emulsion according to any one of claims 1 to 6, characterized in that the microbicidal polymers were prepared from at least one of the following monomers
Methacrylsaure-2-tert -butylaminoethylester, Methacrylsaure-2-diethylaminoethylester, Methacrylsaure-2-diethylaminomethylester, Acrylsaure-2-tert -butylaminoethylester,Methacrylic acid 2-tert-butylaminoethyl ester, methacrylic acid 2-diethylaminoethyl ester, methacrylic acid 2-diethylaminomethyl ester, acrylic acid 2-tert-butylaminoethyl ester,
Acrylsaure-3 -dimethylaminopropylester, Acrylsaure-2-diethylaminoethylester, Acrylsaure-3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, acrylic acid
2-dimethylaminoethylester, Dimethylaminopropylmethacrylamid, Diethylamino- propylmethacrylamid, Acrylsäure-3-dimethylaminopropylamid, 2-Methacryloyloxy- ethyltrimethylammoniummethosulfat, Methacrylsäure-2-diethylaminoethylester, 2- Methacryloyloxyethyltrimethylammoniumchlorid, 3-Methacryloylaminopropyltrime- thylammonium-chlorid, 2-Methacryloyloxyethyltrimethylammoniumchlorid, 2- Acryloyloxyethyl-4-benzoyldimethylammoniumbromid, 2- Methacryloyloxyethyl-4- benzoyldimethylammoniumbromid, Allyltriphenylphosphoniumbromid, Allyltriphenyl- phosphoniumchlorid, 2-Acrylamido-2-methyl-l-propansulfonsäure, 2-Diethylamino- ethylvinylether, 3 -Aminopropylvinylether .2-dimethylaminoethyl ester, dimethylaminopropyl methacrylamide, diethylamino propyl methacrylamide, acrylic acid-3-dimethylaminopropylamide, 2-methacryloyloxy-ethyltrimethylammonium methosulfate, methacrylic acid-2-diethylaminoethyl ester, 2-methacryloyloxyethyltrimethylammonium chloride, 3-methacryloylaminopropyltrimethylammonium methyl-2-methacryloyloxyethyloxy-4-methylethyl-4-methacryloyloxyethyloxy-methyl-4-methacrylate benzoyldimethylammonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-l-propanesulfonic acid, 2-diethylaminoethyl vinyl ether, 3-aminopropyl vinyl ether.
8. Mikrobizide Emulsion nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass mikrobizide Polymere weitere Comonomere enthalten.8. Microbicidal emulsion according to one of claims 1 to 7, characterized in that microbicidal polymers contain further comonomers.
9. Mikrobizide Emulsion nach Anspruch 8, dadurch gekennzeichnet, dass die weiteren Comonomere Verbindungen aus der Gruppe Acrylate, Methacrylate, Styrol, Styrolderivate, Vinylchlorid, Vinylether, Acrylamide, Acrylnitrile, Olefine, Allylverbindungen, Vinylketone, Vinylessigsäure, Vinylacetat oder Vinylester sind.9. Microbicidal emulsion according to claim 8, characterized in that the further comonomers are compounds from the group consisting of acrylates, methacrylates, styrene, styrene derivatives, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins, allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters.
10. Mikrobizide Emulsion nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass die weiteren Comonomere Acrylsäure, tert.-Butylmethacrylat, Metha-crylsäureme- thylester, Methacrylsäureethylester, Methacrylsäurebutylester, Methacrylsäure-tert.- butylester, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäurebutylester, Acrylsäure- tert. -butylester oder tert. -Butylaminoethylester sind.10. Microbicidal emulsion according to claim 8 or 9, characterized in that the further comonomers are acrylic acid, tert-butyl methacrylate, methyl methacrylate, methyl methacrylate, methacrylate butyl ester, methacrylate tert-butyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid , -butyl ester or tert. -Butylaminoethyl esters are.
11. Verfahren zur Herstellung mikrobizider Emulsionen, dadurch gekennzeichnet, dass mikrobizide Polymere durch Emulsionspolymerisation hergestellt werden.11. A process for the preparation of microbicidal emulsions, characterized in that microbicidal polymers are prepared by emulsion polymerization.
12. Verfahren zur Herstellung mikrobizider Emulsionen nach Anspruch 11, wobei die mikrobizid wirksamen Polymere Stickstoffgruppen enthalten. Verfahren zur Herstellung mikrobizider Emulsionen nach Anspruch 11, wobei die mikrobizid wirksamen Polymere Phosphorgruppen enthalten12. A method for producing microbicidal emulsions according to claim 11, wherein the microbicidally active polymers contain nitrogen groups. A method of producing microbicidal emulsions according to claim 11, wherein the microbicidal polymers contain phosphorus groups
Verfahren zur Herstellung mikrobizider Emulsionen nach einem der Ansprüche 11 bis 13, wobei die Emulsion nichtionische Emulgatoren enthaltProcess for the preparation of microbicidal emulsions according to one of claims 11 to 13, wherein the emulsion contains nonionic emulsifiers
Verfahren zur Herstellung mikrobizider Emulsionen nach Anspruch 14, wobei die nichtionischen Emulgatoren Polyethylenglykolderivate sindA method of making microbicidal emulsions according to claim 14, wherein the nonionic emulsifiers are polyethylene glycol derivatives
Verfahren zur Herstellung mikrobizider Emulsionen nach Anspruch 14 oder 15, wobei es sich bei dem nichtionischen Emulgator um 4-Octylphenolpolyethoxylat handeltA method of producing microbicidal emulsions according to claim 14 or 15, wherein the nonionic emulsifier is 4-octylphenol polyethoxylate
Verfahren zur Herstellung mikrobizider Emulsionen, wobei die mikrobizid wirksamen Polymere aus mindestens einem der folgenden Monomere hergestellt wurden Methacrylsaure-2-tert -butylaminoethylester, Methacrylsaure-2-diethylaminoethylester,Process for the preparation of microbicidal emulsions, the microbicidal polymers being prepared from at least one of the following monomers: 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate,
Methacrylsaure-2-diethylaminomethylester, Acrylsaure-2-tert -butylaminoethylester,2-diethylaminomethyl methacrylate, 2-tert-butylaminoethyl acrylate,
Acrylsaure-3 -dimethylaminopropylester, Acrylsaure-2-diethylaminoethylester, Acrylsaure- 2-dimethylaminoethylester, Dimethylaminopropylmethacrylamid, Diethylamino- propylmethacrylamid, Acrylsaure-3 -dimethylaminopropylamid, 2-Methacryloyloxy- ethyltrimethylammoniummethosulfat, Methacrylsaure-2-diethylaminoethylester, 2-3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, diethylamino propyl methacrylamide, 3-dimethylaminopropylamide acrylate, 2-methacryloyloxy-ethyltrimethylammonium methamethyl methacrylate, methacrylate 2, methacrylate,
Methacryloyloxyethyltrimethylammoniumchlorid, 3-Methacryloylaminopropyltrime- thylammonium-chlorid, 2-Methacryloyloxyethyltrimethylammoniumchlorid, 2-Methacryloyloxyethyltrimethylammonium chloride, 3-methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride, 2-
Acryloyloxyethyl-4-benzoyldimethylammoniumbromid, 2- Methacryloyloxyethyl-4- benzoyldimethylammoniumbromid, Allyltriphenylphosphoniumbromid, Allyltriphenyl- phosphoniumchlorid, 2-Acrylamido-2-methyl-l-propansulfonsaure, 2-Diethylamino- ethylvinylether, 3 - AminopropylvinyletherAcryloyloxyethyl-4-benzoyldimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoyldimethylammonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-l-propanesulfonic acid, 2-diethylamino-ethylvinyl
Verfahren zur Herstellung mikrobizider Emulsionen nach einem der Ansprüche 11 bis 17, wobei die mikrobiziden Polymere weitere Comonomere enthaltenProcess for the preparation of microbicidal emulsions according to one of claims 11 to 17, wherein the microbicidal polymers contain further comonomers
Verfahren zur Herstellung mikrobizider Emulsionen nach Anspruch 18, wobei die weiteren Comonomere Verbindungen aus der Gruppe Acrylate, Methacrylate, Styrol, Styrolderivate, Vinylchlorid, Vinylether, Acrylamide, Acrylnitrile, Olefine, Allylverbindungen, Vinylketone, Vinylessigsaure, Vinylacetat oder Vinylester sindA process for the preparation of microbicidal emulsions according to claim 18, wherein the further comonomers are compounds from the group consisting of acrylates, methacrylates, styrene, Styrene derivatives, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins, allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters
Verfahren zur Herstellung mikrobizider Emulsionen nach Anspruch 18 oder 19, wobei die weiteren Comonomere Acrylsaure, tert -Butylmethacrylat, Metha-crylsauremethylester,A process for the preparation of microbicidal emulsions according to claim 18 or 19, wherein the further comonomers are acrylic acid, tert-butyl methacrylate, methyl methacrylate,
Methacrylsaureethylester, Methacrylsaurebutylester, Methacrylsaure-tert -butylester,Methyl methacrylate, butyl methacrylate, tert-butyl methacrylate,
Acrylsauremethylester, Acrylsaureethylester, Acrylsaurebutylester, Acrylsaure-tert - butylester oder tert -Butylaminoethylester sindAcrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid tert-butyl ester or tert-butylaminoethyl ester
Mikrobizide Dispersion, hergestellt durch Trocknen einer mikrobiziden Emulsionen gemäß einem der Ansprüche 1 bis 10 und anschließende Redispergierung in WasserMicrobicidal dispersion, produced by drying a microbicidal emulsions according to one of claims 1 to 10 and subsequent redispersion in water
Verwendung der mikrobiziden Emulsionen nach einem der Ansprüche 1 bis 10 als Zusatz zu anderen EmulsionenUse of the microbicidal emulsions according to one of claims 1 to 10 as an additive to other emulsions
Verwendung nach Anspruch 21 , dadurch gekennzeichnet, dass die anderen Emulsionen Latices, Dispersionsfarben, Lacke auf Wasserbasis, Kühl Schmierstoffe oder kosmetische Formulierungen sindUse according to claim 21, characterized in that the other emulsions are latices, emulsion paints, water-based paints, cooling lubricants or cosmetic formulations
Verwendung der mikrobiziden Emulsionen nach einem der Ansprüche 1 bis 10 zur Entkeimung von KühlwasserkreisläufenUse of the microbicidal emulsions according to one of claims 1 to 10 for the disinfection of cooling water circuits
Verwendung der mikrobiziden Dispersion gemäß Anspruch 21 als Zusatz zu anderen Emulsionen, zu Latices, Dispersionsfarben, Lacke auf Wasserbasis oder zur Entkeimung von KühlwasserkreisläufenUse of the microbicidal dispersion as claimed in claim 21 as an additive to other emulsions, to latices, emulsion paints, water-based paints or for the disinfection of cooling water circuits
Verwendung der mikrobiziden Emulsionen nach einem der Ansprüche 1 bis 10 als EmulgatorUse of the microbicidal emulsions according to one of claims 1 to 10 as an emulsifier
Verwendung der mikrobiziden Emulsionen nach einem der Ansprüche 1 bis 10 zur Herstellung von mikrobiziden Beschichtungen oder als Klebstoff Use of the microbicidal emulsions according to one of claims 1 to 10 for the production of microbicidal coatings or as an adhesive
8. Verwendung der mikrobiziden Dispersionen nach Anspruch 21 zur Herstellung von mikrobiziden Beschichtungen oder als Klebstoff. 8. Use of the microbicidal dispersions according to claim 21 for the production of microbicidal coatings or as an adhesive.
EP02712830A 2001-03-08 2002-01-22 Microbicidal fluid systems using antimicrobial polymers Withdrawn EP1367890A1 (en)

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