WO1991003938A1 - Revetement polymere antimicrobien - Google Patents

Revetement polymere antimicrobien Download PDF

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Publication number
WO1991003938A1
WO1991003938A1 PCT/US1990/003922 US9003922W WO9103938A1 WO 1991003938 A1 WO1991003938 A1 WO 1991003938A1 US 9003922 W US9003922 W US 9003922W WO 9103938 A1 WO9103938 A1 WO 9103938A1
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Prior art keywords
film
monomer
vinyl
acid
sulfonic acid
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PCT/US1990/003922
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English (en)
Inventor
Isaac Shun-Yen Sze
Richard B. Greenwald
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Ecolab Incorporated
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Publication of WO1991003938A1 publication Critical patent/WO1991003938A1/fr

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    • 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
    • A01N25/24—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 containing ingredients to enhance the sticking of the active ingredients

Definitions

  • the invention relates to an antimicrobial composition, particularly to liquid antimicrobial compositions that yield adherent, transparent, abrasion resistant polymeric films having effective, prolonged antimicrobial properties.
  • compositions intended for the controlled release of a disinfectant from a film of stabilized hydrophilic polymer are disclosed in U.S. Patent No. 3,966,902.
  • the polymer complex is stabilized as a metal complex by the addition of an inorganic aluminum, zirconium or zinc salt, such as aluminum chloride hydrate, to the polymerization mixture.
  • the stabilization adjuvant is necessary because, upon contact with water, films of simple hydrogels become highly swollen and rapidly elute their additives. Furthermore, dry films, both simple and metal complexed hydrogels, do not adhere well to ceramic and other hard surfaces and can lose their adhesion completely when wetted.
  • U.S. Patent No. 2,689,837 discloses polymeric vinyl halides having improved resistance to deterioration caused by fungal and bacterial attack, which incorporate copper 8-quinolinolate into the polymer.
  • U.S. Patent No. 3,577,566 discloses a spray-on bandage material using acrylate and methacrylate polymers that may contain germicides or fungicides.
  • Phenols and thiophenols are known antimicrobial agents that have been incorporated into polymeric compounds.
  • U.S. Patent No. 2,875,097 discloses the incorporation of phenolic compounds into polymers comprising heterocyclic nitrogen compounds. These polymers are used to render fabrics resistant to fungi and insects.
  • U.S. Patent No. 2,873,263 discloses an antibacterial polymeric resin used for fabricating plastic articles. These resins are formed by polymerizing an unsaturated monomer, such as alkyl acrylate, in the presence of certain aromatic phenols or thiophenols.
  • antimicrobial systems can provide adequate sanitization of many environmental surfaces.
  • many consumers desire to have a system that can sanitize surfaces without the addition of any small molecule antimicrobial into the environment that can be thought to be potentially harmful. Therefore, a continuing need exists for an antimicrobial composition capable of forming a strong, small molecule antimicrobial free, polymeric film which provides rapid surface kill of pathogenic bacteria and other potentially harmful microorganisms.
  • a need also exists for an antimicrobial polymeric film capable of providing a water-resistant surface with prolonged life and prolonged resistance to microbial growth.
  • the liquid film-forming composition When applied to a target surface, the liquid film-forming composition yields a strongly antimicrobial polymeric film.
  • the film protects the surface from microbial growth by forming an acidic, aqueous layer that can maintain a pH which can kill microbial growth and sanitize the treated surface.
  • the polymer comprises repeating units derived from at least one monomer with a pendent acidic group having a pKa less than 3 or preferably less than 2.
  • the term "prolonged” is intended to refer to retention of substantial antimicrobial action greater than 4 log reduction, preferably greater than 5 log reduction of microbial population as determined by laboratory test methods after 2 water washes and between a 4 log and a 3 log reduction after 2-10 water washes.
  • the polymer is typically applied as a liquid solution or dispersion in a suitable solvent or medium.
  • An aqueous liquid can be used with the benefit that the polymer antimicrobial activity needs no activation because water in the film, when formed, can act to sanitize. Films cast from non-aqueous solution must be wet to create a sanitizing pH.
  • the antimicrobial film must comprise at least one monomer having a pendent acidic group with a pKa of less than 3 or preferably 2.
  • the pendent acidic group may comprise a sulfonic acid group, a phosphoric or phosphonic acid group, a carboxylic acid group activated by a strong electron withdrawing group, or any other pendent groups acting as an acid and capable of being incorporated into the polymer.
  • the acid group can be grafted onto a preformed polymer.
  • the polymer is substantially uncrosslinked, and the acid functional film may be dissolved or suspended in a suitable solvent or medium and the resulting solution used directly as a liquid sanitizing composition.
  • the liquid composition may be applied to a surface by spraying, wiping, pouring and the like.
  • the resultant films may be clear or opaque. The films strongly adhere to a multitude of surfaces and are resistant to abrasion.
  • the film appears to act as an antimicrobial agent by releasing an active antimicrobial concentration of protons [H+] when in contact with water.
  • the film is activated.
  • a thin aqueous layer of a highly acidic nature creates an environment unsuitable for microorganisms to live or reproduce in.
  • a certain mole fraction of monomer, with a carboxylic acid group having a pKa of ⁇ 3 or preferably ⁇ 2 reduces microbial populations by 5 orders of magnitude in as short a time as 15-30 minutes.
  • the film may be reactivated many times by periodic wiping with a damp cloth or sponge or any other means designed to contact the surface with water.
  • a surface that is coated with an antimicrobial film of the invention will provide prolonged protection against microorganisms. Coatings of the instant antimicrobial composition can be applied to surfaces found in homes, hospitals, schools and the workplace. The films will be useful to combat diseases that can be spread by a wide variety of microorganisms.
  • the instant microbial composition may be applied to a surface in a number of ways.
  • the films can be readily deposited from dilute aqueous solutions or dispersions of the copolymer in an aqueous solution.
  • the compound can be dissolved in a suitable solvent, preferably an organic solvent.
  • a suitable solvent preferably an organic solvent.
  • the choice of solvents relates to desired rates of evaporation, of flammability concerns, toxicity concerns, etc.
  • the preferred solvent is a water-alcohol mixture.
  • the instant microbial composition can be applied to a surface by a number of methods including the wiping of the composition onto a surface with a cloth or sponge; pouring the composition onto a surface and spreading it with a mop, squeegee sponge, or cloth; dispensing the composition from a container equipped with a pump spray mechanism; dispensing the composition propelled by an aerosol from a suitable pressurized container; providing the composition in sufficient concentrations on a cloth or other absorbent carrier; and packaging the pre-moistened carriers for disposable uses and other methods capable of applying liquid to surfaces.
  • the film may be activated by contact with moisture from any means. Contact with atmospheric humidity can assist in maintaining treated surfaces in a substantially microbe-free condition, while exposure to larger amounts of water, as whe the surface is moistened by wiping with a damp material, foo residues, dishwater, and the like, can lead to the release of protons, creating an acidic environment.
  • the polymeric films remain clear and non-tacky and, thus, do not detract from the appearance of the surfaces to which they are applied.
  • Hard surfaces suitable for coating the instant polymeric films include surfaces composed of refractory materials, such as glazed and unglazed tile, brick, porcelain, ceramics, metals, and glass; and hard plastics, such as formica, polystyrenes, vinyls, acrylics, polyesters, and the like.
  • the liquid composition is preferably coated at a thickness efficient to form a residual film of about 0.01-5 millimeters, with the most preferred being 0.5-1.0 millimeters.
  • the antimicrobial polymer of the invention can be made in two primary alternative methods.
  • the polymer can be formed from the monomer having a pendent acid group with a pKa of less than 3 or preferably less than 2.
  • a preformed polymer molecule can have grafted onto the polymer chain a group containing the pendent acidic group having a pKa of less than 3.
  • Monomers that can be used either in the formation of the polymer chain or in the formation of an acidic group containing graft moiety include monomers having pendent acid functionality.
  • the monomers of the invention are typically vinyl unsaturated monomers having an ethylenically unsaturated group connected to an acid group with a pKa of less than 3 through a linking moiety.
  • the linking moiety can be formed from a large variety of well known and understood compositions including aromatic groups, aliphatic groups, quaternary amino groups, amide groups, polyether groups, saturated cyclic groups, ester groups, amine groups, etc.
  • the preferred pendent acidic functionality can be in the form of a sulfonic acid group, a phosphoric acid group, an activated phenolic group, an activated carboxylic acid group, or mixtures thereof.
  • Such electron withdrawing groups are common halogen species including fluoride, chloride, bromide, iodine, nitro groups, ethoxy groups, etc. Hydrogen and lower alkyls are not electron withdrawing groups.
  • Typical sulfonic acid containing monomers include vinyl aromatic sulfonic acids such as vinyl benzene sulfonic acid, vinyl benzyl sulfonic acid, etc.; acrylic monomers containing a sulfonic acid group according to the following formula:
  • R comprises a hydrogen or a C ⁇ alkyl group
  • A comprises an alkylene group, a cyclic alkylene group, a phenyl group, or a group consisting of the following:
  • the preferred sulfonic acid containing monomers comprise a hydrophilic acrylamido sulfonic acid or sulfonate monomer of the following formula:
  • R is a straight or branched alkaline group of up to 10 carbon atoms, and R' is hydrogen or a C ⁇ lower alkyl.
  • the monomer can be used in the form of a sodium, potassium, ammonium or other salt of the sulfonic acid group.
  • the most preferred sulfonic acid containing monomer comprises 2-acryloamido-2-methylpropane sulfonic acid (AMPS) having the following structural formula:
  • Phosphoric acid monomers comprise a class of monomers similar to the sulfonic acid monomers except that the monomers have phosphoric or phosphonic acid groups in place of the sulfonic acid group.
  • Active phenolic containing monomers are vinyl unsaturated it -.mers containing activated phenolic groups. Such monomers ha e formulas including:
  • E and E' are electron withdrawing groups and A is a linking group as set forth above for the acrylic monomers.
  • Typical electron withdrawing groups include nitro, common halogens including chloride, fluoride, bromide, and iodide, alkoxy groups, etc.
  • the activated carboxylic acid monomers include vinyl unsaturated carboxylic acids having an electron withdrawing group in a position that can activate the carboxylic acid functionality. Typically the electron withdrawing group is positioned on an atom adjacent to the carboxylic acid group.
  • Such monomers are typically represented by the following formula:
  • E represents a common electron withdrawing group as set forth above.
  • Another activated carboxylic acid includes an electron withdrawing group immediately adjacent the carboxylic acid.
  • A is substituted with an electron withdrawing group and is a common C ⁇ . 6 alkylene or cycloalkylene group.
  • Preferred monomers include 2-chloropropeneoic acid, 2- fluoropropeneoic acid, 2-chlorobuteneoic acid, 2- fluorobuteneoic acid, 2-chloro-4-vinyl-cyclohexane carboxyli acid and others. Homopolymer
  • the monomers described may be homopolymerized to form a film-forming polymer.
  • the resultant film has prolonged antimicrobial properties.
  • the homopolymer, as well as the copolymer and terpolymers described below, can be prepared b carrying out the polymerization of the monomers in a solvent or solvent mixture and at concentrations wherein the resultant polymers remain in solution.
  • Preferred solvents include lower alkanols, such as ethanol; ketones, such as acetone, glycol esters or ethers; lower (alkyl) acetates; tetrahydrofuran; dimethylformamide; and the like.
  • the monomeric starting materials are typically dissolved in a solvent to the desired concentration, e.g., to a total concentration of about 10 to 35% by weight, although somewhat higher or lower concentrations may be employed in some cases.
  • the polymerization reaction is initiated in a conventional manner, preferably by use of a catalytic amount of a suitable initiator.
  • suitable initiators include 2,2'-azobis [2-methyl propionitrile] [AIBN], dibenzoyl peroxide, tert-butyl peroctoate, cumene hydroperoxide, diisopropyl percarbonate, ammonium persulfate, and the like, per se, or in combination with reducing agent in the form of an oxidation-reduction system.
  • the reaction mixture may be agitated and heated, preferably under an inert atmosphere, to about 50 to 100°C, preferably to about 75-95°C
  • a solution of polymer results which can be applied to the target surface without further purification or concentration, or can be collected and redissolved in another solvent.
  • Copolymer The monomers listed above may be copolymerized with alpha, beta-unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, itaconic acid, aconitic acid, cinnamic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid, and the like.
  • the preferred carboxylic acid comonomer is methacrylic acid.
  • the pendent acidic monomers may be copolymerized with alpha, beta-unsaturated carboxylic acid esters of the carboxylic acids described above.
  • esters include aromatic esters, cycloakyl esters, alkyl esters, (hydroxy) alkyl esters, or (alkoxy) alkyl esters.
  • the carboxylic acid ester comonomer typically is present in a concentration of about 5-60% by weight, and preferably about 10-45% by weight of the total polymer.
  • the term "cycloalkyl ester” includes mono-, bi- and tricycloalkyl esters
  • aromatic ester includes heteroaromatic esters.
  • cycloalkyl and aromatic esters are those of acrylic acid, methacrylic acid, or itaconic acid.
  • Useful aromatic esters of these acids include phenyl, benzyl, tolyl, tetrahydro urfuryl, and phenoxyethyl esters.
  • Useful cycloalkyl esters include (C 5 -C 12 ) cycloalkyls, e.g., the cyclohexyl, cyclopentyl, isobornyl and adamantyl esters of these acids.
  • Preferred (hydroxy) alkyl ester comonomers include (2- hydroxyethyl) methacrylate, (2-hydroxyethyl) ethacrylate, (2-hydroxyethyl) acrylate, (3-hydroxypropyl) methacrylate, (3-hydroxypropyl) acrylate, or (3-hydroxy-propyl) ethacrylate.
  • Alkyl and (alkoxy) alkyl esters of alpha, beta-unsaturated carboxylic acids can be used in combination with the aromatic and/or cycloalkyl ester.
  • the alkyl esters will be selected from high alkyl esters, such as those of about 5-22 carbon atoms, most preferably about 7-12 carbon atoms.
  • the alkyl and (alkoxy) alkyl esters of acrylic acid, methacrylic acid and itaconic acid are preferred for use as comonomers.
  • Examples of useful (C 5 -C 12 ) alkyl esters include: hexyl, octyl, ethyl(hexyl) , isodecyl, and lauryl acrylates, methacrylates and itaconates.
  • Examples of (alkoxy)alky1 esters useful as comonomers include (Cj-C 4 ) alkoxyl-(C-Ci)alkyl esters of acrylic, methacrylic or itaconic acids such as (methoxy) ethyl, (ethoxy) ethyl, (methoxy) propyl, (ethoxy) propyl, and the like.
  • esters examples include: (2- hydroxyethyl)acrylate or methacrylate, (hydroxypropyl) acrylate or methacrylate, (dimethyl aminoethyl) methacrylate, (piperidinoethyl) methacrylate, (morpholino-ethyl) methacrylate, methacrylglycolic acid, the monomethacrylates of glycol, glycerol and other polyhydric alcohols, monomethacrylates of dialkylene glycols and polyalkylene glycols.
  • Alpha, beta-unsaturated amides may also be copolymerized with the aforementioned monomers, including acrylamide, methacrylamide, diacetone acrylamide, methylolacrylamide, methylolmethacrylamide, and the like.
  • Terpolymers including acrylamide, methacrylamide, diacetone acrylamide, methylolacrylamide, methylolmethacrylamide, and the like.
  • a preferred terpolymer of the present invention includes acrylamido-2-methylpropane sulfonic acid, ethylmethacrylate and hydroxyethyl methacrylate. Ratios of the monomers of the terpolymer acrylamidopropanesulfonic acid, ethylmethacrylate, hydroxymethylmethacrylate range from 1-2, 1-7, 1-4, respectively.
  • hydroxyethylmethacrylate improves the film properties such as adhesion and durability of the antimicrobial film.
  • Other terpolymers include the use of hydroxy ethyl methacrylate and ethyl methacrylate in conjunction with other monomers such as itaconic acid, acrylic acid, styrene sulfonic acid, styrene phosphonic acid, chloroacrylic acid, bromoacrylic acid, and cyanoacrylic acid.
  • the monomers listed above may be copolymerized with alpha, beta-unsaturated carboxylic acids, such as methacrylic acid, aconitic acid, cinnemic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid, and the like.
  • carboxylic acid termonomer is methacrylic acid.
  • the pendent acidic monomers may be terpolymerized with alpha, beta-unsaturated carboxylic acid esters of the carboxylic acids described above.
  • esters include aromatic esters, cycloalkyl esters, alkyl esters, (hydroxy) lkyl esters, or (alkoxy)alkyl esters.
  • Preferred cycloalkyl and aromatic esters are those of acrylic acid, methacrylic acid, or itaconic acid.
  • Useful aromatic esters of these acids include phenol, benzyl, tolyl, tetrahydrofurfuryl, and phenoxyethyl esters.
  • Useful cycloalkyl esters include (C 5 -C 12 ) cycloalkyls, e.g., the cyclohexyl, cyclopentyl, isobornyl and adamantyl esters of these acids.
  • Preferred (hydroxy)alkyl ester comonomers include (2- hydroxyethyl) methacrylate, (2-hydroxyethyl) and (ethacrylate, (2-hydroxyethyl) acrylate, (3-hydroxy- propyl) methacrylate, (3-hydroxypropyl) acrylate, or (3-hydroxypropyl) ethacrylate.
  • Alkyl and (alkoxy) alkyl esters of alpha, beta-unsaturated carboxylic acids can be used in combination with the aromatic and/or cycloalkyl ester.
  • the alkyl esters will be selected from high alkyl esters, such as those of about 5-22 carbon atoms, most preferably, about 7-12 carbon atoms.
  • Examples of useful (C 5 -C 12 ) alkyl esters include: hexyl, octyl, ethyl(hexyl) , isodecyl, and lauryl acrylates, methacrylates and itaconates.
  • Examples of (alkoxy)alkyl esters useful as comonomers include: (C ⁇ -C 4 ) alkoxyl-JCi-C ⁇ )alkyl esters of acrylic, methacrylic or itaconic acids such as (methoxy) ethyl, (ethoxy) ethyl, (methoxy) propyl, (ethoxy) propyl, and the like.
  • esters examples include: (2-hydroxyethyl) acrylate or methacrylate, (hydroxypropyl) acrylate or methacrylate, (dimethylaminoethyl) methacrylate, (piperidinoethyl) methacrylate, (morpholinoethyl) methacrylate, methacrylglycolic acid, the monomethacrylates of glycol, glycerol and other polyhydric alcohols, monomethacrylates of dialkylene glycols and polyalkylene glycols.
  • Alpha, bet -unsatured amides may also be terpolymerized with the aforementioned monomers, including acrylamide, methacrylamide, diacetone acrylamide, methylolacrylamide, methylolmethacrylamide, and the like.
  • the polymers, copolymers and terpolymers of this invention can be produced using conventional polymerization techniques including bulk, solution, suspension, or other polymerization techniques.
  • the polymers and copolymers of the invention can easily be prepared by polymerizing the selected monomers and typically alcoholic solvents at elevated temperature using free radical, redox o other catalysis. Once polymerization is complete, the polymer can be removed from the reaction medium by removing the volatile solvent, precipitation, dialysis, or other typical purification technique.
  • Example I Into a 3 neck round bottom flask were added 28.4 ml of ethyl alcohol, 3.11 grams of 2-acrylamido-2-methylpropane sulfonic acid and 3.99 grams of ethyl methacrylate. The mixture was stirred under nitrogen at room temperature until all of the solid dissolved. Upon dissolution, 0.0355 grams of 2,2 -azobis(2-methylpropionitrile) was added and the temperature of the solution was raised at 75°C The mixture remained at 75°C for 5 hours and was allowed to cool thereafter. The solution was then poured into a flask containing 200 ml of ether. A white precipitate was formed which was dried in a vacuum oven at 50°C for 12 hours. The yield of the copolymer was 61%.
  • Examples Il-V Examples II-V were prepared following the procedure of Example I except that the mole ratio of ethyl methacrylate (EMA) to 2-acrylamide-2,2-methylpropanesulfonic acid (AMPS) is reduced by 10 mole-% in the Examples.
  • EMA ethyl methacrylate
  • AMPS 2-acrylamide-2,2-methylpropanesulfonic acid
  • Example VI Into a 3 neck round bottom flask was added 27 ml of isopropanol, 2.07 grams of 2-acrylamido-2-methylpropane sulfonic acid, 0.65 grams of 2-hydroxyethylmethacrylate (HEMA) and 3.99 grams of ethyl methacrylate. The solution was stirred under nitrogen at ambient temperature. One ml of water was then added to the solution which was heated to 45°C to dissolve all of the solid. Then 0.0336 grams of 2,2'-azobis(2-methylpropionitrile) was added and the temperature was raised to 83°C to commence the polymerization. The solution was refluxed for 5 hours, after which the solution was cooled to room temperature.
  • HEMA 2-hydroxyethylmethacrylate
  • Example XIV Into a 3 neck round bottom flask were added 18.0 ml of isopropyl alcohol, 2.66 grams (25 mmole) of ⁇ -chloroacrylic acid and 3.25 grams (25 mmole) of 2-hydroxyethyl methacrylate. A reaction was initiated in the flask under nitrogen by 29.6 ml of AIBN (azobisisobutyronitrile) . The reaction was refluxed at 86°C for two hours. The mixture wa then allowed to cool, and thereafter poured into 200 ml of ethyl ether while stirring. A white precipitate formed. Th solvent was decanted and the precipitate was collected, washed and dried in a vacuum oven at room temperature overnight. The yield was 85% of a copolymer of ⁇ -chloroacrylic acid and 2-hydroxyethyl methacrylate.
  • AIBN azobisisobutyronitrile
  • Example XV Into a 3 neck round bottom flask were added 22.2 ml of isopropyl alcohol, 3.73 grams (35 mmole) of ⁇ -chloroacrylic acid, (C1AA) 0.65 grams (5 mmole) ⁇ -hydroxy ethyl methacrylate and 1.14 grams (10 mmole) ethyl methacrylate. reaction was initiated in the flask under nitrogen by 27.6 g of Azobisiso butyronitrile (AIBN) . The reaction was refluxed at 86°C for two hours. The mixture was then allowed to cool, and thereafter poured into 200 ml of ethyl ether while stirring. A white precipitate was formed.
  • AIBN Azobisiso butyronitrile
  • Examples XVI-XVIII were prepared following the same procedure as Example XV except the mole ratios were as follows:
  • Polymeric films for microbiological testing were prepared as follows: 200 milligrams of polymer was dissolved in 4 milliliters of acetone. The solution was poured into 100 x 15 mm glass petri dish. The solvent was evaporated in a hood at 25°C.
  • the film was inoculated as follows: Cells of a 24-hour culture of gram positive Staphylococcus aureus were spun down in a centrifuge and then re-suspended in deionized water. A 0.1 milliliter inoculum of the suspension were spread onto the film. The dish was covered and stored in a humidity chamber to prevent drying of the inoculum.
  • the film was swabbed with a 1 x 1 inch wet cotton swatch which was then added to 9 milliliters of a neutralizer solution (0.1 M Na-K phosphate buffer, pH 7.2) and vortexed.
  • a neutralizer solution 0.1 M Na-K phosphate buffer, pH 7.2
  • Tryptone-Glucose-Yeast extract agar (Difco Inc.). The control was an empty glass petri dish without the film. The results are described in Tables 1 and 2 below.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

Mince couche de revêtement antimicrobien comprenant une pellicule en polymère résistante à l'usure, transparente et adhérente pouvant libérer une concentration antimicrobienne efficace de protons [H+] au contact de l'eau pour créer un environnement antimicrobien acide dans une surface environnementale.
PCT/US1990/003922 1989-09-20 1990-07-12 Revetement polymere antimicrobien WO1991003938A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992014365A1 (fr) * 1991-02-21 1992-09-03 Nippon Chemical Industrial Co., Ltd. Antibacterien
WO2001072859A1 (fr) * 2000-03-24 2001-10-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Revetements antimicrobiens contenant des polymeres d'acides alkylsulfoniques a substitution acryle
US10336850B2 (en) 2015-02-23 2019-07-02 Hallibunon Energy Services, Inc. Methods of use for crosslinked polymer compositions in subterranean formation operations
US10407526B2 (en) 2015-02-23 2019-09-10 Halliburton Energy Services, Inc. Crosslinked polymer compositions with two crosslinkers for use in subterranean formation operations
CN110678521A (zh) * 2017-03-29 2020-01-10 科发龙技术公司 涂料组合物、聚合物涂层和方法
US10662371B2 (en) 2015-02-23 2020-05-26 Halliburton Energy Services, Inc. Crosslinked polymer compositions for use in subterranean formation operations
US10752822B2 (en) 2015-02-23 2020-08-25 Halliburton Energy Services, Inc. Crosslinked polymer compositions and methods for use in subterranean formation operations
RU2807338C1 (ru) * 2023-04-05 2023-11-14 Федеральное государственное бюджетное учреждение науки Пермский федеральный исследовательский центр Уральского отделения Российской академии наук (ПФИЦ УрО РАН) Способ оценки антимикробного пролонгированного действия дезинфектантов на основе полимеров

Citations (2)

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Publication number Priority date Publication date Assignee Title
FR2476441A1 (fr) * 1980-02-27 1981-08-28 Maruzen Oil Co Ltd Agent antifongique et antibacterien renfermant comme ingredient actif un poly(p-hydroxystyrene) de poids moleculaire eleve ou un de ses derives et sels
US4536206A (en) * 1982-10-15 1985-08-20 Wako Pure Chemical Industries, Ltd. Miticidal composition and method for controlling spider mites

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2476441A1 (fr) * 1980-02-27 1981-08-28 Maruzen Oil Co Ltd Agent antifongique et antibacterien renfermant comme ingredient actif un poly(p-hydroxystyrene) de poids moleculaire eleve ou un de ses derives et sels
US4536206A (en) * 1982-10-15 1985-08-20 Wako Pure Chemical Industries, Ltd. Miticidal composition and method for controlling spider mites

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992014365A1 (fr) * 1991-02-21 1992-09-03 Nippon Chemical Industrial Co., Ltd. Antibacterien
US5366727A (en) * 1991-02-21 1994-11-22 Nippon Chemical Industrial Co., Ltd. Antibacterial agent
WO2001072859A1 (fr) * 2000-03-24 2001-10-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Revetements antimicrobiens contenant des polymeres d'acides alkylsulfoniques a substitution acryle
US10336850B2 (en) 2015-02-23 2019-07-02 Hallibunon Energy Services, Inc. Methods of use for crosslinked polymer compositions in subterranean formation operations
US10407526B2 (en) 2015-02-23 2019-09-10 Halliburton Energy Services, Inc. Crosslinked polymer compositions with two crosslinkers for use in subterranean formation operations
US10662371B2 (en) 2015-02-23 2020-05-26 Halliburton Energy Services, Inc. Crosslinked polymer compositions for use in subterranean formation operations
US10752822B2 (en) 2015-02-23 2020-08-25 Halliburton Energy Services, Inc. Crosslinked polymer compositions and methods for use in subterranean formation operations
US11162019B2 (en) 2015-02-23 2021-11-02 Halliburton Energy Services, Inc. Crosslinked polymer compositions for use in subterranean formation operations
US11268006B2 (en) 2015-02-23 2022-03-08 Halliburton Energy Services, Inc. Crosslinked polymer compositions and methods for use in subterranean formation operations
CN110678521A (zh) * 2017-03-29 2020-01-10 科发龙技术公司 涂料组合物、聚合物涂层和方法
RU2807338C1 (ru) * 2023-04-05 2023-11-14 Федеральное государственное бюджетное учреждение науки Пермский федеральный исследовательский центр Уральского отделения Российской академии наук (ПФИЦ УрО РАН) Способ оценки антимикробного пролонгированного действия дезинфектантов на основе полимеров

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