EP0691397B1 - Antimikrobieller Reiniger für harte Oberflächen - Google Patents

Antimikrobieller Reiniger für harte Oberflächen Download PDF

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Publication number
EP0691397B1
EP0691397B1 EP95304637A EP95304637A EP0691397B1 EP 0691397 B1 EP0691397 B1 EP 0691397B1 EP 95304637 A EP95304637 A EP 95304637A EP 95304637 A EP95304637 A EP 95304637A EP 0691397 B1 EP0691397 B1 EP 0691397B1
Authority
EP
European Patent Office
Prior art keywords
cleaner
hard surface
effective amount
surface cleaner
surfactant
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.)
Expired - Lifetime
Application number
EP95304637A
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English (en)
French (fr)
Other versions
EP0691397A2 (de
EP0691397A3 (de
Inventor
Boli Zhou
Anna G. Stanislowski
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.)
Clorox Co
Original Assignee
Clorox Co
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
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Publication of EP0691397A2 publication Critical patent/EP0691397A2/de
Publication of EP0691397A3 publication Critical patent/EP0691397A3/de
Application granted granted Critical
Publication of EP0691397B1 publication Critical patent/EP0691397B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to a non-rinse, isotropic, antimicrobial hard surface cleaner especially adapted to be used on glossy or smooth, hard surfaces, which removes soils deposited thereon and disinfects same, while significantly reducing the amount of residue caused by unremoved soil, cleaner, or a combination thereof.
  • quaternary ammonium based liquid hard surface cleaners are in common use, typically as bathroom cleaners. Certain quaternary ammonium compounds can be effective as antimicrobial agents in small dosages in these cleaners. However, these types of cleaners typically are not effective on glossy, hard surfaces because they tend to leave a visible residue.
  • Corn et al., EP 0393772 and EP 0428816, describe hard surface cleaners containing anionic surfactants with ammonium counterions, and additional adjuncts.
  • GB 2,160,887 describes a cleaning system in which a combination of nonionic and anionic surfactants (including an alkanolamine salt alkyl sulfate) is contended to enhance cleaning efficacy.
  • WO 91/11505 describes a glass cleaner containing zwitterionic surfactant, monoethanolamine and/or beta-aminoalkanols as solvents/buffers for assertedly improving cleaning and reducing filming spotting.
  • the prior art hard surface cleaners fail to achieve the desired goals of reduced residue (streaking and/or filming) and antimicrobial action.
  • EP-A-0621335 (document according to Article 54(3) EPC), which relates to an all purpose cleaning composition
  • US-A-4,540,505 which relates to a disinfectant spray cleaner containing glycol ethers
  • US-A-3,694,365 which relates to compositions for cleaning and sterilizing milk equipment
  • WO 93/16162 which relates to a reduced residue hard surface cleaner.
  • the invention provides an aqueous, antimicrobial hard surface cleaner with significantly improved residue removal and substantially reduced filming/streaking, said cleaner comprising:
  • the invention further comprises a method of cleaning soils from hard surfaces by applying said inventive cleaner to said soil, and removing both from said surface, while disinfecting said surface.
  • the invention is an improved cleaning, substantially non-streaking/filming, antimicrobial hard surface cleaner especially adapted to be used on glossy or smooth, hard surfaces.
  • the cleaner benefits from the presence of a quaternary ammonium surfactant which contributes unexpectedly to both antimicrobial efficacy as well as to the complete removal of soils and the cleaner from the surface being cleaned.
  • the cleaner itself has the following ingredients:
  • adjuncts in small amounts such as fragrance can be included to provide desirable attributes of such adjuncts.
  • the solvent is selected from C 1-6 alkanol, C 3-24 alkylene glycol ether, and mixtures thereof.
  • the alkanol can be selected from methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, their various positional isomers, and mixtures of the foregoing.
  • isopropanol usually in conjunction with a glycol ether.
  • the diols such as methylene, ethylene, propylene and butylene glycols, and mixtures thereof.
  • the alkylene glycol ether solvents can include ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether, and mixtures thereof.
  • Two preferred glycol ethers are ethylene glycol monobutyl ether, also known as butoxyethanol, sold as butyl Cellosolve by Union Carbide, and propylene glycol n-propyl ether, available from a variety of sources..
  • Another preferred alkylene glycol ether is propylene glycol t-butyl ether, which is commercially sold as Arcosolve PTB, by Arco Chemical Co. It has the structure:
  • the invention requires an amine oxide surfactant, such as the trialkyl amino oxides. These have the general configuration: wherein R is C 6-24 alkyl, and R' and R" are both C 1-4 alkyl, although R' and R" do not have to be equal. These amine oxides can also be ethoxylated or propoxylated.
  • the preferred amine oxide is lauryl amine oxide, such as Barlox 12, from Lonza Chemical Company.
  • the present invention can comprise further surfactants selected from nonionic and amphoteric surfactants, and mixtures thereof.
  • the nonionic surfactants are selected from alkoxylated alcohols, alkoxylated ether phenols.
  • the alkoxylated alcohols include ethoxylated, and ethoxylated and propoxylated C 6-16 alcohols, with about 2-10 moles of ethylene oxide, or 1-10 and 1-10 moles of ethylene and propylene oxide per mole of alcohol, respectively.
  • a mixture of nonionic and amine oxide surfactants are most preferred.
  • the ratio of amine oxide:EDTA must be carefully controlled in the invention.
  • the amount of amine oxide must exceed the amount of EDTA, more preferably exceeds 3:1 and most preferably is 4:1 or greater.
  • the amphoteric surfactant is typically an alkylbetaine or a sulfobetaine.
  • alkylamidoalkyldialkylbetaines These have the structure: wherein R 1 is C 6-20 alkyl, R 2 and R 3 are both C 1-4 alkyl, although R 2 and R 3 do not have to be equal, and m can be 1-5, preferably 3, and n can be 1-5, preferably 1.
  • These alkylbetaines can also be ethoxylated or propoxylated.
  • the preferred alkylbetaine is a cocoamidopropyldimethyl betaine called Lonzaine CO, available from Lonza Chemical Co.
  • Other vendors are Henkel KGaA, which provides Velvetex AB, and Sherex Chemical Co., which offers Varion CADG, both of which products are cocobetaines.
  • the amounts of surfactants present are to be somewhat minimized, for purposes of cost-savings and to generally restrict the dissolved actives which could contribute to leaving behind residues when the cleaner is applied to a surface.
  • the amounts added are generally 0.001-5%, more preferably 0.002-2.00% surfactant.
  • the invention further requires a quaternary ammonium surfactant.
  • quaternary ammonium surfactants are typically used in bathroom cleaners because they are generally considered "broad spectrum" antimicrobial compounds, having efficacy against both gram positive (e.g., Staphylococcus sp .) and gram negative (e.g., Escherischia coli ) microorganisms.
  • gram positive e.g., Staphylococcus sp .
  • gram negative e.g., Escherischia coli
  • hard surface cleaners containing quaternary ammonium compounds typically leave residue and thus perform relatively poorly on glossy hard surfaces. Streaking/filming performance, as can be expected, is uniformly poor.
  • the inventive compositions have surprisingly superior streaking/filming performance compared to other quaternary ammonium-based cleaning formulations.
  • the alkali metal ethylene diamine tetraacetate (EDTA) is an important aspect of the invention. As mentioned above, there appears to be an interaction between the amine oxide surfactant EDTA. EDTA is known as a chelant, as well. Buffers, such as ammonium, alkali metal and alkaline earth metal hydroxides, and such as ammonium carbamate, which has the structure NH 2 COO - NH + 4 , may also be desirable for inclusion.
  • guanidine derivatives such as diaminoguanidine and guanidine carbonate
  • alkoxylalkylamines such as isopropoxypropylamine, butoxypropylamine, ethoxypropylamine and methoxypropylamine
  • alkylamines such as ethyleneamine, ethylenediamine, ethylenetriamine, ethylenetetramine, diethylenetetramine, triethylenetetramine, tetraethylenepentamine, N,N-dimethylethylenediamine, N-methylenediamine, and other variations of the alkyl and amine substituents.
  • the amount of EDTA added is in the range of 0.01-2%, more preferably 0.01-1%, by weight of the cleaner, while hydroxide, if present, should be added in the range of 0.001-1% by weight of the cleaner.
  • the cleaner is an aqueous cleaner with relatively low levels of actives
  • the principal ingredient is water, which should be present at a level of at least about 50%, more preferably at least about 80%, and most preferably, at least about 90%. Deionized water is most preferred.
  • adjuncts Small amounts can be added for improving cleaning performance or aesthetic qualities of the cleaner.
  • Adjuncts for cleaning include additional surfactants, such as those described in Kirk-Othmer, Encyclopedia of Chemical Technology , 3rd Ed., Volume 22, pp. 332-432 (Marcel-Dekker, 1983).
  • Aesthetic adjuncts include fragrances, such as those available from Givaudan, IFF, Quest and others, and dyes and pigments which can be solubilized or suspended in the formulation, such as diaminoanthraquinones.
  • the amounts of these cleaning and aesthetic adjuncts should be in the range of 0-2%, more preferably 0-1%.
  • Example 1 Ingredient Wt. % Quaternary ammonium surfactant 0.6 NaOH 0.2 Nonionic surfactant 0.25 Amine oxide surfactant 2.2 Solvent 3.0 Na 4 EDTA 0.56 D.I. H 2 O Q.S. Comparative Example 2 Ingredient Wt. % Quaternary ammonium surfactant 0.6 NaOH 0.2 Nonionic surfactant 0.25 Amine oxide surfactant 0.25 Solvent 2.0 Na 4 EDTA 0.39 D.I. H 2 O Q.S. 1 Unless further identified, all of the ingredients are the same as in the prior Example.
  • Example 1 which had the preferred >3:1 ratio of amine oxide: EDTA, clearly outperformed Example 2, as well as the commercial product Lysol Antibacterial Kitchen Cleaner, as well as commercial products 2-4, all of which are bactericidal products. Additionally, its streaking/filming performance was comparable to that of Formula 409® all purpose cleaner and commercial product 1, both of which are hard surface cleaners without bactericides.
  • Example 4 Example 5 NaOH 0.2% 0.2% 0.2% Quat. 1 0.6% 0.6% 0.6% 0.6% Nonionic 2 0.25% 0.25% 0.25% Solvent 3 2.0% 2.0% 2.0% EDTA 0.5% 1.5% 0.5% Amine Ox. 4 2.0% 6.0% 4.0% D.I. H 2 O Q.S. Q.S. Q.S. Ingredient Example 6 Example 7 Example 8 Example 9 NaOH 0.2% 0.2% 0.2% 0.2% Quat. 1 0.6% 0.6% 0.6% 0.4% Nonionic 6 0.25% 0.36% 0.36% 0.36% Solvent 3 2.0% 3.0% 2.0% 3.0% EDTA 0.5% 0.5% 0.5% 0.5% Amine Ox. 4 2.0% 2.0% 2.0% 2.0% 2.0% D.I. H 2 O Q.S.
  • Q.S. Q.S. Q.S. 1 Quaternary ammonium compound, Barquat MB-50 2
  • Nonionic surfactant Surfonic N-100, ethoxylated C 9 alkylphenol, 10 moles of ethylene oxide, from Texaco Chemical.
  • Example 6 7 S/F Performance 7.9 7.7

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (7)

  1. Wässriger antimikrobieller Oberflächenreiniger mit signifikant verbesserter Rückstandsentfernung und erheblich reduzierter Film-/Streifenbildung, dadurch gekennzeichnet, dass er umfasst:
    (a) eine wirksame Menge von nicht mehr als 50 Gew.-% der Zusammensetzung eines Lösungsmittels ausgewählt aus C1-6-Alkanol, C3-24-Alkylenglykolether und Gemischen davon;
    (b) eine wirksame Menge eines Aminoxid-Tensids;
    (c) eine wirksame Menge eines quaternären Ammoniumtensids;
    (d) eine wirksame Menge von 0,01-2 Gew.-% der Zusammensetzung eines Alkalimetallethylendiamintetraacetat-Builders; und
    (e) zum Rest im Wesentlichen Wasser;
       wobei das Verhältnis von (b):(d) größer als 1:1 ist.
  2. Oberflächenreiniger nach Anspruch 1, worin das Lösungsmittel ein Alkylenglykolether ist, der aus Ethylenglykolmonobutylether, Ethylenglykolmonopropylether, Propylenglykolmonopropylether, Propylenglykolmonobutylether und Gemischen davon ausgewählt ist.
  3. Oberflächenreiniger nach Anspruch 1, der weiterhin ein von dem Amminoxid verschiedenes nicht-ionisches Tensid umfasst.
  4. Oberflächenreiniger nach Anspruch 3, worin das nichtionische Tensid ein ethoxylierter Alkohol ist.
  5. Oberflächenreiniger nach Anspruch 1, worin das Verhältnis von (b):(d) größer als 3:1 ist.
  6. Oberflächenreiniger nach Anspruch 1, worin das Verhältnis von (b):(d) größer als 4:1 ist.
  7. Verfahren zur im Wesentlichen rückstandsfreien Entfernung von Schmutz von einer harten bzw. festen Oberfläche, dadurch gekennzeichnet, dass man einen Reiniger nach den Ansprüchen 1 bis 6 auf den Schmutz einwirken lässt und den Schmutz und den Reiniger entfernt.
EP95304637A 1994-07-07 1995-07-03 Antimikrobieller Reiniger für harte Oberflächen Expired - Lifetime EP0691397B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US27168194A 1994-07-07 1994-07-07
US271681 1994-07-07

Publications (3)

Publication Number Publication Date
EP0691397A2 EP0691397A2 (de) 1996-01-10
EP0691397A3 EP0691397A3 (de) 1997-03-05
EP0691397B1 true EP0691397B1 (de) 2004-10-06

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Family Applications (1)

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EP95304637A Expired - Lifetime EP0691397B1 (de) 1994-07-07 1995-07-03 Antimikrobieller Reiniger für harte Oberflächen

Country Status (6)

Country Link
EP (1) EP0691397B1 (de)
JP (1) JPH0827491A (de)
KR (1) KR100378903B1 (de)
AT (1) ATE278757T1 (de)
DE (1) DE69533603T2 (de)
ES (1) ES2229226T3 (de)

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US8172953B2 (en) 2009-11-06 2012-05-08 Ecolab Usa Inc. Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant

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US20030100465A1 (en) 2000-12-14 2003-05-29 The Clorox Company, A Delaware Corporation Cleaning composition
US7799751B2 (en) 2000-12-14 2010-09-21 The Clorox Company Cleaning composition
GB2370042A (en) * 2000-12-15 2002-06-19 Reckitt Benckiser Inc Hard surface cleaning compositions
EP1245668A3 (de) 2001-03-30 2003-09-17 The Procter & Gamble Company Reinigungsmittel
US6429183B1 (en) * 2001-07-12 2002-08-06 Colgate-Palmolive Company Antibacterial cleaning wipe comprising betaine
GB2391234A (en) * 2002-07-24 2004-02-04 Reckitt Benckiser Inc Hard surface cleaning compositions
JP3980514B2 (ja) * 2003-04-17 2007-09-26 花王株式会社 殺菌洗浄剤組成物
JP5481714B2 (ja) * 2007-09-20 2014-04-23 ライオン株式会社 液体洗浄剤組成物
US8071520B2 (en) 2009-11-06 2011-12-06 Ecolab Usa Inc. Sulfonated alkyl polyglucoside use for enhanced food soil removal
US8389463B2 (en) 2009-11-09 2013-03-05 Ecolab Usa Inc. Enhanced dispensing of solid compositions
US8216994B2 (en) 2009-11-09 2012-07-10 Ecolab Usa Inc. Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal
US8455551B2 (en) * 2011-03-04 2013-06-04 American Sterilizer Company Broad spectrum disinfectant
US20150252310A1 (en) 2014-03-07 2015-09-10 Ecolab Usa Inc. Alkyl amides for enhanced food soil removal and asphalt dissolution
EP4219671A3 (de) * 2015-07-14 2023-08-16 Ecolab USA Inc. Kontrollierte rate des schaumbruchs in reinigern für harte oberflächen
EP3418368A1 (de) 2017-06-21 2018-12-26 The Procter & Gamble Company Lösungsmittel mit zusammensetzung zur reinigung harter oberflächen
EP3417709A1 (de) 2017-06-21 2018-12-26 The Procter & Gamble Company Lösungsmittel mit antimikrobiellen reinigungszusammensetzungen für harte oberflächen
EP3418361A1 (de) 2017-06-21 2018-12-26 The Procter & Gamble Company Lösungsmittel mit zusammensetzung zur reinigung harter oberflächen
EP3418363A1 (de) 2017-06-21 2018-12-26 The Procter & Gamble Company Polymerhaltige antimikrobielle reinigungszusammensetzungen für harte oberflächen
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DE69533603D1 (de) 2004-11-11
ATE278757T1 (de) 2004-10-15
EP0691397A2 (de) 1996-01-10
KR100378903B1 (ko) 2003-05-23
ES2229226T3 (es) 2005-04-16
JPH0827491A (ja) 1996-01-30
DE69533603T2 (de) 2006-02-09
EP0691397A3 (de) 1997-03-05

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