EP1065265A1 - Keimtötende Reinigungsmittelzusammensetzung - Google Patents

Keimtötende Reinigungsmittelzusammensetzung Download PDF

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Publication number
EP1065265A1
EP1065265A1 EP00113168A EP00113168A EP1065265A1 EP 1065265 A1 EP1065265 A1 EP 1065265A1 EP 00113168 A EP00113168 A EP 00113168A EP 00113168 A EP00113168 A EP 00113168A EP 1065265 A1 EP1065265 A1 EP 1065265A1
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EP
European Patent Office
Prior art keywords
salt
composition
acid
germicidal
surfactant
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Granted
Application number
EP00113168A
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English (en)
French (fr)
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EP1065265B1 (de
Inventor
Yuji Kao Corporation Okauchi
Tadashi Kao Corporation Moriyama
Hiroyoshi Kao Corporation Hiramatsu
Yuichi Kao Corporation Hioki
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Kao Corp
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Kao Corp
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/3917Nitrogen-containing compounds

Definitions

  • the present invention relates to a germicidal detergent composition.
  • the term "germicidal” in the present invention may mean bactericidal, sporicidal, sterilizing, germ-eliminating, pasteurizing, disinfectant, microbicidal, germ-(, bacterium-, fungus-, bacillus-, microorganism or the like) lethal or the like. That is, the present invention can be applied to germs, bacteria, spores, funguses, microbes, microorganisms and so on.
  • JP-A 62-63504 a germicide composition containing a cationic surfactant, an inorganic peroxide and an activator for the inorganic peroxide is disclosed; in JP-A 3-131700, a detergent composition for a drainpipe having its germ-eliminating and/or germicidal effect and containing each of an inorganic peroxide, a nonionic surfactant and tetraacetylethylenediamine in a specific proportion is disclosed; and, in JP-A 8-502047, use of an aqueous solution containing an aliphatic peracid and the corresponding aliphatic acid in a specific molar ratio and containing hydrogen peroxide as a germicidal detergent is disclosed.
  • Examples of the germicidal deterging treatment using glutaraldehyde and/or peracetic acid include that, in case of a germicidal deterging of an endoscope, a sterilizing treatment is carried out by means of glutaraldehyde and/or peracetic acid after a primary disinfection using a germicide of a quaternary ammonium salt type, an alcohol, a super-oxidized water, an amphoteric surfactant, etc. and/or a deterging step using an enzyme preparation, a neutral detergent, etc. and, if necessary, a disinfection in an autoclave and/or a dry sterilization by heat is carried out.
  • peracetic acid has a strong irritating smell and a strong oxidizing property, therefore it is feared that the peracetic acid erodes a container thereof, a treated matter thereby, etc. depending upon the material used therefor.
  • An aqueous solution containing peracid and hydrogen peroxide as mentioned in JP-A 8-502047 has the same problem, too.
  • An object of the present invention is to obtain a germicidal detergent composition by which a sure germicidal effect is obtained by a simple operation and which is excellent in safety and workability.
  • the present invention provides a germicidal detergent composition
  • a germicidal detergent composition comprising (a) an inorganic peroxide, (b) tetraacetylethylenediamine and (c) protease at the ratio of (a)/(b) by weight being from 10/1 to 1/2.
  • the inorganic peroxide (a) is preferably sodium percarbonate.
  • the germicidal detergent composition of the present invention may preferably comprise (d) a surfactant.
  • the surfactant (d) is preferably at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, an amphoteric surfactant and a cationic surfactant.
  • the germicidal detergent composition of the present invention may further comprises (e) a salt of an alkali metal with an inorganic acid and/or of an alkaline earth metal with an inorganic acid.
  • the germicidal detergent composition of the present invention is desirably an aqueous solution having pH 6 to 9.
  • the germicidal detergent composition of the present invention may preferably incorporate protease (c) in such an amount that the activity thereof is from 20 APU/L to 10 mAPU/L during a time for use.
  • the present invention provides also a method of killing a germ, which comprises bringing an aqueous solution of a germicidal detergent composition into contact with a microorganism in the range of pH 6 to 9.
  • the method of the invention treats medical instruments, medical goods and other goods to wash and pasteurize. It is applied to a locus where pasterization is intended.
  • the present invention provides use of the composition as shown above for germicidal deterging or for manufacturing an aqueous solution of a germicide.
  • the inorganic peroxide (a) used in the present invention sodium percarbonate, sodium perborate, etc. may be exemplified and sodium percarbonate is preferable.
  • the ratio of the component (a) to tetraacetylethylenediamine (b), i.e. (a)/(b), by weight is from 10/1 to 1/2, preferably from 3/1 to 1/1 and particularly preferably from 2/1 to 1/1 from the viewpoint of the germicidal effect.
  • an alkaline protease is preferable.
  • Particularly preferable one is an alkaline protease produced by Bacillus sp. KSM-K16, deposited as FERM BP-3376 according to Budapest Treaty dated on 19 th April 1990 in Fermentation Research Institute as the international depositary authority, now reorganized to National Institute of Bioscience and Human-Technology Agency of Industrial Science and Technology, at 1-3, Higashi 1 chome Tsukuba-shi Ibaraki-ken 305-8566, Japan.
  • protease (c) is incorporated in the composition in such an amount that the activity thereof is from 20 APU/L to 10 mAPU/L and particularly from 10 APU/L to 100 mAPU/L.
  • the protease activity mentioned here was measured by the following method.
  • a reaction is carried out at the temperature of 25°C in pH 10.5 for 10 minutes in a solution which is prepared so as to make the final concentration of an urea-modified hemoglobin used as a reaction-substrate 14.7 mg/mL and, after that, trichloroacetic acid is added to the reaction solution to make its final concentration 31.25 mg/mL.
  • the parts dissolved in trichloroacetic acid of the reaction solution are colored by folin-ciocalteu's phenol reagent.
  • the degree colored by 1 mmol of tyrosine is calculated in terms of 1APU to make its calibration curve (or line), and then the activity per ten minutes of the reaction is determined by the calibration curve. Then, this is calculated in terms of one minute to measure the degree colored by the above-mentioned floin-ciocalteu's phenol reagent. That is, 1APU is the amount of protease which provides the same degree colored by the parts dissolved in trichloroacetic acid in one minute as those colored by 1mmol of tyrosine with the folin-ciocalteu's phenol reagent.
  • the germicidal detergent composition of the present invention comprises (d) at least one surfactant which is selected from the group consisting of a nonionic surfactant, an anionic surfactant, an amphoteric surfactant and a cationic surfactant.
  • the nonionic surfactant includes a polyoxyethylene alkyl ether, a polyoxyethylene alkylene ether, a polyoxyethylene sorbitan fatty acid ester, an alkyl polyglycoside, a sucrose fatty acid ester and an alkyl polyglycerol ether.
  • a polyoxyethylene (the average number of added ethylene oxide being 2 to 300) alkyl (the number of carbon atoms being 12 to 18) ether is preferable.
  • the anionic surfactant includes a higher fatty acid salt, a higher alcohol sulfate salt, a higher alcohol sulfonate, a sulfated fatty acid salt, a sulfonated fatty acid salt, a phosphate salt, a sulfate salt of a fatty acid ester, a sulfonate salt of a fatty acid ester, a sulfate salt of a higher alcohol ether, a sulfonate salt of a higher alcohol ether, an acetate substituted with a higher alcohol ether, a condensation product of a fatty acid with an amino acid, an alkylolated sulfate salt of a fatty acid amide, an alkylated sulfonate salt of a fatty acid amide, a sulfosuccinate salt, an alkylbenzene sulfonate, an alkylphenol sulfonate, an alkylnaphthal
  • the amphoteric surfactant includes an amine oxide such as an alkyldimethylamine oxide and a betaine such as an alkyldimethylaminofatty acid betaine and an alkylcarboxymethylhydroxyethylimidazolium betaine.
  • a betaine is preferable.
  • the cationic surfactant includes an alkyl trimethyl ammonium salt such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and cetyl trimethyl ammonium chloride; a dialkyl dimethyl ammonium salt such as distearyl dimethyl ammonium chloride and a dialkyl(C 12 -C 18 ) dimethyl ammonium chloride; an alkyl dimethyl benzyl ammonium salt such as an alkyl(C 12 -C 14 ) dimethyl benzyl ammonium chloride; a substituted benzalkonium salt; a mono-cationic compound such as a benzethonium salt and, besides, a polycationic compound such as an N-alkyl-N,N,N',N',N'-pentamethyl-propylene ammonium salt.
  • an alkyl trimethyl ammonium salt such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and
  • an alkyl trimethyl ammonium salt, a dialkyl dimethyl ammonium salt, an alkyl dimethyl benzyl ammonium salt or a substituted benzalkonium salt is preferable.
  • Lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, a dialkyl(C 12 -C 18 ) dimethyl ammonium chloride or an alkyl(C 12 -C 14 ) dimethyl benzyl ammonium chloride is particularly preferable.
  • the surfactant (d) is used in the amount as compared with tetraacetylethylenediamine (b) in terms of the ratio of (b)/(d) of from 20/1 to 2/1 by weight.
  • the germicidal detergent composition of the present invention comprises (e) the salt of the alkali metal with the inorganic acid and/or of the alkali earth metal with the inorganic acid.
  • the component (e) includes sodium sulfate, sodium nitrate, sodium chloride, sodium carbonate, sodium hydrogen carbonate, magnesium sulfate, magnesium nitrate, magnesium chloride and magnesium carbonate. Among them, sodium sulfate or magnesium sulfate is preferable. It is preferable that the component (e) is used in an amount as compared with the inorganic peroxide (a) in terms of the ratio by weight of (a)/(e) of from 1/1 to 4/1.
  • Each of the salts of the alkali metal with the inorganic acid and of the alkali earth metal with the inorganic acid may be used solely. However, they are preferably combined and used from the viewpoint of drying the inorganic peroxide and improving the germicidal activity.
  • the germicidal detergent composition of the present invention When the germicidal detergent composition of the present invention is in a solid form such as a powder, a granule or a tablet, it is used as an aqueous solution at a time for use.
  • the concentration of the organic peracid is made into preferably 150 to 3200 ppm, more preferably 250 to 3200 ppm and particularly preferably 450 to 3200 ppm.
  • the pH of the aqueous solution is preferably 6 to 9 and particularly preferably 6.5 to 7.5.
  • Adjustment of the pH of the aqueous solution can be achieved by an inorganic acid or an organic acid, and the inorganic acid or the organic acid may be previously added to the solid composition or the inorganic acid or the organic acid may be added to the aqueous solution.
  • the rate of dissolving the acid can be adjusted by coating the acid with a water-soluble substance such as a water-soluble inorganic salt. It is also possible to conduct the coating by means of the above-mentioned component (e).
  • the germicidal detergent composition of the present invention is suitable for germ-killing of instruments and furnishings used in medical institutions, etc. Then, it is particularly useful as a germicidal detergent composition for medical devices and instruments including a device or an instrument, for an operation, such as a surgical knife, a scissors and a surgical clamp; a device or an instrument, for a diagnosis, such as endoscope; and a device or an instrument, for a cure, such as an instrument for blood transfusion and a device for dialysis.
  • a device or an instrument for an operation, such as a surgical knife, a scissors and a surgical clamp
  • a device or an instrument for a diagnosis, such as endoscope
  • a device or an instrument for a cure, such as an instrument for blood transfusion and a device for dialysis.
  • a germicidal detergent composition having a high germicidal effect and being excellent in safety and workability can be obatined.
  • the germicidal detergent compositions as shown in Table 1 were prepared and used in the following Examples and Comparative Examples.
  • compositions as shown in Table 1 were diluted stepwise by a sterilized water into 0.5 to 0.01 % by weight to make preparations.
  • Protease [KAP11.1G, manufactured by Kao Corp.] was added into each of the preparations to make it 1APU/L and then Staphylococcus aureus (IFO 12732, being shown in LIST OF CULTURE, MICROORGANISMS 10 TH EDITION 1996 published by INSTITUTE FOR FERMENTATION, OSAKA at 17-85, Juso-honmachi 2-chome, Yodogawa-ku, Osaka 532, Japan) was added in the concentration of 1.0 ⁇ 10 7 cells/mL thereto.
  • the compsitions as shown in Table 1 were diluted stepwise by a sterilized water into 5 to 0.1 % by weigtht to make preparations.
  • Protease [KAP11.1G, manufactured by Kao Corp.] was added into each of the preparations to make it 1APU/L and then the above-mentioned spores were added in concentration of the 1.0 ⁇ 10 7 cells/mL thereto.
  • all of Examples were adjusted to pH 7.0 with citric acid.
  • the resultant solution was allowed to stand at 25°C for 30 minutes, 100 ⁇ L from this solution were taken, 0.9 mL of a 1% aqueous solution of sodium thiosulfate was added to inactivate the preparation, and 5 ⁇ L of the resultant mixture were inoculated on an incubating medium (200 ⁇ L of an SCDLP medium) and incubated at 35°C. Then, the minimum lethal concentration (MLC) was determined.
  • the concentration of the produced organic peracid in each of the preparations was 150 to 10000 ppm and then the concentration of the produced organic peracid in each of the preparations showing the MLC is shown in Table 3.
  • a dirt model by protein (a 30% aqueous solution of a skim milk) is applied on a piece of SUS 304 cut into the size of 2 cm ⁇ 3 cm, and modified by heating at 110°C for 2 hours. Then, 100 ⁇ L of spores (1.0 ⁇ 10 7 spores/mL) of Bacillus cereus (IFO 13494) are applied thereon to obtain a test piece.
  • the composition of Table 1 was mixed with protease [KAP11.1G, manufactured by Kao Corp.] to make it 1 APU/L, the resultant mixture was diluted to the concentration as shown in Table 6. Using the resultant preparation, the following tests were carried out. All of Examples and Comparative Examples were adjusted to pH 7.0 with citric acid except those using the compositions a and b. Then, the concentration of the produced organic peracid in each of the preparations was 240 to 450 ppm for Examples 25 to 30 and 2500 to 3000 ppm for Comparative Examples 18 to 19. For Comparative Examples 17 and 20 to 22, no organic peracid was produced.
  • test piece was dipped for 30 minutes in 10 mL of each of the preparations and then the surface of each of the test pieces was washed with 2 mL of a 1% aqueous solution of sodium thiosulfate. In case there were residual protein components, they were physically peeled off and dispersed in 2 mL of a 1% aqueous solution of sodium thiosulfate. 5 ⁇ L from this solution were taken and inoculated on an incubating medium (200 ⁇ L of an SCDLP medium) whereupon the germicidal effect was evaluated.
  • test piece was dipped for 30 minutes in 10 mL of each of the preparations and then the residual protein components were dyed with erythricin B.
  • the evaluation was carried out according to the following criteria.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP00113168A 1999-06-30 2000-06-30 Keimtötende Reinigungsmittelzusammensetzung Expired - Lifetime EP1065265B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18510199 1999-06-30
JP18510199 1999-06-30

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100353931C (zh) * 2003-06-23 2007-12-12 周彦忠 一种护肤洗浴用品及其应用
WO2009122125A1 (en) * 2008-04-01 2009-10-08 Reckitt Benckiser Inc. Laundry treatment compositions
US8062500B2 (en) 2001-12-05 2011-11-22 Oculus Innovative Sciences, Inc. Method and apparatus for producing negative and positive oxidative reductive potential (ORP) water
US8147444B2 (en) 2006-01-20 2012-04-03 Oculus Innovative Sciences, Inc. Methods of treating or preventing peritonitis with oxidative reductive potential water solution
US8323252B2 (en) 2005-03-23 2012-12-04 Oculus Innovative Sciences, Inc. Method of treating skin ulcers using oxidative reductive potential water solution
US9168318B2 (en) 2003-12-30 2015-10-27 Oculus Innovative Sciences, Inc. Oxidative reductive potential water solution and methods of using the same
US9498548B2 (en) 2005-05-02 2016-11-22 Oculus Innovative Sciences, Inc. Method of using oxidative reductive potential water solution in dental applications
US10342825B2 (en) 2009-06-15 2019-07-09 Sonoma Pharmaceuticals, Inc. Solution containing hypochlorous acid and methods of using same
CN114574292A (zh) * 2021-12-25 2022-06-03 华能酒泉发电有限公司 一种具有抑菌、清洗有机物的超滤膜清洗剂的制备方法及其应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022023250A1 (en) 2020-07-27 2022-02-03 Unilever Ip Holdings B.V. Use of an enzyme and surfactant for inhibiting microorganisms
CR20230492A (es) 2021-04-01 2023-11-23 Sterilex LLC Desinfectante/sanitizante en polvo sin quats

Citations (6)

* Cited by examiner, † Cited by third party
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DE3615787A1 (de) * 1986-05-10 1987-11-12 Fresenius Ag Desinfektionsmittel
US5021182A (en) * 1986-05-10 1991-06-04 Roman A. Epp Bacteriocidal washing agents containing a per-compound and a TAED:PAG mixture
US5273674A (en) * 1990-05-17 1993-12-28 Henkel Kommanditgesellschaft Auf Aktien 2,5-diacyloxy-2,5-dihydrofuran activators for inorganic per compounds
US5691293A (en) * 1993-04-01 1997-11-25 Henkel Kommanditgesellschaft Auf Aktien Stable, dual-function, phosphate-, metasilicate- and polymer-free low-alkali detergent tablets for dishwashing machines and a process for their production
US5773399A (en) * 1993-12-10 1998-06-30 The Procter & Gamble Comapny Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
US5981463A (en) * 1998-06-08 1999-11-09 Noramtech Corporation Anhydrous detergent/bleach composition and method of preparing same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8909254D0 (en) * 1989-04-24 1989-06-07 Unilever Plc Detergent compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3615787A1 (de) * 1986-05-10 1987-11-12 Fresenius Ag Desinfektionsmittel
US5021182A (en) * 1986-05-10 1991-06-04 Roman A. Epp Bacteriocidal washing agents containing a per-compound and a TAED:PAG mixture
US5273674A (en) * 1990-05-17 1993-12-28 Henkel Kommanditgesellschaft Auf Aktien 2,5-diacyloxy-2,5-dihydrofuran activators for inorganic per compounds
US5691293A (en) * 1993-04-01 1997-11-25 Henkel Kommanditgesellschaft Auf Aktien Stable, dual-function, phosphate-, metasilicate- and polymer-free low-alkali detergent tablets for dishwashing machines and a process for their production
US5773399A (en) * 1993-12-10 1998-06-30 The Procter & Gamble Comapny Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
US5981463A (en) * 1998-06-08 1999-11-09 Noramtech Corporation Anhydrous detergent/bleach composition and method of preparing same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8062500B2 (en) 2001-12-05 2011-11-22 Oculus Innovative Sciences, Inc. Method and apparatus for producing negative and positive oxidative reductive potential (ORP) water
CN100353931C (zh) * 2003-06-23 2007-12-12 周彦忠 一种护肤洗浴用品及其应用
US10016455B2 (en) 2003-12-30 2018-07-10 Sonoma Pharmaceuticals, Inc. Method of preventing or treating influenza with oxidative reductive potential water solution
US9642876B2 (en) 2003-12-30 2017-05-09 Sonoma Pharmaceuticals, Inc. Method of preventing or treating sinusitis with oxidative reductive potential water solution
US9168318B2 (en) 2003-12-30 2015-10-27 Oculus Innovative Sciences, Inc. Oxidative reductive potential water solution and methods of using the same
US8840873B2 (en) 2005-03-23 2014-09-23 Oculus Innovative Sciences, Inc. Method of treating second and third degree burns using oxidative reductive potential water solution
US8323252B2 (en) 2005-03-23 2012-12-04 Oculus Innovative Sciences, Inc. Method of treating skin ulcers using oxidative reductive potential water solution
US9498548B2 (en) 2005-05-02 2016-11-22 Oculus Innovative Sciences, Inc. Method of using oxidative reductive potential water solution in dental applications
US8834445B2 (en) 2006-01-20 2014-09-16 Oculus Innovative Sciences, Inc. Methods of treating or preventing peritonitis with oxidative reductive potential water solution
US8147444B2 (en) 2006-01-20 2012-04-03 Oculus Innovative Sciences, Inc. Methods of treating or preventing peritonitis with oxidative reductive potential water solution
US9782434B2 (en) 2006-01-20 2017-10-10 Sonoma Pharmaceuticals, Inc. Methods of treating or preventing inflammation and hypersensitivity with oxidative reductive potential water solution
WO2009122125A1 (en) * 2008-04-01 2009-10-08 Reckitt Benckiser Inc. Laundry treatment compositions
US10342825B2 (en) 2009-06-15 2019-07-09 Sonoma Pharmaceuticals, Inc. Solution containing hypochlorous acid and methods of using same
CN114574292A (zh) * 2021-12-25 2022-06-03 华能酒泉发电有限公司 一种具有抑菌、清洗有机物的超滤膜清洗剂的制备方法及其应用

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DE60040317D1 (de) 2008-11-06

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