EP0748864B1 - Cleaning composition and method for the cleaning of delicate surfaces - Google Patents

Cleaning composition and method for the cleaning of delicate surfaces Download PDF

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Publication number
EP0748864B1
EP0748864B1 EP95870134A EP95870134A EP0748864B1 EP 0748864 B1 EP0748864 B1 EP 0748864B1 EP 95870134 A EP95870134 A EP 95870134A EP 95870134 A EP95870134 A EP 95870134A EP 0748864 B1 EP0748864 B1 EP 0748864B1
Authority
EP
European Patent Office
Prior art keywords
builder
composition
composition according
cleaning
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
EP95870134A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0748864A1 (en
Inventor
Marc François Theophile Evers
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble 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
Priority to DE69524212T priority Critical patent/DE69524212T2/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES95870134T priority patent/ES2168350T3/es
Priority to EP95870134A priority patent/EP0748864B1/en
Priority to AU57510/96A priority patent/AU5751096A/en
Priority to BR9608925-3A priority patent/BR9608925A/pt
Priority to US08/981,315 priority patent/US6110882A/en
Priority to CA002224461A priority patent/CA2224461C/en
Priority to PCT/US1996/007030 priority patent/WO1996041856A2/en
Priority to JP9503059A priority patent/JPH11507688A/ja
Priority to CO96028805A priority patent/CO4700540A1/es
Priority to ARP960103119A priority patent/AR002441A1/es
Publication of EP0748864A1 publication Critical patent/EP0748864A1/en
Priority to MXPA/A/1997/010064A priority patent/MXPA97010064A/es
Application granted granted Critical
Publication of EP0748864B1 publication Critical patent/EP0748864B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C11D2111/24—

Definitions

  • the present invention relates to hard surface cleaning compositions.
  • the compositions herein are specifically designed for the safe cleaning of marble and painted and lacquered surfaces, especially painted and lacquered wood.
  • marble and lacquered surfaces are two types of surfaces which do require particular attention, when formulating cleaning compositions for their cleaning.
  • marble is mainly composed of calcium carbonate, and is therefore incompatible with cleaning compositions which would be acidic to neutral and/or which would comprise a builder.
  • acidity would "dissolve” marble
  • the builder whose function is specifically to bind ions which are present in water and dirt particles, would also bind the calcium in the marble, thereby turning the surface from very shiny to dull, as the introduced surface irregularities lower the reflectance of the surface.
  • the formulation of an alkaline, builder free composition would seem indicated in the present circumstances.
  • an alkaline composition does not accommodate the cleaning of lacquered and painted surfaces, such as painted metal surfaces, or lacquered and painted wooden surfaces e.g. lacquered wooden floors.
  • lacquers are typically made out of polyurethanes or polyacrylates or mixtures of both, and paint is mainly pigmented polyacrylates, polyvinylacetates or alkydresins. Indeed such surfaces are permanently damaged by alkalinity. Specifically, alkalinity would destroy the lacquer and therefore give the lacquered surface the appearance of dullness or a colour change. Thus it would appear that formulating a cleaning composition which is suitable for cleaning both marble and lacquered surfaces is hindered by incompatible pH requirements.
  • a liquid composition which comprises at least one surfactant, which is formulated at a mildly acidic to mildly alkaline pH , which comprises a builder, and positive divalent ions in amounts so as to saturate the builder in the composition.
  • the mildly acidic to neutral pH does damages neither marble nor lacquers.
  • the builder saturated with the positive divalent ions prevents the damage on marble, while it still displays its building action, as evidenced by improved grease cleaning performance.
  • the present invention encompasses a liquid cleaning composition which comprises at least one surfactant, which is formulated in a pH range of from 6 to 9, and which comprises a builder and positive divalent ions in an amount so as to saturate the builder in the composition, wherein said positive divalent ions are Mg 2+ or Ca 2+ or mixtures thereof.
  • the present invention further encompasses a method of cleaning marble or lacquered surfaces, wherein a liquid composition formulated in a pH range of from 6 - 9 and comprising at least one surfactant, a builder and positive divalent ions in amounts so as to saturate the builder in the composition,is applied to clean said marble or lacquered surfaces, and said composition is removed.
  • compositions herein are liquid compositions. They are typically aqueous and typically comprise from 10 % to 99 % by weight of the total composition, preferably from 15 % to 95 %, most preferably from 30 % to 92 % of water.
  • the compositions herein comprise at least one surfactant.
  • the surfactant herein is required for cleaning.
  • Suitable surfactants for use herein include anionic, nonionic, cationic and amphoteric surfactants.
  • Non limiting examples of surfactants useful herein typically include the conventional alkyl benzene sulphonates ("LAS"), typically C 11 -C 18 LAS, alkyl sulphonates, typically C 8 -C 18 alkyl sulphonates and primary, branched-chain and random alkyl sulphates (“AS”), typically C 10 -C 20 AS, the secondary (2,3) alkyl sulphates, typically C 10 -C 18 ones, of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-sol
  • the conventional nonionic and amphoteric surfactants such as the alkyl ethoxylates ("AE") preferably C 12 -C 18 AE, including the so-called narrow peaked alkyl ethoxylates and alkyl phenol alkoxylates, especially the C 6 -C 12 ones, especially ethoxylates and mixed ethoxy-propoxy, betaines and sulfobetaines ("sultaines”), preferably the C 12 -C 18 ones, amine oxides, typically the C 10 -C 18 ones, and the like, can also be included in the overall compositions.
  • the N-alkyl polyhydroxy fatty acid amides typically C 10 -C 18 ones, can also be used.
  • Typical examples include the C 12 -C 18 N-methylglucamides, see WO 9,206,154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl glucamides preferably C 12 -C 18 ones, can be used for low sudsing.
  • C 10 -C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • compositions herein may comprise from 0.1 % to 90 % by weight of the total composition, preferably from 5 % to 85 %, most preferably from 5 % to 70 % of at least one surfactant.
  • the preferred surfactants for use herein are the nonionic surfactants or mixtures of anionics and nonionics, for their cleaning action on grease. It is another benefit of the present invention that anionic surfactants can be used herein without damaging marble. Indeed, it has been observed that anionic surfactants usually also damage marble probably because, like builders, they bind with the calcium in the marble. However the compositions of the present invention can surprisingly afford the presence of anionic surfactants for improved cleaning without having to suffer any negative on safety to marble.
  • compositions herein comprise a builder.
  • the compositions herein comprise from 0.1 % to 20 %, preferably from 0.2 % to 10 %, most preferably from 0.3 % to 6 % by weight of the total composition of builder, or mixtures thereof.
  • Suitable builders for use herein include polycarboxylates and polyphosphates, and salts thereof.
  • Such suitable and preferred polycarboxylates include citrate and complexes of the formula CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH 2 (COOX); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts.
  • A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
  • TDS tartrate disuccinic acid
  • Still other ether polycarboxylates suitable for use herein include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid.
  • ether hydroxypolycarboxylate builders include the ether hydroxypolycarboxylates represented by the structure: HO-[C(R)(COOM)-C(R)(COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl (preferably R is hydrogen).
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • Preferred amongst those cyclic compounds are dipicolinic acid and chelidanic acid.
  • polycarboxylates for use herein are mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • carboxylate builders herein include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973.
  • carboxylates for use herein, but which are less preferred because they do not meet the above criteria are alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
  • polyacetic acid builder salts are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine, tetraacetic acid and nitrilotriacetic acid.
  • Suitable but less preferred polycarboxylates are those also known as alkyliminoacetic builders such as methyl imino diacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxy propylene imino diacetic acid and other alkyl imino acetic acid builders.
  • compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanediotes and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • Useful succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • Alkyl succinic acids typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • succinate builders include : laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0 200 263, published November 5, 1986.
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polyerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • Suitable polyphosphonates for use herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates.
  • the most preferred builder for use herein Is citrate.
  • the compositions herein comprise positive divalent ions in amounts so as to saturate the builder present in the composition.
  • saturated it is meant herein that there should be enough ions to bind substantially all the builder present in the composition, i.e. at least 75% of the builder, preferably at least 80%, most preferably at least 90% or all of the builder.
  • the ions should be present most preferably in a molar ratio of builder ions to builder of at least X:2, where X is the maximum potential number of negative charges carried per mole of builder.
  • said builder is citrate
  • said molar ratio should be at least 3:2, because each mole of citrate can carry 3 negative changes.
  • the form in which the carboxylate or phosphate groups in the builder are present is not critical. In other words, at certain pH values between 6 to 8 where some of the carboxylate or phosphate groups in the builder are in their protonated form, the preferred X:2 ratio still applies.
  • the ions can be introduced in the compositions in any form.
  • MgSO 4 , MgCl 2 , Mg Phosphates and MgNO 3 are a suitable source of Mg ions for the compositions herein.
  • MgSO 4 , MgCl 2 , Mg Phosphates and MgNO 3 are a suitable source of Mg ions for the compositions herein.
  • the positive divalent ions for use herein are Mg 2+ and Ca 2+ , or mixtures thereof.
  • the compositions herein have a pH between 6 and 9, preferably between 6.5 and 8, and most preferably between 7 and 7.5. At lower pH, the composition would damage marble while, at higher pH, it would damage lacquers. Interestingly, even in neutral pH in which the compositions herein can be formulated, damage to marble would be observed in the absence of the saturated citrate.
  • the pH of the compositions herein can be adjusted by any of the means well known to the man skilled in the art, such as addition of NaOH, KOH, MEA,TEA,MDEA,K2CO3,Na2CO3 and the like, or citric acid, sulphuric acid, nitric acid, hydrochloric acid, maleic acid, acetic acid and the like.
  • compositions herein can further comprise a variety of well known optional ingredients, including perfumes, dyes, alkanolamines.
  • the present invention further encompasses a method of cleaning marble or lacquered surfaces.
  • a composition formulated in a pH range of from 6 to 9 and comprising at least one surfactant, a builder, and positive divalent ions in amounts so as to saturate the builder in the composition is applied onto said marble or lacquered surface, and said composition Is optionally removed.
  • the compositions herein can be used undiluted, i.e. neat, or diluted.
  • the compositions herein are used in diluted form, i.e. at dilution levels of from about 0.5% to 1.5%, depending on how concentrated the product is.
  • the compositions herein are applied to said surface, and left to dry, i.e. no rinsing is required.
  • the product can also be applied neat on the surface to remove the encrustated dirt much more easily.
  • neat usage of the composition will be preferred. In neat usage, it is preferable that the composition should be removed, i.e. rinsed off after it has been applied to clean.
  • compositions were made by mixing the listed ingredients in the listed proportions. These compositions were used neat to clean marble and dilute to clean lacquered wooden floors. Excellent cleaning and surface safety performance was observed.
  • Ingredients Compositions (weight %) 1 2 3 4 5 6 7 8 C 7-9 ,C 9-11 EO 6 3.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0
  • Dobanol ® 23-3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5
EP95870134A 1995-06-12 1995-12-18 Cleaning composition and method for the cleaning of delicate surfaces Expired - Lifetime EP0748864B1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
ES95870134T ES2168350T3 (es) 1995-06-12 1995-12-18 Composicion limpiadora y metodo para la limpieza de superficies delicadas.
EP95870134A EP0748864B1 (en) 1995-06-12 1995-12-18 Cleaning composition and method for the cleaning of delicate surfaces
DE69524212T DE69524212T2 (de) 1995-06-12 1995-12-18 Reinigungszusammensetzung und Verfahren zum Reinigen von empfindlichen Oberflächen
CA002224461A CA2224461C (en) 1995-06-12 1996-05-16 Cleaning composition and method for the cleaning of delicate surfaces
BR9608925-3A BR9608925A (pt) 1995-06-12 1996-05-16 Composição para limpeza e processo para limpeza de sperfícies delicadas
US08/981,315 US6110882A (en) 1995-06-12 1996-05-16 Cleaning composition and method for the cleaning of delicate surfaces
AU57510/96A AU5751096A (en) 1995-06-12 1996-05-16 Cleaning composition and method for the cleaning of delicate surfaces
PCT/US1996/007030 WO1996041856A2 (en) 1995-06-12 1996-05-16 Cleaning composition and method for the cleaning of delicate surfaces
JP9503059A JPH11507688A (ja) 1995-06-12 1996-05-16 クリーニング組成物およびデリケートな表面のクリーニング法
CO96028805A CO4700540A1 (es) 1995-06-12 1996-06-04 Composiciones limpiadoras liquidas y metodo para limpiar superficies delicadas con las mismas
ARP960103119A AR002441A1 (es) 1995-06-12 1996-06-12 Una composicion limpiadora y un metodo para limpiar superficies delicadas.
MXPA/A/1997/010064A MXPA97010064A (es) 1995-06-12 1997-12-11 Composicion limpiadora y metodo para la limpieza de superficies delicadas

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP95870067 1995-06-12
EP95870067 1995-06-12
EP95870134A EP0748864B1 (en) 1995-06-12 1995-12-18 Cleaning composition and method for the cleaning of delicate surfaces

Publications (2)

Publication Number Publication Date
EP0748864A1 EP0748864A1 (en) 1996-12-18
EP0748864B1 true EP0748864B1 (en) 2001-11-28

Family

ID=26140803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95870134A Expired - Lifetime EP0748864B1 (en) 1995-06-12 1995-12-18 Cleaning composition and method for the cleaning of delicate surfaces

Country Status (10)

Country Link
EP (1) EP0748864B1 (es)
JP (1) JPH11507688A (es)
AR (1) AR002441A1 (es)
AU (1) AU5751096A (es)
BR (1) BR9608925A (es)
CA (1) CA2224461C (es)
CO (1) CO4700540A1 (es)
DE (1) DE69524212T2 (es)
ES (1) ES2168350T3 (es)
WO (1) WO1996041856A2 (es)

Families Citing this family (10)

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US6165285A (en) * 1995-12-18 2000-12-26 The Procter & Gamble Company Method for the cleaning of delicate surfaces
WO2001083659A1 (en) * 2000-05-02 2001-11-08 Unilever N.V. Composition and process for cleaning floors
US6635609B2 (en) * 2002-02-11 2003-10-21 Johnsondiversey, Inc. Surface maintenance composition
WO2005017083A1 (de) * 2003-08-14 2005-02-24 Henkel Kommanditgesellschaft Auf Aktien Reiniger zur schonenden behandlung säureempfindlicher carbonat-haltiger oberflächen
DE10337805A1 (de) * 2003-08-14 2005-03-10 Henkel Kgaa Reiniger zur schonenden Behandlung säureempfindlicher Carbonat-haltiger Oberflächen
DE102010035329A1 (de) * 2010-08-24 2012-03-01 Burkhard Ponitz Reinigungszusammensetzung insbesondere für Fugen
WO2013004302A1 (en) * 2011-07-05 2013-01-10 Ecolab Inc. Acid marble cleaner
DE102012209506A1 (de) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Geschirrspülmittel
DE102012209507A1 (de) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Geschirrspülmittel
DE102012209505A1 (de) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Geschirrspülmittel

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Also Published As

Publication number Publication date
AU5751096A (en) 1997-01-09
CA2224461A1 (en) 1996-12-27
CA2224461C (en) 2005-07-26
WO1996041856A3 (en) 1997-03-06
WO1996041856A2 (en) 1996-12-27
DE69524212T2 (de) 2002-07-25
CO4700540A1 (es) 1998-12-29
JPH11507688A (ja) 1999-07-06
BR9608925A (pt) 1999-10-19
EP0748864A1 (en) 1996-12-18
ES2168350T3 (es) 2002-06-16
AR002441A1 (es) 1998-03-11
MX9710064A (es) 1998-03-29
DE69524212D1 (de) 2002-01-10

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