[go: up one dir, main page]

EP0748864A1 - Composition de nettoyage et procédé pour le nettoyage des surfaces delicates - Google Patents

Composition de nettoyage et procédé pour le nettoyage des surfaces delicates Download PDF

Info

Publication number
EP0748864A1
EP0748864A1 EP95870134A EP95870134A EP0748864A1 EP 0748864 A1 EP0748864 A1 EP 0748864A1 EP 95870134 A EP95870134 A EP 95870134A EP 95870134 A EP95870134 A EP 95870134A EP 0748864 A1 EP0748864 A1 EP 0748864A1
Authority
EP
European Patent Office
Prior art keywords
builder
composition according
composition
cleaning
marble
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.)
Granted
Application number
EP95870134A
Other languages
German (de)
English (en)
Other versions
EP0748864B1 (fr
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 EP95870134A priority patent/EP0748864B1/fr
Priority to ES95870134T priority patent/ES2168350T3/es
Priority to US08/981,315 priority patent/US6110882A/en
Priority to BR9608925-3A priority patent/BR9608925A/pt
Priority to PCT/US1996/007030 priority patent/WO1996041856A2/fr
Priority to AU57510/96A priority patent/AU5751096A/en
Priority to JP9503059A priority patent/JPH11507688A/ja
Priority to CA002224461A priority patent/CA2224461C/fr
Priority to CO96028805A priority patent/CO4700540A1/es
Priority to ARP960103119A priority patent/AR002441A1/es
Publication of EP0748864A1 publication Critical patent/EP0748864A1/fr
Priority to MXPA/A/1997/010064A priority patent/MXPA97010064A/xx
Application granted granted Critical
Publication of EP0748864B1 publication Critical patent/EP0748864B1/fr
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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/24—Mineral surfaces, e.g. stones, frescoes, plasters, walls or concretes

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 the mildly acidic to mildly alkaline pH range, which comprises a builder and positive divalent ions in an amount so as to saturate the builder in the composition.
  • the present invention further encompasses a method of cleaning marble or lacquered surfaces, where an effective amount of 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 -C20 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 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: H0-[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, all of which are incorporated herein by reference.
  • 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, incorporated herein by reference.
  • 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, incorporated herein by reference.
  • 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, incorporated herein by reference. 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, incorporated herein by reference. 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.
  • Suitable positive divalent ions for use herein include Mg 2+ , Ba 2+ , Fe 2+ , Ca 2+ , Zn 2+ and Ni 2+ . Most Preferred are Mg 2+ and Ca 2+ , or mixtures thereof.
  • the compositions herein are formulated in a mildly acidic to mildly alkaline range. Accordingly, the compositions herein preferably have a pH between 6 and 9, more 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 method of cleaning marble or lacquered surfaces In that method, an effective amount of a composition as herein before described 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

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP95870134A 1995-06-12 1995-12-18 Composition de nettoyage et procédé pour le nettoyage des surfaces delicates Expired - Lifetime EP0748864B1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP95870134A EP0748864B1 (fr) 1995-06-12 1995-12-18 Composition de nettoyage et procédé pour le nettoyage des surfaces delicates
ES95870134T ES2168350T3 (es) 1995-06-12 1995-12-18 Composicion limpiadora y metodo para la limpieza de superficies delicadas.
DE69524212T DE69524212T2 (de) 1995-06-12 1995-12-18 Reinigungszusammensetzung und Verfahren zum Reinigen von empfindlichen Oberflächen
AU57510/96A AU5751096A (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
PCT/US1996/007030 WO1996041856A2 (fr) 1995-06-12 1996-05-16 Composition de nettoyage et procede de nettoyage de surfaces delicates
US08/981,315 US6110882A (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
CA002224461A CA2224461C (fr) 1995-06-12 1996-05-16 Composition de nettoyage et procede de nettoyage de surfaces delicates
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 (en) 1995-06-12 1997-12-11 Cleaning composition and method for cleaning delica surfaces

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP95870067 1995-06-12
EP95870067 1995-06-12
EP95870134A EP0748864B1 (fr) 1995-06-12 1995-12-18 Composition de nettoyage et procédé pour le nettoyage des surfaces delicates

Publications (2)

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

Family

ID=26140803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95870134A Expired - Lifetime EP0748864B1 (fr) 1995-06-12 1995-12-18 Composition de nettoyage et procédé pour le nettoyage des surfaces delicates

Country Status (10)

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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001083659A1 (fr) * 2000-05-02 2001-11-08 Unilever N.V. Composition et processus pour nettoyer des sols
WO2003068900A1 (fr) * 2002-02-11 2003-08-21 Johnsondiversey, Inc. Composition de nettoyage et d'entretien de surfaces en pierre
WO2005017083A1 (fr) * 2003-08-14 2005-02-24 Henkel Kommanditgesellschaft Auf Aktien Produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides
DE10337805A1 (de) * 2003-08-14 2005-03-10 Henkel Kgaa Reiniger zur schonenden Behandlung säureempfindlicher Carbonat-haltiger Oberflächen
WO2012025223A1 (fr) * 2010-08-24 2012-03-01 Burkhard Ponitz Composition nettoyante, en particulier pour joints
WO2013004302A1 (fr) * 2011-07-05 2013-01-10 Ecolab Inc. Nettoyant acide pour le marbre
WO2013182509A1 (fr) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Détergents pour vaisselle
WO2013182508A1 (fr) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Détergents pour vaisselle
WO2013182510A1 (fr) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Détergents pour vaisselle

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6165285A (en) * 1995-12-18 2000-12-26 The Procter & Gamble Company Method for the cleaning of delicate surfaces

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308067A (en) 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3723322A (en) 1969-02-25 1973-03-27 Procter & Gamble Detergent compositions containing carboxylated polysaccharide builders
US3835163A (en) 1973-08-02 1974-09-10 Monsanto Co Tetrahydrofuran polycarboxylic acids
FR2246630A1 (fr) * 1973-10-09 1975-05-02 Procter & Gamble Europ
US4102903A (en) 1977-01-05 1978-07-25 Monsanto Company Tetrahydropyran and 1,4-dioxane polycarboxylate compounds, methods for making such compounds and compositions and methods employing same
US4120874A (en) 1977-01-05 1978-10-17 Monsanto Company Diesters of 6-cyano-2,2-tetrahydropyrandicarboxylates
US4144226A (en) 1977-08-22 1979-03-13 Monsanto Company Polymeric acetal carboxylates
US4158635A (en) 1977-12-05 1979-06-19 Monsanto Company Detergent formulations containing tetrahydropyran or 1,4-dioxane polycarboxylates and method for using same
EP0070587A1 (fr) * 1981-07-17 1983-01-26 THE PROCTER & GAMBLE COMPANY Composition du moyen d'aide de lavage
EP0125711A1 (fr) * 1983-04-19 1984-11-21 Unilever N.V. Composition de nettoyage à tout usage
GB2144763A (en) * 1983-08-11 1985-03-13 Procter & Gamble Liquid detergent compositions with magnesium salts
US4566984A (en) 1984-11-16 1986-01-28 The Procter & Gamble Company Ether polycarboxylates
EP0200263A2 (fr) 1985-05-03 1986-11-05 The Procter & Gamble Company Compositions détergentes homogènes concentrées et liquides contenant un système tensioactif ternaire
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
CN1032360A (zh) 1988-08-08 1989-04-12 抚顺石油学院 天然碳酸钙雕刻物清洗剂
CN1055198A (zh) 1990-03-16 1991-10-09 卢根生 大理石清洗剂
EP0511091A1 (fr) 1991-04-25 1992-10-28 Colgate-Palmolive Company Produit nettoyant pour les surfaces dures
WO1994004644A2 (fr) * 1992-08-25 1994-03-03 Unilever Plc Compositions de nettoyage liquides contenant du sulfate d'alcool primaire et des surfactants non-ioniques

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298180A (en) * 1989-05-18 1994-03-29 Colgate Palmolive Co. Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5298195A (en) * 1992-03-09 1994-03-29 Amway Corporation Liquid dishwashing detergent

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308067A (en) 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3723322A (en) 1969-02-25 1973-03-27 Procter & Gamble Detergent compositions containing carboxylated polysaccharide builders
US3835163A (en) 1973-08-02 1974-09-10 Monsanto Co Tetrahydrofuran polycarboxylic acids
US3923679A (en) 1973-08-02 1975-12-02 Monsanto Co Salts of tetrahydrofuran polycarboxylic acids as detergent builders and complexing agents
FR2246630A1 (fr) * 1973-10-09 1975-05-02 Procter & Gamble Europ
US4102903A (en) 1977-01-05 1978-07-25 Monsanto Company Tetrahydropyran and 1,4-dioxane polycarboxylate compounds, methods for making such compounds and compositions and methods employing same
US4120874A (en) 1977-01-05 1978-10-17 Monsanto Company Diesters of 6-cyano-2,2-tetrahydropyrandicarboxylates
US4144226A (en) 1977-08-22 1979-03-13 Monsanto Company Polymeric acetal carboxylates
US4158635A (en) 1977-12-05 1979-06-19 Monsanto Company Detergent formulations containing tetrahydropyran or 1,4-dioxane polycarboxylates and method for using same
EP0070587A1 (fr) * 1981-07-17 1983-01-26 THE PROCTER & GAMBLE COMPANY Composition du moyen d'aide de lavage
EP0125711A1 (fr) * 1983-04-19 1984-11-21 Unilever N.V. Composition de nettoyage à tout usage
GB2144763A (en) * 1983-08-11 1985-03-13 Procter & Gamble Liquid detergent compositions with magnesium salts
US4566984A (en) 1984-11-16 1986-01-28 The Procter & Gamble Company Ether polycarboxylates
EP0200263A2 (fr) 1985-05-03 1986-11-05 The Procter & Gamble Company Compositions détergentes homogènes concentrées et liquides contenant un système tensioactif ternaire
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
US4663071B1 (fr) 1986-01-30 1992-04-07 Procter & Gamble
CN1032360A (zh) 1988-08-08 1989-04-12 抚顺石油学院 天然碳酸钙雕刻物清洗剂
CN1055198A (zh) 1990-03-16 1991-10-09 卢根生 大理石清洗剂
EP0511091A1 (fr) 1991-04-25 1992-10-28 Colgate-Palmolive Company Produit nettoyant pour les surfaces dures
WO1994004644A2 (fr) * 1992-08-25 1994-03-03 Unilever Plc Compositions de nettoyage liquides contenant du sulfate d'alcool primaire et des surfactants non-ioniques

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001083659A1 (fr) * 2000-05-02 2001-11-08 Unilever N.V. Composition et processus pour nettoyer des sols
WO2003068900A1 (fr) * 2002-02-11 2003-08-21 Johnsondiversey, Inc. Composition de nettoyage et d'entretien de surfaces en pierre
AU2003210797B2 (en) * 2002-02-11 2007-09-20 Diversey, Inc. Cleaning and maintenance composition for stone surfaces
CN100540646C (zh) * 2002-02-11 2009-09-16 约翰逊迪瓦西公司 石料表面的清洁和维护组合物
WO2005017083A1 (fr) * 2003-08-14 2005-02-24 Henkel Kommanditgesellschaft Auf Aktien Produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides
DE10337805A1 (de) * 2003-08-14 2005-03-10 Henkel Kgaa Reiniger zur schonenden Behandlung säureempfindlicher Carbonat-haltiger Oberflächen
WO2012025223A1 (fr) * 2010-08-24 2012-03-01 Burkhard Ponitz Composition nettoyante, en particulier pour joints
WO2013004302A1 (fr) * 2011-07-05 2013-01-10 Ecolab Inc. Nettoyant acide pour le marbre
WO2013182509A1 (fr) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Détergents pour vaisselle
WO2013182508A1 (fr) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Détergents pour vaisselle
WO2013182510A1 (fr) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Détergents pour vaisselle

Also Published As

Publication number Publication date
CA2224461C (fr) 2005-07-26
DE69524212D1 (de) 2002-01-10
BR9608925A (pt) 1999-10-19
WO1996041856A3 (fr) 1997-03-06
CO4700540A1 (es) 1998-12-29
AR002441A1 (es) 1998-03-11
MX9710064A (es) 1998-03-29
WO1996041856A2 (fr) 1996-12-27
AU5751096A (en) 1997-01-09
JPH11507688A (ja) 1999-07-06
ES2168350T3 (es) 2002-06-16
CA2224461A1 (fr) 1996-12-27
EP0748864B1 (fr) 2001-11-28
DE69524212T2 (de) 2002-07-25

Similar Documents

Publication Publication Date Title
AU2006320852B2 (en) Detergent composition containing branched alcohol alkoxylate and compatibilizing surfactant, and method for using
EP0192442B1 (fr) Système de renforcement pour détergents
EP0210220B1 (fr) Procede et compositions de nettoyage de surfaces dures
AU668201B2 (en) Thickened acid microemulsion composition
US6281178B1 (en) Reduced residue hard surface cleaner comprising hydrotrope
EP0900270B1 (fr) Composition acide epaissie
US4911857A (en) Aqueous liquid abrasive cleaning composition: particulate abrasive suspended in aqueous medium
JP2004043828A (ja) ミスト低減性オーブン洗浄剤
EP0748864B1 (fr) Composition de nettoyage et procédé pour le nettoyage des surfaces delicates
EP2970828B1 (fr) Nettoyants pour surfaces dures contenant des esters d'acide phosphorique d'un alkylalcool à modification polyéther
CN111819272B (zh) 水性清洁配制物
US5482647A (en) High soluble carbonate laundry detergent composition containing an acrylic terpolymer
EP0491531A1 (fr) Compositions détérgentes
US6110882A (en) Cleaning composition and method for the cleaning of delicate surfaces
EP0561103B1 (fr) Compositions diluables et procédé de nettoyage de surfaces dures
EP1781765B1 (fr) Utilisation d'un agent de nettoyage presentant des proprietes de repulsion des souillures fecales
WO1995033036A1 (fr) Tensioactifs amphoteres a efficacite amelioree
JPH11152495A (ja) 洗剤及びクリーナ
MXPA97010064A (en) Cleaning composition and method for cleaning delica surfaces
EP1050575B1 (fr) Compositions détergentes alcalines comprenant des alkylbenzènes sulfonates et des alcanolamines
JPH06330087A (ja) 硬表面用洗浄剤組成物
JP2002003890A (ja) 洗浄剤組成物
JP3372108B2 (ja) 硬質表面洗浄剤組成物
EP0808892A1 (fr) Compositions de nettoyage acides
JPH08188794A (ja) 洗浄剤組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB GR IT NL

17P Request for examination filed

Effective date: 19970520

17Q First examination report despatched

Effective date: 20000411

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): DE ES FR GB GR IT NL

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB GR IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011128

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20011228

Year of fee payment: 7

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REF Corresponds to:

Ref document number: 69524212

Country of ref document: DE

Date of ref document: 20020110

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20010402281

Country of ref document: GR

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2168350

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20021112

Year of fee payment: 8

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040701

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20141124

Year of fee payment: 20

Ref country code: ES

Payment date: 20141215

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20141124

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20141215

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20141222

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69524212

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20151217

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20151217

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20151219