CA2264555A1 - Aqueous structured liquid detergent composition comprising aminocarboxylate sequestrant - Google Patents

Aqueous structured liquid detergent composition comprising aminocarboxylate sequestrant Download PDF

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Publication number
CA2264555A1
CA2264555A1 CA002264555A CA2264555A CA2264555A1 CA 2264555 A1 CA2264555 A1 CA 2264555A1 CA 002264555 A CA002264555 A CA 002264555A CA 2264555 A CA2264555 A CA 2264555A CA 2264555 A1 CA2264555 A1 CA 2264555A1
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CA
Canada
Prior art keywords
electrolyte
liquid detergent
liquids
acid
detergent composition
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Abandoned
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CA002264555A
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French (fr)
Inventor
Shang-Ren Wu
Lili Faucia Brouwn
Johannes Cornelis Van De Pas
Johannes J. Verhagen
Petronella C. Wissenburg
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Unilever PLC
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Individual
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Publication of CA2264555A1 publication Critical patent/CA2264555A1/en
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    • 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
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Abstract

The present invention is directed to aqueous structured liquid detergent compositions comprising surfactant material, water and electrolyte, wherein the electrolyte comprises aminocarboxylate sequestrant and builder material.
The invention further relates to a process of preparing liquids.

Description

CA 02264555 1999-02-25WO 98/13467 PCT/EP97/04925AQUEOUS STRUCTURED LIQUID DETERGENT COMPOSITION COMPRISINGAMINOCARBOXYLATE SEQUESTRANT5 Technical FieldThe present invention relates to aqueous liquids, inparticular structured liquids and processes of preparingaqueous liquids.10 Background & Prior ArtLiquid detergent compositions are well—known in the art andoffer several advantages over solid compositions. Forexample, liquid compositions are easier to measure, todispense and to dissolve into a laundering liquor and15 liquid compositions give more confidence to the consumer ofbeing safer and less harsh to the washed or launderedtextile and environment than solid compositions. This maybe the reason that heavy and light duty laundry liquiddetergent products are gaining in popularity ever since20 their introduction on the market at the expense of powdereddetergent products, in particular for coloured fabrics.We have however found that liquid detergent compositionsmay suffer from extensive physical instability, chemical25 instability and/or high viscosity problems as compared tosolid detergent compositions and these problems are evenmore imminent for concentrated aqueous liquids. This isprobably due to the high number of possible interactions ofingredients in liquid detergent compositions. Moreover,30 these interactions will affect not only the stability andviscosity, but also the wash performance.1015202530CA 02264555 1999-02-25W0 98/ 13467 PCT/EP97/04925EP 137474 and EP 137475 disclose aqueous prespottingcompositions comprising surfactant and chelating agent. Thecompositions are said to have good water—borne and oil-borne stain removal characteristics.EP 267,653 discloses detergent compositions comprisingsurfactant, builder and biodegradable EDDS which is said topossess excellent stain removal properties.WO 92/06164 discloses the use of polyhydroxy fatty acidamide surfactants in detergent compositions and refers tothe use of EDDS as chelating agent.WO 94/03553 discloses detergent compositions comprisingbleach and EDDS, as a biodegradable bleach stabiliser.WO 94/03554 discloses detergent compositions comprisingEDDS,are said to have benefits on bleachable and enzymatic stainpercarbonate and layered silicate. The compositionsremoval even when reduced amounts in total of builder,bleach and chelant are used.WO 94/03572 discloses detergent compositions comprisingEDDS and crystalline layered silicate to reduce thedeposition of salt encrustations and multi—cycle build upof such encrustations. As indicated in the abstract anddisclosed in the example, the document relates to granularcompositions. The compositions comprise perborate andlayered silicate material.1015202530CA 02264555 1999-02-25W0 98/13467 PCT/EP97/04925WO 94/20599 discloses detergent compositions comprisingsurfactant and EDDG or HPDDS. The compositions are said tohave good stain removal and cleaning performance.US 3,956,198, US 5,221,496,EP 233,010 disclose the use of aminocarboxylates forUS 5,186,856, US 4,560,492 andimproving stain removal.Aminocarboxylates have further been disclosed in US4,663,071 and FR 2,156,080.We have found that a way of formulating detergentcompositions which have good stain removing performance andenvironmental profile. The compositions have the advantageof being physically and chemically stable with low viscousand good dispersing properties.Consequently, the present invention is directed to anaqueous structured liquid detergent composition comprisingsurfactant material, electrolyte and water, wherein theelectrolyte comprises aminocarboxylate sequestrant andbuilder material.The present invention is further directed to a process ofpreparing an aqueous structured liquid detergentcomposition comprising surfactant material, electrolyte andwater, wherein the electrolyte comprises aminocarboxylatesequestrant, and wherein the process involves mixing theingredients whilst keeping the pH above 6 and keeping thetemperature below 80°C, preferably after addition of thecarboxylate.1015202530CA 02264555 1999-02-25W0 98I13467 PCT/EP97/04925The present invention is further directed to a process forwashing coloured fabric by using a liquid detergentcomposition comprising an aminocarboxylate sequestrant.Detailed Description of the InventionIn View of the consumer confidence, liquids preferably onlycontain safe and non-harsh ingredients. Consequently,oflayered silicate and contain up to 10%, more preferably upto 5%,liquids of the invention are preferably free of bleach,most preferably up to 3%, in particular preferredsubstantially no solvent material.We have found that that liquids of the present inventionwhich meet one or more of these criteria are in particularpreferred for the washing of stained, coloured clothes.Liquid compositionsTwo general and separate classes of liquids compositions,isotropic and structured liquids, are known in the art.Isotropic liquids are liquids in which all ingredients aredissolved and, contrary to structured liquids, there is nostructure present in isotropic liquid.Structured liquids are well-known in the art. They caneither be internally structured, whereby the structure isformed by primary ingredients, preferably by surfactantmaterial, and/or by providing a three dimensional matrixstructure using secondary additives, preferably polymersand/or silicate material. Structuring may be brought aboutto endow properties such as consumer preferred flowproperties and/or turbid appearance. Many structuredliquids are also capable of suspending particulate solids,1015202530CA 02264555 1999-02-25W0 98/ 13467 PCT/EP97/04925such as particles of clay that may be used to provide afabric-softening effect to fabrics. Examples of structuredliquids without suspended solids are given in US—A—4,244,840, whilst examples where solid particles aresuspended are disclosed in EP-A-160 342; EP—A—38 101;EP—A-140 452 and also in the aforementioned US-A-4,244,840.We have found that structured liquids are preferred overisotropic liquids as they provide more formulationflexibility, e.g.concentration. Structured liquids may however suffer fromas regards inclusion of ingredients andviscosity and stability problems.Preferably, liquids of the invention have a viscosity offrom 200 to 2500mPa.s at 21 s‘1at 25°C, more preferablythe viscosity is lower than 2000, most preferably theviscosity is lower than 1200.Preferably, liquids of the invention have a stability of atmost 5mm volume phase separation after 1 month storage atroom temperature, more preferably at most 2mm, mostpreferably there is substantially no phase separation.SurfactantsLiquid detergent compositions of the invention comprisesurfactant materials.In the widest definition the surfactant material ingeneral, may comprise one or more surfactants, and may beselected from anionic, cationic, nonionic, zwitterionic andamphoteric species, and (provided mutually compatible)mixtures thereof.l015202530CA 02264555 1999-02-25W0 98/13467 PCT/EP97/04925Suitable nonionic surfactants include for example aliphaticalcohols, acids, amides or alkyl phenols with alkyl oxides,especially ethylene oxide. Specific nonionic detergentcompounds are alkyl (C6-Cm) primary or secondary linear orbranched alcohols with ethylene oxide, and products made bycondensation of ethylene oxide with the reaction productsof propylene oxide and ethylene—di—amine.We have found that the wash performance of liquids is inparticular improved when nonionics are included incompositions of the invention. Preferably, the level ofnonionic surfactant materials is from 1 to 40% by weight ofthe composition, more preferred from 2 to 25%.Compositions of the present invention may contain syntheticanionic surfactant ingredients. Suitable anionicsurfactants are usually water—soluble alkali metal salts oforganic sulphates and sulphonates having alkyl radicalscontaining from about 8 to about 22 carbon atoms. Examplesof suitable synthetic anionic surfactant compounds aresodium and potassium C8—Cl8 alkyl sulphates, sodium and(C9-Cm) benzene sulphonates and etherthe level of the abovepotassium alkylvariants thereof. Generally,mentioned non—soap anionic surfactant materials is from 1to 40 %to 25%.by weight of the composition, more preferred from 2It is also possible, and sometimes preferred, to include analkali metal soap of a Cl2—Cl8 carboxylic acid. Preferably,the level of soap is from 1 to 35% by weight of thecomposition, more preferred from 5 to 25%.1015202530CA 02264555 1999-02-25WO 98/13467 PCT/EP97/04925Preferably, surfactant material is present at a level of atleast 1% by weight of the composition, more preferred atleast 5% by weight, most preferred at least 10% by weightof the composition; and preferably at a level of at most70% by weight, more preferably at most 40%, most preferablyat most 35% by weight.Preferably, compositions according to the inventioncomprise anionic and nonionic surfactants, more preferablyeach at a level of higher than 5% by weight of thecomposition.Electrolyte MaterialCompositions according to the invention compriseelectrolyte material. It is noted that for the purpose ofthe invention, the term electrolytes includes sequestrantsand builder material.Preferably, the total level of electrolyte is from 1 to 60%by weight of the composition, more preferably from 5 to 45%by weight, most preferably from 10 to 30% by weight.Aminocarboxylate SequestrantsCompositions of the invention comprise an aminocarboxylatesequestrant.the aminocarboxylate sequestrant is3NMost preferably,selected from 1N carboxylates, 2N carboxylates,carboxylates and mixtures thereof.Preferably, aminocarboxylates of the invention are selectedfrom the amino(poly)carboxylates.-::+o-anCA 02264555 1999-02-25W0 93/13467 :*c'r/$1-97.'c492-5selected from—N(MOOCCHfl;‘referably, the estrant iseqIucarboxylate comprises an group and/or anmino~N—CHgHHfiCqpM)(CCOM> group, wherein M isL1!hydrogen, metala;kali metal), ammonium or a mixture thereof, whereinI\..th is optionally substituted with one or mere~SC:Na groups.e sequestrantLin -Hoe, Liquid c\q,-lo/3'-»::JY,the sequestrant of the invention is selectedacid, beta-alanineamine—N,N—disuccini:and mixtures thereof.the prefrom salts of icFdiacetic acid, methyl glycine diaceticethylenediamine—N,N-disuccinic acid andWithin this group, beta-alanine diacetic acid, methylglycine diacetic acid, ethylenediamine—N,N—disuccinic acidand mixtures thereof are preferred.Within this group, methyl glycine diacetic acid,ethylenediamine-N,N—disuccinic acid and mixtures thereofare preferred. S,S ethylenediamine~N,N-disuccinic acid isin particular preferred.. in ‘Hue. c\¢Z}¢ve¢.u+yPreferably, the level of the sequestrant of the inventionis from 0.1 to 5% by weight of the composition, more.\_._.. ___,_“-W/lC,",,d"-r »‘.' “tn--_, A-__.1015202530W0 98/ 13467CA 02264555 1999-02-25PCT/EP97/04925preferably from 0.5 to 4% by weight, most preferably from 1to 3% by weight of the composition.BuilderIn any event, compositions according to the presentinvention include detergency builder material, some or allof which may be electrolyte. In this context it should benoted that some surfactant materials such as for examplesoaps, also have builder properties.Examples of phosphorous containing inorganic detergencybuilders include the water—soluble salts, especially alkalimetalpyrophosphates, orthophosphates, polyphosphates andphosphonates. Examples of non—phosphorus-containingincludeinorganic detergency builders, when present,water—soluble alkali metal carbonates, bicarbonates,silicates and crystalline and amorphous aluminosilicates.Examples of organic detergency builders, when present,include the alkaline metal, ammonium and substitutedammonium polyacetates, carboxylates, polycarboxylates,polyacetyl carboxylates and polyhydroxysulphonates.Preferably, builder material is selected from sodiumcitrate, sodium tripolyphosphate, zeolite and mixturesthereof.Preferably, the builder is included in level to obtain aCa” concentration in the wash liquor is below 10” mol/l,more preferably below 10” mol/l, most preferably below 10”mol/l, e.g. from O to 10* mol/l. We have found that thisfavourably influences the objective of the presentinvention.1015202530CA 02264555 1999-02-25W0 98/ 13467 PCT/EP97/0492510Preferably, the level of non-soap builder material ishigher than 5%, more preferably higher than 7%, mostpreferably higher than 8% by weight of the composition andpreferably lower than 40%, more preferred lower than 38% byweight of the composition.Surprisingly, we have found that in particular thecombination of a sequestrant according to the invention andthe builder material according to the invention at thelevels indicated, leads to stable and high performingliquids.Salting—out electrolyteCompositions according to the invention preferably containa salting—out electrolyte that is able to bring aboutinternal structuring of the liquid, preferably in the formof lamellar droplets of the surfactant material.Salting—out electrolyte has the meaning ascribed to inspecification EP 79,646, i.e. salting—out electrolytes havea lyotropic number of less than 9.5, preferably less than9Ø Examples are sulphate, citrate, NTA.and carbonate.We have found that the aminocarboxylate of the compositionsof the invention is preferably combined with anothersalting—out resistant electrolyte in order to providestable, low viscous structured liquids.Preferably, the compositions contain from 1% to 60%,especially from 10 to 45% of salting—out electrolyte.1015202530CA 02264555 1999-02-25wo 98/13467 PCT/EP97/04925llOptionally, some salting-in electrolyte (as defined EP79,646) may also be included.FEEIt is preferred to prepare highly concentrated liquids,although this is in particular difficult in View of thephysical properties of the liquid. Liquid compositions ofthe invention therefor preferably comprise water at a levelof from 30 to 60%,preferably from 35 to 45% by weight of the composition.more preferably from 32 to 50%, mostPreferably, liquids of the invention have a pH of from 7 to10, more preferably of from 7.5 to 9.Optional ingredientsApart from the ingredients already mentioned, a number ofoptional ingredients may also be present, for examplelather boosters, lather depressants, inorganic salts suchas sodium sulphate, and, usually present in very minorenzymes such as(Tradeamounts, fluorescent agents, perfumes,proteases, amylases and lipases (including LipolaseMark) anti—redepositionex Novo), enzyme stabilisers,agents, germicides and colorants.ProcessingGenerally, liquid detergent compositions of the inventionmay be prepared by any method described in the art. Anexample is to disperse of electrolyte ingredient togetherwith the minor ingredients except for the temperature andetc.such as enzymes, perfumes,followed by thepH sensitive ingredients,if any— in water of elevated temperature,(J12530CA 02264555 1999-02-25wo 98/13467addition of the builder materialf—&§—an7-i the surfactantmaterial (possibly as a premix) under stirring andthereafter cooling the mixture and adding any pH andtemperature sensitive minor ingredients.However, as indicated above, we have found a particularlypreferred process of preparing liquids of the invention.t invention is directed to anliquid detergent compositioprocess of preparing a ncomprising surfactant material, electrolyte and water,wherein the composition has a structure and the electrolytecomprise aminocarbcxylate sequestrant and mixtures thereof,by mixing the ingredients and keeping the pH above 8 andthe temperature below 80°C.Preferably, liquids of the invention are pre_ared by mixingwater and electrolytes, including the sequestrant of theinvention and any builder material, whereafter a premix ofsurfactants is added. We have found that the process of theinvention ensures the best product characteristics asregards solidification and stability. The process has inparticular been found to be beneficial when the sequestrantis added before the zeolite builder material, whereafterthe active premix is added. This would not be expected inview of the presence of the sequestrant which wouldsequester metal present in the builder material.The invention will be illustrated by way of the followingnon-limiting Examples..«:v'iEN2»ED SHEET or PC'I‘.’El‘97/0492510152O2530CA 02264555 1999-02-25W0 98/13467 PCT/EP97/0492513ExamplesExamples 1-6The tetrasodium salt of glutamic acid N,N-diacetic acid,thetrisodium salt of ethylenediamine triaceticacid, thethe trisodium salt of beta-alanine diacetic acid,trisodium salt of methyl glycine diacetic acid, thepentasodium salt of diethylenetriamine penta-acetic acid,the tetrasodium salt of S,S ethylenediamine—N,N-disuccinicacid, the tetrasodium salt of ethylenediamine tetra—aceticacid and the sodium salt of ethylenediaminedi(sulfosuccinate) were incorporated at concentrationsbetween 1 and 4% in the compositions listed in Table l. Theingredients were mixed according the process of theinvention, as indicated in the description.All liquids have good physical properties and show goodperformance. The liquids with a 2/3N carboxylates werepreferred over the lN carboxylates as regards theperformance.Examples 7-14The liquids of Tables 2 and 3 were prepared by mixing theingredients according to the process of the invention asindicated in the description whilst keeping the pH above 6and the temperature below 80°C. The physical properties,wash performance and environmental profile of thecompositions was determined.CA 02264555 1999-02-25W0 98/13467 PCTIEP97/0492514Table 1Ingredients Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6Na—LAS 28 7 24 17.5PAS 1) 10Nonionic 2) 18.4 3 9 18Nonionic 3) 12Sodium Alkyl 6Ethoxy SulphateOleic—acid 10 1 4.5 12NaOH and/or KOH neutralisation up to pH 8-10Glycerol/borax 7.7 8.5 8.5 4.5 3.5 3.5Mono & tri 4ethanolamineSodium citrate 10 7.7 2.8 11.5 11.5Zeolite 15 15STP 20 22Deflocculating 1 1 1 1 1polymer 4)Polymer 5) 0.5 0.5Minors 0.8 1.1 0.8 0.9 0.9Enzymes 1.0 0.6 0.6 0.4 0.7 0.7PVP 0.5Water up to 100CA 02264555 1999-02-25W0 98/13467 PCT/EP97/04925151) Primary Alkyl Sulphate2) Fatty alcohol ethoxylate 7E03) Fatty alcohol ethoxylate 9E04) Polymer All of EP 3469955) Permalose, ex ICITable 2Ingredients Reference Ex. Ex. Ex. Ex.1ONa-LAS 17.5 17. 17. 17. 17.5Fatty 9 9 9 9 9alcoholethoxylate7EOOleic—acid 4.5 4.5 4.5 4.5 4.5NaOH and/or adjust pH to 8.5KOHGlycerol 2.0 2.0 2.0 2.0 2.0Borax 1.5 1.5 1.5 1.5 1.5Sodium 11.5 9.0 9.0 9 9.0citrateZeolite 15 15 15 15 15S,S EDDS 1) 2Trilon ES 22 )Trilon GS 23 )CA 022645551999-02-25WO 98/13467 PCT/EP97/0492516 iNervanaid 2GBS-5 4)Polymer 5) 1 1 1 1 1Oily—Soil 0.5 0.5 0.5 0 5 0.5ReleasepolymerEnzyme 0.7 0.7 0.7 0 7 0.7Minors 0.9 0.9 0.9 0 9 0.9Water up to 100%Productproperties:Physical Okay Okay Okay Okay OkaystabilityPourability Okay Okay Okay Borde OkayrlineStain ref best improved overremoval referenceEnvironment Okay Okay Okay Okay Borderal lineacceptabili‘C Y1) Ethylenediamine—N,N—disuccinic acid2) Methylglycine diacetic acid3) Beta-alanine diacetic acid5 4) Glutamic acid N,N—diacetic acid5) Polymer All of EP 346995CA 02264555 1999-02-25W0 98/13467 PCT/EP97/0492517Table 3Ingredients reference Ex.11 Ex.12 Ex.l3 Ex.14Fatty alcohol 18 18 18 18 18ethoxylate7EOOleic-acid 12 12 12 12 12NaOH and/or adjust pH to 8.5KOHGlycerol 2.0 2.0 2.0 2.0 2.0Borax 1.5 1.5 1.5 1.5 1.5Sodium 11.5 11.5 11.5 11.5 11.5citrateZeolite 15 15 15 15 15S,S EDDS 1) 2Trilon ES 2) 2Trilon GS 3) 2Nervanaid 2GBS—5 4)Polymer 5) 1 1 1 1 1Oi1y—Soil 0.5 0.5 0.5 0.5 0.5Releasepolymer;PermaloseSilicon oil 0.3 0.3 0.3 0.3 0.3Protease 0.4 0.4 0.4 0.4 0.410CA02264555 1999-02-25W0 98/13467 PCT/EP97l0492518Lipolase 0.2 0.2 0 2 0.2 0.2Amylase 0.1 0.1 0 1 0.1 0.1Fluorescent 0.1 0.1 0 1 0.1 0.1whiteningagentPerfume 0.5 0.5 0 5 0.5 0.5Water up to 100%Productproperties:Physical Okay Okay Okay Okay OkaystabilityPourability Okay Okay Okay Border OkaylineStain removal ref best improved overreferenceEnvironmental Okay Okay Okay Okay Borderacceptability lineFrom the results it can be concluded that Trilon ES,Ethylenediamine-N,N—disuccinic acidMethylglycine diacetic acidBeta—alanine diacetic acidGlutamic acid N,N—diacetic acidPolymer All of EP 346995GS and Nervanaid GBS—5 give adequate productTriloncharacteristics in base formulations 5 and 6. However,Trilon ES and Nervanaid GBS—5 are preferred over Trilon GSCA 02264555 1999-02-25W0 98/ 13467 PCT/EP97/0492519for pourability reasons. Trilon ES and G5 are preferred forenvironmental reasons. S,S EDDS is however the mostpreferred sequestrant also with respect to stain removal.

Claims (6)

Claims
1. Aqueous structured liquid detergent composition comprising surfactant material, electrolyte, wherein the electrolyte comprises 0.1 to 5% by weight of aminocarboxylate sequestrant selected from glutamic acid N,N-diacetic acid, beta-alanine diacetic acid, methyl glycine diacetic acid, ethylenediamine-N,N-disuccinic acid and mixtures thereof;

more than 5% by weight of builder material selected from citrate, tripolyphosphate, zeolite and mixtures thereof;

and water.
2. Composition according to claim 1, wherein the aminocarboxylate sequestrant is S,S ethylenediamine-N,N-disuccinic acid.
3. Composition according to claims 1-2, wherein the builder comprises zeolite.
4. Composition according to claims 1-3, wherein the electrolyte comprises aminocarboxylate and a salting-out electrolyte.
5. Process of preparing a liquid detergent composition according any of the preceding claims, by mixing the ingredients and keeping the pH above 6 and the temperature below 80EC.
6. Washing process for stained, coloured fabric in which a liquid detergent composition according to claims 1-4 is used.
CA002264555A 1996-09-27 1997-09-04 Aqueous structured liquid detergent composition comprising aminocarboxylate sequestrant Abandoned CA2264555A1 (en)

Applications Claiming Priority (3)

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US72254696A 1996-09-27 1996-09-27
US08/722546 1996-09-27
PCT/EP1997/004925 WO1998013467A1 (en) 1996-09-27 1997-09-04 Aqueous structured liquid detergent composition comprising aminocarboxylate sequestrant

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CA2264555A1 true CA2264555A1 (en) 1998-04-02

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AU (1) AU715749B2 (en)
BR (1) BR9711419A (en)
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WO (1) WO1998013467A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8110215B2 (en) 2004-04-30 2012-02-07 Kimberly-Clark Worldwide, Inc. Personal care products and methods for inhibiting the adherence of flora to skin
GB0522658D0 (en) * 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
ITCR20060016A1 (en) * 2006-06-07 2007-12-08 Silvia Palladini DETERGENT FORMULATIONS AT LOW ENVIRONMENTAL IMPACT
KR20100039392A (en) 2007-08-17 2010-04-15 로디아 아시아 퍼시픽 피티이, 리미티드 Structured soap compositions
ES2378018T3 (en) 2009-09-14 2012-04-04 The Procter & Gamble Company Detergent composition
EP2302026A1 (en) 2009-09-15 2011-03-30 The Procter & Gamble Company Detergent composition comprising surfactant boosting polymers
ES2399703T3 (en) * 2009-09-15 2013-04-02 The Procter And Gamble Company Detergent composition comprising a mixture of chelators
US8629093B2 (en) 2010-09-01 2014-01-14 The Procter & Gamble Company Detergent composition comprising mixture of chelants
DE102011084934A1 (en) * 2011-10-21 2013-04-25 Henkel Ag & Co. Kgaa Rinse aid and dishwashing detergent
WO2014198547A2 (en) 2013-06-12 2014-12-18 Unilever N.V. Pourable detergent composition comprising suspended particles
MX2017000777A (en) * 2014-07-17 2017-04-27 Basf Se Liquid detergent compositions and their manufacture.
DE102022113400A1 (en) 2022-05-27 2023-11-30 Henkel Ag & Co. Kgaa Flowable detergents and cleaning agents with improved properties

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GB8711060D0 (en) * 1987-05-11 1987-06-17 Unilever Plc Detergent liquid processing
EP0732394A3 (en) * 1995-03-13 1999-02-03 Unilever N.V. Detergent compositions

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BR9711419A (en) 1999-08-24
AU4302197A (en) 1998-04-17
WO1998013467A1 (en) 1998-04-02
EP0929657A1 (en) 1999-07-21

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