EP1299512B1 - Compositions detergentes - Google Patents

Compositions detergentes Download PDF

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Publication number
EP1299512B1
EP1299512B1 EP01936320A EP01936320A EP1299512B1 EP 1299512 B1 EP1299512 B1 EP 1299512B1 EP 01936320 A EP01936320 A EP 01936320A EP 01936320 A EP01936320 A EP 01936320A EP 1299512 B1 EP1299512 B1 EP 1299512B1
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EP
European Patent Office
Prior art keywords
detergent composition
sodium
detergent
alkali metal
bleach
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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
EP01936320A
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German (de)
English (en)
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EP1299512A1 (fr
Inventor
Lesley Unilever Research Port Sunlight Ebbrell
Timothy D. Unilever Research Port Sunlight Finch
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to laundry detergent compositions suitable for washing both white and coloured fabrics.
  • the compositions exhibit improved stain removal, and reduced dye fading due to chlorine in wash water.
  • Chlorine as alkali metal hypochlorite
  • Chlorine is used in many parts of the world to purify water. To make sure that the water is safe, a small residual amount, typically about 0.5 ppm, of chlorine is left in the water. It has been found that even this small amount of chlorine can cause fading of chlorine-sensitive fabric dyes in the wash and in the rinse.
  • laundry detergent compositions containing low levels of peroxy bleaches such as sodium perborate exhibit improved stain removal and better chlorine scavenging if iminodisuccinate (IDS) or hydroxyiminodisuccinate (HIDS) is present.
  • IDS iminodisuccinate
  • HIDS hydroxyiminodisuccinate
  • WO 91 17234A discloses low-pH granular laundry detergent compositions containing chlorine scavengers which minimise the fading of pH-sensitive and chlorine-sensitive fabric dyes during laundering.
  • chlorine scavengers include peroxide bleaches, for example, perborate.
  • Iminodisuccinate is known as a detergency builder and, in bleaching detergent compositions, as a stabiliser for peroxy bleach precursors.
  • US 3 697 453 discloses detergent compositions having a pH of from 9 to 12, containing iminodisuccinate as a detergency builder, used together with detergent surfactant in a weight ratio of 0.25:1 to 10:1.
  • IDS as a detergency builder is also disclosed in EP 757 094A (Bayer).
  • IDS and hydroxyiminodisuccinate (HIDS) are disclosed in JP 09 110 813A (Nippon Shokubai) and JP 09 104 897A (Nippon Shokubai).
  • HIDS as a detergency builder and complexing agent is disclosed in US 5 318 726 (Henkel KGaA).
  • EP 509 382A W R Grace & Co/Hampshire Chemical Corporation
  • DE 43 11 440A Henkel KGaA
  • a bleaching detergent composition comprising a bleaching agent and a bleach stabiliser of defined formula which includes IDS.
  • JP 09 249 895A (Lion) and JP 09 310 097A (Lion) disclose detergent compositions containing 3 to 20 wt% IDS or HIDS to improve the stability or fabric substantivity of fluorescers (optical brighteners).
  • IDS as a processing aid for detergent powders and detergent powder ingredients is disclosed in JP 09 100 497A (Lion) and JP 09 279 188A (Lion).
  • the present invention accordingly provides a laundry detergent composition
  • a laundry detergent composition comprising surfactant, builder, and optionally other non-bleach detergent ingredients, and also containing from 0.5 to 3 wt% of alkali metal persalt bleach and from 0.05 to 5 wt% of a compound of the formula (I): wherein Y is H or OH and X is H or a solubilising cation.
  • a further subject of the invention is a method of removing stains from textile fabrics, which comprises laundering the fabrics by hand or machine in a wash liquor containing a detergent composition as defined above and also containing hypochlorite ions.
  • a further subject of the invention is the use of a compound of the formula I above, in an amount of from 0.05 to 5 wt%, in a laundry detergent composition containing from 0.5 to 3 wt% of alkali metal persalt bleach, to improve stain removal performance and as a chlorine scavenger to prevent the fading of chlorine-sensitive dyes on coloured textile fabrics during laundering.
  • the detergent compositions of the invention contain, as an essential ingredient, a compound of the formula I: wherein Y is H or OH; and X is H or a solubilising cation, preferably a sodium ion.
  • I iminodisuccinic acid or a water-soluble salt thereof.
  • IDS in the following description, the abbreviation "IDS" will be used to denote this material whether in acid or salt form. IDS is commercially available from Bayer AG, Leverkusen, Germany, and from Nippon Shokubai KK, Japan.
  • the formula I represents hydroxyiminodisuccinic acid or a water-soluble salt thereof.
  • HIDS HIDS
  • Nippon Shokubai KK Japan.
  • the IDS or HIDS may be, and preferably is, in the form of a salt, i.e. X in the formula I is a stable solubilising cation, preferably an alkali metal cation, more preferably sodium.
  • IDS or HIDS is present in an amount of from 0.05 to 5 wt%, more preferably from 0.05 to 2.5 wt%, most preferably from 0.2 to 2.5 wt%.
  • the IDS or HIDS is preferably in sodium salt form.
  • the alkali metal persalt bleach is present in an amount of from 0.5 to 3 wt%, preferably from 1 to 3 wt%. This amount can be distinguished from the higher levels typically used in bleaching detergent compositions.
  • the alkali metal, preferably sodium, persalt bleach is preferably selected from perborates and percarbonate.
  • the most preferred material is sodium perborate, in monohydrate or tetrahydrate form. Especially preferred is sodium perborate monohydrate.
  • the ratio of alkali metal persalt to IDS or HIDS is preferably within the range of from 3:1 to 1:3, more preferably from 2:1 to 1:2.
  • composition of the invention also contains other conventional detergent ingredients, other than bleaching ingredients.
  • Essential ingredients are surfactants (detergent-active compounds) and detergency builders, and other non-bleach ingredients may optionally be present.
  • a preferred detergent composition according to the invention comprises:
  • the detergent compositions of the invention may be of any physical form.
  • the detergent compositions will contain, as essential ingredients, one or more detergent active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • the preferred detergent active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkylsulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N + X wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
  • R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group
  • R 2 is a methyl group
  • R 3 and R 4 which may be the same or different, are methyl or hydroxy
  • R 1 represents a C 8 -C 10 or C 12 -C 14 alkyl group
  • R 2 and R 3 represent methyl groups
  • R 4 presents a hydroxyethyl group.
  • Amphoteric surfactants for example, amine oxides, and zwitterionic surfactants, for example, betaines, may also be present.
  • the quantity of anionic surfactant is in the range of from 5 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 8 to 35% by weight.
  • Nonionic surfactant if present, is preferably used in an amount within the range of from 1 to 20% by weight.
  • the total amount of surfactant present is preferably within the range of from 5 to 60 wt%.
  • compositions may suitably contain from 10 to 80%, preferably from 15 to 70% by weight, of detergency builder.
  • the quantity of builder is in the range of from 15 to 50% by weight.
  • the detergent compositions may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite).
  • a crystalline aluminosilicate preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite).
  • the zeolite used as a builder may be the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders.
  • the zeolite may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever), and commercially available as Doucil (Trade Mark) A24 from Crosfield Chemicals Ltd, UK.
  • Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used.
  • phosphate builders especially sodium tripolyphosphate. This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate.
  • inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate, amorphous aluminosilicates.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
  • polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
  • polyaspartates monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl-
  • Organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites.
  • supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and polymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%.
  • Suitable polymers include homo- and copolymers of acrylic acid and maleic acid, especially polyacrylates, acrylic/maleic copolymers, and copolymers of maleic acid and methyl vinyl ether.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • the detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
  • Preferred proteolytic enzymes are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available. Proteases of both high and low isoelectric point are suitable.
  • enzymes that may suitably be present include lipases, amylases, and cellulases including high-activity cellulases such as "Carezyme”).
  • detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
  • Antiredeposition agents for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present.
  • compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
  • soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
  • Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie).
  • ingredients that may be present include solvents, hydrotropes, fluorescers, photobleaches, foam boosters or foam controllers (antifoams) as appropriate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, calcium chloride, other inorganic salts, fabric conditioning compounds, and perfumes.
  • compositions of the invention may be of any suitable physical form, for example, particulates (powders, granules, tablets), liquids, pastes, gels or bars.
  • the detergent composition is in particulate form.
  • the IDS may be incorporated in particulate compositions in the form of granules containing an inert carrier material.
  • compositions in powder form may be of any bulk density and may be prepared by spray-drying, non-tower granulation, or any combination of these techniques.
  • IDS when low levels of alkali metal persalt are present has also been found to reduce the fading upon laundering of chlorine-sensitive dyes. This fading occurs due to the presence of sodium hypochlorite, which is routinely put into supply water for hygiene purposes: as indicated previously, residual levels of 0.5 ppm are typical. This causes fading of dyes of a wide range of colours.
  • the incorporation of IDS in accordance with the present invention can significantly reduce the amount of fading attributable to chlorine in the wash water.
  • the IDS used in the Examples was tetrasodium iminodisuccinate ex Bayer.
  • the HIDS used in the Examples was tetrasodium hydroxyiminodisuccinate ex Nippon Shokubai.
  • Particulate laundry detergent compositions were prepared by conventional spray-drying and postdosing techniques to the following general formulation: Component wt% Sodium linear alkylbenzene sulphonate (NaLAS) 23.71 Sodium silicate (anhydrous) 7.37 Sodium tripolyphosphate 18.77 Sodium carbonate 7.00 Sodium carboxymethyl cellulose 0.52 Polyacrylate polymer 0.54 Calcite 9.88 Sodium perborate monohydrate (if present) 0 or 2 IDS or HIDS (Na salt) (if present) 0 or 1 Sodium sulphate, fluorescer, zeolite, perfume, enzymes, water, impurities to 100
  • Red and black cotton test cloths were prepared by dyeing white cotton cloths with red or black reactive dyes at a loading of 1 g/kg.
  • test cloths were washed four times in tergotometers using the following wash conditions:
  • the washed fabrics were then line-dried in the shade.
  • White cotton test cloths stained with red wine (EMPA 114) were washed in tergotometers using the same formulations and under the same conditions as described above, and line-dried in the shade.
  • Stain removal was assessed by measuring reflectance changes at 580 nm. An increase in reflectance indicates removal of the stain so the larger the figures, the better.
  • the total wash duration was 20 minutes. Reflectance measurements were taken after 5 minutes, after 10 minutes and after 20 minutes.

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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)

Claims (10)

  1. Composition détergente pour la lessive comprenant un tensioactif, un édificateur et optionnellement d'autres ingrédients, caractérisée en ce qu'elle comprend en outre de 0,5 à 3 % en poids d'un blanchissant persel de métal alcalin et de 0,05 à 5 % en poids d'un composé de formule I :
    Figure 00240001
       dans laquelle Y est H ou OH, et X est H ou un cation solubilisant.
  2. Composition détergent selon la revendication 1, caractérisée en ce qu'elle comprend :
    (a) de 5 à 60 % en poids d'un ou de plusieurs tensioactifs détergents ;
    (b) de 10 à 80 % en poids d'un ou de plusieurs édificateurs de détergence ;
    (c) de 0,5 à 3 % en poids de blanchissant persel de métal alcalin ;
    (d) de 0,05 à 5 % en poids d'IDS ou d'HIDS ;
    (e) optionnellement d'autres ingrédients non blanchissants, jusqu'à 100 %.
  3. Composition détergente selon la revendication 1 ou la revendication 2, caractérisée en ce qu'elle comprend de 0,2 à 2,5 % en poids du composé de formule I.
  4. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce que le composé de formule I est de l'acide iminodisuccinique ou un sel de celui-ci, de préférence le sel de sodium.
  5. Composition détergente selon l'un quelconque des revendications précédentes, caractérisée en ce que le blanchissant persel de métal alcalin est présent dans une quantité allant de 1 à 3 % en poids.
  6. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce que le blanchissant persel de métal alcalin est du perborate de sodium, de préférence du monohydrate de perborate de sodium.
  7. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle est sous la forme de particules.
  8. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend un ou plusieurs ingrédients détergents non blanchissants sélectionnés à partir des enzymes, des polymères anti-redéposition, des polymères de libération des salissures, des polymères qui inhibent le transfert de couleur, des solvants, des hydrotropes, des agents de fluorescence, des photo-blanchissants, des amplificateurs de mousse, des agents de contrôle du moussage (anti-moussants), du carbonate de sodium, du bicarbonate de sodium, du silicate de sodium, du sulfate de sodium, du chlorure de calcium, d'autres sels inorganiques, des composés de conditionnement des tissus et des parfums.
  9. Procédé pour éliminer les taches des tissus textiles, caractérisé en ce qu'il comprend le fait de laver en machine ou à la main les tissus dans une liqueur de lavage contenant une composition détergente selon l'une quelconque des revendications 1 à 8 et contenant également des ions d'hypochlorite.
  10. Utilisation d'un composé de formule I :
    Figure 00260001
    dans laquelle Y est H ou OH, et X est H ou un cation solubilisant, dans une quantité allant de 0,05 % à 5 % en poids, dans une composition détergente pour la lessive contenant de 0,5 à 3 % en poids d'un blanchissant persel de métal alcalin, pour améliorer les performances d'élimination des taches de la composition et en tant qu'un épurateur du chlore pour réduire la décoloration des teintures sensibles au chlore en présence des ions d'hypochlorite.
EP01936320A 2000-05-15 2001-05-03 Compositions detergentes Expired - Lifetime EP1299512B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0011678.0A GB0011678D0 (en) 2000-05-15 2000-05-15 Detergent compositions
GB0011678 2000-05-15
PCT/EP2001/005015 WO2001088077A1 (fr) 2000-05-15 2001-05-03 Compositions detergentes

Publications (2)

Publication Number Publication Date
EP1299512A1 EP1299512A1 (fr) 2003-04-09
EP1299512B1 true EP1299512B1 (fr) 2003-11-12

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EP (1) EP1299512B1 (fr)
CN (1) CN1283770C (fr)
AT (1) ATE254165T1 (fr)
AU (1) AU6225801A (fr)
BR (1) BR0110686A (fr)
DE (1) DE60101228T2 (fr)
ES (1) ES2210165T3 (fr)
GB (1) GB0011678D0 (fr)
TR (1) TR200302312T4 (fr)
WO (1) WO2001088077A1 (fr)
ZA (1) ZA200208005B (fr)

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Publication number Priority date Publication date Assignee Title
US6455487B1 (en) * 2002-03-21 2002-09-24 Colgate Palmolive Company Liquid cleaning composition containing a preservative and an effective chelating agent
KR101652559B1 (ko) * 2009-09-07 2016-08-30 라이온 가부시키가이샤 제균제 조성물 및 제균 방법
DE102012218021A1 (de) 2012-10-02 2014-04-03 Henkel Ag & Co. Kgaa Leistungsgesteigerte Wasch- oder Reinigungsmittel mit Komplexbildnern II
DE102012218019A1 (de) * 2012-10-02 2014-04-03 Henkel Ag & Co. Kgaa Leistungsgesteigerte Wasch- oder Reinigungsmittel mit Komplexbildnern I

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4024552A1 (de) * 1990-08-02 1992-02-06 Henkel Kgaa Derivat der aminobernsteinsaeure als komplexierungsmittel
US5362412A (en) * 1991-04-17 1994-11-08 Hampshire Chemical Corp. Biodegradable bleach stabilizers for detergents
JP3623971B2 (ja) * 1993-02-26 2005-02-23 ライオン株式会社 高嵩密度粒状洗剤組成物
DE4311440A1 (de) * 1993-04-07 1994-10-13 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel
EP0678572A1 (fr) * 1994-04-20 1995-10-25 The Procter & Gamble Company Compositions de poudres détergentes
DE19528059A1 (de) * 1995-07-31 1997-02-06 Bayer Ag Wasch- und Reinigungsmittel mit Iminodisuccinaten
JPH09279183A (ja) * 1996-04-10 1997-10-28 Kao Corp 高密度粒状洗剤組成物
DE69811786T2 (de) * 1997-07-16 2003-10-23 Nagase Chemtex Corp., Osaka Verwendung von Chelat bildenden Zusammensetzungen zum Reinigen
JP3290382B2 (ja) * 1997-07-18 2002-06-10 花王株式会社 粉末洗剤組成物
JP2000290698A (ja) * 1999-04-02 2000-10-17 Asahi Denka Kogyo Kk 粉末洗浄剤組成物

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ES2210165T3 (es) 2004-07-01
AU6225801A (en) 2001-11-26
DE60101228T2 (de) 2004-04-22
WO2001088077A1 (fr) 2001-11-22
EP1299512A1 (fr) 2003-04-09
GB0011678D0 (en) 2000-07-05
DE60101228D1 (de) 2003-12-18
ATE254165T1 (de) 2003-11-15
BR0110686A (pt) 2003-03-18
ZA200208005B (en) 2003-10-06
TR200302312T4 (tr) 2004-01-21
CN1522297A (zh) 2004-08-18
CN1283770C (zh) 2006-11-08

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