EP0534525A2 - Waschmittelpulver und Verfahren zu deren Herstellung - Google Patents

Waschmittelpulver und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0534525A2
EP0534525A2 EP92202764A EP92202764A EP0534525A2 EP 0534525 A2 EP0534525 A2 EP 0534525A2 EP 92202764 A EP92202764 A EP 92202764A EP 92202764 A EP92202764 A EP 92202764A EP 0534525 A2 EP0534525 A2 EP 0534525A2
Authority
EP
European Patent Office
Prior art keywords
citric acid
weight
composition
detergent
composition according
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
EP92202764A
Other languages
English (en)
French (fr)
Other versions
EP0534525A3 (en
EP0534525B2 (de
EP0534525B1 (de
Inventor
Galip Akay
Andrew Paul Unilever Research Chapple
Peter Robert Unilever Resaerch Garrett
Peter Cory Unilever Resaerch Knight
John William H. Unilever Resaerch Yorke
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0534525A2 publication Critical patent/EP0534525A2/de
Publication of EP0534525A3 publication Critical patent/EP0534525A3/en
Application granted granted Critical
Publication of EP0534525B1 publication Critical patent/EP0534525B1/de
Publication of EP0534525B2 publication Critical patent/EP0534525B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates
    • 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
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065High-density particulate detergent compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof

Definitions

  • the present invention relates to detergent powders intended for use in drum-type fabric washing machines.
  • the invention is of especial applicability to detergent powders containing no, or reduced levels of, phosphate builders and to powders of high bulk density, which have a tendency to dispense poorly.
  • the invention also relates to a process for preparing these detergent powders.
  • US-A-4,414,130 discloses detergent compositions comprising an effervescent material which promotes dissolution and dispersion of the detergent particles.
  • the detergent particles may comprise sodium carbonate or bicarbonate and that the balance of the composition may include citric acid.
  • the present invention provides a granular detergent composition having a bulk density of from 650 to 1100 kg/m3 and comprising anionic and/or nonionic surfactants, from 5 to 30% by weight of sodium carbonate and/or -bicarbonate and/or sesquicarbonate, other builder material, and from 1 to 15% by weight of particulate citric acid, whereby more than 80% by weight of the citric acid has a particle size which is in the range of from 350 to 1500 ⁇ m.
  • the invention also provides a process for preparing this composition, wherein the citric acid is added as a separate granular component to a granular detergent base composition.
  • the first aspect of the invention is a granular detergent composition having a bulk density of from 650 to 1100 kg/m3, preferably from 700 to 1100 kg/m3.
  • the composition comprises a base composition to which particulate citric acid, and optionally a foam depressing agent, has been added.
  • the base composition may be prepared by spray-drying and dry-mixing/agglomeration. For obtaining high bulk densities, it is preferably prepared by dry-mixing/agglomeration.
  • the base composition contains one or more anionic and/or nonionic surfactants, and builder material.
  • the base composition preferably also comprises sodium carbonate and/or sodium bicarbonate and/or sodium sesquicarbonate.
  • the granular composition of the invention may further contain any of the materials conventionally included in detergent compositions. These are described in more detail below.
  • the surfactant component is the surfactant component
  • the total amount of surfactant present in the composition of the invention will generally range from 5 to 40 % by weight, more preferably from 10 to 30% by weight, and especially from 12 to 20% by weight. These figures are typical for fully formulated detergent compositions, and as a spray-dried or dry-mixed/agglomerated base forms only part of such a composition the surfactant content of that base, as a percentage, may of course be higher.
  • the invention is of especial applicability to compositions containing anionic and nonionic surfactants.
  • the amount of anionic surfactant present is desirably at least 3% by weight, and may suitably be in the range of from 3 to 30% by weight, these figures again being based on the fully formulated composition.
  • Anionic surfactants are well known to those skilled in the art. Examples of suitable anionic surfactants include alkylbenzene sulphonates,particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; primary and secondary alkyl sulphates, particularly sodium C12-C15 primary alkyl sulphates; sodium salts of fatty acids (i.e. soaps); olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic surfactants are alkyl (C6-C22) phenols-ethylene oxide condensates, generally with 5 to 25 units of ethylene oxide (i.e.: 5-25 EO) per molecule, and the condensation products of aliphatic ( C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 3-40 EO.
  • alkyl polyglycosides and glucose ethers and esters may be effectively used as nonionic surfactants.
  • the sodium carbonate and/or bicarbonate and/or - sesquicarbonate may be added to the base composition but is preferably present in it.
  • the amount of this material present in the composition of the invention is in the range of from 5 to 30% by weight based on a fully formulated detergent composition. In zeolite built detergent powder according to the invention this amount is preferably in the range of from 5 to 15% by weight, whereas in detergent powder including a calcite/sodium carbonate builder system this amount is preferably in the range of from 15 to 30% by weight.
  • the citric acid is a separate granular component and needs to be added to the base composition.
  • the amount of particulate citric acid needed to obtain the desired good dispensing characteristics and storage stability is in the range of from 1 to 15% by weight, preferably from 2 to 12% by weight, more preferably from 3 to 10% by weight, based on a fully formulated composition.
  • more than 80% by weight of the particulate citric acid has a particle size of from 350 to 1500 ⁇ m, preferably from 350 to 1000 ⁇ m, a particle size range of 350-750 ⁇ m being most preferred.
  • the composition according to the invention includes at least one further builder material capable of reducing the level of free calcium ions in the wash liquor and preferably providing the composition with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.
  • the total level of the detergency builder may be from 10% to 70% by weight, preferably from 25% to 50% by weight of the detergent composition.
  • Preferred builders are ion exchange builders such as the crystalline (zeolite) or amorphous alkali metal alumino-silicates.
  • organic and inorganic polymers may be present, for example, polycarboxylate polymers such as polyacrylates, acrylic-maleic copolymers such as SOKALAN types of polymers may be present.
  • polycarboxylate polymers such as polyacrylates
  • acrylic-maleic copolymers such as SOKALAN types of polymers
  • Other preferred builder systems are precipitant builders such as those containing calcite and sodium carbonate as described in EP-A-267,042.
  • the detergent composition according to the invention is preferably essentially free of phosphates-containing builders such as orthophosphates and alkali metal tripolyphosphates.
  • the incorporation of citric acid and sodium (bi)carbonate and/or sodium sesquicarbonate preferably results in a reduction in the residue of at least 10 percentage points, most preferably at least 20 percentage points.
  • an improvement of this magnitude can only be observed if the control powder exhibits poor dispensing properties.
  • the present invention is therefore especially applicable to powders which, without citric acid and sodium (bi)carbonate and/or -sesquicarbonate, give dispenser residues of at least 20% by weight. That is especially likely to be the case if the powder is a zero-phosphate composition built with amorphous or crystalline (zeolite) sodium alumino-silicate; and/or if it has a bulk density of at least 650, preferably of at least 700 kg/m3.
  • the granular detergent composition of the invention preferably also contains one or more foam depressing agents.
  • Silicone oil based compositions containing high or low viscosity silicone oil, particularly high viscosity silicone oil, may be effectively used as antifoaming agents.
  • bleaches are the oxygen bleaches, for example in the form of an inorganic persalt, preferably with a precursor, or as a peroxy acid compound. From an environmental point of view, the most preferred bleach compound is percarbonate. Effective amounts of these bleach compounds present in the detergent composition of the invention range from 5 to 20% by weight, preferably from 10 to 20% by weight.
  • the powder of the invention may contain sodium silicate.
  • High levels of silicate can in themselves have a beneficial effect on dispensing, as well as on powder structure and prevention of machine corrosion, but are undesirable in powders containing alumino-silicate because the two components react together to form insoluble siliceous species.
  • the present invention enables the dispensing behaviour of zeolite-built powders to be improved without a corresponding increase in the level of insoluble material. Accordingly, the invention is of especial applicability to powders containing less than 10% by weight, more especially less than 5% by weight, of sodium silicate.
  • fluorescers include fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, bleach activators, and bleach stabilizers. These may be included in the spray-dried base powder or postdosed according to their known suitability for undergoing spray-drying processes and their compatibility with other slurry ingredients.
  • a phosphate-free detergent base powder was prepared, by slurry-making, spray-drying and subsequently densifying in a Lödige "Recycler/ploughshare", as described in EP-A-367,339, to form the following nominal composition: Parts LAS 8.3 Nonionic EO 6.7 Soap 1.8 Zeolite 4A 28.0 Sokalan CP5 4.5 Carbonate 8.5 Minor ingredients + moisture 14.8
  • the bulk density of the detergent powder obtained was 850 kg/m3.
  • citric acid of which more than 80% by weight has a particle size in the range of 350-1000 ⁇ m was added at four different levels.
  • the dispensing properties of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine using 100 g powder, and 5 litres of water at 20°C flowing in over a period of 1 minute.
  • Other samples were stored during 6 weeks in wax-laminated cartons at 28 °C and 70% RH, and thereafter tested in the Philips washing machine.
  • Table 1 shows the resulting dispenser residues. TABLE 1 1 2 3 4 Parts citric acid added 0 1 2 3 Dispenser Residue (%) 80 50 0 0 Dispenser Residue after After storage for 6 weeks 80 65 10 0
  • the bulk density of the detergent powder obtained was 850 kg/m3.
  • citric acid of which more than 80% by weight has a particle size in the range of 350-1000 ⁇ m was added at four different levels.
  • Samples of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine, as described above. Other samples were stored during 6 weeks in wax-laminated cartons at 28°C and 70% RH, and thereafter tested in the Philips washing machine.
  • Table 2 shows the resulting dispenser residues. TABLE 2 5 6 7 8 9 Parts citric acid added 0 2 4 6 8 Dispenser Residue (%) 80 70 40 0 0 Dispenser Residue after Storage for 6 weeks (%) 80 70 40 10 0
  • particulate citric acid of which more than 80% by weight has a larger partical size than according to the present invention is not very effective at improving dispensing, neither immediately after preparation of the detergent powder nor after storage for 4 weeks.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP92202764A 1991-09-27 1992-09-11 Waschmittelpulver und Verfahren zu deren Herstellung Expired - Lifetime EP0534525B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9120657 1991-09-27
GB919120657A GB9120657D0 (en) 1991-09-27 1991-09-27 Detergent powders and process for preparing them

Publications (4)

Publication Number Publication Date
EP0534525A2 true EP0534525A2 (de) 1993-03-31
EP0534525A3 EP0534525A3 (en) 1993-09-01
EP0534525B1 EP0534525B1 (de) 1996-12-27
EP0534525B2 EP0534525B2 (de) 2007-10-10

Family

ID=10702133

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92202764A Expired - Lifetime EP0534525B2 (de) 1991-09-27 1992-09-11 Waschmittelpulver und Verfahren zu deren Herstellung

Country Status (9)

Country Link
EP (1) EP0534525B2 (de)
JP (1) JPH05202398A (de)
AU (1) AU651732B2 (de)
BR (1) BR9203769A (de)
CA (1) CA2078718C (de)
DE (1) DE69216191T3 (de)
ES (1) ES2097860T3 (de)
GB (1) GB9120657D0 (de)
ZA (1) ZA927383B (de)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014767A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Detergent compositions
WO1997024423A1 (en) * 1995-12-28 1997-07-10 Rhone-Poulenc Surfactants & Specialties, L.P. Processes for producing solid surfactant compositions with enhanced dissolution rates
WO1997028245A1 (de) * 1996-02-02 1997-08-07 Henkel Kommanditgesellschaft Auf Aktien Feste reinigungsmittelzubereitungen
US5683976A (en) * 1996-01-11 1997-11-04 Reckitt & Colman Inc. Powdered carpet cleaning compositions
WO1998004662A1 (en) * 1996-07-31 1998-02-05 The Procter & Gamble Company A detergent composition comprising an acid source with a specific particle size
WO1998004672A1 (en) * 1996-07-31 1998-02-05 The Procter & Gamble Company A process and composition for detergents
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
WO1998035011A1 (de) * 1997-02-06 1998-08-13 Henkel Kommanditgesellschaft Auf Aktien Verwendung von cobuilder-haltigen additiven in wasch- oder reinigungsmitteln
EP0866118A2 (de) * 1997-03-20 1998-09-23 The Procter & Gamble Company Waschmittelteilchen
WO1998055574A1 (de) * 1997-06-05 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Granulares waschmittel
EP0888425A1 (de) * 1996-03-15 1999-01-07 Amway Corporation Freifliessendes agglomerisiertes niotensidhaltiges waschmittel sowie verfahren zu seiner herstellung
EP0906385A1 (de) * 1996-05-17 1999-04-07 The Procter & Gamble Company Waschmittelzusammensetzung
EP0990697A1 (de) 1996-03-11 2000-04-05 Kao Corporation Granulares waschmittel für kleidung
WO2000022087A1 (de) * 1998-10-14 2000-04-20 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittelformkörper mit organischen oligocarbonsäuren
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
EP1004658A2 (de) * 1998-11-24 2000-05-31 Henkel Kommanditgesellschaft auf Aktien Citronensäurehaltiges Waschmittel
GB2344597A (en) * 1998-12-08 2000-06-14 Procter & Gamble Effervescence components
US6162784A (en) * 1996-07-31 2000-12-19 The Procter & Gamble Company Process and composition for detergents
US6191095B1 (en) 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
WO2001064035A2 (en) * 2000-02-28 2001-09-07 The Procter & Gamble Company Acidic antimicrobial compositions for treating food and food contact surfaces and methods of use thereof
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO2002092752A1 (en) * 2001-05-16 2002-11-21 Unilever Plc Particulate laundry detergent composition containing zeolite
US6534474B1 (en) 1998-06-04 2003-03-18 Kao Corporation Surfactant composition
WO2003035813A1 (en) * 2001-10-19 2003-05-01 Unilever Plc Detergent compositions
US6573231B2 (en) 2000-03-13 2003-06-03 Unilever Home & Personal Care Division Of Conopco, Inc. Detergent compositions
US6683043B1 (en) 1998-12-08 2004-01-27 The Procter & Gamble Company Process for manufacturing effervescence components
EP0700427B2 (de) 1993-05-26 2005-08-10 Unilever Plc Waschmittelzusammensetzungen
US7186677B2 (en) * 2001-12-21 2007-03-06 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Method for the production of surfactant granulates containing builders
EP0975724B2 (de) 1997-04-14 2014-11-26 The Procter & Gamble Company Brausezusammensetzungen sowie trockene brausegranulate

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GB1374105A (en) * 1970-12-03 1974-11-13 Scherico Ltd Effervescent compositions
GB1379734A (en) * 1971-04-27 1975-01-08 Eldib Eng Research Inc Cleansing and laundering composition
US4028262A (en) * 1972-10-16 1977-06-07 Colgate-Palmolive Company Citrate-carbonate built detergent
GB1515299A (en) * 1974-08-28 1978-06-21 Unilever Ltd Stabilisation of sodium percarbonate
US4231887A (en) * 1979-06-26 1980-11-04 Union Carbide Corporation Zeolite agglomerates for detergent formulations
US4414130A (en) * 1976-08-17 1983-11-08 Colgate Palmolive Company Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them
EP0220024A2 (de) * 1985-10-09 1987-04-29 The Procter & Gamble Company Granulierte Reinigungsmittel mit Löslichkeit
EP0367339A2 (de) * 1988-11-02 1990-05-09 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte
EP0419036A2 (de) * 1989-08-21 1991-03-27 Unilever Plc Reinigungsverstärkeradditiv und dies enthaltendes Detergentsystem
EP0456315A2 (de) * 1990-05-08 1991-11-13 The Procter & Gamble Company Niedrig-pH-Waschmittelgranulate enthaltend Aluminiumsilikat, Zitronensäure und Carbonatbuilder

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GB1374105A (en) * 1970-12-03 1974-11-13 Scherico Ltd Effervescent compositions
GB1379734A (en) * 1971-04-27 1975-01-08 Eldib Eng Research Inc Cleansing and laundering composition
US4028262A (en) * 1972-10-16 1977-06-07 Colgate-Palmolive Company Citrate-carbonate built detergent
GB1515299A (en) * 1974-08-28 1978-06-21 Unilever Ltd Stabilisation of sodium percarbonate
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EP0220024A2 (de) * 1985-10-09 1987-04-29 The Procter & Gamble Company Granulierte Reinigungsmittel mit Löslichkeit
EP0367339A2 (de) * 1988-11-02 1990-05-09 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte
EP0419036A2 (de) * 1989-08-21 1991-03-27 Unilever Plc Reinigungsverstärkeradditiv und dies enthaltendes Detergentsystem
EP0456315A2 (de) * 1990-05-08 1991-11-13 The Procter & Gamble Company Niedrig-pH-Waschmittelgranulate enthaltend Aluminiumsilikat, Zitronensäure und Carbonatbuilder

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Hoffman la Roche sales brochure on citric acid on the market in 1988; Jungbunzlauer sales brochure on citric acid on the market before 1991 ADM sales brochure on citric acid, confirmed by ADM to be of essentially the same specification as the citric acid on the market before 1991; and CEH market research report on citric acid,of 1996, 1992 and 1989 *
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Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0700427B2 (de) 1993-05-26 2005-08-10 Unilever Plc Waschmittelzusammensetzungen
WO1995014767A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Detergent compositions
US5583098A (en) * 1993-11-24 1996-12-10 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
AU698980B2 (en) * 1993-11-24 1998-11-12 Unilever Plc Detergent compositions
WO1997024423A1 (en) * 1995-12-28 1997-07-10 Rhone-Poulenc Surfactants & Specialties, L.P. Processes for producing solid surfactant compositions with enhanced dissolution rates
US5683976A (en) * 1996-01-11 1997-11-04 Reckitt & Colman Inc. Powdered carpet cleaning compositions
WO1997028245A1 (de) * 1996-02-02 1997-08-07 Henkel Kommanditgesellschaft Auf Aktien Feste reinigungsmittelzubereitungen
EP0990697B2 (de) 1996-03-11 2010-05-26 Kao Corporation Granulares waschmittel für kleidung
EP0990697A1 (de) 1996-03-11 2000-04-05 Kao Corporation Granulares waschmittel für kleidung
EP0888425A4 (de) * 1996-03-15 2000-08-23 Amway Corp Freifliessendes agglomerisiertes niotensidhaltiges waschmittel sowie verfahren zu seiner herstellung
EP0888425A1 (de) * 1996-03-15 1999-01-07 Amway Corporation Freifliessendes agglomerisiertes niotensidhaltiges waschmittel sowie verfahren zu seiner herstellung
EP0906385A4 (de) * 1996-05-17 1999-06-09 Procter & Gamble Waschmittelzusammensetzung
EP0906385A1 (de) * 1996-05-17 1999-04-07 The Procter & Gamble Company Waschmittelzusammensetzung
GB2315761A (en) * 1996-07-31 1998-02-11 Procter & Gamble Detergent composition comprising a particulate acid source and an alkaline source
US6162784A (en) * 1996-07-31 2000-12-19 The Procter & Gamble Company Process and composition for detergents
WO1998004662A1 (en) * 1996-07-31 1998-02-05 The Procter & Gamble Company A detergent composition comprising an acid source with a specific particle size
WO1998004672A1 (en) * 1996-07-31 1998-02-05 The Procter & Gamble Company A process and composition for detergents
WO1998035011A1 (de) * 1997-02-06 1998-08-13 Henkel Kommanditgesellschaft Auf Aktien Verwendung von cobuilder-haltigen additiven in wasch- oder reinigungsmitteln
EP0866118A3 (de) * 1997-03-20 1998-12-16 The Procter & Gamble Company Waschmittelteilchen
EP0866118A2 (de) * 1997-03-20 1998-09-23 The Procter & Gamble Company Waschmittelteilchen
EP0975724B2 (de) 1997-04-14 2014-11-26 The Procter & Gamble Company Brausezusammensetzungen sowie trockene brausegranulate
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
US6191095B1 (en) 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
WO1998055574A1 (de) * 1997-06-05 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Granulares waschmittel
US6534474B1 (en) 1998-06-04 2003-03-18 Kao Corporation Surfactant composition
WO2000022087A1 (de) * 1998-10-14 2000-04-20 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittelformkörper mit organischen oligocarbonsäuren
EP1004658A2 (de) * 1998-11-24 2000-05-31 Henkel Kommanditgesellschaft auf Aktien Citronensäurehaltiges Waschmittel
EP1004658A3 (de) * 1998-11-24 2000-08-09 Henkel Kommanditgesellschaft auf Aktien Citronensäurehaltiges Waschmittel
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Publication number Publication date
BR9203769A (pt) 1993-04-20
ES2097860T3 (es) 1997-04-16
AU651732B2 (en) 1994-07-28
CA2078718C (en) 2003-12-09
EP0534525A3 (en) 1993-09-01
CA2078718A1 (en) 1993-03-28
GB9120657D0 (en) 1991-11-06
EP0534525B2 (de) 2007-10-10
JPH05202398A (ja) 1993-08-10
DE69216191T2 (de) 1997-06-05
AU2535592A (en) 1993-04-01
ZA927383B (en) 1994-03-25
EP0534525B1 (de) 1996-12-27
DE69216191D1 (de) 1997-02-06
DE69216191T3 (de) 2008-03-13

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