EP1328611A1 - Compositions pour lave-vaisselle - Google Patents

Compositions pour lave-vaisselle

Info

Publication number
EP1328611A1
EP1328611A1 EP01982443A EP01982443A EP1328611A1 EP 1328611 A1 EP1328611 A1 EP 1328611A1 EP 01982443 A EP01982443 A EP 01982443A EP 01982443 A EP01982443 A EP 01982443A EP 1328611 A1 EP1328611 A1 EP 1328611A1
Authority
EP
European Patent Office
Prior art keywords
composition
machine
nonionic surfactant
water
less
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
EP01982443A
Other languages
German (de)
English (en)
Other versions
EP1328611B1 (fr
Inventor
Marco Franciscus Van Dijk
Alan Digby Tomlinson
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 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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP01982443A priority Critical patent/EP1328611B1/fr
Publication of EP1328611A1 publication Critical patent/EP1328611A1/fr
Application granted granted Critical
Publication of EP1328611B1 publication Critical patent/EP1328611B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention is in the field of machine dishwashing. More specifically, the invention encompasses compositions for use in a machine dish wash formulation, which do not necessitate the addition of salt or rinse aid to the machine .
  • To wash articles in a commercially available dish washing machine usually entails using three product types. Salt is added to the salt compartment to soften the water, a dishwashing formulation is used to clean the articles, and a rinse aid is used to ensure that the articles are rinsed with no streaks or smears .
  • WO 00/06684 discloses a machine dish wash tablet.
  • the tablet has a base composition that carries out it's function in the main wash cycle, and a separate core that acts as a rinse aid in the rinse cycle of the machine.
  • a separate core that acts as a rinse aid in the rinse cycle of the machine.
  • Such a tablet is complicated to manufacture.
  • WO 95/07330 Procter & Gamble
  • US 5358655 Hexkel
  • the present invention relates to a composition for washing dishes that obviates the need for salt and rinse aid in the machine dishwashing process .
  • the present invention relates to a machine dish wash composition
  • a machine dish wash composition comprising at least 4.0 wt% of an ethoxylated and/or propoxylated nonionic surfactant in which the nonionic surfactant has a cloud point in water of 14 or less, preferably 12 or less.
  • Also described is a process for washing articles in a dishwasher comprising the steps of:
  • kits of parts comprising a composition as described above, and instructions stating that no rinse aid or salt is to be added to the dishwashing machine.
  • This invention also relates to the use of 4.0 wt% of an ethoxylated and/or propoxylated nonionic surfactant in which the nonionic surfactant has a cloud point in water of 12 or less in a dish washing composition, so that the composition can be used in a dishwasher without a separate rinse aid composition (and ideally without separate salt) present in the machine .
  • the surfactant system comprises ethoxylated and/or propoxylated nonionic surfactants, more preferably selected from nonionic ethoxylated/propoxylated fatty alcohol surfactants having a cloud point in water of 14°C or less, preferably of 12°C or less, most preferably 10°C or less.
  • nonionic surfactants having the required cloud points for use in the invention are found in the low- to non-foaming ethoxylated straight-chain alcohols of the Plurafac ® LF series, supplied by the BASF Company; Synperoni ' c RA series supplied by ICI Triton ® DF series, supplied by the Rohm & Haas Company.
  • a suitable nonionic surfactant is SLF 18 B 45, ex. Olin Chemicals. Suitable surfactants must however have the appropriate cloud point .
  • the ethoxylated and/or propoxylated nonionic surfactants are present at levels of at least 4.0 wt%, preferably 4-6 wt%, and in some instances more preferably 5 to 8 wt% of the total composition.
  • An anti-foam to suppress foaming is preferably present
  • an anionic surfactant it is advantageously present at levels of 2 wt% or below.
  • An anti-scaling agent is present in the composition as a preferred feature. It is preferable if the level antiscaling agent is from 0.2 to 10 wt% of the total composition, preferably from 0.5 to 5 wt%.
  • Suitable anti-scaling agents include organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof.
  • anti-scaling agents are organic phosphonates such as ⁇ -hydroxy-2 phenyl ethyl diphosphonate, ethylene diphosphonate, hydroxy 1, 1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate and hydroxy-ethylene 1,1 diphosphonate. Most preferred is hydroxy-ethylene 1,1 diphosphonate (EDHP) and 2 phosphono- butane, 1,2,4 tricarboxylic acid (Bayhibit) .
  • EDHP hydroxy-ethylene 1,1 diphosphonate
  • Bayhibit 1,2,4 tricarboxylic acid
  • water soluble polymers prepared from an allyloxybenzenesulfonic acid monomer, a methallyl sulfonic acid monomer, a copolymerizable nonionic monomer and a copolymerizable olefinically unsaturated carboxylic acid monomer as described in US 5 547 612, or known as acrylic sulphonated polymers as described in EP 851 022.
  • Polymers of this type include polymers with as monomer units acrylic acid, methyl methacrylic acid, 4-sulfophenyl methylallyl ether and sodium methallyl sulfonate, such as Alcoperse 240 supplied by Alco. ⁇ ; Also suitable is a terpolymer containing polyacrylate with 2-acrylamido-2-methylpropane sulfonic acid such as Acumer 3100 supplied by Rohm & Haas. It is preferable if polymers of this type have a molecular weight from 1,000 to 15,000, more preferably from 3,000 to 10,000.
  • polymers and co-polymers of acrylic acid having a molecular weight between 500 and 20,000 can also be used, such as homo-polymeric polycarboxylic acid compounds with acrylic acid as the monomeric unit.
  • the average weight of such homo-polymers in the acid form preferably ranges from 1,000 to 100,000, particularly from 3,000 to 10,000.
  • polymeric polycarboxylates are co-polymers derived from monomers of acrylic acid and maleic acid.
  • the average molecular weight of these polymers in the acid form preferably ranges from 4,000 to 70,000.
  • a mixture of anti-scaling agents may be used, particularly useful are a mixture of organic phosphonates and a polymers having as monomer units acrylic acid, methyl methacrylic acid, 4-sulfophenyl methylallyl ether and sodium methallyl sulfonate, Preferred ratios of antiscaling agent to nonionic surfactant are 1:3 to 3:1, more preferably 1:1 to 1:2
  • compositions of the invention may contain a builder.
  • the builder may be a phosphate or non-phosphate builder.
  • compositions of the invention preferably comprise a water- soluble phosphate builder.
  • Phosphate builders are particularly preferred. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from about 6 to 21, and salts of phytic acid. Sodium or potassium tripolyphosphate is most preferred.
  • the level of builder is from 50 to 90% by weight, preferably from 55 to 80% by weight.
  • compositions of the present invention may comprise a water-soluble nonphosphate builder.
  • non-phosphorus-containing inorganic builders include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, including layered silicates such as SKS-6 ex. Clarent, metasilicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds) , potassium carbonate, sodium and potassium bicarbonates, silicates including layered silicates and zeolites .
  • Organic detergent builders can also be used as nonphosphate builders in the present invention.
  • organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidised starches, oxidised heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylate
  • Such carboxylates are described in U.S. Patent Nos . 4,144,226, 4,146,495 and 4,686,062.
  • Alkali metal citrates, nitrilotriacetates, oxydisuccinates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred nonphosphate builders.
  • Silica Silica material may be included in the composition.
  • Suitable forms of silica include amorphous silica, such as precipitated silica, pyrogenic silica and silica gels, such as hydrogels, xerogels and aerogels, or the pure crystal forms quartz, tridymite or crystobalite, but the amorphous forms of silica are preferred.
  • Suitable silicas may readily be obtained commercially. They are sold, for example under the Registered Trade Name Gasil 200 (ex Crosfield, UK) .
  • the silica is in the product in such a form that ⁇ .:> it can dissolve when added to the wash liquor. Therefore, addition of silica by way of addition anti-foam particles of silica and silicone oil is not preferred.
  • silica material are used that have a particle size (as determined with a Malvern Laser, i.e. "aggregated" particles size) of at most 40 ⁇ m, most preferably at most 20 ⁇ m provides better results in the wash.
  • particle size of the silica material is at least l ⁇ m, more preferably at least 2 ⁇ m, most preferably at least 5 ⁇ m.
  • the silica material is present in the cleaning composition at a level of at least 0.1%, more preferably at least 0.5%, most preferably at least 1% by weight of the cleaning composition and preferably at most 10%, more preferably at most 8%, most preferably at most 5% by weight of the cleaning composition.
  • the composition optionally comprises alkali metal silicates.
  • the Si0 2 level should be from 1% to 35%, preferably from 2% to 20%, more preferably from 3% to 10%, based on the weight of the ADD.
  • the alkali metal silicate is hydrous, having from 15% to 25% water, more preferably, from 17% to 20%.
  • the highly alkali metasilicates can in general be employed, although the less alkaline hydrous alkali metal silicates having a Si0 2 :M 2 0 ratio of from 2.0 to 2.4 are, as noted, greatly preferred.
  • Anhydrous forms of the alkali metal silicates with a Si0 2 :M 2 0 ratio of 2.0 or more are also less preferred, because they tend to be significantly less soluble than the hydrous alkali metal silicates having the same ratio.
  • a particularly preferred alkali metal silicate is a granular hydrous sodium silicate having a Si0 2 :Na 2 0 ratio of from 2.0 to 2.4 available from PQ Corporation, named Britesil H20 and Britesil H24. Most preferred is a granular hydrous sodium silicate having a Si0 2 :Na 2 0 ratio of 2.0. While typical forms, i.e. powder and granular, of hydrous silicate particles are suitable, preferred silicate particles having a mean particle size between 300 and 900 microns and less than 40% smaller than 150 microns and less than 5% larger than 1700 microns.
  • compositions of the present invention having a pH of 9 or less preferably will be substantially free of alkali metal silicate.
  • Enzymes may be present in the compositions of the invention.
  • Examples of enzymes suitable for use in the cleaning compositions of this invention include lipases, peptidases, amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removal.
  • the enzymes most commonly used in machine dishwashing compositions are amylolytic enzymes.
  • the composition of the invention also contains a proteolytic enzyme. Enzymes may be present in a weight percentage amount of from 0.2 to 7% by weight.
  • amylolytic enzymes the final composition will have amylolytic activity of from 10 2 to 10 e Maltose units/kg.
  • proteolytic enzymes the final composition will have proteolytic enzyme activity of from 10 s to 10 9 Glycine Units/kg.
  • Bleach material is preferably incorporated in the composition.
  • the bleach material may be a chlorine- or bromine-releasing agent or a peroxygen compound. Peroxygen based bleach materials are however preferred.
  • Organic peroxy acids or the precursors therefor are typically utilized as the bleach material.
  • the peroxyacids usable in the present invention are solid and, preferably, substantially water-insoluble compounds.
  • substantially water-insoluble is meant herein a water-solubility of less than about 1% by weight at ambient temperature.
  • peroxyacids containing at least about 7 carbon atoms are sufficiently insoluble in water for use herein.
  • Inorganic peroxygen-generating compounds are also typically used as the bleaching material of the present invention. Examples of these materials are salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate .
  • Monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g. peroxy-alpha- naphthoic acid) ; aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid) ; and phthaloyl amido peroxy caproic acid (PAP) .
  • alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g. peroxy-alpha- naphthoic acid) ; aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid) ; and phthaloyl amido peroxy caproic acid (PAP) .
  • PAP phthaloyl amido peroxy caproic
  • diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1, 12-di-peroxy- dodecanedioic acid (DPDA) ; 1, 9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy- isophthalic acid; and 2-decyldiperoxybutane-l, 4-dioic acid.
  • DPDA 1, 12-di-peroxy- dodecanedioic acid
  • 1, 9-diperoxyazelaic acid diperoxybrassylic acid, diperoxysebacic acid and diperoxy- isophthalic acid
  • 2-decyldiperoxybutane-l, 4-dioic acid 2-decyldiperoxybutane-l, 4-dioic acid.
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N' ,N' -tetraacetyl ethylene diamine (TAED) , sodium nonanoyloxybenzene sulphonate (SNOBS) , sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4, 751, 015.
  • TAED N,N,N' ,N' -tetraacetyl ethylene diamine
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • SBOBS sodium benzoyloxybenzene sulphonate
  • SPCC cationic peroxyacid precursor
  • a bleach catalyst such as the manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397, or the sulphonimines of US-A-5, 041, 232 and US-A-5, 047, 163 , this may be presented in the form of a second encapsulate separately from the bleach capsule or granule. Cobalt catalysts can also be used.
  • a suitable range is also from 0.5% to 3% avO (available Oxygen).
  • the amount of bleach material in the wash liquor is at least 12.5xl0 "4 % and at most 0.03% avO by weight of the liquor.
  • Anti-tarnishing agents such as benzotriazole and those described in EP 723 577 (Unilever) may also be included.
  • Optional ingredients are, for example, buffering agents, reducing agents, e.g., borates, alkali metal hydroxide and the well-known enzyme stabilisers such as the polyalcohols, e.g. glycerol and borax; crystal-growth inhibitors, threshold agents; perfumes and dyestuffs and the like.
  • buffering agents e.g., borates, alkali metal hydroxide and the well-known enzyme stabilisers such as the polyalcohols, e.g. glycerol and borax; crystal-growth inhibitors, threshold agents; perfumes and dyestuffs and the like.
  • Reducing agents may e.g. be used to prevent the appearance of an enzyme-deactivating concentration of oxidant bleach compound.
  • Suitable agents include reducing sulphur-oxy acids and salts thereof.
  • Most preferred for reasons of availability, low cost, and high performance are the alkali metal and ammonium salts of sulphuroxy acids including ammonium sulphite ( (NH 4 ) 2 S0 3 ) , sodium sulphite (Na 2 S0 3 ) , sodium bisulphite (NaHS0 3 ) , sodium metabisulphite (Na 2 S 2 0 3 ) , potassium metabisulphite ( ⁇ S- s ) , lithium hydrosulphite (Li 2 S 2 0 4 ) , etc., sodium sulphite being particularly preferred.
  • Another useful reducing agent is ascorbic acid.
  • the amount of reducing agents to be used may vary from case to case depending on the type of bleach and the form it is in, but normally a range of about 0.01% to about 1.0% by weight, preferably from about 0.02% to about 0.5% by weight, will be sufficient .
  • compositions according to the invention are preferably processed to be in the form of a tablet, although in some embodiments other product forms (e.g. as a powder) may be contemplated and preferred.
  • the invention relates to washing processes in mechanical dish washing machines wherein the wash liquor has a low pH.
  • low pH is meant here that the pH of the wash liquor is preferably higher than about 6.5, more preferably 7.5 or higher, most preferably 8.5 or higher.
  • the pH is lower than about 11, more preferably lower than about 10.5, more preferably lower than about 9.5.
  • the most advantageous pH range is from 8.5 to 10.5.
  • the plates were removed from the solution and placed in a beaker containing 5 litre of water at 60°C with 15ml of the original solution (this simulates carry over in the rinse cycle, rinse simulation) for 5 minutes.
  • the plates were removed and their contact angle with the rinse solution was measured using a Contact angle Goniometer model A-l 00.
  • Example A Experiment conducted with Example A in the main wash simulation, the rinse simulation and used to measure the contact angle - Treatment A
  • Example 1 diluted as for rinsing procedure (30g in 5 litres of water, diluted by taking 15 ml of this solution and adding to a further 5 litres of water) used to measure the contact angle - Treatment B
  • Example A diluted as for rinsing procedure (30g in 5 litres of water, diluted by taking 15 ml of this solution and adding to a further 5 litres of water) used to measure the contact angle - Treatment C

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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)
  • Detergent Compositions (AREA)

Abstract

L'invention se rapporte à une composition pour lave-vaisselle comportant au moins 4,0 % en poids d'un tensioactif non ionique éthoxylé et/ou propoxylé, ledit tensioactif non ionique possédant un point de trouble dans l'eau inférieur ou égal à 14. L'invention se rapporte également à un procédé de lavage des articles dans un lave-vaisselle consistant à ajouter à la liqueur de lavage une composition comportant un tensioactif non ionique éthoxylé et/ou propoxylé ayant un point de trouble dans l'eau inférieur ou égal à 14 et à traiter les articles devant être nettoyés avec ladite composition, aucun produit de rinçage supplémentaire ni aucun sel n'étant présent dans le lave-vaisselle.
EP01982443A 2000-10-25 2001-10-18 Compositions pour lave-vaisselle Expired - Lifetime EP1328611B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01982443A EP1328611B1 (fr) 2000-10-25 2001-10-18 Compositions pour lave-vaisselle

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00309394 2000-10-25
EP00309394 2000-10-25
EP01982443A EP1328611B1 (fr) 2000-10-25 2001-10-18 Compositions pour lave-vaisselle
PCT/EP2001/012351 WO2002034869A1 (fr) 2000-10-25 2001-10-18 Compositions pour lave-vaisselle

Publications (2)

Publication Number Publication Date
EP1328611A1 true EP1328611A1 (fr) 2003-07-23
EP1328611B1 EP1328611B1 (fr) 2005-12-28

Family

ID=8173339

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01982443A Expired - Lifetime EP1328611B1 (fr) 2000-10-25 2001-10-18 Compositions pour lave-vaisselle

Country Status (6)

Country Link
EP (1) EP1328611B1 (fr)
AR (1) AR031043A1 (fr)
AT (1) ATE314448T1 (fr)
AU (1) AU2002214027A1 (fr)
DE (1) DE60116358T2 (fr)
WO (1) WO2002034869A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2491842B1 (fr) 2011-02-22 2017-01-25 Miele & Cie. KG Procédé destiné à l'exécution d'un programme de lavage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7285171B2 (en) 2002-12-19 2007-10-23 The Procter & Gamble Company Anti-filming materials, compositions and methods

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US4306987A (en) * 1979-11-19 1981-12-22 Basf Wyandotte Corporation Low-foaming nonionic surfactant for machine dishwashing detergent
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DE4110510A1 (de) * 1991-03-30 1992-10-01 Henkel Kgaa Niederalkalische, chlor- und phosphatfreie maschinengeschirrspuelmittel in form von schwerpulvern und -granulaten
DE4112075A1 (de) * 1991-04-12 1992-10-15 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phospat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
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JP2000502750A (ja) * 1996-09-11 2000-03-07 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物
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WO1999041349A1 (fr) * 1998-02-17 1999-08-19 Agency Design Services Limited Composition de lavage et de revetement pour les surfaces en verre, ceramique et metal.
DE19834180A1 (de) * 1998-07-29 2000-02-03 Benckiser Nv Zusammensetzung zur Verwendung in einer Geschirrspülmaschine
AU2110500A (en) * 1999-02-05 2000-08-25 Unilever Plc Dish washing process and compositions relating thereto
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2491842B1 (fr) 2011-02-22 2017-01-25 Miele & Cie. KG Procédé destiné à l'exécution d'un programme de lavage

Also Published As

Publication number Publication date
AU2002214027A1 (en) 2002-05-06
WO2002034869A1 (fr) 2002-05-02
DE60116358T2 (de) 2006-06-22
EP1328611B1 (fr) 2005-12-28
ATE314448T1 (de) 2006-01-15
DE60116358D1 (de) 2006-02-02
AR031043A1 (es) 2003-09-03

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