EP1328613B1 - Geschirrspuelmittelzusammensetzungen - Google Patents

Geschirrspuelmittelzusammensetzungen Download PDF

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Publication number
EP1328613B1
EP1328613B1 EP01988756A EP01988756A EP1328613B1 EP 1328613 B1 EP1328613 B1 EP 1328613B1 EP 01988756 A EP01988756 A EP 01988756A EP 01988756 A EP01988756 A EP 01988756A EP 1328613 B1 EP1328613 B1 EP 1328613B1
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EP
European Patent Office
Prior art keywords
composition according
composition
acid
hydrophobically modified
nonionic surfactant
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.)
Revoked
Application number
EP01988756A
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English (en)
French (fr)
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EP1328613A1 (de
Inventor
Naresh Dhirajlal LFEDC Vlaardingen GHATLIA
Alan Digby Lever Development Centre 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 PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP01988756A priority Critical patent/EP1328613B1/de
Publication of EP1328613A1 publication Critical patent/EP1328613A1/de
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Anticipated expiration legal-status Critical
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites

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 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 its 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.
  • 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:
  • Also described is a process for washing articles in a dishwasher comprising the steps of:
  • compositions according to the invention have been found to be particularly effective at antiscaling and antispotting in the machine dishwash process.
  • this can lead to a cloudy surface apearing on e.g. glass.
  • a combination of antiscaling/antispotting agents are present in the composition of the invention.
  • the first is a hydrophobically modified polycarboxylic acid, preferably a co-polymer containing as polymerised units from 20 to 75 wt% maleic acid, maleic anhydride or salts thereof and from 25 to 80 wt% of a hydrophobe which is at least one monomer selected from the group consisting of isobutylene, diisobutylene, styrene, decane and eicosene.
  • the hydrophobically modified polycarboxylic acid preferably has a molecular weight from 200 to 1 million, more preferably from 1,000 to 750,000.
  • a preferred hydrophobically modified polycarboxylic acid is Acusol 820, a copolymer of acrylic acid with C 18 and with EO 20 C 18 side chains, MW about 500,000, supplied by Rohm and Haas Company; particularly preferred is Acusol 460, a co-polymer of diisobutylene and maleic acid, MW 15,000, supplied by Rohm and Haas Company;
  • the level of hydrophobically modified polycarboxylic acid is from 0.1 to 10 wt% of the total composition, more preferably from 0.5 to 7 wt%, most preferably from 1 to 5 wt%.
  • the preferred range of modified polycarboxylic acid may be from 0.1% to 10%, preferably 0.15 to 1.0%, even more preferably 0.3 to 0.6% by weight of the composition.
  • Organic phosphonates are also present as antiscaling agents.
  • antiscaling 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 phosphonobutane-1,2,4-tricarboxylic acid (Bayhibit).
  • EDHP hydroxy-ethylene 1,1 diphosphonate
  • Bayhibit 2 phosphonobutane-1,2,4-tricarboxylic acid
  • 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.
  • the level antiscaling agent is from 0.2 to 10 wt% of the total composition, preferably from 0.5 to 5 wt%.
  • Preferred ratios of antiscaling agent to nonionic surfactant are 1:3 to 3:1, more preferably 1:1 to 1:2
  • WO-A-96/00277 discloses the use of a hydrophic modified coplymer of acrylic acid to reduce the formation of white deposits caused by the interaction of calcium ions with fatty acids liberatured by the action of lipase on fatty (triglyceride) contaminants on treated artciles.
  • EP-A-551670 discloses a stable formulation of anti-scalants in general in the context of Zero-P and Low-P detergents.
  • the composition also comprises a surfactant system, which preferably comprises ethoxylated and/or propoxylated nonionic surfactants, more preferably selected from nonionic ethoxylated/propoxylated fatty alcohol surfactants which preferably have a cloud point in water of 14 or less, preferably of 12 or less, most preferably 10°C or less.
  • a surfactant system which preferably comprises ethoxylated and/or propoxylated nonionic surfactants, more preferably selected from nonionic ethoxylated/propoxylated fatty alcohol surfactants which preferably have a cloud point in water of 14 or less, preferably of 12 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; Synperonic RA series supplied by ICI Triton® DF series, supplied by the Rohm & Haas Company.
  • Suitable surfactants include epoxy capped poly (oxyalkylated) alchols, such as e.g. SLB 18B 45, ex. olin Chemicals.
  • the surfactants are preferably present at levels of at least 4.0 wt%, preferably 4-6 wt%, more preferably 5 to 8 wt% of the total composition.
  • An antifoam to surpress foaming is preferably present.
  • an anionic surfactant it is advantageously present at levels of 2 wt% or below.
  • 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 35% to 90%, preferably 50% to 90% by weight, preferably from 55% to 80% by weight.
  • compositions of the present invention may comprise a water-soluble non-phosphate 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 and metasilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates and silicates including layered silicates.
  • 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 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 1 ⁇ m, more preferably at least 2 ⁇ m, and 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 SiO 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 automatic dishwasher detergent.
  • 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 SiO 2 :M 2 O ratio of from 2.0 to 2.4 are, as noted, greatly preferred.
  • Anhydrous forms of the alkali metal silicates with a SiO 2 :M 2 O 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 SiO 2 :Na 2 O 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 SiO 2 :Na 2 O 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 6 Maltose units/kg.
  • proteolytic enzymes the final composition will have proteolytic enzyme activity of from 10 6 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.
  • 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.
  • 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).
  • 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-1,4-dioic acid.
  • DPDA 1,12-di-peroxy-dodecanedioic acid
  • 1,9-diperoxyazelaic acid diperoxybrassylic acid, diperoxysebacic acid and diperoxy-isophthalic acid
  • 2-decyldiperoxybutane-1,4-dioic acid 2-decyldiperoxybutane-1,4-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, is to be incorporated, 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 are also from 0.5% to 3% avO (available Oxygen).
  • the amount of bleach material in the wash liquor is at least 12.5x10 -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 SO 3 ), sodium sulphite (Na 2 SO 3 ), sodium bisulphite (NaHSO 3 ), sodium metabisulphite (Na 2 S 2 O 3 ), potassium metabisulphite (K 2 S 2 O 5 ), lithium hydrosulphite (Li 2 S 2 O 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.
  • 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 dishwashing composition is formed into a tablet and sold in a package with directions to add the dishwashing composition to the dishwashing machine as a 3-in-1 product.
  • a dishwasher is charged with the dishwashing composition of this invention without having to add to the dishwasher conventional rinse aid compositions and sodium chloride.
  • compositions may also be in powder form.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (13)

  1. Maschinengeschirrspülzusammensetzung, umfassend:
    a) eine hydrophob modifizierte Polycarbonsäure
    b) ein organisches Phosphonat und
    c) ein Polymer von Acrylsäure.
  2. Zusammensetzung nach Anspruch 1, worin die hydrophob modifizierte Polycarbonsäure ein Copolymer ist, das als polymerisierte Einheiten 20 bis 75 Gew.-% Maleinsäure, Maleinsäureanhydrid oder Salze davon, und 25 bis 80 Gew.-% einer hydrophoben Verbindung, die mindestens ein Monomer ist, ausgewählt aus der Gruppe, bestehend aus Isobutylen, Diisobutylen, Styrol, Decan und Eicosen, enthält.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, worin die hydrophob modifizierte Polycarbonsäure bei einem Niveau von 0,3 bis 0,6 Gew.-% der Zusammensetzung vorliegt.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das organische Phosphonat aus Hydroxyethylen-1,1-diphosphonat oder 2-Phosphonobutan-1,2,4-tricarbonsäure ausgewählt ist.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das Polymer von Acrylsäure ein Molekulargewicht zwischen 500 und 20.000 hat.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das Niveau des Mittels gegen die Kesselsteinbildung, das eine hydrophob modifizierte Polycarbonsäure und ein organisches Phosphonat umfaßt, 0,5 bis 5 Gew.-% der Zusammensetzung beträgt.
  7. Zusammensetzung nach einem der vorhergehenden Ansprüche, ferner umfassend mindestens 4,0 Gew.-% eines ethoxylierten und/oder propoxylierten, nicht-ionischen oberflächenaktiven Mittels, wobei das nicht-ionische oberflächenaktive Mittel einen Trübungspunkt in Wasser von 14 °C oder weniger hat.
  8. Zusammensetzung nach Anspruch 7, worin das nicht-ionische oberflächenaktive Mittel einen Trübungspunkt in Wasser von 12 °C oder weniger hat.
  9. Zusammensetzung nach Anspruch 7 oder Anspruch 8, worin das Niveau des nicht-ionischen oberflächenaktiven Mittels 5 bis 8 Gew.-% der Gesamtzusammensetzung beträgt.
  10. Zusammensetzung nach einem der vorhergehenden Ansprüche, umfassend mehr als 50 Gew.-% eines Aufbaustoffes.
  11. Zusammensetzung nach Anspruch 10, worin der Aufbaustoff ein wasserlösliches Phosphat ist.
  12. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin die Zusammensetzung in Form einer Tablette vorliegt.
  13. Verfahren zum Waschen von Gegenständen in einem Geschirrspüler, umfassend die folgenden Schritte:
    i) Zugabe einer Zusammensetzung nach einem der vorhergehenden Ansprüche zu der Waschflüssigkeit des Geschirrspülers, gefolgt von;
    ii) der Behandlung der Gegenstände, die der Reinigung mit der Waschflüssigkeit bedürfen, auf herkömmliche Art und Weise;
    wobei in dem Geschirrspüler kein zusätzliches Spülhilfsmittel vorhanden ist, und
    wobei dem Geschirrspüler kein Salz zur Regenerierung des Ionenaustauschers zugegeben wird.
EP01988756A 2000-10-25 2001-10-17 Geschirrspuelmittelzusammensetzungen Revoked EP1328613B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01988756A EP1328613B1 (de) 2000-10-25 2001-10-17 Geschirrspuelmittelzusammensetzungen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00309395 2000-10-25
EP00309395 2000-10-25
PCT/EP2001/012083 WO2002034870A1 (en) 2000-10-25 2001-10-17 Dish-washing compositions
EP01988756A EP1328613B1 (de) 2000-10-25 2001-10-17 Geschirrspuelmittelzusammensetzungen

Publications (2)

Publication Number Publication Date
EP1328613A1 EP1328613A1 (de) 2003-07-23
EP1328613B1 true EP1328613B1 (de) 2006-09-20

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ID=8173340

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01988756A Revoked EP1328613B1 (de) 2000-10-25 2001-10-17 Geschirrspuelmittelzusammensetzungen

Country Status (6)

Country Link
EP (1) EP1328613B1 (de)
AR (1) AR031044A1 (de)
AT (1) ATE340239T1 (de)
AU (1) AU2002221703A1 (de)
DE (1) DE60123263D1 (de)
WO (1) WO2002034870A1 (de)

Families Citing this family (6)

* 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
EP1491621B2 (de) † 2003-06-28 2014-10-01 Dalli-Werke GmbH & Co. KG Alpha Olefin- und Alpha Olefin-Cellulose Granulate als Sprengmittel
WO2009050123A2 (de) * 2007-10-12 2009-04-23 Basf Se Geschirrreinigungsformulierungen enthaltend ein gemisch aus hydrophob modifizierten polycarboxylaten und hydrophil modifizierten polycarboxylaten
US8975221B2 (en) 2010-08-27 2015-03-10 Ecolab Usa Inc. Use of sugars in a stabilization matrix and solid compositions
AU2021226695B2 (en) * 2020-02-28 2024-05-30 Unilever Global Ip Limited Dishwash detergent product
WO2024089079A1 (en) 2022-10-25 2024-05-02 Symrise Ag Dish cleaning and/or dish rinsing composition with improved finishing properties

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2552506A1 (de) * 1975-11-22 1977-05-26 Henkel & Cie Gmbh Maschinell anwendbares kombiniertes geschirreinigungs- und klarspuelmittel und verfahren zum gleichzeitigen reinigen und klarspuelen von geschirr in geschirrspuelmaschinen
DE4112075A1 (de) * 1991-04-12 1992-10-15 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phospat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
US5281351A (en) * 1991-12-06 1994-01-25 Lever Brothers Company, Division Of Conopco, Inc. Processes for incorporating anti-scalants in powdered detergent compositions
US5559089A (en) * 1992-03-12 1996-09-24 The Procter & Gamble Company Low-dosage automatic dishwashing detergent with monopersulfate and enzymes
DE69511091T2 (de) * 1994-06-23 1999-11-18 Unilever N.V., Rotterdam Geschirrspülmittelzusammensetzungen
EP0717102A1 (de) * 1994-12-09 1996-06-19 The Procter & Gamble Company Flüssige Waschmittelzusammensetzungen für automatische Geschirrreinigung enthaltend Diacylperoxyde
DE19518693A1 (de) * 1995-05-22 1996-11-28 Henkel Kgaa Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel
FR2739866A1 (fr) * 1995-10-13 1997-04-18 Rohm & Haas France Compositions de nettoyage contenant un dispersant de savon de chaux et leur procede de preparation
AU2110500A (en) * 1999-02-05 2000-08-25 Unilever Plc Dish washing process and compositions relating thereto

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Publication number Publication date
EP1328613A1 (de) 2003-07-23
AR031044A1 (es) 2003-09-03
DE60123263D1 (de) 2006-11-02
WO2002034870A1 (en) 2002-05-02
ATE340239T1 (de) 2006-10-15
AU2002221703A1 (en) 2002-05-06

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