EP1741774B1 - Maschinengeschirrspülmittel und deren Verwendung - Google Patents

Maschinengeschirrspülmittel und deren Verwendung Download PDF

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EP1741774B1
EP1741774B1 EP06116118A EP06116118A EP1741774B1 EP 1741774 B1 EP1741774 B1 EP 1741774B1 EP 06116118 A EP06116118 A EP 06116118A EP 06116118 A EP06116118 A EP 06116118A EP 1741774 B1 EP1741774 B1 EP 1741774B1
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Prior art keywords
nonionic surfactant
charge
complex
manganese
composition according
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EP1741774A1 (de
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Huig c/o UNILEVER R & D VLAARDINGEN Euser
Jean-Paul UNILEVER R & D VLAARDINGEN Janssens
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to PL06116118T priority patent/PL1741774T3/pl
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    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • This invention relates to detergent cleaning compositions especially adapted for use in automatic dishwashing machines.
  • phosphate or phosphate-free compositions which contain an oxygen bleach and enzymes, especially amylolytic and proteolytic enzymes, such as amylases and proteases.
  • the oxygen bleach is typically sodium perborate or sodium percarbonate which advantageously may be used in conjunction with an organic activator or bleach precursor, e.g. N, N, N', N'-tetraacetylethylene diamine (TAED), which upon dissolution will react to form an organic peroxyacid, e.g. peracetic acid, as the bleaching species.
  • an organic activator or bleach precursor e.g. N, N, N', N'-tetraacetylethylene diamine (TAED)
  • the starch removal properties of an automatic machine dishwashing composition containing a peroxygen bleach can be improved by incorporation of a dinuclear manganese complex.
  • products of this kind ofter also contain nonionic surfactants. When the amount of nonionic surfactant is relatively high, particularly at or above 1% by weight of the composition, the manganese complex causes discolouration of the product.
  • a first aspect of the present invention now provides an automatic machine dishwashing composition
  • a peroxygen bleach compound and a dinuclear manganese-complex having the general formula: wherein Mn is manganese which can individually be in the III or IV oxidation state; each x represents a coordinating or bridging species selected from the group consisting of H 2 O, O 2 2- , O 2- , OH - , HO 2 - , SH - , S 2- , >SO, Cl - , N 3- , SCN - , RCOO - , NH 2 - and NR 3 , with R being H, alkyl or aryl, (optionally substituted); L is a ligand which is an organic molecule containing a number of nitrogen atoms which coordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can
  • a second aspect of the present invention provides use of one or more nonionic surfactant components (a) as defined in the first aspect of the present invention for reducing discolouration in a composition comprising a peroxygen bleach compound and a dinuclear manganese complex as defined in the first aspect of the present invention.
  • the machine dishwashing composition is a mildly alkaline product having a solution pH below 12, e.g. from 8-12, preferably from 9-11.
  • the solution pH as meant here is the pH as determined from a solution of 3g/l of the compositions in distilled water.
  • Preferred manganese-complexes are those wherein x is either CH 3 COO - or O 2 or mixtures thereof, most preferably wherein the manganese is in the IV oxidation state and x is O 2- .
  • Preferred ligands are those which coordinate via three nitrogen atoms to one of the manganese centres, preferably being of a macrocyclic nature. Particularly preferred ligands are:
  • the type of counter-ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, any of the following counter-ions: chloride; sulphate; nitrate; methylsulphate; surfanctant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate (ClO 4 - ), BPh 4 - , and PF 6 - ' though some counter-ions are more preferred than others for reasons of product property and safety.
  • the preferred manganese complexes useable in the present invention are:
  • compositions of the invention must contain at least 1%, preferably at least 2% by weight of nonionic surfactant. At least 50%, preferably at least 65%, optionally up to 90% or up t 100% by weight of the total nonionc surfactant must be selected from
  • nonionic surfactants of group (a) are present in the composition of the invention.
  • Preferred nonionic surfactants of group (a) include hydroxyalkyl glycolether surfactants having a melting point above 35°C, preferably above 40°C.
  • a preferred class of such materials has from 6 to 20, preferably from 8 to 14 carbon atoms in the alkyl chain thereof and from 15 to 50, preferably from 20 to 40 glycol ether units.
  • One such material is Dehypon 3697 GRAM, ex Cognis.
  • nonionic surfactants of this group are high melting point polyalkoxylated alcohols, optionally with the -OH group endcapped such as with an alkyl group and typically having an average of 10 to 20 alkyl groups and more than 30 alkylene oxide groups, eg ethylene oxide and/or proplylene oxide groups.
  • one or more other nonionics may be present in the amounts indicated by the foregoing.
  • These may includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to some protein soil.
  • nonionic surfactants for use in the invention are the low- to non-foaming ethoxylated strraightchain alcohols of the Plurafac® RA and LF series, supplied by the BASF, including Plurafac SLF 18B45; of the Lutensol® LF series, supplied by the BASF; of the Tritons DF series, supplied by the Rohm & Hass Company, and of the Synperonic® LF and NCA series, supplied by the ICI, Uniqema company.
  • the peroxygen compound bleaches which can be utilized in the present invention include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating compounds, as well as the organic and inorganic peroxyacids and watersoluble salts thereof, and mixtures thereof.
  • the total amount of peroxygen bleach compound(s) is preferably from 5% to 25%, more preferably from 10% to 20% by weight of the composition.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates and persulphates. Mixtures or two or more of such compounds may also be suitable. Particularly preferred is sodium percarbonate. However, sodium perborate, eg in the form sodium perborate monohydrate may also be used. Sodium perborate monohydrate is preferred to tetrahydrate because of its better storage stability while also dissolving very quickly in aqueous solutions. These bleaching agents may be utilied alone or in conjunction with a peroxyacid bleach precursor, such as TAED or any other bleach precursors known in the art, so long as it does not affect the starch-removing properties of the catalyst.
  • a peroxyacid bleach precursor such as TAED or any other bleach precursors known in the art
  • organic peroxyacids usable in this invention are those compounds known in the art having normally one or more peroxycarboxyl groups: in their molecular structure, e.g. 1,12 - diperoxydodecanedioic acid (DPDA) and phthaloylamido peroxycaproic acid (PAP).
  • An inorganic peroxyacid salt usable herein is, for example, potassium monopersulphate.
  • Compositions according to the present invention may also normally contain a detergency and water-softening builder.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphospates, such as sodium tripoly phosphate;nitrilotriacetic acid, dipicolinic acid, chelidamic acid and their water-solubel salts; the alkali metal salts of ether polycarboxylates, such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid; ethylene diamine tetraacetic acid; benzene polycarboxylic acids; citric acid; and polyacetal carboxylates as disclosed in US Patents 4,144,226 and 4,146,495 .
  • alkali metal polyphospates such as sodium tripoly phosphate;nitrilotriacetic acid, dipicolinic acid, chelidamic acid and their water-solubel salts
  • the alkali metal salts of ether polycarboxylates such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid
  • precipitating builder materials examples include sodium orthophosphate, sodium carbonate and sodium carbonate/calcite.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best-known representatives.
  • Other useful materials are, for example, layered silicates, such as SKS®-6 ex Hoechst.
  • compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof, although phosphates are less preferred.
  • the organic or inorganic builder materials such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof, although phosphates are less preferred.
  • compositions are, however, essentially free of phosphates and will contain, for example, alkali metal citrate, alkali carbonate, alkali metal carbonate/calcite, aluminosilicates (zeolites) or mixtures thereof as preferred builder materials.
  • alkali metal is sodium or potassium, preferably sodium.
  • the citrates are especially preferred.
  • Suitable non-phosphate builders which may be used alone or in combination with any one or more other builders include methyl glycine diacetic acid (MGDA), eg sold as Trilon M, ex BASF, imino disuccinate (IDS) eg sold as Baypure CS, ex Lanxess and dipicolinic acid (DPA), eg available from Raschig.
  • MGDA methyl glycine diacetic acid
  • IDS imino disuccinate
  • DPA dipicolinic acid
  • alkali metal salts eg sodium salts
  • inorganic detergency builders may have a dual role, eg the carbonates may also act as buffering agents (see below).
  • the total amount of detergency builder for example comprising any one or more of any of the foregoing may for example be from 10% to 80%, preferably from 30% to 60% by weight of the total composition.
  • An optional but highly desirable additive ingredient with multi-functional characteristics, particularly in non-phosphate compositions is from 1% to 10%, preferably about 5% by weight of a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone methyl- or ethyl-, vinyl ethers and other polymerizable vinyl monomers.
  • polyacrylic acid or polyacrylate are polyacrylic acid or polyacrylate; polymaleic acid/acrylic acid copolymer; 70:30 acrylic acid/hydroxyethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/maleic acid copolymers; methyl- and ethyl-vinylether/maleic acid copolymers;ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer. These polymers are believed to function as co-builders, although under certain conditions they may also function as main builders.
  • Buffering agents may be used in compositions according to the present invention in order to adjust and to maintain the alkalinity and pH at the desired level. These are for example, the alkali metal carbonates and bicarbonates, sometimes also borates, and silicates. If used, sodium silicates preferably have Na 2 O:SiO 2 ratios of from about 2:1 to 1:4. Another possible buffering agent is sodium disilicate having Na 2 O:SiO 2 ratio of about 1:1.8 to 1:2.5.
  • the cleaning compositions in which the catalyst is used according to the invention may, as desired, contain an amylolytic enzyme, though conceivably a much smaller amount will now be sufficient.
  • amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those prepared and described in British Patent Specification No. 1 296 839 , cultivated from the strains of Bacillus licheniformis NClB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11 945, ATCC 8480 and ATCC 9945.
  • Examples of such amylolytic enzumes are amylolytic enzymes produced and distributed under the trade name of Sp-95® or Termamyl® by Novo Industri A/S, Copenhagen, Denmark, as well as Termanyl and Duramyl, ex Novozymes and Properase and Purastar ex Genecor.
  • amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose units/milligram. Enzyme granules containing only minor proportions, e.g. less than 30%, particularly not more than 10% by weight of chloride to substantially nil, are preferably used in the compositions of the invention.
  • amylolytic activity can be determined by the method as described by P.Bernfeld in "Method of Enzymology” Volume 1 (1955), page 149 .
  • composition in which the catalyst is used according to the invention preferably also contains a proteolytic enzyme.
  • subtilisins which are obtained from particular strains of B. subtilis and B.licheniformis, such as the commercially available subtilisins Maxatase® supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase®, supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strainof Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from Novo Industri A/S under the registered trade names of Esperase® and Savinase®. The preparation of these and analogous enzymes is described in British Patent No. 1 243 784 .
  • Another suitable protease useful herein is a fairly recent commercial product sold by Novo Industry A/S under the trade name "Durazym®" as described in WO-A-89/06279 .
  • These enzymes are generally presented as granules, e.g. marumes, prills, T-granulates etc., and may have enzyme activities of from about 500 to 1700 glycine units/milligram.
  • Enzyme granules containing only minor proportions, e.g. less than 30%, particularly not more than 10% by weight of chloride to substantially nil, are preferably used in the composition of the invention.
  • these enzymes can each be present in a weight percentage amounts of from 0.2 to 5% by weight, such that, for amylolytic enzymes, the final composition will have amylolytic activity of from 10 2 to 10 6 Maltose units/kg, and, for proteolytic enzymes, the final composition will have proteolytic enzyme activity of from about 10 6 to 10 9 Glycine Units/kg.
  • compositions according to the present invention may further contain any of the following additional ingredients.
  • Stabilizing and anti-scaling agents include those belonging to the class of phosphonates sold under the trade name "Dequest®", such as ethylene diamine tetra-(methylene phosphonate), deithylene triamine penta-(methylene phosphonate) and ethylene hydroxyl diphosphonate.
  • Dequest® such as ethylene diamine tetra-(methylene phosphonate), deithylene triamine penta-(methylene phosphonate) and ethylene hydroxyl diphosphonate.
  • Another suitable class of anti-scaling agents are the low molecular weight polyacryalates, polymaleates and mixtures thereof or the copolymers thereof, having molecular weights of up to about 6000.
  • a further suitable class of anti-scaling agents are polypeptides.
  • Benzotriazide may be used as a silver protection agent.
  • Zinc salts may be used as glass corrosion inhibitors and sulphonated polymers (eg Alcosperse 240) may be used as anti-scaling polymers.
  • Clays such as hectorites and montmorillonites, may be included in the composition of the invention. These assist in reduction of spot formation on glassware, and may be present at from 0.5 to 10% by weight, preferably from 0.5 to 7% by weight. Particularly preferred is the addition of Laponite® clay at about 0.5 to 5% b weight, which is a synthetic hectorite. "Dequest” and “Laponite” are Trade Marks owned by, respectively, Monsanto and Laporte Industries.
  • a filler may be required to complete the composition, though, in compacted powdered compositions it should preferably be avoided.
  • a preferred filler is sodium sulphate.
  • a typical composition according to the present invention may include from 0 to 80%, preferably from 5 to 60% by weight of a detergency and water-softening builder, from 0 to 80%, preferably 5 to 75% by weight of a buffering agent, from 1 to 40%, preferably from 2 to 20% by weight of a peroxygen compound bleach, and optionally an enzyme and fillers and may further comprise a dinuclear manganese complex as defined above, in an amount corresponding to an Mn-content of from 0.0001 to abut 1.0% by weight, preferably from 0.0005 to 0.5% by weight.
  • compositions of the present invention may be in any suitable physical form, for example powdered and/or granular compositions or tablets. Tablets may be unitary or comprise two or more layers having differing compositions from each other, the tablet as a whole having the total constituents making-up the composition according to the present invention. Some or all of the dinuclear manganese complex may be in the same or in a different layer from a layer containing some or all of the nonionic surfactant, eg some or all of the nonionic surfactant component(s) (a) - (c) and/or any other non-ionic surfactant. Cavity tablets, eg with a spherical or ball component set into the cavity are also preferred. Again the manganese complex may in this way optionally be at least partially segregated from some or all of any or all of the nonionic surfactant component(s), whether components (a) - (c) or any other nonionic surfactant.
  • Example 1 Two tablets were made, respectively designated "Comparative Example A” and “Example 1", the latter being in accordance with the present invention.
  • the respective components were incorporated in powdered or granular form and dry-mixed before being compacted to form tablets.

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Claims (10)

  1. Maschinengeschirrspülmittel, umfassend wenigstens 1 Gew.-%, vorzugsweise wenigstens 2 Gew.-% nicht-ionisches Tensid, eine Peroxygen-Bleichmittelverbindung und einen zweikernigen Mangankomplex mit der allgemeinen Formel:
    Figure imgb0007
     worin Mn Mangan ist, welches individuell in der III- oder IV-Oxidationsstufe sein kann; jedes x eine koordinierende oder brückenbildende Species darstellt, ausgewählt aus der Gruppe, bestehend aus H2O, O2 2-, O2-, OH-, HO2 -, SH-, S2-, >SO, CI-, N3-, SCN-, RCOO-, NH2 - und NR3, wobei R H, Alkyl oder Aryl (gegebenenfalls substituiert) ist; L ein Ligand ist, welcher ein organisches Molekül ist, das eine Reihe von Stickstoffatomen enthält, das über alle oder einige seiner Stickstoffatome an die Manganzentren koordiniert; z die Ladung des Komplexes bezeichnet und eine ganze Zahl ist, die positiv oder negativ sein kann; Y ein monovalentes oder multivalentes Gegenion ist, das zur Ladungsneutralität führt, das von der Ladung z des Komplexes abhängig ist, und q = z/[Ladung Y]:
    wobei wenigstens 50 Gew.-% des nicht-ionischen Tensids ausgewählt sind aus:
    (a) wenigstens einem nicht-ionischen Tensid mit einem Schmelzpunkt von höher als 35 °C, vorzugsweise höher als 40 °C.
  2. Mittel nach Anspruch 1, wobei das nicht-ionische Tensid, das einen Schmelzpunkt von höher als 35 °C hat, ausgewählt ist aus einem oder mehreren Hydroxyalkylpolyglykolethern und gegebenenfalls endverkappten polyalkoxylierten Alkoholen, die wenigstens 30 Alkylenoxygruppen haben, und Gemischen davon.
  3. Mittel nach einem vorangehenden Anspruch, umfassend ein nicht-ionisches Tensid in der Form eines Körnchens, das Poren mit einer zahlenmittleren Porengröße von weniger als 5 µm hat, wobei die Poren das nicht-ionische Tensid enthalten; und Gemische davon, wobei das Körnchen aus einem oder mehreren Alkalicarbonaten, -bicarbonaten, -sulfaten und Gemischen davon gebildet ist.
  4. Mittel nach einem vorangehenden Anspruch, wobei die Peroxygen-Bleichmittelverbindung ein Alkalimetallpercarbonat umfasst.
  5. Mittel nach einem vorangehenden Anspruch, das außerdem einen Bleichmittelvorläufer oder -aktivator umfasst.
  6. Mittel nach einem vorangehenden Anspruch, wobei das Mittel im Wesentlichen frei von Phosphatmaterial ist.
  7. Mittel nach einem vorangehenden Anspruch, das außerdem einen Citrat-Builder umfasst.
  8. Mittel nach einem vorangehenden Anspruch, wobei der zweikernige Mangankomplex einen Liganden, ausgewählt aus
    (1) 1,4,7-Trimethyl-1,4,7-triazacyclononan, (Me-TACN), und
    (2) 1,2,4,7-Tetramethyl-1,4,7-triazacyclononan, (Me-Me-TACN)
    und Gemischen davon, umfasst.
  9. Tablette, umfassend das Mittel nach einem vorangehenden Anspruch.
  10. Verwendung eines oder mehrerer nicht-ionischer Tensidkomponente(n) (a)
    (a) wenigstens eines nicht-ionischen Tensids, das einen Schmelzpunkt von höher als 35 °C, vorzugsweise höher als 40 °C, hat,
    zur Verringerung einer Verfärbung in einem Mittel, das eine Peroxygen-Bleichmittelverbindung und einen zweikernigen Mangankomplex mit der allgemeinen Formel:
    Figure imgb0008
     umfasst, worin Mn Mangan ist, welches individuell in der III- oder IV-Oxidationsstufe sein kann; jedes x eine koordinierende oder brückenbildende Species darstellt, ausgewählt aus der Gruppe, bestehend aus H2O, O2 2-, O2-, OH-, HO2 -, SH-, S2-, >SO, Cl-, N3-, SCN-, RCOO-, NH2 - und NR3, wobei R H, Alkyl oder Aryl (gegebenenfalls substituiert) ist; L ein Ligand ist, welcher ein organisches Molekül ist, das eine Reihe von Stickstoffatomen enthält, das über alle oder einige seiner Stickstoffatome an die Manganzentren koordiniert; z die Ladung des Komplexes bezeichnet und eine ganze Zahl ist, die positiv oder negativ sein kann; Y ein monovalentes oder multivalentes Gegenion ist, das zur Ladungsneutralität führt, das von der Ladung z des Komplexes abhängig ist, und q = z/[Ladung Y].
EP06116118A 2005-07-08 2006-06-27 Maschinengeschirrspülmittel und deren Verwendung Active EP1741774B1 (de)

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EP06116118A EP1741774B1 (de) 2005-07-08 2006-06-27 Maschinengeschirrspülmittel und deren Verwendung
PL06116118T PL1741774T3 (pl) 2005-07-08 2006-06-27 Kompozycje przeznaczone do automatycznego zmywania naczyń

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EP05076571 2005-07-08
EP06116118A EP1741774B1 (de) 2005-07-08 2006-06-27 Maschinengeschirrspülmittel und deren Verwendung

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AT (1) ATE403711T1 (de)
DE (1) DE602006002075D1 (de)
ES (1) ES2312089T3 (de)
PL (1) PL1741774T3 (de)
PT (1) PT1741774E (de)

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GB201218415D0 (en) * 2012-10-15 2012-11-28 Reckitt & Colman Overseas Ultrasonic method of cleaning
CN105164241A (zh) * 2013-05-02 2015-12-16 艺康美国股份有限公司 用于在餐具洗涤应用中的改进的淀粉去除的浓缩洗涤剂组合物
PT3107987T (pt) 2014-02-20 2019-01-17 Unilever Nv Composição de lavagem de louça à máquina
GB201413859D0 (en) 2014-08-05 2014-09-17 Reckitt Benckiser Brands Ltd New automatic washing machine and method
GB201809123D0 (en) 2018-06-04 2018-07-18 Reckitt Benckiser Finish Bv Composition
GB201814188D0 (en) 2018-08-31 2018-10-17 Reckitt Benckiser Finish Bv Automatic dishwashing product
GB201814981D0 (en) 2018-09-14 2018-10-31 Reckitt Benckiser Finish Bv Granulate
GB201818827D0 (en) 2018-11-19 2019-01-02 Reckitt Benckiser Finish Bv Composition
AU2020210492A1 (en) 2019-01-22 2021-08-05 Reckitt Benckiser Finish B.V. Method of forming an automatic dishwashing pouch, vacuum forming system and pouch
GB201903318D0 (en) 2019-03-11 2019-04-24 Reckitt Benckiser Finish Bv Product
CN115052961A (zh) * 2020-01-31 2022-09-13 埃科莱布美国股份有限公司 在器皿清洗应用中淀粉酶与氧漂白剂的协同作用
GB202005911D0 (en) 2020-04-23 2020-06-10 Reckitt Benckiser Finish Bv Composition
GB202010046D0 (en) 2020-07-01 2020-08-12 Reckitt Benckiser Finish Bv Method
GB202010074D0 (en) 2020-07-01 2020-08-12 Reckitt Benckiser Finish Bv Use
GB202103439D0 (en) 2021-03-12 2021-04-28 Reckitt Benckiser Finish Bv Composition
GB2607585A (en) 2021-06-03 2022-12-14 Reckitt Benckiser Finish Bv Detergent gel composition comprising a fatty alcohol ethoxylate
GB202202002D0 (en) 2022-02-15 2022-03-30 Reckitt Benckiser Finish Bv Dishwashing detergent composition
GB202209521D0 (en) 2022-06-29 2022-08-10 Reckitt Benckiser Finish Bv A dishwashing detergent composition, a water-soluble container, and an autodosing automatic dishwashing system
GB202209523D0 (en) 2022-06-29 2022-08-10 Reckitt Benckiser Finish Bv Dishwashing, preferably an automatic dishwashing, detergent composition

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PT1741774E (pt) 2008-11-17
DE602006002075D1 (de) 2008-09-18
EP1741774A1 (de) 2007-01-10
ES2312089T3 (es) 2009-02-16
ATE403711T1 (de) 2008-08-15
PL1741774T3 (pl) 2009-01-30

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