EP0826768A1 - Constituants granulaires contenant du benzotriazole pour compositions pour lave-vaisselle automatique, et procédé pour leur préparation - Google Patents

Constituants granulaires contenant du benzotriazole pour compositions pour lave-vaisselle automatique, et procédé pour leur préparation Download PDF

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Publication number
EP0826768A1
EP0826768A1 EP97113068A EP97113068A EP0826768A1 EP 0826768 A1 EP0826768 A1 EP 0826768A1 EP 97113068 A EP97113068 A EP 97113068A EP 97113068 A EP97113068 A EP 97113068A EP 0826768 A1 EP0826768 A1 EP 0826768A1
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EP
European Patent Office
Prior art keywords
group
component
solid
granular
surfactants
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
EP97113068A
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German (de)
English (en)
Other versions
EP0826768B1 (fr
Inventor
Thomas Dr. Holderbaum
Jürgen Dr. Härer
Hans-Josef Dr. Beaujean
Oliver Kurth
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0826768A1 publication Critical patent/EP0826768A1/fr
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Publication of EP0826768B1 publication Critical patent/EP0826768B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring

Definitions

  • the application relates to granular components containing benzotriazole for the Use in MGSM and process for its production
  • Granular cleaning agents for MGSM are known because they are easy to dose pourable and pourable, stable in storage and visually appealing to the consumer are.
  • Benzotriazole is a corrosion protection component that in active oxygen Cleaners is widely used today.
  • the chemical stability in these systems is only given to a limited extent, since benzotriazole is easily oxidized is broken down. This is especially the case with longer storage, e.g. yellow colored and unpleasant smelling oxidation products that discolor the Cleaner, the loss of corrosion protection and the lack of Acceptance of the product by the consumer.
  • WO 95/1416 (Procter & Gamble) describes a bleaching composition which is suitable for automatic dishwashing, the one Contains oxygen bleach, paraffin oil and a benzotriazole component, the entire component is intended for use in detergents.
  • the Components can be powder, granules, pastes, liquids, gels, Tablets are present, with granular preparation forms being preferred. Densities of at least 650 g / l or usually at least 700 g / l and preferably between 800 and 1200 g / l and particle sizes which are distributed in such a way that no more than 5% of the particles are larger than 1.4 mm in diameter and not more than 5% of the particles are less than 0.15 mm in diameter prefers.
  • a preferred process for making the connection involves premixing paraffin oil and a dispersant, where this premix is sprayed onto the rest of the composition.
  • the dispersant is advantageously nonionic surfactant.
  • one Method of spraying paraffin oil and dispersant on the Bleach, with the associated reduction in dissolving speed of the bleaching agent in water, the so-called "coating”, is preferred, the coated bleach particles thereafter in a dry mixing process with the rest the composition is mixed.
  • The is also described Compact the bleach before mixing it with the rest of the ingredients the composition mixed dry. There is no instruction how Benzotriazole homogeneously in a free-flowing dishwasher detergent component should be incorporated.
  • the task was to provide a free-flowing, storage-stable, homogeneous granulate to make, which contains benzotriazole and as silver protection for the machine dishwashing is suitable.
  • the one contained in the granulate Benzotriazole should be protected against oxidative attack.
  • the present invention relates to a granular, free-flowing Component containing one at a temperature above 50 ° C meltable solid (I) from the group organic redox-active Substances, preferably from the group of benzotriazoles and one of the Melting temperature fixed inventory component (II) selected from the group of in Dishwasher detergents usual builder components and one or more others Components from the group of hydrocarbons or their mixtures and one or more further constituents from the group comprising the polar contains organic solvents and the surfactants, the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferred between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3 and the component has a particle size between 0.01 and 2 Millimeters, preferably 0.05 and 1.8 millimeters and particularly preferred between 0.1 and 1.6 millimeters.
  • Water-soluble and water-insoluble builders can be used. There are water-soluble builders preferred as they are usually less on dishes and hard surfaces tend to form insoluble residues. Usual builders present may be the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. For the components according to the invention are preferably trisodium citrate and / or soda and / or bicarbonate and / or Alkali tripolyphosphates and / or disilicate and / or metasilicate used.
  • the granular components according to the invention contain between 0.001 % By weight and 50% by weight, preferably between 0.05 and 20% by weight and particularly preferably between 0.5 and 10% by weight of benzotriazole compounds.
  • benzotriazole compounds all chemical Derivatives of the benzotriazole skeleton.
  • Derivatives of benzotriazole, in the sense of present invention, above all, those on the aromatic ring are whole or partially substituted compounds, with suitable substituents can be linear or branched alkyl chains with 1 to 20 carbon atoms. But OH, SH, vinyl or halogen groups are also conceivable.
  • the ratio between Solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3.
  • An important parameter for the present means is the particle size of the Component that is between 0.01 and 2 millimeters, preferably 0.05 and 1.8 Millimeters and particularly preferably between 0.1 and 1.6 millimeters should.
  • Another object of the invention is the use of these granular trickle-shaped component as a silver protection agent in automatic dishwashing detergents.
  • Another object of the invention is a method for manufacturing granular free-flowing components, which is characterized in that the solid (I) melting above 50 ° C. in liquid form sprayed onto the solid (II) at elevated temperature.
  • coarse-grained solid (I) preferably coarse-grained sodium citrate and / or coarse-grain soda and / or coarse-grained sodium bicarbonate is combined in one commercial mixer, preferably a ploughshare mixer, if possible low energy input and in a way that reduces the abrasion of the grain minimized, for example without the use of a knife ring, inside short time, preferably between 1 and 5 minutes, particularly preferably 3 Minutes at a spray temperature of above 100 ° C, preferably above 105 ° C particularly preferably between 110 and 120 ° C with the organic Brushed solid (II) in liquid form, and optionally cooled or let cool.
  • the melt of the organic solid (I) can be used in this process will.
  • the Substance (I) in the form of a solution in an organic solvent (III) is preferred in polar organic liquids, particularly preferably in concentrations of more than 30% by weight.
  • This solvent (III) is preferred selected from the group consisting of methanol, ethanol, isopropanol, Ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, polyethylene glycols and polypropylene glycols.
  • the solvent is the group of surfactants, the nonionic surfactants being particularly preferred. Most notably preferred in the sense of the invention are the surfactants from the group of Alkyl polyglycosides, the fatty alcohol ethoxylates or propoxylates and their esters.
  • a final spraying of the after has a particularly positive effect Granular components with hydrocarbons produced by the above method or a mixture of hydrocarbons with a melting point between 30 ° C and 120 ° C, preferably between 30 and 80 ° C, particularly preferably between 45 ° C and 65 ° C at elevated temperature.
  • Prefers are used above all in the sense of the present invention macrocrystalline paraffins with melting points between 40 ° C and 60 ° C, microcrystalline paraffins with melting points between 60 ° C and 75 ° C and Mixtures between macro and micro crystalline paraffins with melting points from e.g. between 45 ° C and 65 ° C. But also other hydrocarbons and Mixtures of hydrocarbons can be used.
  • dishwashing detergent containing granular component, preferably in amounts between 1 and 40% by weight based on the entire mixture, the dishwashing detergent also others Components common in dishwashing detergents, such as builder substances, sheet metal detergents, Surfactants, corrosion protection agents, polymers, other silver protection agents, May contain defoamers, perfumes and fragrances and others.
  • Water-soluble and water-insoluble builders especially for binding calcium and magnesium be used.
  • Water-soluble builders are preferred because they are based on Dishes and hard surfaces tend to be less insoluble To form residues.
  • Usual builders that are within the scope of the invention 10 and 90% by weight, based on the total preparation, can be present, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates.
  • Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances.
  • For the cleaning agents according to the invention are preferred trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of disilicates used.
  • Alkali carriers can be present as further constituents.
  • Alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used.
  • bleach activators are compounds that contain one or more N or O-acyl groups, like substances from the class of anhydrides, contain Esters, the imides and the acylated imidazoles or oximes.
  • examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activator proportions between 1 and 5% by weight based on the entire preparation.
  • Enzymes between 0 and 5% by weight of the cleaning agent Enzymes based on the entire preparation are added to the To increase the performance of the cleaning agents or under milder conditions To ensure cleaning performance of the same quality.
  • the most common Enzymes used include lipases, amylases, cellulases and proteases.
  • Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
  • Celluzym® 0.7 T and. are particularly suitable cellulases and lipases Lipolase® 30 T from Novo Nordisk. Special use as amylases find Termamyl® 60 T, and Termamyl® 90 T and Duramyl® from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades but also other enzymes can be used.
  • Surfactants can also be added to the dishwashing detergent according to the invention , in particular the nonionic surfactants, such as alkyl polyglycosides, ethoxylated fatty alcohols and glucamides are preferred.
  • Alkyl polyglycosides are surfactants caused by the reaction of sugars and Alcohols according to the relevant procedures of preparative organic Chemistry can be obtained, depending on the type of manufacture to one Mixture of monoalkylated, oligomeric or polymeric sugar comes.
  • Preferred Alkyl polyglycosides can be alkyl polyglucosides, with particular preference the alcohol is a long chain fatty alcohol or a mixture of long chain Is fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.
  • alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or mixtures thereof end-capped fatty alcohol ethoxylates.
  • Fatty acid polyhydroxylamides are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents.
  • Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in S ⁇ FW-Journal, 119, (1993), 794-808.
  • Carbon chain lengths of C 8 to C 12 in the fatty acid residue are preferably used.
  • Dishwashing agents according to the invention can be used to protect the items to be washed or the machine contain other corrosion inhibitors, especially Silver protection agent in the field of automatic dishwashing a special one Have meaning as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 are described.
  • active chlorine-containing agents which corrode the Can significantly reduce the silver surface.
  • oxygen and nitrogenous organic redox-active compounds such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Zinc compounds can also be used to prevent corrosion on the wash ware.
  • composition of the component according to the invention is a composition of the component according to the invention:
  • This component was in amounts up to 6 wt .-%, based on the finished Means in one or more subsequent mixing steps with other Recipe ingredients for a dishwashing detergent for the machine Dishwashing mixed.
  • Table (I) shows the compositions of the granules used.
  • Surfactants e.g. Dehydol® LS4 (nonionic surfactant: coconut alcohol-4EO), Dehypon® LS54 (Nonionic surfactant: coconut alcohol-5EO4PO), Plurafac® LF 403 (nonionic surfactant C11-C13, 4EO-3PO),
  • Polyethylene glycols Different molecular weights were used, e.g. B. 1500.
  • Paraffins Macrocrystalline paraffins with melting points were preferred between 40 ° C and 60 ° C and microcrystalline paraffins with melting points between 60 ° C and 75 ° C, as well as mixtures of macrocrystalline and microcrystalline Paraffins with melting points between 45 ° C and 65 ° C used.
  • Components I-VII had a particle size between 0.1 and 1.6 millimeters.
  • Components I to VII were with percarbonate / TAED or perborate / TAED and the usual detergent components (citrate / phosphate, alkali carrier, enzymes) mixed up.
  • the powder mixture is spread on crystallizing dishes and stored open for four days at 30 ° C and 80% relative humidity. Find oxidative processes and decomposition of the benzotriazole take place, that's it Powder colored yellow and has an unpleasant smell of garlic or Almond oil.

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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)
EP97113068A 1996-08-07 1997-07-30 Constituants granulaires pour compositions pour lave-vaisselle automatique, et procédé pour leur préparation Expired - Lifetime EP0826768B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19631787 1996-08-07
DE19631787A DE19631787C2 (de) 1996-08-07 1996-08-07 Benzotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung

Publications (2)

Publication Number Publication Date
EP0826768A1 true EP0826768A1 (fr) 1998-03-04
EP0826768B1 EP0826768B1 (fr) 2001-10-24

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EP97113068A Expired - Lifetime EP0826768B1 (fr) 1996-08-07 1997-07-30 Constituants granulaires pour compositions pour lave-vaisselle automatique, et procédé pour leur préparation

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Country Link
EP (1) EP0826768B1 (fr)
AT (1) ATE207525T1 (fr)
DE (2) DE19631787C2 (fr)
ES (1) ES2166032T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999063044A1 (fr) * 1998-06-03 1999-12-09 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules contenant de l'alkylpolyglycoside
WO2001072949A1 (fr) * 2000-03-28 2001-10-04 Henkel Kommanditgesellschaft Auf Aktien Agents particulaires pour lavage de vaisselle en machine, a effet rinçant
DE10313455A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19758262A1 (de) * 1997-12-31 1999-07-08 Henkel Kgaa Alkylaminotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung
DE10049657C2 (de) * 2000-10-07 2003-02-27 Henkel Kgaa Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz
DE102011077098A1 (de) * 2011-06-07 2012-12-13 Henkel Kgaa Silberschützendes Geschirrspülmittel
DE102018212206A1 (de) 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Reinigungsmittel mit Silberschutz

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032236A1 (fr) * 1980-01-12 1981-07-22 Henkel Kommanditgesellschaft auf Aktien Détergent pour le lavage de la vaisselle
WO1993004153A1 (fr) * 1991-08-13 1993-03-04 The Procter & Gamble Company Procede de production d'un detergent granulaire de lavage automatique de vaiselle
WO1994026860A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produits de protection de l'argent contre la corrosion ii
WO1995001416A1 (fr) * 1993-07-01 1995-01-12 The Procter & Gamble Company Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent
EP0634478A1 (fr) * 1993-07-16 1995-01-18 The Procter & Gamble Company Compositions détergentes pour le lavage en machine de la vaisselle
WO1995010588A1 (fr) * 1993-10-14 1995-04-20 Unilever N.V. Compositions detergentes contenant des agents empechant le ternissement de l'argent
EP0682105A2 (fr) * 1994-04-13 1995-11-15 The Procter & Gamble Company Compositions de blanchiment
EP0690122A2 (fr) * 1994-06-30 1996-01-03 The Procter & Gamble Company Compositions détergentes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2285052A (en) * 1993-12-23 1995-06-28 Procter & Gamble Detergent composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032236A1 (fr) * 1980-01-12 1981-07-22 Henkel Kommanditgesellschaft auf Aktien Détergent pour le lavage de la vaisselle
WO1993004153A1 (fr) * 1991-08-13 1993-03-04 The Procter & Gamble Company Procede de production d'un detergent granulaire de lavage automatique de vaiselle
WO1994026860A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produits de protection de l'argent contre la corrosion ii
WO1995001416A1 (fr) * 1993-07-01 1995-01-12 The Procter & Gamble Company Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent
EP0634478A1 (fr) * 1993-07-16 1995-01-18 The Procter & Gamble Company Compositions détergentes pour le lavage en machine de la vaisselle
WO1995010588A1 (fr) * 1993-10-14 1995-04-20 Unilever N.V. Compositions detergentes contenant des agents empechant le ternissement de l'argent
EP0682105A2 (fr) * 1994-04-13 1995-11-15 The Procter & Gamble Company Compositions de blanchiment
EP0690122A2 (fr) * 1994-06-30 1996-01-03 The Procter & Gamble Company Compositions détergentes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999063044A1 (fr) * 1998-06-03 1999-12-09 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules contenant de l'alkylpolyglycoside
WO2001072949A1 (fr) * 2000-03-28 2001-10-04 Henkel Kommanditgesellschaft Auf Aktien Agents particulaires pour lavage de vaisselle en machine, a effet rinçant
DE10313455A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel

Also Published As

Publication number Publication date
DE19631787A1 (de) 1998-02-12
EP0826768B1 (fr) 2001-10-24
ES2166032T3 (es) 2002-04-01
ATE207525T1 (de) 2001-11-15
DE59705054D1 (de) 2001-11-29
DE19631787C2 (de) 2000-06-29

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