EP0915955B1 - Waschmittelzusammensetzung für geschirrspülmaschinen mit einem korrosionsschutzmittel - Google Patents

Waschmittelzusammensetzung für geschirrspülmaschinen mit einem korrosionsschutzmittel Download PDF

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EP0915955B1
EP0915955B1 EP97933743A EP97933743A EP0915955B1 EP 0915955 B1 EP0915955 B1 EP 0915955B1 EP 97933743 A EP97933743 A EP 97933743A EP 97933743 A EP97933743 A EP 97933743A EP 0915955 B1 EP0915955 B1 EP 0915955B1
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Prior art keywords
silicate
alkali metal
detergent composition
preformulation
washing medium
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French (fr)
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EP0915955A1 (de
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Eric Aubay
Agnès Froute
Aude Guirauden
Daniel Joubert
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Priority claimed from FR9609064A external-priority patent/FR2751340B1/fr
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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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the subject of the present invention is a detergent composition for a dishwasher, based on alkali metal silicate, non-corrosive to glass, crystal, glass porcelain and decorations; it also relates to the use of said composition non-corrosive dishwasher detergent, as well as the dishwasher washing process implementing it.
  • Dishwasher compositions comprising lamellar alkali silicates largely insoluble in water have been described in EP-A-0 416 366.
  • compositions for dishwashers comprising mixtures of metasilicate and silicate with an SiO 2 / M 2 O molar ratio greater than 1, for cleaning and caring for glass articles .
  • the Applicant has found a solution making it possible to resolve at the same time the two problems, namely loss of mass and damage to articles.
  • a first object of the invention consists in the use, for eliminating or limiting corrosion of articles in glass, crystal, porcelain and decorations on glass or porcelain by repeated washing in the dishwasher, of a detergent composition generating a medium detergent having a concentration of protonated silicic monomer Si (OH) 4 of at least 2.5 x 10 -3 mole / liter of detergent medium, preferably at least 3 x 10 -3 mole / liter of detergent medium, all particularly of the order of 3 x 10 -3 to 9 x 10 -3 mole / liter of detergent medium.
  • a second object of the invention consists of a process for the non-corrosive washing in a dishwasher of glass, crystal and porcelain articles, possibly decorated, by using a detergent composition generating a detergent medium having a concentration of protonated silicic monomer Si (OH) 4 of at least 2.5 x 10 -3 mole / liter of detergent medium, preferably of at least 3 x 10 -3 mole / liter of detergent medium, very particularly of the order from 3 x 10 -3 to 9 x 10 -3 mole / liter of detergent medium.
  • Said detergent medium preferably has a pH greater than 9.8, while particularly around 9.9 to 11.1.
  • One means of obtaining this sufficient concentration of protonated silicic monomer Si (OH) 4 in the detergent bath consists in using, via a detergent composition, a sufficient quantity of at least one alkali metal silicate in order to obtain a high SiO 2 content capable of generating said monomer and of promoting the formation of said monomer by adjusting the pH of the bath by choosing the nature of said silicate and of the other ingredients of the composition according to the chosen silicate.
  • All of the amorphous or crystalline soluble alkali metal silicates with a SiO 2 / M 2 O ratio of the order of 1 to 4.2 make it possible to achieve the desired objective.
  • these are soluble amorphous silicates.
  • a particularly preferred means consists in using in the detergent composition at least one soluble alkali metal silicate, with an average SiO 2 / M 2 O molar ratio of the order of 2.5 to 4.2, preferably amorphous, allowing d '' obtain a high SiO 2 content in the detergent bath and favor a low pH of the bath compatible with an adequate content of protonated silicic monomer Si (OH) 4 .
  • soluble silicate is understood to mean any silicate of which at least 50% of the silicon network is dissolved in the washing medium after 10 minutes under the washing conditions.
  • average SiO 2 / M 2 O molar ratio is understood to mean the ratio of the total number of moles of SiO 2 to the total number of moles of M 2 O originating from the alkali metal silicate (s) present in the detergent composition.
  • a third subject of the invention consists of a detergent composition for a dishwasher, based on at least one alkali metal silicate, with an average SiO 2 / M 2 O molar ratio of the order of 1 to 4.2. , preferably of the order of 2.5 to 4.2, M representing an alkali metal, non-corrosive towards glass, crystal, porcelain and decorations, generating, at the concentration of use, a detergent medium having a concentration of protonated silicic monomer Si (OH) 4 of at least 2.5 x 10 -3 mole / liter of detergent medium, preferably at least 3 x 10 -3 mole / liter of detergent medium, especially of the order of 3 x 10 -3 to 9 x 10 -3 mole / liter of detergent medium.
  • a detergent medium having a concentration of protonated silicic monomer Si (OH) 4 of at least 2.5 x 10 -3 mole / liter of detergent medium, preferably at least 3 x 10 -3 mole / liter of detergent medium, especially of the
  • alkali metal silicate is understood below to mean both an alkali metal silicate alone and a mixture of several alkali metal silicates which may have molar ratios SiO 2 / M 2 O different; the expression “average SiO 2 / M 2 O molar ratio” therefore corresponds either to a silicate alone, when a single silicate is present, or to a mixture of silicates, when several silicates of different molar ratios are present.
  • concentration of total soluble SiO 2 in the washing medium means the amount of SiO 2 soluble in the washing medium, originating from the soluble alkali metal silicate used.
  • the concentration of protonated silicic monomer Si (OH) 4 in the detergent medium is of the order of 3 ⁇ 10 -3 to 9 ⁇ 10 -3 mole / liter of detergent medium.
  • Said detergent composition can be in solid form (powder, tablets), in liquid or gel form.
  • the concentration of use of a detergent composition for dishwashers is generally of the order of 3 to 12 g / liter of detergent bath. This is more precisely of the order of 4 to 10 g / liter for a powder composition, of the order of 3 to 6 g / liter for a composition in tablet form and of the order of 4 to 12 g / liter for a liquid or gel composition.
  • the pH of the washing medium is regulated by the nature and the amount of the alkali metal silicate and of the other additives influencing the pH present in the composition. This is preferably set to a value greater than 9.8, in particular to a value of the order of 9.9 to 11.1.
  • the amount by dry weight of alkali metal silicate generally represents, depending on the form of detergent composition chosen, of the order of 5 to 55%, preferably of the order of 10 to 40% of the dry weight of said composition. More specifically, for a solid detergent composition (powder or tablet) the amount of silicate represents of the order of 5 to 55%, preferably of the order of 10 to 40% of the dry weight of said composition, for a liquid composition or in the form of a gel, the amount of silicate represents of the order of 5 to 40%, preferably of the order of 10 to 30% of the dry weight of said composition.
  • the pH of the medium detergent is then adjusted by the choice and quantities of the other ingredients influencing on the pH of the detergent composition.
  • any type of alkali metal silicate soluble can be used in the detergent composition of the invention.
  • anhydrous and / or hydrated metasilicates (SiO 2 / M 2 O molar ratio of 1) in the form of powder or granules can be present according to the invention in a detergent composition in powder or in tablets.
  • the pH of the detergent bath can be adjusted to a pH greater than 9.8, preferably of the order of 9.9 to 11.1 by the presence in said composition of an acidifying agent or additive such as citric acid. , sodium bicarbonate, sodium sesquicarbonate or any other acidifying agent.
  • the amorphous "disilicates" may be present, in atomized form compacted in a detergent composition in powder or in tablets, in the form of a concentrated solution generally about 45% dry matter in a liquid detergent composition or in gel form; they can also be present in the form of solid preformulation in a powder or tablet composition, preformulation, preferably in the form of cogranules, obtained by adsorption and / or absorption of a concentrated solution of alkali metal silicate generally at about 45% dry matter on a soluble mineral support of the alkali metal tripolyphosphate type and / or alkali metal carbonate and / or alkali metal bicarbonate and / or alkali metal sesquicarbonate and / or alkali metal sulfate, the amount of water remaining associated with the silicate corresponding to a water associated with silicate / silicate ratio expressed as dryness of at least 20/100, preferably at
  • water associated with silicate means the water of the supported solution which is not combined with the mineral support, in particular in the form of crystallized hydrate. This can be measured in particular by X-ray diffraction, NMR of the solid, proton, phosphorus, etc.).
  • the pH of the detergent bath can be adjusted to a pH greater than 9.8, preferably of the order of 9.9 to 11.1 by the presence in said composition of an acidifying agent or additive such as citric acid. , sodium bicarbonate, sodium sesquicarbonate or any other acidifying agent.
  • the alkali metal silicate, in particular sodium, used in the detergent compositions of the invention is amorphous and has an average SiO 2 / M 2 O molar ratio of the order of 2.5 to 4.2. Its mode of implementation within a detergent composition depends on the form of the detergent composition for which it is intended, namely a solid detergent composition (powder or tablets) or a liquid or gel detergent composition.
  • Said alkali metal silicate having an average SiO 2 / M 2 O molar ratio of the order of 2.5 to 4.2 can be very particularly used in the form of a concentrated aqueous solution generally at about 25 to 50% dry matter or a liquid preformulation in a liquid detergent or gel composition, or in the form of a solid preformulation in a powder or tablet composition.
  • a solid detergent composition When it is intended for a solid detergent composition, it can preferably be used in the form of a solid preformulation, in particular in the form of cogranules, obtained by adsorption and / or absorption of a concentrated solution of alkali metal silicate.
  • a concentrated solution of alkali metal silicate on at least one non-water-soluble or preferably water-soluble mineral support, the amount of water remaining associated with the silicate corresponding to a water-associated silicate / silicate ratio expressed as dry of at least 20/100, preferably at least 30/100.
  • non-water-soluble mineral supports mention may be made of natural or synthetic, amorphous or crystalline sodium silicoaluminates, calcium carbonate, clays, magnesium, calcium silicates, silica, etc.
  • the pH of the detergent bath can be adjusted to a pH greater than 9.8, preferably of the order of 9.9 to 10.8, by the presence in said composition of an alkalizing agent or additive or of an acidifying agent or additive.
  • a first type of solid preformulation consists of cogranules obtained by adsorption and / or absorption of a concentrated solution of alkali metal silicate molar ratio SiO 2 / M 2 O mean of the order 2.5 to 4.2, preferably of the order of 2.6 to 3.5, adsorbed and / or absorbed on at least one water-soluble mineral support compatible with the desired pH, in particular of the sodium sesquicarbonate type and / or mixtures of sodium carbonate and sodium bicarbonates and / or preferably sodium tripolyphosphate, the weight ratio, expressed in dry terms, silicate / mineral support being of the order of 20/80 to 60/40, preferably of the order of 25/75 to 50/50, and optionally drying until the amount of water present in said preformulation represents of the order of 10 to 35% of the weight of said preformulation, and the amount of water remaining associated with the silicate corresponds to a water ratio associated with silicate / silicate expressed at least dry s 20/100, preferably at least 30/100.
  • a first particular type of solid detergent composition which is the subject of the invention consists of a solid detergent composition as described above, in which the alkali metal silicate has a molar SiO 2 / M 2 O ratio of l '' order 2.5 to 4.2, preferably of the order 2.6 to 3.5, and is implemented via said first type of solid preformulation, preformulation whose pH at its concentration in the medium detergent is greater than 9.8, preferably of the order of 9.9 to 10.8, and this in accordance with equation (I) mentioned above.
  • a second type of solid preformulation consists of cogranules obtained by adsorption and / or absorption of a concentrated solution of alkali metal silicate molar ratio SiO 2 / M 2 O means of the order of 3 to 4.2, preferably of 3.3 to 4, adsorbed and / or absorbed on sodium carbonate, the weight ratio, expressed as dry, silicate / carbonate being of the order of 40/60 to 80/20, preferably of the order of 50/50 to 70/30, and optionally drying until the amount of water present in said preformulation represents of the order of 15 to 35% of the weight of said preformulation, and the amount of water remaining associated with silicate corresponds to a water ratio associated with silicate / silicate expressed as dryness of at least 20/100, preferably at least 30/100.
  • a second particular type of solid detergent composition which is the subject of the invention consists of a solid detergent composition as described above, in which the alkali metal silicate has a molar ratio SiO 2 / M 2 O average of 1 '' order 3 to 4.2, preferably of the order 3.3 to 4, and is implemented via said second type of solid preformulation, preformulation whose pH at its concentration in the washing medium is greater than 9.8, preferably of the order of 9.9 to 10.8, and this in accordance with equation (I) mentioned above.
  • silicate When said silicate is intended for a liquid detergent composition or in the form of a gel, the latter has an average SiO 2 / M 2 O molar ratio of the order of 2.5 to 3.5, preferably of the order of 2, 6 to 3.3; it is used in the form of a concentrated aqueous commercial solution containing approximately 25 to 50% of dry matter, or of a liquid preformulation in the form of a dispersion in said concentrated solution of silicate of a water-soluble mineral compound.
  • One type of liquid preformulation consists of a dispersion, in a concentrated silicate solution, of average SiO 2 / M 2 O molar ratio of the order of 2.5 to 3.5, preferably of the order of 2.6 to 3.3 to about 25 to 50% of dry matter, of a water-soluble mineral compound sodium tripolyphosphate, preferably atomized, and / or sodium carbonate, the weight ratio, expressed as dry, silicate / water-soluble mineral compound being l '' from 70/30 to 30/70, preferably from 60/40 to 35/65, the amount of water present in said preformulation representing around 40 to 65% of the weight of said preformulation .
  • a particular type of liquid detergent composition which is the subject of the invention consists of a liquid detergent composition as described above, in which the alkali metal silicate has a molar ratio SiO 2 / M 2 O of the medium. on the order of 2.5 to 3.5, preferably on the order of 2.6 to 3.3, and is implemented via said type of liquid preformulation, preformulation whose pH at its concentration in the washing medium is greater than 9.8, preferably of the order of 9.9 to 10.9, and this in accordance with equation (I) mentioned above.
  • the concentration of Si (OH) 4 is calculated in accordance with equation (I), from the measurement of the pH of the washing medium and the amount of total SiO 2 .
  • the temperature cycle chosen is 65 ° C; the dose of detergent composition used each wash is 30g for a volume of wash water of 5 liters; after each washing-rinsing-drying cycle, the door is left closed for 10 minutes then open for 10 minutes.
  • Corrosion evaluation is done visually with a scale ranging from 1 to 5 points, in taking as reference the glasses in new condition, by 9 trained people.
  • Measuring the relative mass loss (PM) of the samples makes it possible to quantify the thickness of the damaged (dissolved) surface; it is expressed in thousands of%.
  • composition of the L3 formulation is close to that of the commercial formulations.
  • the three compositions are used at a rate of 32 g per wash.
  • Corrosion tests are carried out as described above, on white glasses standard (wine and fruit flask, round) and on standard decorated glasses (patterned cherry and red stripe pattern), after 100 washing cycles.
  • This simplified glass corrosion test reproduces certain washing conditions for dishwasher machines, in particular washing, rinsing and drying cycles.
  • the slide is weighed after cooling to room temperature and the change in relative mass (in% x 1000) is calculated. The test is reproduced another times for confirmation of results.
  • Corrosion visible to the eye is evaluated, compared to a non-subject reference blade to the test.

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Claims (15)

  1. Verwendung einer Waschmittelzusammensetzung (Tensidzusammensetzung) zur Beseitigung oder Verringerung der Korrosion von Glas-, Kristall-, Porzellangegenständen und Dekoren auf Glas oder Porzellan durch wiederholtes Waschen in Geschirrspülmaschinen, wobei die Waschmittelzusammensetzung ein Waschmilieu erzeugt, das eine Konzentration an protoniertem Siliciummonomer Si(OH)4 von mindestens 2,5 • 10-3 mol/Liter Waschmilieu, vorzugsweise mindestens 3 • 10-3 mol/Liter Waschmilieu, besonders bevorzugt etwa 3 • 10-3 bis 9 • 10-3 mol/Liter Waschmilieu, erzeugt.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß das Waschmilieu einen pH-Wert größer als 9,8, vorzugsweise etwa 9,9 bis 11,1, aufweist.
  3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Waschmittelzusammensetzung mindestens ein vorzugsweise amorphes, lösliches Alkalimetallsilicat mit einem mittleren SiO2/M2O-Molverhältnis von etwa 1 bis 4,2, vorzugsweise etwa 2,5 bis 4,2, enthält, wobei M ein Alkalimetall darstellt.
  4. Verfahren zum nichtkorrosiven Reinigen von gegebenenfalls mit Dekoren versehenen Glas-, Kristall- und Porzellangegenständen in einer Geschirrspülmaschine durch Verwendung einer Waschmittelzusammensetzung (Tensidzusammensetzung), die ein Waschmilieu erzeugt, das eine Konzentration an protoniertem Siliciummonomer Si(OH)4 von mindestens 2,5 • 10-3 mol/Liter Waschmilieu, vorzugsweise mindestens 3 • 10-3 mol/Liter Waschmilieu, besonders bevorzugt etwa 3 • 10-3 bis 9 • 10-3 mol/Liter Waschmilieu, erzeugt.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Waschmilieu einen pH-Wert größer als 9,8, vorzugsweise etwa 9,9 bis 11,1, aufweist.
  6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß die Waschmittelzusammensetzung mindestens ein vorzugsweise amorphes Alkalimetallsilicat mit einem mittleren SiO2/M2O-Molverhältnis von etwa 1 bis 4,2, vorzugsweise etwa 2,5 bis 4,2, enthält, wobei M ein Alkalimetall darstellt.
  7. Waschmittelzusammensetzung (Tensidzusammensetzung) für Geschirrspülmaschinen auf Basis von vorzugsweise amorphem(n), löslichem(n) Alkalimetallsilicat(en) mit einem mittleren SiO2/M2O-Molverhältnis von etwa 1 bis 4,2, vorzugsweise etwa 2,5 bis 4,2, wobei M ein Alkalimetallatom darstellt, wobei die Waschmittelzusammensetzung nichtkorrosiv gegenüber Glas, Kristall, Porzellan und Dekoren ist und bei der Verwendungskonzentration ein Waschmilieu erzeugt, das eine Konzentration an protoniertem Siliciummonomer Si(OH)4 von mindestens 2,5 • 10-3 mol/Liter Waschmilieu, vorzugsweise mindestens 3 • 10-3 mol/Liter Waschmilieu, besonders bevorzugt etwa 3 • 10-3 bis 9 • 10-3 mol/Liter Waschmilieu, aufweist.
  8. Waschmittelzusammensetzung nach Anspruch 7, dadurch gekennzeichnet, daß das Waschmilieu einen pH-Wert größer als 9,8, vorzugsweise etwa 9,9 bis 11,1, aufweist.
  9. Waschmittelzusammensetzung nach Anspruch 7 oder 8 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß die Trockengewichtsmenge des oder der Alkalimetallsilicate etwa 5 bis 55 %, vorzugsweise etwa 10 bis 40 %, des Trokkengewichts der Zusammensetzung darstellt.
  10. Waschmittelzusammensetzung nach Anspruch 9 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß das Alkalimetallsilicat ein Metasilicat in Form eines Pulvers oder Granulats ist.
  11. Waschmittelzusammensetzung nach Anspruch 9 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß das Alkalimetallsilicat ein amorphes Disilicat in Form einer festen Vorformulierung, vorzugsweise in Form von Cogranulaten, ist, die durch Adsorption und/oder Absorption einer konzentrierten Lösung des Alkalimetallsilicats im allgemeinen bei 45 % Trockensubstanz auf einem löslichen Mineralträger vom Typ Alkalimetalltripolyphosphat und/oder Alkalimetallcarbonat und/oder Alkalimetallbicarbonat und/oder Alkalimetallsesquicarbonat und/oder Alkalisulfat erhalten ist, wobei die Menge an Wasser, die am Silicat gebunden bleibt, einem Verhältnis silicatgebundenes Wasser/Silicat, bezogen auf die Trockensubstanz, von mindestens 20/100, vorzugsweise mindestens 30/100, entspricht.
  12. Waschmittelzusammensetzung nach Anspruch 9 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß das Alkalimetallsilicat ein mittleres SiO2/M2O-Molverhältnis von etwa 2,5 bis 4,2 aufweist und in Form einer auf 25 bis 50 % des Trockenmaterials konzentrierten wäßrigen Lösung oder in Form einer flüssigen Vorformulierung in einer flüssigen oder gelartigen Waschmittelzusammensetzung oder in Form einer festen Vorformulierung in einer Pulveroder Tablettenzusammensetzung eingesetzt wird.
  13. Waschmittelzusammensetzung nach Anspruch 12 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß das Alkalimetallsilicat ein mittleres SiO2/M2O-Molverhältnis von etwa 2,5 bis 4,2, vorzugsweise etwa 2,6 bis 3,5, aufweist und über die Zwischenstufe (Intermediat) einer festen Vorformulierung eingesetzt wird, die aus Cogranulaten besteht, die erhalten sind durch Adsorption und/oder Absorption einer konzentrierten Lösung des Alkalimetallsilicats mit mittlerem SiO2/M2O-Molverhältnis von etwa 2,5 bis 4,2, vorzugsweise etwa 2,6 bis 3,5, wobei die Vorformulierung auf mindestens einem wasserlöslichen, mit dem gewählten pH-Wert kompatiblen Mineralträger adsorbiert und/oder absorbiert ist, der ausgewählt ist aus Natriumsesquicarbonat und/oder Mischungen aus Natriumcarbonat und Natriumbicarbonat und/oder vorzugsweise Natriumtripolyphosphat, wobei das Gewichtsverhältnis Silicat/Mineralträger, bezogen auf die Trockensubstanz, etwa 20/80 bis 60/40, vorzugsweise etwa 25/75 bis 50/50, beträgt, wobei die Vorformulierung gegebenenfalls getrocknet wird, bis die Menge an in der Vorformulierung enthaltenem Wasser etwa 10 bis 35 Gew.-% der Vorformulierung beträgt und die Menge an am Silicat gebunden verbliebenen Wasser einem Verhältnis silicatgebundenes Wasser/Silicat, bezogen auf die Trockensubstanz, von mindestens 20/100, vorzugsweise mindestens 30/100, entspricht, wobei der pH-Wert der Vorformulierung bei ihrer Konzentration in dem Waschmilieu insbesondere größer als 9,8, vorzugsweise etwa 9,9 bis 10,8, ist.
  14. Waschmittelzusammensetzung nach Anspruch 12 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß das Alkalimetallsilicat ein mittleres SiO2/M2O-Molverhältnis von etwa 3 bis 4,2, vorzugsweise etwa 3,3 bis 4, aufweist und über die Zwischenstufe (Intermediat) einer festen Vorformulierung eingesetzt wird, die aus Cogranulaten besteht, die erhalten sind durch Adsorption und/oder Absorption einer konzentrierten Lösung des Alkalimetallsilicats mit mittlerem SiO2/M2O-Molverhältnis von etwa 3 bis 4,2, vorzugsweise etwa 3,3 bis 4, wobei die Vorformulierung auf Natriumcarbonat adsorbiert und/oder absorbiert ist, wobei das Gewichtsverhältnis Silicat/Carbonat, bezogen auf die Trockensubstanz, etwa 40/60 bis 80/20, vorzugsweise etwa 50/50 bis 70/30, beträgt, wobei die Vorformulierung gegebenenfalls getrocknet wird, bis die Menge an in der Vorformulierung enthaltenem Wasser etwa 15 bis 35 Gew.-% der Vorformulierung beträgt und die Menge an am Silicat gebunden verbliebenen Wasser einem Verhältnis silicatgebundenes Wasser/Silicat, bezogen auf die Trockensubstanz, von mindestens 20/100, vorzugsweise mindestens 30/100, entspricht, wobei der pH-Wert der Vorformulierung bei ihrer Konzentration in dem Waschmilieu insbesondere größer als 9,8, vorzugsweise etwa 9,9 bis 10,8, ist.
  15. Waschmittelzusammensetzung nach Anspruch 12 oder Verwendung einer Waschmittelzusammensetzung gemäß Anspruch 3 oder Waschmittelzusammensetzung zur Durchführung des Verfahrens gemäß Anspruch 6, dadurch gekennzeichnet, daß das Alkalimetallsilicat ein mittleres SiO2/M2O-Molverhältnis von etwa 2,5 bis 3,5, vorzugsweise etwa 2,6 bis 3,3, aufweist und eingesetzt wird über die Zwischenstufe (Intermediat) einer flüssigen, aus einer Dispersion bestehenden Vorformulierung in einer konzentrierten Lösung des Silicats mit mittlerem SiO2/M2O-Molverhältnis von etwa 2,5 bis 3,5, vorzugsweise etwa 2,6 bis 3,3, bei etwa 25 bis 50 % Trockensubstanz, einer vorzugsweise feinverteilten wasserlöslichen Mineralverbindung von Natriumtripolyphosphat und/oder Natriumcarbonat, wobei das Gewichtsverhältnis Silicat/wasserlösliche Mineralverbindung, bezogen auf die Trockensubstanz, etwa 70/30 bis 30/70, vorzugsweise etwa 60/40 bis 35/65, beträgt, wobei die Menge an in der Vorformulierung vorhandenem Wasser etwa 40 bis 65 Gew.-% der Vorformulierung darstellt und der pH-Wert der Vorformulierung bei ihrer Konzentration in dem Waschmilieu insbesondere größer als 9,8, vorzugsweise etwa 9,9 bis 10,8, ist.
EP97933743A 1996-07-16 1997-07-15 Waschmittelzusammensetzung für geschirrspülmaschinen mit einem korrosionsschutzmittel Expired - Lifetime EP0915955B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9609064A FR2751340B1 (fr) 1996-07-16 1996-07-16 Composition detergente pour lave-vaisselle, son utilisation en lave-vaisselle contre la corrosion de la vaisselle et procede de levage non-corrosif de la vaisselle
FR9609064 1996-07-16
FR9614137A FR2751341B1 (fr) 1996-07-16 1996-11-20 Composition detergente pour lave-vaisselle, son utilisation en lave-vaisselle contre la corrosion de la vaisselle et procede de lavage non-corrosif de la vaisselle
FR9614137 1996-11-20
PCT/FR1997/001311 WO1998002515A1 (fr) 1996-07-16 1997-07-15 Composition detergente pour lave-vaisselle contenant un agent anti-corrosif

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EP0915955A1 EP0915955A1 (de) 1999-05-19
EP0915955B1 true EP0915955B1 (de) 2002-09-25

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CA (1) CA2261090C (de)
DE (1) DE69715871T2 (de)
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DE19860670A1 (de) * 1998-12-29 2000-08-10 Benckiser Nv Wasserlösliches Glas als Korrosionsschutz in einer Geschirrspülmaschine
DE10104469A1 (de) * 2001-02-01 2002-08-08 Basf Ag Copolymere zur Verhinderung von Glaskorrosion
GB0107593D0 (en) * 2001-03-27 2001-05-16 Reckitt Benckiser Nv A device
CA2475115A1 (en) * 2002-02-09 2003-08-14 Reckitt Benckiser N.V. Glassware corrosion inhibitor
US20070179073A1 (en) * 2005-11-09 2007-08-02 Smith Kim R Detergent composition for removing polymerized food soils and method for cleaning polymerized food soils
AU2008247433B2 (en) 2007-05-04 2012-12-06 Ecolab Inc. Water treatment system and downstream cleaning methods
US20120159727A1 (en) * 2010-12-14 2012-06-28 Hill Robert E Multipurpose cleaner compostion
US11279900B1 (en) * 2017-10-04 2022-03-22 Nano-Tek Solutions LLC Cleaning agent and method of using the same

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US3933670A (en) * 1973-11-12 1976-01-20 Economic Laboratories, Inc. Process for making agglomerated detergents
JPS6050240B2 (ja) * 1978-07-19 1985-11-07 旭電化工業株式会社 硬表面の膜状汚れを除去することの出来る洗浄剤
DE3929896A1 (de) * 1989-09-08 1991-03-14 Hoechst Ag Geschirrspuelmittel
FR2688798B1 (fr) * 1992-03-20 1994-10-14 Rhobb Poulenc Chimie Agent "builder" a base de silicate et d'un produit mineral.
US5703027A (en) * 1994-11-29 1997-12-30 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching

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CA2261090A1 (fr) 1998-01-22
EP0915955A1 (de) 1999-05-19
DE69715871T2 (de) 2003-05-08
DE69715871D1 (de) 2002-10-31
FR2751341A1 (fr) 1998-01-23
FR2751341B1 (fr) 2003-06-13
AU3698997A (en) 1998-02-09
CA2261090C (fr) 2004-11-16
US6299701B1 (en) 2001-10-09
WO1998002515A1 (fr) 1998-01-22
JPH11514035A (ja) 1999-11-30

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