EP0120421B1 - Use of a pasty cleaning agent in dishwashers - Google Patents

Use of a pasty cleaning agent in dishwashers Download PDF

Info

Publication number
EP0120421B1
EP0120421B1 EP84102909A EP84102909A EP0120421B1 EP 0120421 B1 EP0120421 B1 EP 0120421B1 EP 84102909 A EP84102909 A EP 84102909A EP 84102909 A EP84102909 A EP 84102909A EP 0120421 B1 EP0120421 B1 EP 0120421B1
Authority
EP
European Patent Office
Prior art keywords
sodium
agent
sodium metasilicate
sodium tripolyphosphate
active chlorine
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.)
Expired
Application number
EP84102909A
Other languages
German (de)
French (fr)
Other versions
EP0120421A2 (en
EP0120421A3 (en
Inventor
Horst Prühs
Theodor Dr. Altenschöpfer
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
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT84102909T priority Critical patent/ATE42966T1/en
Publication of EP0120421A2 publication Critical patent/EP0120421A2/en
Publication of EP0120421A3 publication Critical patent/EP0120421A3/en
Application granted granted Critical
Publication of EP0120421B1 publication Critical patent/EP0120421B1/en
Expired legal-status Critical Current

Links

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
    • C11D3/395—Bleaching agents
    • C11D3/3956—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in 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
    • C11D3/395—Bleaching agents

Definitions

  • the invention relates to the use of hydrated sodium tripolyphosphate and the use of hydrated sodium metasilicate.
  • the hexahydrate completely present in this form is preferably used as the hydrated sodium tripolyphosphate.
  • Commercial products that are not completely in this hydration level may have to be rehydrated separately.
  • the so-called pentahydrate is preferred. This gives pastes with a particularly white color, which makes them appear more attractive to the user. It is also possible to dispense with the addition of further alkaline components when using hydrated metasilicates.
  • the viscosities of the cleaning agents used according to the invention range up to 850 Pa-s, measured at 20 ° C. with a Brookfield rotary viscometer, type RTV, at 5 revolutions per minute.
  • the cleaners used according to the invention can also be used free of chlorine carriers.
  • the dishes to be cleaned are then restricted to soiling on which the active chlorine effect is in any case without influence.
  • the cleaners to be used according to the invention therefore optionally also contain an active chlorine compound, preferably of sodium, potassium or lithium hypochlorite.
  • Chlorinated trisodium or tripotassium o-phosphate can be used as a further useful compound.
  • Organic chlorine carriers such as trichloroisocyanuric acid or alkali metal dichloroisocyanurates or N-chlorinated sulfamides or triazines, are less preferred since they are less stable in storage in the cleaners to be used according to the invention.
  • the amount of the chlorine carrier is then preferably such that the cleaners contain 0.1 to 3.0% by weight, in particular 0.5 to 2.0% by weight, of active chlorine.
  • the natural or synthetic layered silicates of the hectorite type have also proven to be particularly suitable for component (B). Both the processed natural and the synthetic hectorites can still contain certain impurities which do not interfere with the use of the compositions according to the invention. In the processed natural hectorites, these are other layered silicate types or small additions to calcite, with synthetically produced z. B. sodium carbonate or sodium sulfate. The water-soluble by-products of the synthesis do not need to be washed out or not completely, which considerably reduces the production outlay.
  • synthetic hectorite If synthetic hectorite is used, it does not need to be dewatered before the cleaner is produced, but can, after the majority of the water has been removed, by centrifuging or filtration as an aqueous slurry or moist filter cake without further pretreatment to the cleaners to be used according to the invention to be processed further.
  • Hectorites are generally understood to mean trioctahedral layered magnesium silicates of the general formula wherein x is a value greater than 0 and less than 6, y is a value from 0 to 4 and n is an integer from 1 to 3 and M is a cation.
  • the water content of an air-dry product is generally 5 to 10% by weight.
  • the layered silicates are used in fine-grained form, i. H. the proportion of the sieve analysis on a sieve with a mesh size of 0.25 mm should be less than 5% by weight, preferably less than 1% by weight.
  • the amount of the layered silicate to be used depends primarily on its ability to swell. In the case of hectorite, 1 to 10% by weight, preferably 2 to 6% by weight (based on hectorite dried at 105 ° C.) are generally used.
  • nonionic surfactants with low foaming power which do not decompose in the presence of active chlorine, are also considered as further optional constituents.
  • chlorine and alkali-resistant colors and fragrances can be added to the dish detergents.
  • Additional components of the active substances used such as sodium sulfate, sodium chloride or mineral admixtures of the layered silicate, are also suitable as optional components.
  • complexing agents that can be used are active chlorine-resistant, generally nitrogen-free complexing agents, e.g. B. polyvalent phosphonic acids.
  • a lithium-containing layered silicate of the hectorite type was used here as a thickener.
  • the product referred to below as "Hectorite III” is the commercial product Laponite RD m from Laporte Ind. Ltd.
  • the water content of the product (loss on drying at 105 ° C) was 7-8% by weight.
  • the sieve analysis showed a residue of less than 1 percent by weight on a 0.25 mm sieve according to DIN.
  • the viscosity of a 5% by weight aqueous gel determined using a Brookfield rotary viscometer at a spindle speed of 5 rpm (20 ° C.), was 108 Pas.
  • the viscosity of the paste thus obtained was measured at 20 ° C. using a Brookfield rotary viscometer of the type RTV at 5 spindle revolutions per minute 304 Pa. s.
  • the viscosity of the paste obtained after 10 days of storage at room temperature was 480 Pa ⁇ s.
  • the active chlorine loss after storage for 2 months at room temperature was 12%.
  • the viscosity measured as in Example 1, was 696 Pa after 10 days of storage at 20 ° C. s.
  • the active chlorine loss after 10 months at room temperature was 10%.

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A detergent paste for use in dishwashers comprised of a pasty, thixotropic cleaning agent with a viscosity of at least 30 Pa.s at 20 DEG C. as determined with a rotational viscosimeter at a spindle speed of 5 revolutions per minute and (A) essentially a mixture of hydrated sodium tripolyphosphate and hydrated sodium metasilicate in the form of sodium tripolyphosphate hexahydrate and sodium metasilicate pentahydrate as finely ground substances having an average particle size of less than 0.3 mm, (B) an optional active chlorine compound and (C) a thickening agent compatible therewith for example foliated silicates of the hectorite type and a method of washing dishes in a dishwasher.

Description

In der nicht vorveröffentlichten EP-A-0 075 813 wird die Verwendung eines wäßrigen, im Ruhezustand bei Raumtemperatur pastösen, thixotropen Reinigungsmittels in Geschirrspülmaschinen beschrieben, dessen bei 20°C mittels eines Rotationsviskosimeters bei 5 Spindelumdrehungen pro Minute bestimmte Viskosität mindestens 30 Pa - s beträgt und das

  • (A) mindestens eine reinigend wirkende bzw. härtebildende Ionen bindende Verbindung ausgewählt aus der Gruppe bestehend aus Polyphosphaten, Alumosilikaten, Silikaten, Hydroxiden und Carbonaten des Natriums oder Kaliums,
  • (B) eine Aktivchlorverbindung und
  • (C) ein damit verträgliches Verdickungsmittel enthält.
EP-A-0 075 813, which has not been published beforehand, describes the use in dishwashers of an aqueous, thixotropic detergent which is pasty at room temperature in the idle state and whose viscosity, determined at 20 ° C. by means of a rotary viscometer at 5 spindle revolutions per minute, is at least 30 Pa-s and the
  • (A) at least one cleaning compound or hardness-forming ion-binding compound selected from the group consisting of polyphosphates, aluminosilicates, silicates, hydroxides and carbonates of sodium or potassium,
  • (B) an active chlorine compound and
  • (C) contains a compatible thickener.

Die danach erfindungsgemäß zu verwendenden Mittel enthalten als reinigend wirkende Komponente (A) unter anderem die als besonders geeignet bezeichneten Pentanatrium- bzw. Pentakaliumtriphosphate und Natrium- bzw. Kaliumsilikate der Zusammensetzung Me20 : Si02 wie 1 : 0,5 bis 1 : 3,5 (mit Me = Na, K) sowie Gemische verschieden zusammengesetzter Silikate z. B. solche der Zusammensetzung Me20 : Si02 = 1 : 0,5 bis 1 : 1 mit solchen der Zusammensetzung 1 : 2 bis 1 : 3,5.The agents to be used according to the invention then contain, as cleaning component (A), inter alia, the pentasodium or pentapotassium triphosphates and sodium or potassium silicates of the composition Me 2 0: Si0 2, such as 1: 0.5 to 1: 3, which are designated as particularly suitable , 5 (with Me = Na, K) and mixtures of different silicates z. B. those of the composition Me 2 0: Si0 2 = 1: 0.5 to 1: 1 with those of the composition 1: 2 to 1: 3.5.

Die Komponente (A) weist danach in einer bevorzugten Anwendungsform die folgende Zusammensetzung auf:

  • 3 - 40 Gew.-% Natrium- und/oder Kaliumtripolyphosphat,
  • 5 - 30 Gew.-% Natrium- und/oder Kaliumsilikate,
  • 0 - 25 Gew.-% feinteiliges, Calciumsalze bindendes Natriumalumosilikat,
  • 0 - 20 Gew.-% Carbonat und/oder Hydroxid des Natriums und/oder Kaliums, wobei

das Natrium- oder Kaliumsilikat vorzugsweise aus einem Gemisch von Metasilikaten der Zusammensetzung Me20 : Si02 = 1 : 1 und Disilikaten bzw. Wasserglas der Zusammensetzung Me20 : Si02 = 1 : 2 bis 1 : 3,5 im Mischungsverhältnis 2 : 1 bis 1 : 10, insbesondere 1 : 1 bis 1 : 5, jeweils als wasserfreie Substanz gerechnet, besteht. In den Beispielen des EP-A-0 075 813 werden in Komponente (A) Kaliumtripolyphosphat und wasserfreies Natriummetasilikat eingesetzt.In a preferred application form, component (A) then has the following composition:
  • 3 - 40% by weight sodium and / or potassium tripolyphosphate,
  • 5 - 30% by weight sodium and / or potassium silicates,
  • 0 - 25% by weight of finely divided sodium aluminosilicate which binds calcium salts,
  • 0-20% by weight of carbonate and / or hydroxide of sodium and / or potassium, where

the sodium or potassium silicate preferably from a mixture of metasilicates with the composition Me 2 0: Si0 2 = 1: 1 and disilicates or water glass with the composition Me 2 0: Si0 2 = 1: 2 to 1: 3.5 in a mixing ratio of 2: 1 to 1:10, in particular 1: 1 to 1: 5, each calculated as an anhydrous substance. In the examples of EP-A-0 075 813, potassium tripolyphosphate and anhydrous sodium metasilicate are used in component (A).

Die Erfindung betrifft den Einsatz von hydratisiertem Natriumtripolyphosphat und den Einsatz von hydratisiertem Natriummetasilikat. Als hydratisiertes Natriumtripolyphosphat wird vorzugsweise das vollständig in dieser Form vorliegende Hexahydrat verwendet. Nicht vollständig in dieser Hydratationsstufe vorliegende Handelsprodukte müssen gegebenenfalls gesondert nachhydratisiert werden. Von den verschiedenen Natriummetasilikat-Hydraten wird das sogenannte Pentahydrat bevorzugt. Hierdurch werden Pasten mit besonders weißer Farbe erhalten, was sie für den Anwender attraktiver erscheinen läßt. Auch kann man bei Einsatz hydratisierter Metasilikate auf die Zugabe weiterer alkalischer Bestandteile verzichten.The invention relates to the use of hydrated sodium tripolyphosphate and the use of hydrated sodium metasilicate. The hexahydrate completely present in this form is preferably used as the hydrated sodium tripolyphosphate. Commercial products that are not completely in this hydration level may have to be rehydrated separately. Of the various sodium metasilicate hydrates, the so-called pentahydrate is preferred. This gives pastes with a particularly white color, which makes them appear more attractive to the user. It is also possible to dispense with the addition of further alkaline components when using hydrated metasilicates.

Da Natriumtripolyphosphat-Hexahydrat weniger gut wasserlöslich ist als Kaliumtripolyphosphat, kommt man durch dessen Einsatz auf Grund des heterogenen Charakters der resultierenden Pasten zu einer höheren Viskosität, die darüber hinaus als sogenannte starke Strukturviskosität bei höheren Spindelumdrehungen stark ab-, bei niedrigen Spindelumdrehungen stark zunimmt. Hierbei wird auf Messungen mit einem Brookfield-Rotationsviskosimeter Bezug genommen.Since sodium tripolyphosphate hexahydrate is less readily water-soluble than potassium tripolyphosphate, its use leads to a higher viscosity due to the heterogeneous nature of the resulting pastes, which moreover, as a so-called high structural viscosity, decreases sharply with higher spindle revolutions and increases sharply with low spindle revolutions. Here, reference is made to measurements using a Brookfield rotational viscometer.

Die Viskositäten der erfindungsgemäß verwendeten Reinigungsmittel reichen bis zu 850 Pa - s, gemessen bei 20°C mit einem Brookfield-Rotationsviskosimeter, Typ RTV, bei 5 Umdrehungen pro Minute.The viscosities of the cleaning agents used according to the invention range up to 850 Pa-s, measured at 20 ° C. with a Brookfield rotary viscometer, type RTV, at 5 revolutions per minute.

Es versteht sich von selbst, daß die erfindungsgemäß verwendeten Reiniger auch chlorträgerfrei verwendbar sind. Jedoch ist dann das zu reinigende Geschirr auf solche Anschmutzungen beschränkt, auf die die Aktivchloreinwirkung ohnehin ohne Einfluß ist.It goes without saying that the cleaners used according to the invention can also be used free of chlorine carriers. However, the dishes to be cleaned are then restricted to soiling on which the active chlorine effect is in any case without influence.

Die erfindungsgemäß zu verwendenden Reiniger enthalten daher gegebenenfalls auch eine Aktivchlorverbindung, vorzugsweise aus Natrium-, Kalium- oder Lithiumhypochlorit. Als weitere brauchbare Verbindung kommen chloriertes Trinatrium- oder Trikalium-o-phosphat in Frage. Organische Chlorträger, wie Trichlorisocyanursäure oder Alkalimetall-dichlorisocyanurate bzw. N-chlorierte Sulfamide oder Triazine sind weniger bevorzugt, da sie in den erfindungsgemäß zu verwendenden Reinigern weniger lagerbeständig sind. Die Menge der Chlorträger ist dann vorzugsweise so bemessen, daß die Reiniger 0,1 bis 3,0 Gew.-%, insbesondere 0,5 bis 2,0 Gew.-% an aktivem Chlor enthalten.The cleaners to be used according to the invention therefore optionally also contain an active chlorine compound, preferably of sodium, potassium or lithium hypochlorite. Chlorinated trisodium or tripotassium o-phosphate can be used as a further useful compound. Organic chlorine carriers, such as trichloroisocyanuric acid or alkali metal dichloroisocyanurates or N-chlorinated sulfamides or triazines, are less preferred since they are less stable in storage in the cleaners to be used according to the invention. The amount of the chlorine carrier is then preferably such that the cleaners contain 0.1 to 3.0% by weight, in particular 0.5 to 2.0% by weight, of active chlorine.

Als für die Komponente (B) besonders geeignet haben sich auch hier die natürlichen oder synthetischen Schichtsilikate vom Hectorit-Typ erwiesen. Sowohl die aufbereiteten natürlichen als auch die synthetischen Hectorite können noch gewisse Verunreinigungen enthalten, die bei der erfindungsgemäßen Verwendung der Mittel nicht stören. Bei den aufbereiteten natürlichen Hectoriten sind dies andere Schichtsilikat-Typen bzw. geringe Beimengungen an Calcit, bei synthetisch hergestellten z. B. Natriumcarbonat bzw. Natriumsulfat. Die wasserlöslichen Nebenprodukte der Synthese brauchen nicht oder nicht vollständig ausgewaschen zu werden, was den Herstellungsaufwand erheblich vermindert. Wird synthetischer Hectorit eingesetzt, braucht dieser vor der Herstellung des Reinigers auch nicht entwässert zu werden, sondern kann nach Abtrennung der Hauptmenge des Wassers durch Zentrifugieren oder Filtration als wäßrige Aufschlämmung bzw. feuchter Filterkuchen ohne weitere Vorbehandlung zu den erfindungsgemäß zu verwendenden Reinigern weiterverarbeitet werden.The natural or synthetic layered silicates of the hectorite type have also proven to be particularly suitable for component (B). Both the processed natural and the synthetic hectorites can still contain certain impurities which do not interfere with the use of the compositions according to the invention. In the processed natural hectorites, these are other layered silicate types or small additions to calcite, with synthetically produced z. B. sodium carbonate or sodium sulfate. The water-soluble by-products of the synthesis do not need to be washed out or not completely, which considerably reduces the production outlay. If synthetic hectorite is used, it does not need to be dewatered before the cleaner is produced, but can, after the majority of the water has been removed, by centrifuging or filtration as an aqueous slurry or moist filter cake without further pretreatment to the cleaners to be used according to the invention to be processed further.

Unter Hectoriten versteht man im allgemeinen trioctaedrische Magnesium-Schichtsilikate der allgemeinen Formel

Figure imgb0001
worin x ein Wert größer als 0 und kleiner als 6, y ein Wert von 0 bis 4 und n eine ganze Zahl von 1 bis 3 ist und M für ein Kation steht. Vorzugsweise steht das Kation M für Natrium, wobei der Wert für n = 1 ist. Der Wassergehalt eines lufttrockenen Produktes beträgt im allgemenen 5 bis 10 Gew.-%.Hectorites are generally understood to mean trioctahedral layered magnesium silicates of the general formula
Figure imgb0001
 wherein x is a value greater than 0 and less than 6, y is a value from 0 to 4 and n is an integer from 1 to 3 and M is a cation. The cation M preferably stands for sodium, the value for n = 1. The water content of an air-dry product is generally 5 to 10% by weight.

Die Schichtsilikate kommen in feinkörniger Form zum Einsatz, d. h. der Anteil der bei der Siebanalyse auf einem Sieb mit 0,25 mm Maschenweite soll weniger als 5 Gew.-%, vorzugsweise weniger als 1 Gew.-% betragen. Die Menge des einzusetzenden Schichtsilikats hängt in erster Linie von dessen Quellfähigkeit ab. Im Falle des Hectorits werden im allgemeinen 1 bis 10 Gew.-%, vorzugsweise 2 bis 6 Gew.-% (bezogen auf bei 105°C getrockneten Hectorit) eingesetzt.The layered silicates are used in fine-grained form, i. H. the proportion of the sieve analysis on a sieve with a mesh size of 0.25 mm should be less than 5% by weight, preferably less than 1% by weight. The amount of the layered silicate to be used depends primarily on its ability to swell. In the case of hectorite, 1 to 10% by weight, preferably 2 to 6% by weight (based on hectorite dried at 105 ° C.) are generally used.

Als weitere fakultative Bestandteile kommen auch hier bekannte nichtionische Tenside mit geringem Schaumvermögen in Betracht, die sich in Gegenwart von Aktivchlor nicht zersetzen.Known nonionic surfactants with low foaming power, which do not decompose in the presence of active chlorine, are also considered as further optional constituents.

Bei Bedarf können den Geschirreinigungsmitteln auch chlor- und alkalibeständige Farb- und Duftstoffe zugesetzt werden.If necessary, chlorine and alkali-resistant colors and fragrances can be added to the dish detergents.

Als fakultative Bestandteile kommen ferner Begleitstoffe der eingesetzten Wirkstoffe, wie Natriumsulfat, Natriumchlorid oder mineralische Beimengungen des Schichtsilikats in Betracht.Additional components of the active substances used, such as sodium sulfate, sodium chloride or mineral admixtures of the layered silicate, are also suitable as optional components.

Weitere einsetzbare Komplexbildner sind gegen Aktivchlor beständige, in der Regel stickstofffreie Komplexbildner, z. B. mehrwertige Phosphonsäuren.Other complexing agents that can be used are active chlorine-resistant, generally nitrogen-free complexing agents, e.g. B. polyvalent phosphonic acids.

BeispieleExamples

Als Verdickungsmittel wurde hier ein Lithium enthaltendes Schichtsilikat vom Hectorit-Typ verwendet. Bei dem im folgenden mit "Hectorit III" bezeichneten Produkt handelt es sich um das Handelsprodukt Laponite RDm der Fa. Laporte Ind. Ltd. Der Wassergehalt des Produktes (Trockenverlust bei 105°C) lag bei 7 - 8 Gew.-%. Die Siebanalyse ergab einen Rückstand von weniger als 1 Gewichtsprozent auf einem 0,25 mm Sieb nach DIN. Die mit einem Rotationsviskosimeter nach Brookfield bei einer Spindeldrehzahl von 5 UpM (20° C) bestimmte Viskosität eines 5gewichtsprozentigen wäßrigen Gels betrug 108 Pa - s.A lithium-containing layered silicate of the hectorite type was used here as a thickener. The product referred to below as "Hectorite III" is the commercial product Laponite RD m from Laporte Ind. Ltd. The water content of the product (loss on drying at 105 ° C) was 7-8% by weight. The sieve analysis showed a residue of less than 1 percent by weight on a 0.25 mm sieve according to DIN. The viscosity of a 5% by weight aqueous gel, determined using a Brookfield rotary viscometer at a spindle speed of 5 rpm (20 ° C.), was 108 Pas.

Beispiel 1example 1

Ein pastenförmiges Reinigungsmittel, enthaltend in Gewichtsprozent

  • 22 % Natriumtripolyphosphat-Hexahydrat (durchschnittliche Korngröße unterhalb von 0,3 mm),
  • 31 % Natriummetasilikat-Pentahydrat (durchschnittliche Korngröße unterhalb von 0,3 mm),
  • 10 % Chlorbleichlauge (13 % Aktivchlorgehalt),
  • 3 % Hectorit III (Laponite RD®),
  • 34 % Wasser
wurde dadurch hergestellt, daß man den Hectorit III in das vorgelegte, ca. 40° C warme Wasser einrührte. Nachdem das Schichtsilikat gequollen war und mit Wasser ein klares, viskoses Gel gebildet hatte, was etwa 10 Minuten dauerte, wurde auf Raumtemperatur abgekühlt und unter starkem Rühren die Chlorbleichlauge, das feingemahlene Natriummetasilikat-Pentahydrat und das feingemahlene Natriumtripolyphosphat-Hexahydrat zugegeben. Nachdem sich eine homogene creme-artige Paste gebildet hatte, wurde sie einer 24stündigen Reifezeit überlassen und dann nochmals stark durchgerührt.A paste-like cleaning agent containing in percent by weight
  • 22% sodium tripolyphosphate hexahydrate (average grain size below 0.3 mm),
  • 31% sodium metasilicate pentahydrate (average grain size below 0.3 mm),
  • 10% chlorine bleach (13% active chlorine),
  • 3% hectorite III (Laponite RD®),
  • 34% water
was prepared by stirring the hectorite III into the water at about 40 ° C. After the layered silicate had swollen and formed a clear, viscous gel with water, which took about 10 minutes, the mixture was cooled to room temperature and the chlorine bleach, the finely ground sodium metasilicate pentahydrate and the finely ground sodium tripolyphosphate hexahydrate were added with vigorous stirring. After a homogeneous cream-like paste had formed, it was left to ripen for 24 hours and then stirred again vigorously.

Die Viskosität der so erhaltenen Paste betrug nach 10tägiger Lagerung bei Raumtemperatur, gemessen bei 20°C mit einem Brookfield-Rotationsviskosimeter vom Typ RTV bei 5 Spindelumdrehungen pro Minute 304 Pa . s.After 10 days of storage at room temperature, the viscosity of the paste thus obtained was measured at 20 ° C. using a Brookfield rotary viscometer of the type RTV at 5 spindle revolutions per minute 304 Pa. s.

Der Aktivchlorverlust lag nach 2 Monaten bei nur 15 %.The active chlorine loss was only 15% after 2 months.

Beispiel 2Example 2

  • 25 % Natriumtripolyphosphat-Hexahydrat,25% sodium tripolyphosphate hexahydrate,
  • 36 % Natriummetasilikat-Pentahydrat,36% sodium metasilicate pentahydrate,
  • 5 % Chlorbleichlauge (13 % Aktivchlorgehalt),5% chlorine bleach (13% active chlorine),
  • 3 % Hectorit III (Laponite RD®),3% hectorite III (Laponite RD®),
  • 31 % Wasser.31% water.

Die Herstellung erfolgte wie in Beispiel 1.The preparation was carried out as in Example 1.

Die Viskosität der erhaltenen Paste betrug nach 10tägiger Lagerung bei Raumtemperatur, gemessen mit einem Brookfield-Rotationsviskosimeter (RTV) bei 20° C und mit 5 Umdrehungen pro Minute 480 Pa ·s.The viscosity of the paste obtained after 10 days of storage at room temperature, measured using a Brookfield rotary viscometer (RTV) at 20 ° C. and at 5 revolutions per minute, was 480 Pa · s.

Der Aktivchlorverlust betrug nach 2 Monaten Lagerung bei Raumtemperatur 12 %.The active chlorine loss after storage for 2 months at room temperature was 12%.

Beispiel 3Example 3

  • 23 % Natriumtripolyphosphat-Hexahydrat,23% sodium tripolyphosphate hexahydrate,
  • 33 % Natriummetasilikat-Pentahydrat,33% sodium metasilicate pentahydrate,
  • 5 % Chlorbleichlauge (13 % Aktivchlorgehalt),5% chlorine bleach (13% active chlorine),
  • 4 % Hectorit III (Laponite RD®),4% hectorite III (Laponite RD®),
  • 35% Wasser.35% water.

Die Herstellung erfolgte wie in Beispiel 1.The preparation was carried out as in Example 1.

Die Viskosität, gemessen wie in Beispiel 1 betrug nach 10 Tagen Lagerzeit bei 20° C 696 Pa . s.The viscosity, measured as in Example 1, was 696 Pa after 10 days of storage at 20 ° C. s.

Der Aktivchlorverlust betrug nach 2 Monaten Lagerzeit bei Raumtemperatur 10 %.The active chlorine loss after 10 months at room temperature was 10%.

Claims (4)

1. The use in dishwashing machines of an aqueous, thixotropic cleaning agent, optionally containing active chlorine, in the form of a paste when standing at room temperature, of which the viscosity is at least 30 Pa · s, as measured at 20°C using a rotational viscosimeter at a spindle speed of 5 revolutions per minute and which contains
(A) a compound which has a cleaning effect and which binds ions responsible for hardness,
(B) a thickening agent optionally compatible with active chlorine,
(A) essentially consisting of a mixture of hydrated sodium tripolyphosphate and hydrated sodium metasilicate.
2. The use of an agent as claimed in claim 1, (A) consisting essentially of a mixture of sodium tripolyphosphate hexahydrate and sodium metasilicate pentahydrate.
3. The use of an agent as claimed in claim 2, the sodium tripolyphosphate hexahydrate and the sodium metasilicate pentahydrate being used in the form of finely ground substances having an average particle size of less than 0.3 mm.
4. The use of an agent as claimed in claims 1 to 3, its viscosity ranging up to 850 Pa s.
EP84102909A 1983-03-24 1984-03-16 Use of a pasty cleaning agent in dishwashers Expired EP0120421B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84102909T ATE42966T1 (en) 1983-03-24 1984-03-16 USE OF A PASTY DETERGENT IN DISHWASHERS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833310684 DE3310684A1 (en) 1983-03-24 1983-03-24 USE OF A PASTOUS DETERGENT IN DISHWASHER
DE3310684 1983-03-24

Publications (3)

Publication Number Publication Date
EP0120421A2 EP0120421A2 (en) 1984-10-03
EP0120421A3 EP0120421A3 (en) 1987-04-08
EP0120421B1 true EP0120421B1 (en) 1989-05-10

Family

ID=6194496

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84102909A Expired EP0120421B1 (en) 1983-03-24 1984-03-16 Use of a pasty cleaning agent in dishwashers

Country Status (4)

Country Link
US (1) US4511487A (en)
EP (1) EP0120421B1 (en)
AT (1) ATE42966T1 (en)
DE (2) DE3310684A1 (en)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4740327A (en) * 1982-01-18 1988-04-26 Colgate-Palmolive Company Automatic dishwasher detergent compositions with chlorine bleach having thixotropic properties
FR2571712B1 (en) * 1984-10-15 1987-01-09 Rhone Poulenc Chim Base SODIUM TRIPOLYPHOSPHATE WITH HIGH HYDRATION SPEED, METHOD FOR PREPARING SAME AND APPLICATION THEREOF
US5064553A (en) * 1989-05-18 1991-11-12 Colgate-Palmolive Co. Linear-viscoelastic aqueous liquid automatic dishwasher detergent composition
GB8719776D0 (en) * 1987-08-21 1987-09-30 Unilever Plc Machine dishwashing compositions
US4968445A (en) * 1987-09-29 1990-11-06 Colgate-Palmolive Co. Thixotropic aqueous liquid automatic dishwashing detergent composition
US4970016A (en) * 1987-09-29 1990-11-13 Colgate-Palmolive Co. Thixotropic aqueous liquid automatic dishwashing detergent composition
US4968446A (en) * 1987-11-05 1990-11-06 Colgate-Palmolive Co. Thixotropic aqueous liquid automatic dishwashing detergent composition
US5160448A (en) * 1987-12-30 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Gel detergent compositions containing a clay and a cross-linked polycarboxylic polymer
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
US5019290A (en) * 1988-03-22 1991-05-28 Dubois Chemicals, Inc. Method of formulating high caustic paste dishwashing compositions made compositions thereby, wherein phosphate reversion is minimized
GB2223028A (en) * 1988-06-28 1990-03-28 Unilever Plc Detergent composition including fabric softening clay
US4950416A (en) * 1988-10-19 1990-08-21 Vista Chemical Company Liquid dishwasher detergent composition
US5089162A (en) * 1989-05-08 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Cleaning compositions with bleach-stable colorant
EP0517311A1 (en) 1991-06-07 1992-12-09 Colgate-Palmolive Company Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5468410A (en) * 1993-10-14 1995-11-21 Angevaare; Petrus A. Purine class compounds in detergent compositions
US5480576A (en) * 1993-10-14 1996-01-02 Lever Brothers Company, Division Of Conopco, Inc. 1,3-N azole containing detergent compositions
US5374369A (en) * 1993-10-14 1994-12-20 Lever Brothers Company, Division Of Conopco, Inc. Silver anti-tarnishing detergent composition
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
DE19526380A1 (en) * 1995-07-19 1997-01-23 Henkel Ecolab Gmbh & Co Ohg Pasty dishwashing detergent and its preparation
US7060469B2 (en) * 1998-04-02 2006-06-13 The Board Of Regents Of The University Of Oklahoma Polymer grafting by polysaccharide synthases
DE19854960A1 (en) * 1998-11-29 2000-05-31 Clariant Gmbh Dishwasher detergent
DE10061897A1 (en) * 2000-12-12 2002-06-13 Clariant Gmbh Washing or cleaning composition, useful for fabrics or hard surfaces, contains microdisperse, hydrophilic silicate particles that improve soil removal and prevent resoiling
WO2008153436A1 (en) * 2007-06-14 2008-12-18 Intel Corporation Unified decoder for convolutional, turbo, and ldpc codes

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558496A (en) * 1967-11-13 1971-01-26 Barney Joseph Zmoda Thickened liquid bleach and process for preparing same
DE2254195A1 (en) * 1972-11-06 1974-05-16 Albright & Wilson Liq detergent (compsn) contg caustic alkali and polyphosphates
AR208392A1 (en) * 1973-05-07 1976-12-27 Henkel & Cie Gmbh COMPOSITION TO WASH, WHITE OR CLEAN RESISTANT MATERIALS, ESPECIALLY TEXTILES ADDITIONAL TO PATENT NO 201687 ADDITIONAL TO NO 253286
US4005027A (en) * 1973-07-10 1977-01-25 The Procter & Gamble Company Scouring compositions
US4115308A (en) * 1976-12-27 1978-09-19 The Procter & Gamble Company High-shear process for preparing silicate-containing paste-form detergent compositions
FR2380986A1 (en) * 1977-02-16 1978-09-15 Rhone Poulenc Ind NEW PROCESS FOR STABILIZING ANHYDROUS SODIUM METASILICATE AND THUS OBTAINED PRODUCT
US4116849A (en) * 1977-03-14 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
US4116851A (en) * 1977-06-20 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
DE3138425A1 (en) * 1981-09-26 1983-04-14 Henkel KGaA, 4000 Düsseldorf "USE OF A PASTOESE CLEANER IN DISHWASHER"
US4411810A (en) * 1981-11-06 1983-10-25 Basf Wyandotte Corporation Low-foaming nonionic surfactant for machine dishwashing detergent

Also Published As

Publication number Publication date
EP0120421A2 (en) 1984-10-03
DE3310684A1 (en) 1984-10-11
ATE42966T1 (en) 1989-05-15
EP0120421A3 (en) 1987-04-08
DE3478122D1 (en) 1989-06-15
US4511487A (en) 1985-04-16

Similar Documents

Publication Publication Date Title
EP0120421B1 (en) Use of a pasty cleaning agent in dishwashers
AT396935B (en) AQUEOUS THIXOTROPICAL DISHWASHER
EP0075813B1 (en) Application of a pasty cleaning agent in dish washers
DE2902236A1 (en) BLEACHING AGENT
CH654849A5 (en) DISHWASHER ON AQUEOUS BASE FOR AUTOMATIC DISHWASHER.
CH675591A5 (en)
DE4134914A1 (en) DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS
DE1467686A1 (en) cleaning supplies
EP0541523B1 (en) Paste-like, phosphate-free detergent with reduced frothing tendency
DE69712132T2 (en) Microporous crystalline material, process for its preparation and its use in detergent compositions
CH669958A5 (en)
DE2530539A1 (en) ADDUCT MADE FROM SODIUM SULPHATE, HYDROGEN PEROXYDE AND SODIUM CHLORIDE AND A BLEACHING COMPOSITION CONTAINING THIS ADDUCT
DE2161699C3 (en) Detergents and cleaning agents
EP0377807B1 (en) Highly alkaline phosphate-free liquid detergent
DE2544019A1 (en) METHOD OF WASHING TEXTILES, AND MEANS OF CARRYING OUT THE METHOD
EP0569365B1 (en) Phosphate-free cleaning agent
DE3420334A1 (en) Granular detergent and cleaner composition
EP0118658A1 (en) Process for the production of a pasty detergent
DE69025728T2 (en) Process for increasing the bleaching effect when washing and using certain amphoteric compounds in a detergent composition to increase the bleaching effect
DE1792163A1 (en) Detergent compositions
DE2244554A1 (en) METHOD OF MANUFACTURING A DETERGENT
DE2539071B2 (en)
DE4101070A1 (en) WASHING POWDER
DE2438136A1 (en) DETERGENT MIXTURE
DE3803640A1 (en) AQUEOUS SUSPENSION OF THIXOTROPME CLAY

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19870514

17Q First examination report despatched

Effective date: 19871215

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 42966

Country of ref document: AT

Date of ref document: 19890515

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3478122

Country of ref document: DE

Date of ref document: 19890615

ET Fr: translation filed
ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19900116

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19900216

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19900222

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19900301

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19900314

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19900319

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19900330

Year of fee payment: 7

ITTA It: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19900331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19900331

Year of fee payment: 7

Ref country code: GB

Payment date: 19900331

Year of fee payment: 7

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19910316

Ref country code: AT

Effective date: 19910316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19910317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19910331

Ref country code: CH

Effective date: 19910331

Ref country code: BE

Effective date: 19910331

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19910331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19911001

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19911129

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 84102909.3

Effective date: 19911009