EP0075813B2 - Application of a pasty cleaning agent in dish washers - Google Patents

Application of a pasty cleaning agent in dish washers Download PDF

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Publication number
EP0075813B2
EP0075813B2 EP82108636A EP82108636A EP0075813B2 EP 0075813 B2 EP0075813 B2 EP 0075813B2 EP 82108636 A EP82108636 A EP 82108636A EP 82108636 A EP82108636 A EP 82108636A EP 0075813 B2 EP0075813 B2 EP 0075813B2
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EP
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Prior art keywords
weight
detergent
sodium
potassium
viscosity
Prior art date
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EP82108636A
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German (de)
French (fr)
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EP0075813A3 (en
EP0075813A2 (en
EP0075813B1 (en
Inventor
Theodor Dr. Altenschöpfer
Klaus Dr. Schumann
Peter Dr. Christophliemk
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT82108636T priority Critical patent/ATE25108T1/en
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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
    • 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
    • C11D3/12—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
    • 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

Definitions

  • the detergents used in dishwashers usually consist of powders or granules or tablets. Accordingly, the input devices in which the detergents are deposited before rinsing in these machines are also designed for test products and usually consist of lockable chambers which open during the main wash cycle and release the contents.
  • a number of disadvantages result from this method of working. B. when entering the cleaner, the housewife must shake the storage pack or measuring cup so that the powder slides into the chamber, and it often happens that more or less large portions of the powder are spilled and / or get on the skin. These spilled parts are mostly lost in the rinsing process because they are pumped out together with the cold prewash solution at the end of the pre-rinse cycle.
  • the object of the invention is to develop a cleaner which can be used in dishwashers and which does not have the disadvantages described and which can be used in conventional dishwashers and can also be used in machines to be developed with a stored cleaner. In these cases, automatic dosing from a detergent supply would then take place.
  • the viscosity of the cleaner is preferably 80 to 150 Pa-s.
  • the thixotropy of the cleaner is not significantly disturbed by the measuring process. Such disturbances do not occur at a rotational speed of the spindle inserted into the sample of 5 rpm.
  • a Brookfield viscometer for example, is suitable, but other measurement methods can also be used for the determination, which allow measurement under comparable conditions.
  • the rheological behavior of the cleaner is such that the gel-like paste is affected mechanical forces, for example by shaking or pressure on a deformable storage bottle or tube or liquefied by means of a metering pump and easily squeezed out of a spray nozzle or can be transferred into the induction chamber.
  • the agent solidifies again into a gel which remains unchanged in the induction chamber when the flap is closed. It can thus be achieved that the product survives one or two pre-rinse cycles as a paste and is therefore only available as intended in the cleaning cycle.
  • the closure flap has opened and the agent comes into contact with the moving detergent solution, the gel instantaneously liquefies and the agent distributes itself in the detergent solution in a short time. It is therefore available from the moment the cleaner is released to its cleaning power, which is why the cleaning effect is more intensive than in the conventional rinsing process.
  • the tripolyphosphate used in the cleaners used according to the invention can be completely or partially replaced by water-insoluble, finely divided, bound water-containing alkali alumosilicates which have a calcium binding capacity of 50 to 200 mg CaO / g active substance (AS) and the formula preferably correspond.
  • AS CaO / g active substance
  • Such connections are known for example under the name SASIL®.
  • the calcium binding capacity of the aluminosilicates is determined in the following way:
  • component (A) is also suitable for commercial dishwashers. Less preferred constituents of component (A) are the carbonates or hydrogen carbonates of sodium or potassium, which are generally only used together with alkali compounds which have a more cleaning action.
  • component (A) has the following composition:
  • Component (B) preferably consists of sodium, potassium or lithium hypochlorite.
  • Other useful active chlorine compounds that can be used are chlorinated trinatium or tripotassium o-phosphate.
  • 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 active chlorine carrier is 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.
  • Component (C) consists of a thickener resistant to alkalis and active chlorine, which is able to form a thixotropic gel in water.
  • Swellable layered silicates of the montmorillonite type have proven to be suitable which, in 5% by weight aqueous suspension after complete swelling with a conventional rotary viscometer and a speed of the measuring spindle of 5 revolutions per minute, have a viscosity of at least 30 Pa-s (20 ° C.).
  • Complete swelling means that after the thickeners have been completely distributed in water, which is expediently carried out with the aid of a highly effective stirring device at temperatures of 30-60 ° C., after several days of aging or standing at room temperature, the viscosity, even with further thermal or mechanical treatment no longer increases.
  • Natural or synthetic phyllosilicates have proven particularly suitable for component (C) proven of the hectorite type. Both the processed natural and the synthetic hectorites can still contain certain impurities which do not interfere with the use according to the invention by means. 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 it does not need to be dewatered before the cleaner is manufactured, but can be processed further after centrifuging or filtration as an aqueous slurry or moist filter cake without further pretreatment to give the cleaners to be used according to the invention.
  • Hectorites are generally understood to mean trioctahedral layered magnesium silicates of the general formula where 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 jiculate to be used depends primarily on its ability to swell. In the case of hectorite, generally 1 to 10% by weight, preferably 2 to 6% by weight (based on hectorite dried at 105 ° C.) are used.
  • Optional non-ionic surfactants with low foaming power are used as optional components, which do not decompose in the presence of active chlorine compounds and possibly alkali metal hydroxides.
  • Suitable addition products are the adduct of 10 to 30% by weight of ethyleneokide with a polypropylene glycol with a molecular weight of 1750, the adduct of 20 mol of ethylene oxide or 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, the adduct of 5 to 12 mol of ethylene oxide to a fatty alcohol mixture of chain lengths C 12 -C 18 with a share of about 30% in oleyl alcohol and the like.
  • the proportion of the non-ionic surfactants can be up to 5% by weight, preferably 0.1 to 1% by weight.
  • chlorine and alkali-resistant dyes and fragrances can be added to the dishwashing detergents.
  • Optional components of the active ingredients used such as sodium sulfate, sodium chloride or mineral admixtures of the layered silicate, are also possible.
  • Other usable complexing agents are active chlorine-resistant, generally non-pollutant-free complexing agents, e.g. B. polyvalent phosphonic acids such as methylenediphosphonic acid or polyhydric P h ospho- include aminocarboxylic as 1.1 diphosphonopropane-1,2-dicarboxylic acid, 1-phosphonopropane-1.2,3-tricarboxylic acid or 2-phosphonobutane-2.3,4-tricarboxylic acid or their sodium or potassium salts. In addition, useful complexing agents are the active chlorine-resistant polycarboxylic acids and their salts.
  • the cleaning agents to be used according to the invention are advantageously prepared by mixing an aqueous solution or slurry containing the cleaning constituents of components (A), in particular the tripolyphosphate and, if appropriate, the alkali silicate (water glass), or a mixture thereof the thickener with heating to 40 to 65 ° C with a high shear agitator, for example an Ultra-Turrax® device, stirred until the thickening takes place. Then the remaining components of component (A), e.g. . B. metasilicate, water glass and possibly the residues of triphosphate and the optional components, such as nonionic surfactants and dyes, are stirred in. After cooling to room temperature, the active chlorine compound is finally added, for example in the form of a sodium hypochlorite solution (chlorine bleach).
  • a sodium hypochlorite solution chlorine bleach
  • the funds can be filled into the storage containers immediately after they have been produced.
  • the maximum value of the viscosity is generally reached after a standing time of 2 to 10 days.
  • a brief liquefaction occurs through vigorous shaking or pressing, however, the gel state is restored just a few seconds after the mechanical stress has ended, i. H. the cleaner introduced into the storage chamber of the dishwasher solidifies sufficiently quickly that it does not flow out after the closure cap of the storage chamber or the loading door of the dishwasher is closed.
  • the cleaners to be used according to the invention are distinguished by a high cleaning power and in particular by a long shelf life.
  • the active chlorine loss during a 6-month service life at 25 ° C was of the same order of magnitude as that of commercially available detergent granules stored in a dry place.
  • repeated heating of the cleaner to temperatures of around 60 ° C. has not proven to be disadvantageous to the storage stability or the active chlorine content.
  • the detergent paste which was repeatedly warmed up by heat transfer, did not suffer any loss of active chlorine which would have an adverse effect on the wash result within the test period of 5 days (2 rinse cycles per day).
  • Another particular advantage is that the agents can be dosed much more easily and precisely than conventional granular or powdered cleaners, which are often spilled when filling the spatially limited induction compartments due to the mostly necessary shaking of the supply package or the dosing cup.
  • the majority contain foam-active surfactants, bleaches containing active chlorine, clay-like fillers, including hectorite, and a special abrasive component as the main component.
  • the thickener primarily serves to prevent the specific light abrasive from settling.
  • DE-A-28 10 187 discloses alkaline agents and a process for pretreating heavily soiled kitchen appliances which are free of abrasives, about 0.25 to about 20% of a clay as a thickener and about 0.5 to about 9% of one Contain alkali metal silicate with a ratio of SiO 2 : M 2 0 of more than about 1 with M equal to sodium or potassium, which have a hypohalite concentration with an active chlorine content of about 0.5 to 10% and whose viscosity is about 1 to about 10,000 Pa- s and are applied to kitchen appliances with dirt that is difficult to remove. Then everything is covered with an excess of water at a temperature of more than about 38 ° C.
  • the viscosity of the preferably thixotropic agents tends to be considerably higher than with the agents of the present invention, since they should adhere well and long to the soiled surfaces, in order to be able to act there, while the consistency of the cleaners according to the invention is only intended to ensure their meterability. In addition, they should be released quickly in the dishwasher cleaning cycle.
  • the devices pre-cleaned according to DE-A-28 10 187 can subsequently be introduced into dishwashers. Their used coating is supposed to suppress foam, but then no longer has a cleaning effect due to a lack of tripolyphosphates.
  • Hectorite 1 is a commercial product from Lanco. in the case of the commercial product Laponite B @ from Laporte ind. Ltd.
  • the water content of the products was 7-8% by weight, the grain size (sieve analysis) was less than 0.2 mm with an average grain size of approx. 0.006-0.008 mm.
  • the viscosity of a 5% by weight aqueous gel was 75 Pa.s for hectorite 1 and 95 Pa.s for hectorite II.
  • the commercial granular cleaner used for comparison has the following composition:
  • a pasty cleaner containing (in% by weight) was produced by stirring the 50% triphosphate solution heated to 55 ° C. with the addition of the hectorite until it had thickened with an intensive stirrer (Ultra-Turrax®). Then 2% by weight sodium metasilicate was stirred in as a powdery powder. After the disilicate had been added in the form of a 54.5% by weight solution, the paste was cooled and the sodium hypochlorite in the form of a NaCl-containing chlorine bleach (active chlorine content 13%) and the rest of the sodium metasilicate were incorporated.
  • the viscosity measured after a standing time of 10 days under the specified conditions was 125 Pa.s.
  • Example 1 was repeated, except that dry potassium tripolyphosphate was stirred into an aqueous swelling made from filter-moist hectorite 1 with an unchanged amount of water. The further processing was carried out as indicated in Example 1. The viscosity of the paste determined under the specified conditions was 115 Pa.s.
  • Example 3 was repeated using the thickener labeled "Hectorite I".
  • the viscosity of the agent was 103 Pa ⁇ s.
  • the cleaner of the following composition was prepared by mixing the ingredients in the order given at 55 ° with an intensive stirrer.
  • the chlorine bleach was incorporated after the paste cooled.
  • the viscosity determined by definition after 10 days of standing was 98 Pa.s.
  • the chlorine bleach was added after the mixture had been heated to 60 ° C.
  • the viscosity was 120 Pa ⁇ s after standing for 10 days.
  • Example 6 was repeated except that prior to addition of chlorine bleaching liquor in addition 0.3% polymeric polypropylene oxide polyethylene oxide block of a nonionic non-foaming surfactant from the class of releasing was added i.
  • the viscosity of the paste after 118 days of standing was 118 Pa.s.

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Abstract

This invention is directed to an aqueous, thixotropic dishwater detergent composition which is at room temperature a paste having a viscosity of at least about 30 Pa.s as measured at 20 DEG C. with a rotational viscometer at 5 spindle revolutions per minute, the dishwasher detergent composition comprising: (a) at least one compound with cleaning action or binding capacity for ions causing hardness selected from the group consisting of polyphosphates, aluminosilicates, silicates, hydroxides, and carbonates of sodium or potassium in an amount sufficient to effect cleaning or binding; (b) an active chlorine compound in an amount sufficient to provide active chlorine to the detergent composition; and (c) a thickener compatible with components (a) and (b) in an amount sufficient to give the desired viscosity.

Description

Die in Geschirrspülmaschinen eingesetzten Reiniger bestehen üblicherweise aus Pulvern bzw. Granulaten oder aus Tabletten. Dementsprechend sind in diesen Maschinen auch die Eingabevorrichtungen in denen die Reiniger vor dem Spülen deponiert werden, auf teste Produkte ausgelegt und bestehen üblicherweise aus verschließbären Kammern die sich während des Hauptspülgangs öffnen und den Inhalt freigeben. Aus dieser Arbeitsweise resultiert eine Reihe von Nachteilen. B.eim Eingeben des Reinigers muß die Haustrau die Vorratspackung bzw. den Meßbecher rütteln, damit das Pulver in die Kammer gleitet, wobei es häufig vorkommt, daß mehr oder weniger große Anteile des Pulvers verschüttet werden und/oder auf die Haut gelangen. Diese verschütteten Anteile gehen türden Spülvorgang meistvertoren, da sie am Ende des Vorspülgangs zusammen mit der kalten Vorspüllauge abgepumpt werden. Gelangt Pulver beim Einfüllen in den Öffnungsmechanismus der Kammer, so kann es geschehen, daß sich der Deckel nicht vollständig schließen läßt bzw. der bei einigen Konstruktionen übliche Magnetverschluß oder mechanisch/elektrische Verschluß nicht fest genug schließt, so daß beim Schließen der Beschickungstüre der Spülmaschine das Pulver oder ein Teil davon herausrieselt und ebenfalls im Hauptspülgang nicht mehr zur Verfügung steht Probleme können weiterhin in solchen Maschinen auftreten, in denen die Kammer zusätzlich mit einem Schutzgitter gesichert ist und Reiniger verwendet werden, die hinsichtlich ihrer Lösungsgeschwindigkeit nicht optimiert oder durch längeres Stehenlassen angebrauchter Packungen zusammengeballt sind. Ein nicht vollständig während des Spülvorgangs gelöster Reiniger führt zu einem schlechteren Reinigungsergebnis und beeinträchtigt die Wirkung des sauren Klarspülmittels. Bei Leitfähigkeitsmessungen hat sich weiterhin gezeigt, daß auch leichtlösliche Reiniger nach der Freigabe längere Zeit, unter ungünstigen Umständen bis zu 10 Minuten, zur vollständigen Auflösung benötigen, was dazu führt, daß während einer erheblichen Zeitspanne mit einer Unterkonzentration an Reinigern gearbeitet wird. Soweit in den letzten Jahren Verbesserungen angestrebt und erzielt wurden, bezogen sie sich auf der apparativen Seite auf den Einspülmechanismus, auf der Reinigerseite auf eine verbesserte Rieselfähigkeit und erhöhte Lösungsgeschwindigkeit des stets festen Reinigers. Die Möglichkeit, flüssige Mittel einzusetzen, beschränkte sich auf saure Klarspüler, die in der Regel in einem Vorratsbehälter deponiert werden.The detergents used in dishwashers usually consist of powders or granules or tablets. Accordingly, the input devices in which the detergents are deposited before rinsing in these machines are also designed for test products and usually consist of lockable chambers which open during the main wash cycle and release the contents. A number of disadvantages result from this method of working. B. when entering the cleaner, the housewife must shake the storage pack or measuring cup so that the powder slides into the chamber, and it often happens that more or less large portions of the powder are spilled and / or get on the skin. These spilled parts are mostly lost in the rinsing process because they are pumped out together with the cold prewash solution at the end of the pre-rinse cycle. If powder gets into the opening mechanism of the chamber during filling, it may happen that the lid cannot be closed completely or the magnetic lock or mechanical / electrical lock that is common in some constructions does not close tight enough, so that when the loading door of the dishwasher closes Powder or a part of it trickles out and is also no longer available in the main wash cycle. Problems can still occur in machines in which the chamber is additionally secured with a protective grille and cleaners are used which are not optimized in terms of their dissolution speed or due to longer standing of used packs are clustered together. A detergent that is not completely dissolved during the rinsing process will lead to a poorer cleaning result and impair the effect of the acidic rinse aid. Conductivity measurements have also shown that even slightly soluble cleaners take a long time to dissolve under unfavorable circumstances, up to 10 minutes under unfavorable circumstances, which means that a low concentration of cleaners is used for a considerable period of time. Insofar as improvements have been sought and achieved in recent years, on the apparatus side they relate to the induction mechanism, and on the cleaner side to improved flowability and increased dissolving speed of the permanently solid cleaner. The ability to use liquid agents was limited to acidic rinse aids, which are usually deposited in a storage container.

Der Gedanke, flüssige Reiniger anstelle der Pulver in Geschirrspülmaschinen einzusetzen, lag völlig fern, da die weithin üblichen Eingabevorrichtungen aufgrund ihrer Konstruktion sich nicht für flüssige Mittel eignen und weiterhin befürchtet werden mußte. daß sich ein in der Maschine integrierter Vorratstank bei jedem Spülvorgang erheblich erwärmen und der im Reiniger üblicherweise enthaltene Aktivchlorträger zersetzen würde.The idea of using liquid detergents instead of powders in dishwashers was completely remote, since the widely used input devices, because of their design, are not suitable for liquid detergents and must continue to be feared. that a storage tank integrated in the machine heats up considerably with each rinsing process and the active chlorine carrier normally contained in the cleaner would decompose.

Der Erfindung liegt die Aufgabe zugrunde, einen in Geschirrspülmaschinen verwendbaren Reiniger zu entwickeln, der die geschilderten Nachteile nicht besitzt und sowohl in herkömmlichen Spülmaschinen eingeserzt werden kann als auch in noch zu entwickeinden Maschinen mit bevorratetem Reiniger brauchbar ist. In diesen Fällen würde dann also eine automatische Dosierung aus einer Reinigerbevorratung erfolgen.The object of the invention is to develop a cleaner which can be used in dishwashers and which does not have the disadvantages described and which can be used in conventional dishwashers and can also be used in machines to be developed with a stored cleaner. In these cases, automatic dosing from a detergent supply would then take place.

Gegenstand der Erfindung ist die Verwendung eines wäßrigen, im Ruhezustand bei Raumtemperatur pastösen, thixotropen Reinigers mit einem Gehalt an

  • (A) 3 bis 40 Gew.-% Natrium- und/oder Kaliumtripolyphosphat,
    • 5 bis 30 Gew.-% Natrium- und/oder Kaliumsilikaten, bestehend aus einem Gemisch von Metasilikaten und Disilikaten beziehungsweise Wasserglas im Mischungsverhältnis 2 : 1 bis 1 : 10, berechnet auf die wasserfreien Substanzen,
    • 0 bis 25 Gew.-% feinteiligem;_Calciumsalze bindenden Natriumalumosilikat und
    • 0 bis 20 Gew.-% Carbonat und/oder Hydroxid des Natriums und/oder Kaliums,
  • (B) einer Aktivchlorverbindung mit einem AktivchlQrgehalt, bezogen auf den gesamten Reiniger, von 0,1 bis 3,0 Gew.-% und
  • (C) 1 bis 10 Gew.-% eines quellfähigen Schichtsilikats mit hohem Verdickungsvermögen in wäßrigen Medien, dessen bei 20°C mittels eines Rotationsviskosimeters nach Brookfield bei 5 Spindelumdrehungen pro Minute bestimmte Viskosität, bezogen auf eine 5 gew.-%ige wäßrige,
  • vollständig gequollene Suspension, mindestens 30 Pa.s beträgt,
dessen bei 20°C mittels eines Rotationsviskosimeters bei 5 Spindelumdrehungen pro Minute bestimmte Viskosität 70 bis 200 Pa.s beträgt, zur Dosierung über die Einspülvorrichtung in Geschirrspülmaschinen.The invention relates to the use of an aqueous, at room temperature pasty, thixotropic cleaner with a content of
  • (A) 3 to 40% by weight sodium and / or potassium tripolyphosphate,
    • 5 to 30% by weight of sodium and / or potassium silicates, consisting of a mixture of metasilicates and disilicates or water glass in a mixing ratio of 2: 1 to 1:10, calculated on the anhydrous substances,
    • 0 to 25 wt .-% finely divided ; _Sodium aluminosilicate and calcium salts
    • 0 to 20% by weight carbonate and / or hydroxide of sodium and / or potassium,
  • (B) an active chlorine compound with a Aktivchl Q rgehalt, based on the total detergent, of 0.1 to 3.0 wt .-% and
  • (C) 1 to 10% by weight of a swellable sheet silicate with a high thickening capacity in aqueous media, the viscosity of which, at 20 ° C., using a Brookfield rotary viscometer at 5 spindle revolutions per minute, based on a 5% by weight aqueous,
  • completely swollen suspension, at least 30 Pa.s,
whose viscosity, determined at 20 ° C by means of a rotary viscometer at 5 spindle revolutions per minute, is 70 to 200 Pa.s for dosing via the induction device in dishwashers.

VorzugsweIse beträgt die unter den angegebenen Bedingungen bestimmte Viskosität des Reinigers 80 bis 150 Pa-s.The viscosity of the cleaner, determined under the specified conditions, is preferably 80 to 150 Pa-s.

Bei der Bestimmung der Viskosität ist zu beachten, daß die Thixotropie des Reinigers durch den Meßvorgang nicht wesentlich gestört wird. Bei einer Umdrehungsgeschwindigkeit der in die Probe eingeführten Spindel von 5 Upm treten derartige Störungen nicht auf. Geeignet ist beispielsweise ein Brookfield-Viskosimeter, jedoch können auch andere Meßmethoden zur Bestimmung herangezogen werden, die eine Messung unter vergleichbaren Bedingungen zulassen.When determining the viscosity, it should be noted that the thixotropy of the cleaner is not significantly disturbed by the measuring process. Such disturbances do not occur at a rotational speed of the spindle inserted into the sample of 5 rpm. A Brookfield viscometer, for example, is suitable, but other measurement methods can also be used for the determination, which allow measurement under comparable conditions.

Das rheologische Verhalten des Reinigers ist so bemessen, daß sich die gelartige Paste durch Einwirkung mechanischer Kräfte, beispielsweise durch Schütteln oder Druckeinwirkung auf eine verformbare Vorratsflasche bzw. Tube oder mittels einer Dosierpumpe verflüssigt und leicht aus einer Spritzdüse ausdrücken bzw. in die Einspülkammer überführen läßt. Sobald die mechanische Einwirkung beendet ist, erstarrt das Mittel wieder zu einem Gel, das bei geschlossener Klappe unverändert in der Einspülkammerverbleibt. So läßt sich erreichen, daß das Produkt einen oder zwei Vorspülgänge als Paste überdauert und damit erst im Reinigungsgang bestimmungsgemäß zur Verfügung steht. Sobald sich die Verschlußklappe geöffnet hat und das Mittel mit der bewegten Spüllauge in Berührung kommt, tritt eine augenblickliche Verflüssigung des Gels ein, und das Mittel verteilt sich in kurzer Zeit in der Spüllauge. Es steht dahervom Augenblick der Freigabe des Reinigers an dessen Reinigungskraft zur Verflügung, weshalb die Reinigungswirkung intensiver als beim herkömmlichen Spülprozeß ist.The rheological behavior of the cleaner is such that the gel-like paste is affected mechanical forces, for example by shaking or pressure on a deformable storage bottle or tube or liquefied by means of a metering pump and easily squeezed out of a spray nozzle or can be transferred into the induction chamber. As soon as the mechanical action has ended, the agent solidifies again into a gel which remains unchanged in the induction chamber when the flap is closed. It can thus be achieved that the product survives one or two pre-rinse cycles as a paste and is therefore only available as intended in the cleaning cycle. As soon as the closure flap has opened and the agent comes into contact with the moving detergent solution, the gel instantaneously liquefies and the agent distributes itself in the detergent solution in a short time. It is therefore available from the moment the cleaner is released to its cleaning power, which is why the cleaning effect is more intensive than in the conventional rinsing process.

Das in den erfindungsgemäß verwendeten Reinigern eingesetzte Tripolyphosphat kann ganz oder teilweise ersetzt sein durch wasserunlösliche, feinteilige, gebundenes Wasser enthaltende Alkalialumosilikate, die ein Calciumbindevermögen von 50 bis 200 mg CaO/g Aktivsubstanz (AS) aufweisen und der Formel

Figure imgb0001
vorzugsweise
Figure imgb0002
entsprechen. Derartige Verbindungen sind beispielsweise unter der Bezeichnung SASIL® bekannt. Das Calciumbindevermögen der Alumosilikate wird in folgender Weise bestimmt :The tripolyphosphate used in the cleaners used according to the invention can be completely or partially replaced by water-insoluble, finely divided, bound water-containing alkali alumosilicates which have a calcium binding capacity of 50 to 200 mg CaO / g active substance (AS) and the formula
Figure imgb0001
 preferably
Figure imgb0002
 correspond. Such connections are known for example under the name SASIL®. The calcium binding capacity of the aluminosilicates is determined in the following way:

1 I einerwäßrigen, 0,594 g CaCI (= 300 mg CaO/I = 30°C) enthaltenden und mit verdünnter NaOH auf einen pH-Wert von 10 eingestellten Lösung wird mit 1 g Aluminiumsilikat versetzt (auf AS bezogen). Dann wird die Suspension 15 Minuten lang bei einer Temperatur von 22 °C (=2 °C) kräftig gerührt. Nach Abfiltrieren des Aluminiumsilikates bestimmt man die Resthärte x des Filtrates. Daraus erreichnetsich das Calciumbindevermögen in mg CaO/g AS nach der Formel :

Figure imgb0003
1 g of an aqueous solution containing 0.594 g CaCI (= 300 mg CaO / I = 30 ° C) and adjusted to pH 10 with dilute NaOH is mixed with 1 g aluminum silicate (based on AS). Then the suspension is stirred vigorously for 15 minutes at a temperature of 22 ° C (= 2 ° C). After filtering off the aluminum silicate, the residual hardness x of the filtrate is determined. This results in the calcium binding capacity in mg CaO / g AS according to the formula:
Figure imgb0003

Bestimmt man das Calciumbindevermögen bei höheren Temperaturen, z. B. bei 60 °C, so findet man durchweg bessere Werte als bei 22 °C. Dieser Umstand zeichnet die Aluminiumsilikate gegenüber den meisten der bisherzurVerwendung als Phosphatersatz vorgeschlagenen löslichen Komplexbildnern aus und stellt bei ihrer Verwendung einen besonderen technischen Fortschritt dar.If one determines the calcium binding capacity at higher temperatures, e.g. B. at 60 ° C, you will find consistently better values than at 22 ° C. This fact distinguishes aluminum silicates from most of the soluble complexing agents previously proposed for use as a phosphate substitute and represents a particular technical advance in their use.

Fürgewerblich betriebene Geschirrspülmaschinen, ist ferner der Zusatz von Natriumhydroxid bzw. Kaliumhydroxid geeignet. Weniger bevorzugte Bestandteile der Komponente (A) sind die Carbonate bzw. Hydrogencarbonate des Natriums- oder Kaliums, die in der Regel nur zusammen mit stärker reinigend wirkenden Alkaliverbindungen eingsetzt werden.The addition of sodium hydroxide or potassium hydroxide is also suitable for commercial dishwashers. Less preferred constituents of component (A) are the carbonates or hydrogen carbonates of sodium or potassium, which are generally only used together with alkali compounds which have a more cleaning action.

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

Figure imgb0004
In a particularly preferred application form, component (A) has the following composition:
Figure imgb0004

Das Natrium- oder Kaliummetasilikat hat die Zusammensetzung Me2O : SiO2 =1 :1 und die Disilikate bzw. Wasserglas die Zusammensetzung Me2O : Si02 = 1 : 2 bis 1 : 3.5.The sodium or potassium metasilicate has the composition Me 2 O: SiO 2 = 1: 1 and the disilicates or water glass the composition Me 2 O: Si0 2 = 1: 2 to 1: 3.5.

Die Komponente (B) besteht vorzugsweise aus Natrium-, Kalium- oder Lithiumhypochlorit. Als weitere brauchbare Aktivchlorverbindungen kommen chloriertes Trinatium- oderTrikalium-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 Reinigem weniger lagerbeständig sind. Die Menge der Aktivchlorträger ist vorzugsweise so bemessen, daß die Reiniger 0,1 bis 3.0 Gew.-%, insbesondere 0.5 bis 2.0 Gew.-% an aktivem Chlor enthalten.Component (B) preferably consists of sodium, potassium or lithium hypochlorite. Other useful active chlorine compounds that can be used are chlorinated trinatium or tripotassium o-phosphate. 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 active chlorine carrier is 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.

Die Komponente (C) besteht aus einem gegen Alkalien und Aktivchlor beständigen Verdickungsmittel, das in Wasser ein thixotropes Gel zu bilden vermag. Als geeignet haben sich quellfähige Schichtsilikate vom Montmorillonit-Typ erwiesen, die in 5-gewichtsprozentigerwäßriger Suspension nach vollständiger Quellung mit einem üblichen Rotationsviskosimeter bei einer Drehzahl der Meßspindel von 5 Umdrehungen pro Minute eine Viskosität von mindestens 30 Pa-s (20 °C) aufweisen. Eine vollständige Quellung bedeutet, daß nach vollständiger Verteilung der Verdickungsmittels in Wasser, die zweckmäßigerweise unter Zuhilfenahme einer hochwirksamen Rührvorrichtung bei Temperaturen von 30-60 °C vorgenommen wird, nach mehrtägiger Alterung bzw. Standzeit bei Raumtemperatur auch bei weiterer thermischer bzw. mechanischer Behandlung die Viskosität nicht mehr zunimmt.Component (C) consists of a thickener resistant to alkalis and active chlorine, which is able to form a thixotropic gel in water. Swellable layered silicates of the montmorillonite type have proven to be suitable which, in 5% by weight aqueous suspension after complete swelling with a conventional rotary viscometer and a speed of the measuring spindle of 5 revolutions per minute, have a viscosity of at least 30 Pa-s (20 ° C.). Complete swelling means that after the thickeners have been completely distributed in water, which is expediently carried out with the aid of a highly effective stirring device at temperatures of 30-60 ° C., after several days of aging or standing at room temperature, the viscosity, even with further thermal or mechanical treatment no longer increases.

Als für die Komponente (C) besonders geeignet haben sich natürliche oder synthetische Schichtsilikate vom Hectorit-Typ erwiesen. Sowohl die aufbereiteten natürlichen als auch die synthetischen Hectorite können noch gewisse Verunreinigungen enthalten, die bei der erfindungsgemäßen Verwendung per 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 vermindet. Wird synthetischer Hectorit eingesetzt, braucht dieser vor der Herstellung des Reinigers auch nichfentwässert 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 erfinaüngsgemäß zu verwendenden Reinigem weiterverarbeitet werden.Natural or synthetic phyllosilicates have proven particularly suitable for component (C) proven of the hectorite type. Both the processed natural and the synthetic hectorites can still contain certain impurities which do not interfere with the use according to the invention by means. 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 manufactured, but can be processed further after centrifuging or filtration as an aqueous slurry or moist filter cake without further pretreatment to give the cleaners to be used according to the invention.

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

Figure imgb0005
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 allgemeinen 5 bis 10 Gew.-%.Hectorites are generally understood to mean trioctahedral layered magnesium silicates of the general formula
Figure imgb0005
 where 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 is preferably sodium, the value n = 1. The water content of an air-dry product is generally 5 to 10% by weight.

Die Synthese der Hectorite ist beispielsweise aus der Zeitschrift « Clay and Clay Minerals », Vol. 8. (1960), Seiten 150-169 bzw. der DE-PS 11 84 742 bekannt.The synthesis of hectorites is known, for example, from the magazine “Clay and Clay Minerals”, vol. 8 (1960), pages 150-169 and DE-PS 11 84 742.

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 Schichtsjlikats 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 jiculate to be used depends primarily on its ability to swell. In the case of hectorite, generally 1 to 10% by weight, preferably 2 to 6% by weight (based on hectorite dried at 105 ° C.) are used.

Als fakultative Bestandteile kommen nichtionische Tenside mit geringem Schäumvermögen zum Einsatz, die sich in Gegenwart von Aktivchlorverbindungen und ggf. Alkalihydroxiden nicht zersetzen. Es handelt sich vorzugsweise um Ethylenoxidaddukte an höhermolekulare Polypropylenglycole der Molgewichte 900 bis 4 000 sowie Addukte von Ethylenoxid bzw. Ethylenoxid und Propylenoxid an höhere Fettalkohole wie Dodecylalkohol, Palmitylalkohol, Stearylalkohol, Oleylalkohol oder deren Gemische sowie synthetische, beispielsweise durch Oxosynthese hergestellte Alkohole der Kettenlängen C12-C18 und entsprechende Alkylenoxidaddukte an Alkylphenole, vorzugsweise Nonylphenol in Betracht. Beispiele für geeignete Anlagerungsprodukte sind das Addukt von 10 bis 30 Gew.-% Ethylenokid an ein Polypropylenglycol des Molgewichtes 1750, das Addukt von 20 Mol Ethylenoxid bzw. von 9 Mol Ettiylenoxid und 10 Mol Propylenoxid an Nonylphenol, das Addukt von 5 bis 12 Mol Ethylenoxid an ein Fettalköhölgemisch der Kettenlängen C12-C18 mit einem Anteil an etwa 30 % an Oleylalkohol und ähnliche. Diese beispielhafte Aufzählung stellt keine Beschränkung dar. Der Anteil der nichtlonischen Tenside kann bis 5 Gew.-%, vorzugsweise 0,1 bis 1 Gew.-% betragen.Optional non-ionic surfactants with low foaming power are used as optional components, which do not decompose in the presence of active chlorine compounds and possibly alkali metal hydroxides. There are preferably ethylene oxide adducts of higher molecular weight polypropylene glycols of molecular weights of 900-4000, as well as adducts of ethylene oxide or ethylene oxide and propylene oxide with higher fatty alcohols such as dodecyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol or mixtures thereof as well as synthetic, produced for example by oxo process alcohols of chain length C 12 -C 18 and corresponding alkylene oxide adducts with alkylphenols, preferably nonylphenol. Examples of suitable addition products are the adduct of 10 to 30% by weight of ethyleneokide with a polypropylene glycol with a molecular weight of 1750, the adduct of 20 mol of ethylene oxide or 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, the adduct of 5 to 12 mol of ethylene oxide to a fatty alcohol mixture of chain lengths C 12 -C 18 with a share of about 30% in oleyl alcohol and the like. This list by way of example does not represent any restriction. The proportion of the non-ionic surfactants can be up to 5% by weight, preferably 0.1 to 1% by weight.

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

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

Weitere einsetzpare Komplexbildner sind gegen Aktivchlor beständige, in der Regel stichstofffreie Komplexbildner, z. B. mehrwertige Phosphonsäuren, wie Methylendiphosphonsäure bzw. mehrwertige Phospho- nocarbonsäuren, wie 1.1-Diphosphonopropan-1,2-dicarbonsäure, 1-Phosphonopropan-1.2,3-tri-carbonsäure oder 2-Phosphonobutan-2.3,4-tricarbonsäure bzw. deren Natrium- oder Kaliumsalze, Zusätzlich brauchbare Komplexbildner sind auch die aktivchlorbeständigen Polycarbonsäuren und deren Salze.Other usable complexing agents are active chlorine-resistant, generally non-pollutant-free complexing agents, e.g. B. polyvalent phosphonic acids such as methylenediphosphonic acid or polyhydric P h ospho- include aminocarboxylic as 1.1 diphosphonopropane-1,2-dicarboxylic acid, 1-phosphonopropane-1.2,3-tricarboxylic acid or 2-phosphonobutane-2.3,4-tricarboxylic acid or their sodium or potassium salts. In addition, useful complexing agents are the active chlorine-resistant polycarboxylic acids and their salts.

Die Herstellung der erfindungsgemäß zu verwendenden Reiniger erfolgtvorteilhaft in der Weise, daß man eine wäßrige Lösung bzw. Aufschlämmung, enthaltend die reinigend wirkenden Bestandteile der Komponenten (A), insbesondere das Tripolyphosphat und ggf. das Alkalisilikat (Wasserglas), oder einen Tell derselben zusammen mit dem Verdickungsmittel unter Erwärmen auf 40 bis 65 °C mit einem hohe Scherkräfte ausübenden Rührwerk, beispielsweise einem Ultra-Turrax®-Gerät, bis zur erfolgen Verdickung verrührt Anschließend können die restlichen, in fester oder gelöster Form vorliegenden Bestandteile der Komponente (A), z. B. Metasilikat, Wasserglas und ggf. der Reste des Triphosphats sowie die fakultativen Bestandteile, wie nichtionische Tenside und Farbstoffe, eingerührt werden. Nach dem Abkühlen auf Raumtemperatur erfolgt abschließend die Zugabe der Aktivchlorverbindung, beispielsweise in Form einer Natriumhypochloritlösung (Chlorbleichlauge).The cleaning agents to be used according to the invention are advantageously prepared by mixing an aqueous solution or slurry containing the cleaning constituents of components (A), in particular the tripolyphosphate and, if appropriate, the alkali silicate (water glass), or a mixture thereof the thickener with heating to 40 to 65 ° C with a high shear agitator, for example an Ultra-Turrax® device, stirred until the thickening takes place. Then the remaining components of component (A), e.g. . B. metasilicate, water glass and possibly the residues of triphosphate and the optional components, such as nonionic surfactants and dyes, are stirred in. After cooling to room temperature, the active chlorine compound is finally added, for example in the form of a sodium hypochlorite solution (chlorine bleach).

Die Mittel können unmittelbar nach ihrer HerstelJung in die Vorratsbehälter abgefüllt werden. Der Maximalwert der Viskosität ist im allgemeinen nach einer Standzeit von 2 bis 10 Tagen erreicht. Durch kräftiges Schütteln oder Anpressen tritt eine kurzzeitige Verflüssigung ein, jedoch stellt sich der Gelzustand bereits wenige Sekunden nach Beendigung der mechanischen Beanspruchung wieder ein, d. h. der in die Vorratskammer der Spülmaschine eingebrachte Reiniger erstarrt hinreichend schnell, so daß er nach Schließen der Verschlußlkappe der Vorratskammer bzw. der Beschickungstür der Spülmaschine nicht ausfließt.The funds can be filled into the storage containers immediately after they have been produced. The maximum value of the viscosity is generally reached after a standing time of 2 to 10 days. A brief liquefaction occurs through vigorous shaking or pressing, however, the gel state is restored just a few seconds after the mechanical stress has ended, i. H. the cleaner introduced into the storage chamber of the dishwasher solidifies sufficiently quickly that it does not flow out after the closure cap of the storage chamber or the loading door of the dishwasher is closed.

Die erfindungsgemäß zu verwendenden Reiniger zeichnen sich durch eine hohe Reinigungskraft und insbesondere durch hohe Lagerbeständigkeit aus. Der Aktivchlorverlust während einer 6 monatigen Standzeit bei 25 °C lag in der gleichen Größenordnung wie der bei trocken gelagerten handelsüblichen Reiniger-Granulaten. Überraschenderweise erwies sich auch ein wiederholtes Erwärmen des Reinigers auf Temperaturen um 60 °C als nicht nachteilig auf die Lagerbeständigkeit bzw. den Aktivchlorgehalt. Dies zeigte sich bei einer Versuchsanordnung, bei der ein für 10 Spülgänge ausreichender Vorratsbehälter mit angeschlossener Dosierpumpe in die Beschickungstür einer handelsüblichen Spülmaschine eingebaut und das Zudosieren des Reinigers über eine Programmsteuerung vorgenommen wurde. Die durch Wärmeübergang wiederholt angewärmte Reinigerpaste erlitt innerhalb des Versuchszeitraums von 5 Tagen (2 Spülgänge pro Tag) keinen das Spülergebnis beeinträchtigenden Aktivchlorverlust.The cleaners to be used according to the invention are distinguished by a high cleaning power and in particular by a long shelf life. The active chlorine loss during a 6-month service life at 25 ° C was of the same order of magnitude as that of commercially available detergent granules stored in a dry place. Surprisingly, repeated heating of the cleaner to temperatures of around 60 ° C. has not proven to be disadvantageous to the storage stability or the active chlorine content. This was shown in a test arrangement in which a storage container for 10 rinsing cycles with a connected metering pump was installed in the loading door of a standard dishwasher and the detergent was added using a program control. The detergent paste, which was repeatedly warmed up by heat transfer, did not suffer any loss of active chlorine which would have an adverse effect on the wash result within the test period of 5 days (2 rinse cycles per day).

Bei der Beobachtung des Einspülverhaltens durch Leitfähigkeitsmessungen wurde festgestellt, daß der Reiniger innerhalb von 1 bis 4 Minuten nach Öffnen der Vorratskammer vollständig ausgespült und innerhalb von 2 bis 5 Minuten vollständig gelöst bzw. suspendiert war. Bei pulverförmigen bzw. granulierten Reinigem nimmt dieser Vorgang in der Regel 7 bis 15 Minuten, in ungünstigen Fällen bis zu 20 Minuten in Anspruch.When observing the induction behavior by conductivity measurements, it was found that the cleaner was completely rinsed out within 1 to 4 minutes after opening the storage chamber and completely dissolved or suspended within 2 to 5 minutes. In the case of powdered or granulated cleaners, this process usually takes 7 to 15 minutes, in unfavorable cases up to 20 minutes.

Als besondererVorteil istweiterhin anzusehen, daß die Mittel sich wesentlich einfacher und genauer dosieren lassen als übliche körnige bzw. pulverförmige Reiniger, die beim Einfüllen in die räumlich begrenzten Einspülkammern wegen des meist notwendigen Rüttelns derVorratspakkung bzw. des Dosierbechers häufig zum Teil verschüttet werden. Die Gefahr, daß durch verschütteten Reiniger die Funktion des Öffnungsmechanismusses beeinträchtigt wird, insbesondere bei Kammern mit Magnetverschluß der Kontakt nicht ausreichend fest ist, so daß die Klappe vorzeitig aufspringt, ist bei Verwendung der erfindungsgemäßen Mittel nicht gegeben.Another particular advantage is that the agents can be dosed much more easily and precisely than conventional granular or powdered cleaners, which are often spilled when filling the spatially limited induction compartments due to the mostly necessary shaking of the supply package or the dosing cup. The risk that the function of the opening mechanism is impaired by spilled cleaner, in particular in the case of chambers with a magnetic lock, the contact is not sufficiently firm, so that the flap opens prematurely, when using the agents according to the invention.

Es waren aus der GB-PS 1 237 199 zwar pastöse Bleichmittel bekannt, die zwei verschiedenartige Tone, darunter Hectorit, als Verdickungsmittel sowie Aktivchlorverbindungen enthalten, wobei die Mittel bei der Anwendung auf das zu bleichende Gut aufgetragen werden und aufgrund ihrer Geistruktur längere Zeit auf der Kontaktstelle verbleiben und daher besonders nachhaltig wirken. Dieser Patentschrift war jedoch nicht zu entnehmen, daß Mittel, wie sie in dervorstehenden Erfindung beschrieben sind, sich als Reiniger in Geschirrspülmaschinen eignen würden. Weiterhin sind in den US-A-4 051 055 und 4 051 056 sowie den DE-A-25 39 733 und 27 39 776 pastöse Scheuermittel beschrieben, die anionische, nicthionische, zwitterrionische oder ampholytische, d. h. in der Mehrzahl schaumaktive Tenside, ferner aktivchlorhaltige Bleichmittel, tonartige Füllmittel, darunter auch Hectorit, sowie als Hauptbestandteil eine spezielle Abrasivkomponente enthalten. Das Verdickungsmittel dient vor allem dazu, das Absetzen des spezifisch leichten Abrasivmittels zu verhindern. Der Gedanke, schaumarme, von Abrasivstoffen freie Reiniger anstelle üblicher pulverförmiger bzw. granulierter Produkte in Geschirrspülmaschinen einzusetzen, ist diesen Veröffentlichungen völlig fremd, zumal auch die Aufgabenstellung eine gänzlich andere ist.From GB-PS 1 237 199 pasty bleaching agents were known, which contain two different types of clays, including hectorite, as a thickening agent and active chlorine compounds, the agents being applied to the material to be bleached during use and, due to their ghost structure, for a long time on the Contact point remain and therefore have a particularly sustainable effect. However, it was not apparent from this patent that agents as described in the present invention would be useful as detergents in dishwashers. Furthermore, in US-A-4 051 055 and 4 051 056 and DE-A-25 39 733 and 27 39 776 pasty abrasives are described, the anionic, nicthionic, zwitterrionic or ampholytic, i.e. H. the majority contain foam-active surfactants, bleaches containing active chlorine, clay-like fillers, including hectorite, and a special abrasive component as the main component. The thickener primarily serves to prevent the specific light abrasive from settling. The idea of using low-foaming, abrasive-free cleaning agents instead of conventional powdered or granulated products in dishwashers is completely foreign to these publications, especially since the task is also completely different.

Aus der DE-A-28 10 187 sind alkalische Mittel und ein Verfahren zum Vorbehandeln stark verschmutzter Küchengeräte bekannt, die frei von Schleifmitteln sind, etwa 0,25 bis etwa 20 % eines Tons als Verdickungsmittel und etwa 0,5 bis etwa 9 % eines Alkalimetallsilikats mit einem Verhältnis von SiO2 : M20 von mehr als etwa 1 mit M gleich Natrium oder Kalium enthalten, die eine Hypohalogenitkonzentration mit einem Aktivchlorgehalt von etwa 0,5 bis 10 % aufweisen und deren Viskosität etwa 1 bis etwa 10 000 Pa-s beträgt und die auf Küchengeräte mit schwer entfernbarem Schmutz aufgebracht werden. Danach wird alles mit einem Überschuß an Wasser mit einer Temperatur von mehr als etwa 38 °C bedeckt Die Viskosität der vorzugsweise thixotropen Mittel ist tendenziell erheblich höher als bei den Mitteln der vorliegenden Erfindung, da sie ja gut und lange an den verschmutzten Oberflächen haften sollen, um dort einwirken zu können, während die Konsistenz der erfindungsgemäßen Reiniger nur deren Dosierfähigkeit gewährleisten soll. Im übrigen sollen sie sich schnell im Reinigungsgang von Geschirrspülmaschinen lösen. Natürlich kann man auch die nach der DE-A-28 10 187 vorgereinigten Geräte anschließend in Geschirrspülmaschinen einbringen. Deren verbrauchte Beschichtung soll zwar eine Schaumunterdrückung bewirken, wirkt dann aber auch wegen eines Mangels an Tripolyphosphaten nicht mehr reinigend.DE-A-28 10 187 discloses alkaline agents and a process for pretreating heavily soiled kitchen appliances which are free of abrasives, about 0.25 to about 20% of a clay as a thickener and about 0.5 to about 9% of one Contain alkali metal silicate with a ratio of SiO 2 : M 2 0 of more than about 1 with M equal to sodium or potassium, which have a hypohalite concentration with an active chlorine content of about 0.5 to 10% and whose viscosity is about 1 to about 10,000 Pa- s and are applied to kitchen appliances with dirt that is difficult to remove. Then everything is covered with an excess of water at a temperature of more than about 38 ° C. The viscosity of the preferably thixotropic agents tends to be considerably higher than with the agents of the present invention, since they should adhere well and long to the soiled surfaces, in order to be able to act there, while the consistency of the cleaners according to the invention is only intended to ensure their meterability. In addition, they should be released quickly in the dishwasher cleaning cycle. Of course, the devices pre-cleaned according to DE-A-28 10 187 can subsequently be introduced into dishwashers. Their used coating is supposed to suppress foam, but then no longer has a cleaning effect due to a lack of tripolyphosphates.

BeispieleExamples

Als Verdickungsmittel wurden zwei verschiedene. Lithium und Fluor enthaltende Schichtsilikate vom Hectorit-Typ verwenden. Bei dem im Folgenden mit « Hectorit 1 » bezeichneten Produkt handelt es sich um ein Handelsprodukt der Fa. Lanco. bei dem mit Hectorit II » bezeichneten um das Handelsprodukt Laponite B@ der Fa. Laporte ind. Ltd. Der Wassergehalt der Produkte (Trockenverlust bei 105 °C) lag bei 7-8 Gew.-% die Korngröße (Siebanalyse) unter 0.2 mm bei einer mittleren Korngröße von ca. 0.006-0.008 mm. Die mit einem Rotationsviskosimeter nach Brookfield bei einer Spindeldrehzahl von 5 UpM (20 °C) bestimmte Viskosität eines 5 gewichtsprozentigen wäßrigen Gels betrug 75 Pa.s bel Hectorit 1 bzw. 95 Pa.s bei Hectorit II.Two different thickeners were used. Use layered silicates of the hectorite type containing lithium and fluorine. The product referred to below as “hectorite 1” is a commercial product from Lanco. in the case of the commercial product Laponite B @ from Laporte ind. Ltd. The water content of the products (loss on drying at 105 ° C) was 7-8% by weight, the grain size (sieve analysis) was less than 0.2 mm with an average grain size of approx. 0.006-0.008 mm. 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 75 Pa.s for hectorite 1 and 95 Pa.s for hectorite II.

Das Reinigungsvermögen der in den folgenden Beispielen aufgeführten pastenförmigen Reiniger wurde im sogenannten Normalprogramm einer marktüblichen Haushaltsgeschirrspülmaschine (Miele G 5.03®) geprüft.The cleaning power of the paste-like cleaners listed in the following examples was tested in the so-called normal program of a standard household dishwasher (Miele G 5.03®).

Zur Prüfung der Reinigungsergebnisse wurden Glasschalen mit unter definierten Bedingungen bei 300 °C angebrannten Speiserückstanden von Milch, Schokoladenpudding und Hackfleisch, ferner Teller mit eingetrockneten Rückständen von Haferbrei und Stärke sowie Tassen mit eingetrockneten Tee-Rückständen (entsprechend der Veröffentlichung « Prüfung von Reinigern und Klarspülem für das maschinelle Geschirrspülen » in Seiten-Öle-Fette-Wachse, 98(1972), Seiten 763-766 und 801-806) in der Haushaltsgeschirrspülmaschine mit 3 g Reiniger pro Liter Spüllauge (bezogen auf im Reiniger enthaltene Reinigungssubstanz) in üblicherweise gespült, wobei ein Nachspülen mit saurem Klarspüler unterblieb. Die Anschmutzungen sind so gewählt, daß eine Entfernung auch mit sonstigen üblichen Reinigern, die eine hohe Reinigungskraft besitzen, nur teilweise möglich ist, um auch bei diesen hochleistungsfähigen Produkten noch Differenzierungsmöglichkeiten zu haben. Die Bewertung erfolgt nach einem Punkt-system, das von 0-10 reicht, wobei 0 Punkte « ohne erkennbare Reinigungswirkung und 10 Punkte « restlose Beseitigung der Testanschmutzungen » bedeuten.To test the cleaning results, glass dishes with food residues of milk, chocolate pudding and minced meat burned under defined conditions at 300 ° C, plates with dried residues of oatmeal and starch as well as cups with dried tea residues (according to the publication «Testing detergents and rinse aid for machine dishwashing »in Seiten-Öle-Fette-Wwachs, 98 (1972), pages 763-766 and 801-806) in the household dishwasher with 3 g of detergent per liter of detergent solution (based on the cleaning substance contained in the detergent) in the usual way, whereby there was no rinsing with acidic rinse aid. The soiling is selected so that removal with other conventional cleaners which have a high cleaning power is only partially possible in order to still have differentiation options even with these high-performance products. The evaluation is carried out according to a point system that ranges from 0-10, with 0 points meaning “without a recognizable cleaning effect and 10 points meaning“ complete removal of the test soiling ”.

Der zum Vergleich eingeseizte handelsübliche körnige Reiniger weist die folgende Zusammensetzung auf :

Figure imgb0006
The commercial granular cleaner used for comparison has the following composition:
Figure imgb0006

Zur Ermittlung der Aktivchlorverluste wurden Lagerversuche bei ca. 25 °C und 80 % relativer Luftfeuchte über 6 Monate durchgeführt, wobei die Pasten und die körnigen Vergleichsproben in braunen Glasflaschen gelagert wurden.To determine the active chlorine losses, storage tests were carried out at approx. 25 ° C and 80% relative air humidity for 6 months, the pastes and the granular comparative samples being stored in brown glass bottles.

Die Ergebnisse sind in der Tabelle zu Beispiel 7 zusammengestellt.The results are summarized in the table for Example 7.

Beispiel 1example 1

Ein pastenförmiger Reiniger, enthaltend (in Gew.-%)

Figure imgb0007
wurde hergestellt, indem die auf 55 °C erwärmte 50 %ige Triphosphatlösung unter Zusatz des Hectorits bis zur erfolgten Verdickung mit einem Intensivrührer (Ultra-Turrax® gerührt wurde, Anschließend wurden 2 Gew.- % Natriummetasilikat als staubförmiges Pulver eingerührt. Nach Zugabe des Disilikats in Form einer 54.5- gewichtsprozentigen Lösung wurde die Paste abgekühlt und das Natriumhypochlorit in Form einer NaCl-haltigen Chlorbleichlauge (Aktivchlorgehalt 13 %) sowie der Rest des Natriummetasilikats eingearbeitet.A pasty cleaner containing (in% by weight)
Figure imgb0007
 was produced by stirring the 50% triphosphate solution heated to 55 ° C. with the addition of the hectorite until it had thickened with an intensive stirrer (Ultra-Turrax®). Then 2% by weight sodium metasilicate was stirred in as a powdery powder. After the disilicate had been added in the form of a 54.5% by weight solution, the paste was cooled and the sodium hypochlorite in the form of a NaCl-containing chlorine bleach (active chlorine content 13%) and the rest of the sodium metasilicate were incorporated.

Die nach einer Standzeit von 10 Tagen unter den angegebenen Bedingungen gemessene Viskosität betrug 125 Pa.s.The viscosity measured after a standing time of 10 days under the specified conditions was 125 Pa.s.

Beispiel 2Example 2

Beispiel 1 wurde wiederholt, wobei jedoch trockenes Kaliumtripolyphosphat in eine wäßrige, aus filterfeuchtem Hectorit 1 hergestellte Anquellung bei insgesamt unveränderter Wassermenge eingerührt wurde. Die Weiterverarbeitung erfolgte wie in Beispiel 1 angegeben. Die unter den angegebenen Bedingungen ermittelte Viskosität der Paste betrug 115 Pa.s.Example 1 was repeated, except that dry potassium tripolyphosphate was stirred into an aqueous swelling made from filter-moist hectorite 1 with an unchanged amount of water. The further processing was carried out as indicated in Example 1. The viscosity of the paste determined under the specified conditions was 115 Pa.s.

Beispiel 3Example 3

Wie vorstehend beschrieben, wurden

Figure imgb0008
Figure imgb0009
durch Verrühren einer mit dem Hectorit versetzten 50 %igen Triphosphat-Lösung bei 60 °C. Zufügen von feinpulvrigem Metasilikat, feinpulvrigem Wasserglas und in 54.5 %iger Losung vorliegendem Natriumdisilikat. Abkühlen und Einarbeiten der Chlorbleichlauge (Aktivchlorgehalt 13 %) zu einer Paste verarbeitet. die nach 10tägigem Stehen bei Raumtemperatur eine Viskosität von 105 Pa.s aufwies.As described above,
Figure imgb0008
Figure imgb0009
 by stirring a 50% triphosphate solution mixed with the hectorite at 60 ° C. Add finely powdered metasilicate, finely powdered water glass and sodium disilicate in 54.5% solution. Cooling and incorporation of the chlorine bleach (active chlorine content 13%) processed into a paste. which had a viscosity of 105 Pa.s after standing for 10 days at room temperature.

Beispiel 4Example 4

Beispiel 3 wurde unter Verwendung des mit « Hectorit I » bezeichneten Verdickungsmittels wiederholt. Die Viskosität des Mittels betrug 103 Pa·s.Example 3 was repeated using the thickener labeled "Hectorite I". The viscosity of the agent was 103 Pa · s.

Beispiel 5Example 5

Der Reiniger der nachstehenden Zusammensetzung wurde hergestellt, indem die Bestandteile in derangegebenen Reihenfolge bei 55° mittels Intensivrührer vermischt wurden. Die Chlorbleichlauge wurde nach dem Abkühlen der Paste eingearbeitet.

Figure imgb0010
The cleaner of the following composition was prepared by mixing the ingredients in the order given at 55 ° with an intensive stirrer. The chlorine bleach was incorporated after the paste cooled.
Figure imgb0010

Die definitionsgemäß nach 10tägiger Standzeit bestimmte Viskosität betrug 98 Pa.s.The viscosity determined by definition after 10 days of standing was 98 Pa.s.

Beispiel 6Example 6

In der aufgeführten Reihenfolge wurden folgende Bestandteile gemischt :

Figure imgb0011
The following ingredients were mixed in the order listed:
Figure imgb0011

Die Chlorbleichlauge wurde nach Abkühlen der auf 60°C erwärmten Mischung zugesetzt. Die Viskositäf betrug 120 Pa·s nach 10tägiger Standzeit.The chlorine bleach was added after the mixture had been heated to 60 ° C. The viscosity was 120 Pa · s after standing for 10 days.

Beispiel 7Example 7

Beispiel 6 wurde wiederholt, wobei vor Zugabe der Chlorbleichlauge zusätzlich 0.3 % eines nichtionischen nichtschäumenden Tensids aus der Klasse der Polypropylenoxid-Polyethylenoxid-Block-polymeren zugesetzi wurde. Die Viskosität der Paste betrug nach 10tägiger Standzeit 118 Pa.s.Example 6 was repeated except that prior to addition of chlorine bleaching liquor in addition 0.3% polymeric polypropylene oxide polyethylene oxide block of a nonionic non-foaming surfactant from the class of releasing was added i. The viscosity of the paste after 118 days of standing was 118 Pa.s.

Die Versuchsergebnisse über das Reinigungsvermögen und die Chlorbeständigkeit sind in der folgender Tabelle zusammengestellt (Dosierung 4.5 g/l pastöser Reiniger und 3.0 g/l pulverförmiger Vergleichsreiniger) (Siehe Tabelle Seite 8 f.)

Figure imgb0012
The test results on the cleaning ability and chlorine resistance are summarized in the following table (dosage 4.5 g / l pasty cleaner and 3.0 g / l powdered comparative cleaner) (See table on page 8 f.)
Figure imgb0012

Die Ergebnisse der Spülversuche bei den pastösen Reinigern sind im Vergleich mit den bekannten granulierten Reinigern teils gleichwertig, teils deutlich besser. Die nach den Angaben in Beispiel 1 bestimmte Chlorbeständigkeit liegt ebenfalls in der gleichen Größenordnung.The results of the rinsing tests with the pasty cleaners are, in comparison to the known granulated cleaners, partly equivalent, partly significantly better. The chlorine resistance determined according to the information in Example 1 is also of the same order of magnitude.

Claims (7)

1. The use of an aqueous detergent which is paste-like and thixotropic when standing at room temperature, containing
(A) 3 to 40% by weight sodium and/or potassium tripolyphosphate,
5 to 30% by weight sodium and/or potassium silicates consisting of a mixture of metasilicates and disilicates or waterglass in a mixing ratio of 2:1 to 1:10, based on the anhydrous substances,
0 to 25% by weight finely divided sodium alumosilicate binding calcium salts and
0 to 20% by weight carbonate and/or hydroxide of sodium and/or potassium,
(B) an active chlorine compound containing 0.1 to 3.0% by weight active chlorine, based on the detergent as a whole and
(C) 1 to 10% by weight of a swellable layer silicate having high thickening power in aqueous media of which the viscosity, as determined at 20°C using a Brookfield rotational viscosimeter at 5 spindle revolutions per minute, based on a 5% by weight aqueous, fully swollen suspension, is at least 30 Pa.s,
and of which the viscosity, as determined at 20°C using a rotational viscosimeter at 5 spindle revolutions per minute, is 70 to 200 Pa.s,
for dispensing via the dispensing compartment in dishwashing machines.
2. The use of a detergent as claimed in claim 1, of which the viscosity is from 80 to 150 Pa.s.
3. The use of a detergent as claimed in claims 1 and 2, in which component (A) consists of the following components: 5 to 30% by weight sodium and/or potassium tripolyphosphate, 5 to 30% by weight sodium and/or potassium silicate in the form of a mixture of metasilicates and disilicates or waterglass in a mixing ratio of 2:1 to 1:10 and preferably 1:1 to 1:5, based on the anhydrous substances, 0 to 10% by weight sodium alumosilicate, 0 to 5% by weight sodium and/or potassium hydroxide.
4. The use of a detergent as claimed in claims 1 to 3, in which component (B) consists of an alkali metal hypochlorite.
5. The use of a detergent as claimed in claims 1 to 4, in which component (B) consists of sodium hypochlorite and the active chlorine content of the detergent as a whole is from 0.5 to 2.0% by weight.
6. The use of a detergent as claimed in claims 1 to 5, in which component (C) consists of hectorite.
7. The use of a detergent as claimed in claims 1 to 6, in which the quantity of component (C) is from 2 to 6% by weight.
EP82108636A 1981-09-26 1982-09-18 Application of a pasty cleaning agent in dish washers Expired - Lifetime EP0075813B2 (en)

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DE19813138425 DE3138425A1 (en) 1981-09-26 1981-09-26 "USE OF A PASTOESE CLEANER IN DISHWASHER"
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US4801396A (en) 1989-01-31
DE3138425A1 (en) 1983-04-14
ATE25108T1 (en) 1987-02-15
DE3275205D1 (en) 1987-02-26

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