EP0711826B1 - Dimensionally stable dish cleaner - Google Patents

Dimensionally stable dish cleaner Download PDF

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Publication number
EP0711826B1
EP0711826B1 EP95117602A EP95117602A EP0711826B1 EP 0711826 B1 EP0711826 B1 EP 0711826B1 EP 95117602 A EP95117602 A EP 95117602A EP 95117602 A EP95117602 A EP 95117602A EP 0711826 B1 EP0711826 B1 EP 0711826B1
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EP
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Prior art keywords
parts
weight
alkali
mixture
water
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EP95117602A
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German (de)
French (fr)
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EP0711826A3 (en
EP0711826A2 (en
Inventor
Jörg Schmidtke
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SCHMIDTKE IDEAL-CHEMIE GMBH
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Schmidtke Ideal-Chemie GmbH
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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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/78—Neutral esters of acids of phosphorus
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites

Definitions

  • the present invention relates to methods of manufacture of dimensionally stable dishwashing detergents that follow the procedure manufactured cleaning agents and their use for Cleaning dishes in automatic dishwashers, especially those with dosing devices.
  • alkali silicate, Alkali hydroxide, alkali nitrate phosphate and an active chlorine splitting Combination with water to form a pourable, homogeneous mass stirred see EP-A-203 526
  • the pourable mass can also be free from alkali hydroxides (see US-A-4 690 770); or alkali silicate, alkali hydroxide, Alkaline triphosphate and an organic complexing agent together melted at about 60 ° C (see. DE-A-3 519 353).
  • melt block-shaped Detergents A disadvantage of the known melt block-shaped Detergents that they because of their poor solubility and because of their different transfer amounts only with special Dosing systems can be used. This redeems itself Melting block slowly in the time available and can thus be completed over a longer period of time Consumption can be used in the dosing device.
  • the slow dissolution of the melting block is at the dosage of the Detergents, for example in commercial Dishwashers wanted so that the cleaner is not for each rinse must be added in portions.
  • manufacture of such a melting block occurs Problems in that the melting block when cooling becomes cracked or if necessary an uneven distribution the detergent components in the block and consequently a uniform concentration in the soapy water is not guaranteed.
  • EP-0 297 273 describes a process for the production of dimensionally stable cleaning agents have been proposed, the resulting cleaning agents have a low density and which should easily disintegrate when in contact with water.
  • the Solution according to EP-0 297 273 is that one Partial phosphoric acid with water in a weight ratio of (1: 2) to (1:80), preferably from (1: 3.5) to (1:72), with intensive stirring foamed that the other Components with stirring and / or kneading into the foam incorporated that the resulting mixture into moldings processed and that the moldings 0.5 to 15 hours can set.
  • the object of the invention is to keep its shape Detergents that differ from the state of the art Formulations known through good technology Solubility rate in the flushed water and the Soapy water combined with long durability and usability in the dosing device as well as a good shelf life without Loss of external form and excellent Characterize detergent properties, for use in especially commercial dishwashers and a To provide processes for their preparation.
  • a dimensionally stable cleaning agent with excellent properties in terms of shape stability and resolving power for the Use especially in commercial dishwashers is accessible by using a phosphoric acid partial ester in alkaline solution in the presence of silicates and Alkali hydroxide with the addition of gas-releasing agents intensive stirring foamed and with stirring and / or kneading further detergent components in powder form in the Foam incorporated.
  • the present invention is therefore directed to a Process for the production of cleaning agents in Foam block shape, at least consisting of 50 to 400 Parts by weight of alkali silicates, 50 to 400 parts by weight Alkali hydroxides, alkali carbonates or - hydrogen carbonates, 10 to 400 parts by weight Alkali phosphates, 1 to 10 parts by weight Phosphoric acid partial esters and up to 150 parts by weight of water and, if appropriate, others usually in cleaning agents contained ingredients, in which one Phosphoric acid partial esters with an aqueous solution of Alkali silicate and alkali hydroxide stirred and with the addition of Alkali hydrogen carbonate and alkali phosphate and the rest Components in powder form with stirring and / or kneading foamed, the foamy mixture processed into moldings and let set.
  • the alkaline aqueous solution Add the powdered components of the water content withdrawn, and the entire mixture solidifies with solidification to the desired foam block.
  • the main cause of the alkalinity of the cleaner Components of alkali silicates, alkali carbonates and - Hydrogen carbonates and alkali hydroxides partly in aqueous Solution and partially used in powder form.
  • the others used usually in Detergents contained ingredients such as Thickeners, complexing agents, surfactants usually in added in an amount of up to 150 parts by weight.
  • foam block-shaped Detergent accessible which is characterized by excellent Solution properties for use in dosing devices in distinguish commercial dishwashers.
  • Foam formation presumably through decomposition of the gas-releasing By means of foam blocks with sufficient Porosity, so that compared to the melt block-shaped Detergents an increase in surface area and thus a Enlargement of the attack surface for the rinse water results.
  • the foam block produced in this way has Contrary to those produced according to EP-0 297 273 Clean up enough strength to use in the dosing devices already mentioned via a longer period without loss of shape stability enable.
  • the sum is Parts by weight of the components used preferably 1000 Parts by weight.
  • Process will be 1 to 10 parts by weight Phosphoric acid partial esters with an aqueous solution, consisting of 80 to 200 parts by weight powder Alkali silicate, 10 to 200 parts by weight of alkali hydroxide and 50 up to 150 parts by weight of water, mixed and with the addition of 50 to 100 parts by weight of alkali hydrogen carbonate, 15 to 350 Parts by weight of alkali phosphate, up to 70 parts by weight Alkali sulfate, 10 to 100 parts by weight of alkali carbonate, 50 to 150 parts by weight of alkali water glass, 10 to 100 parts by weight Alkali hydroxide and optionally up to 100 parts by weight Bleaching agent foamed with stirring and / or kneading, after which the foamy mixture is processed into moldings and can set.
  • an aqueous solution consisting of 80 to 200 parts by weight powder Alkali silicate, 10 to 200 parts by weight of alkali hydroxide and 50 up to 150 parts by weight of water, mixed and with the addition of 50 to 100
  • alkali silicate and alkali hydroxide in aqueous solution mixed with the amount of phosphoric acid partial ester, then alkali bicarbonate and alkali phosphate, such as. B. Sodium tripolyphosphate added. Only when adding the last-mentioned component is a strong foaming too observe. In the resulting foam are considered Thickening agent, optionally sodium sulfate, further Alkali carbonate and, as further components, alkali water glass, preferably potash water glass and alkali hydroxide in pearl form and optionally a bleach, preferably chloramine T, or its precursor compound mixed.
  • the in components in liquid form of the aforementioned Embodiment first mixed together, then the Partial phosphoric acid added and this mixture with the mixture of the other powdered form Components mixed and stirred vigorously. It sets immediately a strong foam development, and stirring is for continued for a few minutes. The resulting mixture becomes too Shaped moldings, and then allowed to set. in the The molding can also be provided with recessed grips be the later handling, especially the insertion in a dosing device.
  • a phosphorylating agent for the production of Phosphoric acid partial esters used according to the invention can Polyphosphoric acids of various degrees of condensation are used become; suitable organic hydroxyl compounds are for example oligoglycol ethers of alcohols with 6 to 15 carbon atoms per molecule or corresponding technical ones Mixtures of alcohols or of (alkyl) phenols with 6 to 15 carbon atoms per molecule, each with 2 to 12 ethylene oxide and / or Propylene oxide units per molecule of alkyl or (Alkyl) aryl oligoglycol ether.
  • suitable organic hydroxyl compounds are for example oligoglycol ethers of alcohols with 6 to 15 carbon atoms per molecule or corresponding technical ones Mixtures of alcohols or of (alkyl) phenols with 6 to 15 carbon atoms per molecule, each with 2 to 12 ethylene oxide and / or Propylene oxide units per molecule of alkyl or (Alkyl) aryl oligoglycol ether.
  • organic Hydroxyl components for the reaction with the Phosphorylating agents can also contain mixtures of monovalent organic hydroxyl compounds of the above described type with polyvalent organic Hydroxyl compounds, for example according to the procedure according to DE-C-26 45 211, are used.
  • the cleaning agent according to the invention can be used as Alkali phosphates, for example monosodium dihydrogen monophosphate, Disodium hydrogen monophosphate, trisodium monophosphate, Monopotassium dihydrogen monophosphate, dipotassium hydrogen monophosphate, Tripotassium monophosphate, disodium dihydrogen diphosphate, Trisodium hydrogen diphosphate, Tetrasodium diphosphate, tetrapotassium diphosphate, pentasodium triphosphate, Pentapotassium triphosphate or high molecular weight, contain water-soluble polyphosphates such as graham salt. The use of sodium tripolyphosphate is preferred.
  • silicates can also be added in the form of water glass, the use of potassium water glass being preferred.
  • the cleaning agent according to the invention contains at least Sodium and / or potassium hydroxide (anhydrous or as Monohydrate) and sodium or potassium carbonate.
  • Alkali hydrogen carbonates used which are believed to be caused by Reaction with the phosphoric acid partial ester carbon dioxide split off and thus mainly cause foaming.
  • the cleaning agent according to the invention can also Complexing agents such as phosphonates and / or sodium salts Ethylenediaminetetraacetic acid or nitrilotriacetic acid and the complexing carboxylic acids such as citric acid or Contain tartaric acid in amounts of 0.5 to 5% by weight.
  • Complexing agents such as phosphonates and / or sodium salts Ethylenediaminetetraacetic acid or nitrilotriacetic acid and the complexing carboxylic acids such as citric acid or Contain tartaric acid in amounts of 0.5 to 5% by weight.
  • the cleaning agent according to the invention Contain surfactants, for example fatty alcohol polyglycol ether with 12 to 18 carbon atoms and 3 to 25 moles of ethylene oxide, Ethylene diamine-ethylene oxide-propylene oxide adducts, fatty alcohol-ethylene oxide-propylene oxide adducts or block polymers Propylene oxide and ethylene oxide.
  • surfactants for example fatty alcohol polyglycol ether with 12 to 18 carbon atoms and 3 to 25 moles of ethylene oxide, Ethylene diamine-ethylene oxide-propylene oxide adducts, fatty alcohol-ethylene oxide-propylene oxide adducts or block polymers Propylene oxide and ethylene oxide.
  • 0.1 to 10% by weight of active oxygen or active chlorine Compounds such as perborates, persulfates, chlorinated Isocyanuric acids or "chloramine T" (sodium N-chloro-p-toluenesulfonamide) be included.
  • the present invention is illustrated by the following Manufacturing examples and the comparative example further illustrated.
  • Example 2 The procedure described in Example 1 was followed except that sodium hydroxide in pearl form was mixed in in equal parts by weight instead of sodium sulfate.
  • the product obtained had a density of about 1.3 g / cm 3 .
  • the moldings obtained had a high mechanical strength, which did not deteriorate even after storage in the air for several weeks.
  • Example 1 The procedure described in Example 1 was followed except that instead of sodium sulfate in equal parts by weight sodium hydroxide in pearl form and instead of 30 parts by weight of water glass 30 parts by weight sodium hydroxide in pearl form were used.
  • the product obtained had a density of about 1.3 g / cm 3 .
  • the moldings obtained had a high mechanical strength, which did not deteriorate even after storage in the air for several weeks.
  • Example 2 The same production connections as in Example 1 used.
  • Those prepared in Preparation Example 2 Moldings had the same properties in terms of Density and shelf life like those in manufacturing example 1 manufactured moldings.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Filters For Electric Vacuum Cleaners (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
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  • Enzymes And Modification Thereof (AREA)

Abstract

A process for the prepn. of cleaning agents in the form of foam blocks is claimed. The blocks comprise 50-400 pts. wt. (A); 50-400 pts. wt. (B); 10-400 pts. wt. (C); 1-10 pts. wt. (D); up to 150 pts. wt. water; and opt. other standard cleaning agent components. (A) are alkali silicates; (B) are alkali hydroxides and/or (hydrogen)carbonates; (C) are alkali phosphates; (D) are phosphoric acid partial esters. The process comprises reacting (D) with an aq. soln. of (B), followed by the addn. of the remaining powdered components whilst stirring and/or kneading to form a foam, and then processing the foamed mixts. into small moulds and leaving them to set. Cleaning agents prepd. by this method are also claimed.

Description

Die vorliegende Erfindung betrifft Verfahren zur Herstellung von formstabilen Geschirreinigern, die nach dem Verfahren hergestellten Reinigungsmittel und deren Verwendung zur Reinigung von Geschirr in automatischen Geschirrspülmaschinen, insbesondere solchen mit Dosiervorrichtungen.The present invention relates to methods of manufacture of dimensionally stable dishwashing detergents that follow the procedure manufactured cleaning agents and their use for Cleaning dishes in automatic dishwashers, especially those with dosing devices.

Da pulverförmige Reinigungsmittel häufig stark staubende Produkte sind, welche darüber hinaus wegen ihres Gehaltes an hygroskopischen Bestandteilen, beispielsweise Alkalihydroxiden oder Alkalimetasilikaten, zum Verbacken oder Verklumpen neigen, ist vorgeschlagen worden, zur Verwendung in den Dosiergeräten von Melkmaschinen und gewerblichen Geschirrspülmaschinen schmelzblockförmige Reinigungsmittel einzusetzen, welche durch Vergießen einer homogenen Masse in Formen erhalten wurden. Dabei werden entweder Alkalisilikat, Alkalihydroxid, Alkalitriphosphat und eine aktivchlorspaltende Verbindung mit Wasser zu einer gießfähigen homogenen Masse angerührt (vergl. EP-A-203 526); die gießfähige Masse kann auch frei von Alkalihydroxiden sein (vergl. US-A- 4 690 770); oder es werden Alkalisilikat, Alkalihydroxid, Alkalitriphosphat und ein organischer Komplexbildner gemeinsam bei etwa 60° C aufgeschmolzen (vergl. DE-A-3 519 353).Since powder detergents are often very dusty Products are, which also because of their content hygroscopic components, for example alkali hydroxides or alkali metal silicates, for baking or clumping have been suggested for use in the Metering devices of milking machines and commercial Dishwashers in the form of melting block detergents use, which by pouring a homogeneous mass in Shapes were obtained. Either alkali silicate, Alkali hydroxide, alkali nitrate phosphate and an active chlorine splitting Combination with water to form a pourable, homogeneous mass stirred (see EP-A-203 526); the pourable mass can also be free from alkali hydroxides (see US-A-4 690 770); or alkali silicate, alkali hydroxide, Alkaline triphosphate and an organic complexing agent together melted at about 60 ° C (see. DE-A-3 519 353).

Nachteilig ist bei den bekannten schmelzblockförmigen Reinigungsmitteln, daß sie wegen ihrer Schwerlöslichkeit und wegen ihrer unterschiedlichen Ablösemengen nur mit speziellen Dosiersystemen verwendet werden können. Dabei löst sich ein Schmelzblock in der zur Verfügung stehenden Zeit langsam auf und kann so über einen längeren Zeitraum bis zum vollständigen Verbrauch in der Dosiervorrichtung verwendet werden. Das langsame Auflösen des Schmelzblockes ist bei der Dosierung des Reinigungsmittels beispielsweise in gewerblichen Geschirrspülmaschinen erwünscht, damit der Reiniger nicht für jeden Spülgang portioniert zugegeben werden muß. Bei der Herstellung eines solchen Schmelzblockes treten jedoch Probleme dahingehend auf, daß der Schmelzblock beim Abkühlen rissig wird oder gegebenfalls eine ungleichförmige Verteilung der Reinigungsmittelkomponenten im Block aufweist und demzufolge eine einheitliche Konzentration in der Spüllauge nicht gewährleistet ist.A disadvantage of the known melt block-shaped Detergents that they because of their poor solubility and because of their different transfer amounts only with special Dosing systems can be used. This redeems itself Melting block slowly in the time available and can thus be completed over a longer period of time Consumption can be used in the dosing device. The slow dissolution of the melting block is at the dosage of the Detergents, for example in commercial Dishwashers wanted so that the cleaner is not for each rinse must be added in portions. In the However, manufacture of such a melting block occurs Problems in that the melting block when cooling becomes cracked or if necessary an uneven distribution the detergent components in the block and consequently a uniform concentration in the soapy water is not guaranteed.

In der EP-0 297 273 ist ein Verfahren zur Herstellung von formstabilen Reinigungsmitteln vorgeschlagen worden, wobei die resultierenden Reinigungsmittel eine geringe Dichte aufweisen und die bei Berührung mit Wasser leicht zerfallen sollen. Die Lösung gemäß der EP- 0 297 273 besteht darin, daß man einen Phosphorsäurepartialester mit Wasser im Gewichtsverhältnis von (1 : 2) bis (1 : 80), vorzugsweise von (1 : 3,5) bis (1 : 72), unter intensiven Rühren verschäumt, daß man die übrigen Komponenten unter Rühren und/oder Kneten in den Schaum einarbeitet, daß man die resultierende Mischung zu Formlingen verarbeitet und daß man die Formlinge 0,5 bis 15 Stunden abbinden läßt.EP-0 297 273 describes a process for the production of dimensionally stable cleaning agents have been proposed, the resulting cleaning agents have a low density and which should easily disintegrate when in contact with water. The Solution according to EP-0 297 273 is that one Partial phosphoric acid with water in a weight ratio of (1: 2) to (1:80), preferably from (1: 3.5) to (1:72), with intensive stirring foamed that the other Components with stirring and / or kneading into the foam incorporated that the resulting mixture into moldings processed and that the moldings 0.5 to 15 hours can set.

Die gemäß dem in der EP-0 297 273 beschriebenen Verfahren hergestellten Reinigungsmittel sollen die Eigenschaft besitzen, daß sie bei Kontakt mit Wasser sehr leicht zerfallen, um eine schnelle Auflösung der Reinigerkomponenten zu gewährleisten. So sind diese Mittel für den Einsatz in automatischen, insbesondere den kontinuierlich arbeitenden Geschirrspülmaschinen, die hauptsächlich im gewerblichen Bereich eingesetzt werden, ungeeignet, da bei diesen Maschinen in der üblicherweise eingesetzten Dosiervorrichtung Wasser oder Spüllauge in solchen Mengen verwendet werden, daß ein schneller Zerfall des in der Trockene relativ formstabilen Reinigungsmittel bewirkt wird und so eine zu schnelle und zu hohe Dosierung des Reinigers hervorgerufen wird.The according to the method described in EP-0 297 273 Cleaning agents manufactured are said to have the property possess that they are very light in contact with water disintegrate to a quick dissolution of the cleaner components to ensure. So these funds are for use in automatic, especially the continuously working Dishwashers mainly used in commercial Area used, unsuitable because of these machines water in the commonly used dosing device or soapy water are used in such amounts that a rapid disintegration of what is relatively dimensionally stable when dry Detergent is caused and so too fast and too high dosage of the cleaner is caused.

Die Aufgabe der Erfindung besteht nun darin, formstabile Reinigungsmittel, die sich gegenüber den aus dem Stand der Technik bekannten Formulierungen durch gute Löslichkeitsgeschwindigkeit in dem zugespülten Wasser und der Spüllauge verbunden mit langer Haltbarkeit und Verwendbarkeit in der Dosiervorrichtung sowie eine gute Lagerfähigkeit ohne Verlust von äußerer Form und hervorragende Reinigungsmitteleigenschaften auszeichnen, zum Einsatz in insbesondere gewerblichen Geschirrspülmaschinen und ein Verfahren zur deren Herstellung bereitzustellen.The object of the invention is to keep its shape Detergents that differ from the state of the art Formulations known through good technology Solubility rate in the flushed water and the Soapy water combined with long durability and usability in the dosing device as well as a good shelf life without Loss of external form and excellent Characterize detergent properties, for use in especially commercial dishwashers and a To provide processes for their preparation.

Seitens der Erfinder wurde nun überraschend gefunden, daß ein formstabiles Reinigungsmittel mit hervorragenden Eigenschaften in bezug auf die Formstabilität und Auflösevermögen für den Einsatz insbesondere in gewerblichen Geschirrspülmaschinen dadurch zugänglich ist, daß man einen Phosphorsäurepartialester in alkalischer Lösung in Gegenwart von Silikaten und Alkalihydroxid unter Zusatz von gasabspaltenden Mitteln bei intensivem Rühren verschäumt und unter Rühren und/oder Kneten weitere Reinigungsmittelkomponenten in Pulverform in den Schaum einarbeitet.The inventors have now surprisingly found that a dimensionally stable cleaning agent with excellent properties in terms of shape stability and resolving power for the Use especially in commercial dishwashers is accessible by using a phosphoric acid partial ester in alkaline solution in the presence of silicates and Alkali hydroxide with the addition of gas-releasing agents intensive stirring foamed and with stirring and / or kneading further detergent components in powder form in the Foam incorporated.

Überraschenderweise ist unter den alkalischen Bedingungen, vermutlich infolge der Zersetzung der gasabspaltenden Mittel, eine starke Schaumbildung zu beobachten. Eine besonders starke Schaumentwicklung ist nach der Zugabe des Alkaliphosphats, insbesondere nach Zugabe von Natriumtripolyphosphat zu beobachten.Surprisingly, under the alkaline conditions, presumably as a result of the decomposition of the gas-releasing agents, a strong foaming is observed. A particularly strong one Foam development is after the addition of the alkali phosphate, especially after adding sodium tripolyphosphate observe.

Die vorliegende Erfindung ist daher gerichtet auf ein Verfahren zur Herstellung von Reinigungsmitteln in Schaumblockform, mindestens bestehend aus 50 bis 400 Gewichtsteilen Alkalisilikaten, 50 bis 400 Gewichtsteilen Alkalihydroxiden, Alkalicarbonaten bzw. - hydrogencarbonaten, 10 bis 400 Gewichtsteilen Alkaliphosphaten, 1 bis 10 Gewichtsteilen Phosphorsäurepartialester und bis zu 150 Gewichtsteilen Wasser sowie gegebenfalls weiteren üblicherweise in Reinigungsmitteln enthaltenen Inhaltsstoffen, bei dem man den Phosphorsäurepartialester mit einer wässrigen Lösung von Alkalisilikat und Alkalihydroxid verrührt und unter Zusatz von Alkalihydrogencarbonat und Alkaliphosphat sowie der restlichen Komponenten in Pulverform unter Rühren und/oder Kneten verschäumt, die schaumige Mischung zu Formlingen verarbeitet und abbinden läßt. Die genauen Gründe für die überraschende Stabilität des Schaumblockes sind noch nicht bekannt, vermutlich wird aber der alkalischen wässrigen Lösung bei Zugabe der pulverförmigen Komponenten der Wasseranteil entzogen, und die gesamte Mischung erstarrt unter Verfestigung zu dem gewünschten Schaumblock. Erfindungsgemäß werden die, die Alkalität des Reinigers hauptsächlich verursachenden Komponenten Alkalisilikate, Alkalicarbonate und - hydrogencarbonate sowie Alkalihydroxide teilweise in wässriger Lösung und teilweise in Pulverform eingesetzt. Dabei werden die gegebenfalls eingesetzten weiteren, üblicherweise in Reinigungsmitteln enthaltenen Inhaltsstoffen wie Verdickungsmittel, Komplexbildner, Tenside in der Regel in einer Menge von bis zu 150 Gewichtsteilen zugesetzt.The present invention is therefore directed to a Process for the production of cleaning agents in Foam block shape, at least consisting of 50 to 400 Parts by weight of alkali silicates, 50 to 400 parts by weight Alkali hydroxides, alkali carbonates or - hydrogen carbonates, 10 to 400 parts by weight Alkali phosphates, 1 to 10 parts by weight Phosphoric acid partial esters and up to 150 parts by weight of water and, if appropriate, others usually in cleaning agents contained ingredients, in which one Phosphoric acid partial esters with an aqueous solution of Alkali silicate and alkali hydroxide stirred and with the addition of Alkali hydrogen carbonate and alkali phosphate and the rest Components in powder form with stirring and / or kneading foamed, the foamy mixture processed into moldings and let set. The exact reasons for the surprising Stability of the foam block is not yet known but presumably the alkaline aqueous solution Add the powdered components of the water content withdrawn, and the entire mixture solidifies with solidification to the desired foam block. According to the invention, the main cause of the alkalinity of the cleaner Components of alkali silicates, alkali carbonates and - Hydrogen carbonates and alkali hydroxides partly in aqueous Solution and partially used in powder form. In doing so the others used, usually in Detergents contained ingredients such as Thickeners, complexing agents, surfactants usually in added in an amount of up to 150 parts by weight.

Mit Hilfe dieses Verfahrens sind schaumblockförmige Reinigungsmittel zugänglich, die sich durch hervorragende Lösungseigenschaften für den Einsatz in Dosiervorrichtungen in gewerblichen Geschirrspülmaschinen auszeichnen. Infolge der Schaumbildung vermutlich durch Zersetzung des gasabspaltenden Mittels ergeben sich Schaumblöcke mit einer ausreichenden Porosität, so daß gegenüber den schmelzblockförmigen Reinigungsmitteln eine Oberflächenvergrößerung und somit eine Vergrößerung der Angriffsfläche für das Spülwasser ergibt.With the help of this procedure are foam block-shaped Detergent accessible, which is characterized by excellent Solution properties for use in dosing devices in distinguish commercial dishwashers. As a result of Foam formation presumably through decomposition of the gas-releasing By means of foam blocks with sufficient Porosity, so that compared to the melt block-shaped Detergents an increase in surface area and thus a Enlargement of the attack surface for the rinse water results.

Auf der anderen Seite weist der so hergestellte Schaumblock im Gegensatz zu den gemäß der EP-0 297 273 hergestellten Reinigern eine ausreichend hohe Festigkeit auf, um den Einsatz in den bereits erwähnten Dosiervorrichtungen über einen längeren Zeitraum ohne Verlust der Formstabilität zu ermöglichen.On the other hand, the foam block produced in this way has Contrary to those produced according to EP-0 297 273 Clean up enough strength to use in the dosing devices already mentioned via a longer period without loss of shape stability enable.

Die erfindungsgemäß hergestellten Reinigungsmittel zeichnen sich gegenüber den aus dem Stand der Technik bekannten Reinigungsmitteln durch ausgewogene Eigenschaften hinsichtlich der Porosität, Oberfläche und Festigkeit des Schaumblockes aus. So ist auf der einen Seite eine hohe Festigkeit auch über einen langen Lagerzeitraum wie bei den bekannten schmelzblockförmigen Reinigern gegeben, auf der anderen Seite ist aber eine vergrößerte Oberfläche des Schaumblockes vorhanden und somit ist eine optimal angepasste Auflösung des Blockes an dieser Oberfläche, um eine ausreichende Konzentration an Reinigungsmittelkomponenten in der Spüllauge verbunden mit minimalem Einsatz an Wasser zu erhalten, gewährleistet. Es wird durch die erfindungsgemäßen Reiniger insbesondere ermöglicht, die Menge an zur Auflösung eingesetztem Wasser gegenüber den Reinigersystemen auf Schmelzblockbasis drastisch zu verringern.Draw the cleaning agents produced according to the invention compared to those known from the prior art Detergent due to balanced properties the porosity, surface and strength of the foam block out. So on the one hand a high strength is also about a long storage period as with the known given block-shaped cleaners, on the other hand but is an enlarged surface of the foam block is available and therefore an optimally adapted resolution of the Block on this surface to be sufficient Concentration of detergent components in the soapy water combined with minimal use of water, guaranteed. It is due to the cleaners according to the invention in particular, allows the amount of resolution water used compared to the cleaning systems Reduce melting block base dramatically.

Bei dem erfindungsgemäßen Verfahren beträgt die Summe der Gewichtsteile der eingesetzten Komponenten bevorzugt 1000 Gewichtsteile.In the method according to the invention, the sum is Parts by weight of the components used preferably 1000 Parts by weight.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden 1 bis 10 Gewichtsteile Phosphorsäurepartialester mit einer wässrigen Lösung, bestehend aus 80 bis 200 Gewichtsteilen pulverförmigem Alkalisilikat, 10 bis 200 Gewichtsteilen Alkalihydroxid und 50 bis 150 Gewichtsteilen Wasser, vermengt und unter Zusatz von 50 bis 100 Gewichtsteilen Alkalihydrogencarbonat, 15 bis 350 Gewichtsteilen Alkaliphosphat, bis zu 70 Gewichtsteilen Alkalisulfat, 10 bis 100 Gewichtsteilen Alkalicarbonat, 50 bis 150 Gewichtsteilen Alkaliwasserglas, 10 bis 100 Gewichtsteilen Alkalihydroxid sowie gegebenfalls bis zu 100 Gewichtsteilen Bleichmittel unter Rühren und/oder Kneten verschäumt, wonach man die schaumige Mischung zu Formlingen verarbeitet und abbinden läßt.In a preferred embodiment of the invention Process will be 1 to 10 parts by weight Phosphoric acid partial esters with an aqueous solution, consisting of 80 to 200 parts by weight powder Alkali silicate, 10 to 200 parts by weight of alkali hydroxide and 50 up to 150 parts by weight of water, mixed and with the addition of 50 to 100 parts by weight of alkali hydrogen carbonate, 15 to 350 Parts by weight of alkali phosphate, up to 70 parts by weight Alkali sulfate, 10 to 100 parts by weight of alkali carbonate, 50 to 150 parts by weight of alkali water glass, 10 to 100 parts by weight Alkali hydroxide and optionally up to 100 parts by weight Bleaching agent foamed with stirring and / or kneading, after which the foamy mixture is processed into moldings and can set.

Gemäß einer Weiterbildung dieses letztgenannten Verfahrens werden 1 bis 10 Gewichtsteile Phosphorsäurepartialester mit einer wässrigen Lösung, bestehend aus 80 bis 200 Gewichtsteilen pulverförmigem Alkalisilikat, 10 bis 200 Gewichtsteilen Alkalihydroxid und 50 bis 150 Gewichtsteilen Wasser, vermengt und unter Zusatz von 50 bis 100 Gewichtsteilen Alkalihydrogencarbonat, 15 bis 300 Gewichtsteilen Alkaliphosphat, bis zu 70 Gewichtsteilen Alkalisulfat, 10 bis 100 Gewichtsteilen Alkalicarbonat, 50 bis 150 Gewichtsteilen Alkaliwasserglas, 10 bis 50 Gewichtsteilen Alkalihydroxid sowie gegebenfalls bis zu 50 Gewichtsteilen Bleichmittel unter Rühren und/oder Kneten verschäumt, dann wird die schaumige Mischung zu Formlingen verarbeitet und man läßt abbinden.According to a development of this latter method 1 to 10 parts by weight of phosphoric acid partial esters an aqueous solution consisting of 80 to 200 Parts by weight of powdered alkali silicate, 10 to 200 Parts by weight of alkali hydroxide and 50 to 150 parts by weight Water, mixed and with the addition of 50 to 100 Parts by weight of alkali hydrogen carbonate, 15 to 300 Parts by weight of alkali phosphate, up to 70 parts by weight Alkali sulfate, 10 to 100 parts by weight of alkali carbonate, 50 to 150 parts by weight of alkali water glass, 10 to 50 parts by weight Alkali hydroxide and optionally up to 50 parts by weight Bleaching agent foamed with stirring and / or kneading, then the foamy mixture is processed into moldings and one lets set.

In einer weiter bevorzugten Ausführungsform des Verfahrens werden Alkalisilikat und Alkalihydroxid in wässriger Lösung mit der Menge an Phosphorsäurepartialester vermischt, dann werden Alkalihydrogencarbonat und Alkaliphosphat, wie z. B. Natriumtripolyphosphat hinzugegeben. Erst bei Zugabe der letztgenannten Komponente ist eine starke Schaumbildung zu beobachten. In den entstehenden Schaum werden als Verdickungsmittel gegebenenfalls Natriumsulfat, weiterhin Alkalicarbonat sowie als weitere Komponenten Alkaliwasserglas, vorzugsweise Kaliwasserglas und Alkalihydroxid in Perlenform und gegebenenfalls ein Bleichmittel, vorzugsweise Chloramin T, oder dessen Vorläuferverbindung untergemengt.In a further preferred embodiment of the method become alkali silicate and alkali hydroxide in aqueous solution mixed with the amount of phosphoric acid partial ester, then alkali bicarbonate and alkali phosphate, such as. B. Sodium tripolyphosphate added. Only when adding the last-mentioned component is a strong foaming too observe. In the resulting foam are considered Thickening agent, optionally sodium sulfate, further Alkali carbonate and, as further components, alkali water glass, preferably potash water glass and alkali hydroxide in pearl form and optionally a bleach, preferably chloramine T, or its precursor compound mixed.

In einer anderen bevorzugten Ausführungsform werden die in flüssiger Form vorliegenden Komponenten der zuvor erwähnten Ausführungsform zunächst miteinander gemischt, dann wird der Phosphorsäurepartialester hinzugegeben und diese Mischung mit der Mischung der übrigen, in Pulverform vorliegenden Komponenten vermischt und kräftig gerührt. Es setzt sofort eine starke Schaumentwicklung ein, und das Rühren wird für wenige Minuten fortgesetzt. Die resultierende Mischung wird zu Formlingen geformt, und man läßt diese dann abbinden. Im Formschritt kann der Formling auch mit Griffmulden versehen werden, die die spätere Handhabung, besonders das Einsetzen in eine Dosiervorrichtung, erleichtern. In another preferred embodiment, the in components in liquid form of the aforementioned Embodiment first mixed together, then the Partial phosphoric acid added and this mixture with the mixture of the other powdered form Components mixed and stirred vigorously. It sets immediately a strong foam development, and stirring is for continued for a few minutes. The resulting mixture becomes too Shaped moldings, and then allowed to set. in the The molding can also be provided with recessed grips be the later handling, especially the insertion in a dosing device.

Bevorzugt läßt man die so hergestellt schaumbreiartige Mischung über einen Zeitraum von mehreren Stunden in der Herstellungsform abbinden. Auf diese Weise erhält man ein für Handhabung und Transport geschütztes Produkt, das dann unmittelbar vor seiner Verwendung entnommen und in die Dosiervorrichtung eingesetzt werden kann. Bevorzugt können als Herstellungsform einfache Becher aus Polyethylen verwendet werden. Alternativ kann ein aus der Herstellungsform entnommener Schaumblock auch mittels einer Folie aus Polyethylen während Transport oder Lagerung vor Umwelteinflüssen geschützt werden. Gegebenfalls kann der Formling auch mit einer Folie aus einem wasserlöslichen Material wie Polyvinylalkohol umschlossen werden, was die Handhabung besonders einfach macht.It is preferred to leave the foam paste-like so produced Mix over a period of several hours in the Set the production mold. This way you get a for Handling and transport protected product, which then removed immediately before use and into the Dosing device can be used. Preferred as Form of production used simple cups made of polyethylene become. Alternatively, one from the manufacturing mold removed foam block also using a film Polyethylene before transportation or storage Environmental influences are protected. If necessary, the Shaped also with a film made of a water-soluble Material such as polyvinyl alcohol are encased in what the Handling makes it particularly easy.

Es ist ebenso möglich, die Formlinge durch Strangpressen der Mischung herzustellen. Dazu werden erfindungsgemäß übliche Extruder verwendet. Anschließend werden die gepreßten Stränge in Stücke zerschnitten und gegebenfalls mit einem Schutzüberzug versehen, der die Formlinge bei Transport und Lagerung schützt.It is also possible to extrude the moldings To produce a mixture. According to the invention, this is customary Extruder used. Then the pressed strands cut into pieces and if necessary with a Provide protective cover that the moldings during transport and Storage protects.

Als Phosphorylierungsmittel zur Herstellung der erfindungsgemäß verwendeten Phosphorsäurepartialester können Polyphosphorsäuren verschiedener Kondensationsgrade verwendet werden; geeignete organische Hydroxylverbindungen sind beispielsweise Oligoglykolether von Alkoholen mit 6 bis 15 C-Atomen pro Molekül bzw. diesen entsprechende technische Mischungen von Alkoholen oder von (Alkyl-)Phenolen mit 6 bis 15 C-Atomen pro Molekül, jeweils mit 2 bis 12 Ethylenoxid- und/oder Propylenoxid-Einheiten pro Molekül des Alkyl- bzw. (Alkyl-)Aryloligoglykolethers. Als organische Hydroxylkomponenten für die Umsetzung mit den Phosphorylierungsmitteln können ferner Gemische von einwertigen organischen Hydroxylverbindungen der vorstehend beschriebenen Art mit mehrwertigen organischen Hydroxylverbindungen, beispielsweise nach der Arbeitsweise gemäß der DE-C-26 45 211, zum Einsatz kommen.As a phosphorylating agent for the production of Phosphoric acid partial esters used according to the invention can Polyphosphoric acids of various degrees of condensation are used become; suitable organic hydroxyl compounds are for example oligoglycol ethers of alcohols with 6 to 15 carbon atoms per molecule or corresponding technical ones Mixtures of alcohols or of (alkyl) phenols with 6 to 15 carbon atoms per molecule, each with 2 to 12 ethylene oxide and / or Propylene oxide units per molecule of alkyl or (Alkyl) aryl oligoglycol ether. As organic Hydroxyl components for the reaction with the Phosphorylating agents can also contain mixtures of monovalent organic hydroxyl compounds of the above described type with polyvalent organic Hydroxyl compounds, for example according to the procedure according to DE-C-26 45 211, are used.

Das Reinigungsmittel gemäß der Erfindung kann als Alkaliphosphate beispielsweise Mononatrium-dihydrogen-monophosphat, Dinatrium-hydrogen-monophosphat, Trinatrium-monophosphat, Monokalium-dihydrogen-monophosphat, Dikalium-hydrogen-monophosphat, Trikalium-monophosphat, Dinatrium-dihydrogen-diphosphat, Trinatrium-hydrogen-diphosphat, Tetranatrium-diphosphat, Tetrakalium-diphosphat, Pentanatrium-triphosphat, Pentakalium-triphosphat oder hochmolekulare, wasserlösliche Polyphosphate wie Grahamsalz enthalten. Bevorzugt ist die Verwendung von Natriumtripolyphosphat.The cleaning agent according to the invention can be used as Alkali phosphates, for example monosodium dihydrogen monophosphate, Disodium hydrogen monophosphate, trisodium monophosphate, Monopotassium dihydrogen monophosphate, dipotassium hydrogen monophosphate, Tripotassium monophosphate, disodium dihydrogen diphosphate, Trisodium hydrogen diphosphate, Tetrasodium diphosphate, tetrapotassium diphosphate, pentasodium triphosphate, Pentapotassium triphosphate or high molecular weight, contain water-soluble polyphosphates such as graham salt. The use of sodium tripolyphosphate is preferred.

Als Silikate kann das erfindungsgemäße Reinigungsmittel Natriummetasilikat, Wasserglaslösungen im Verhältnis Na2O : SiO2 = 1 : 2,0 bis 1 : 3,5, Kaliwasserglas, Schichtsilikate oder Zeolith A enthalten. Die Silikate können aber auch in Form von Wasserglas zugesetzt werden, wobei die Verwendung von Kaliwasserglas bevorzugt ist.The cleaning agent according to the invention can contain, as silicates, sodium metasilicate, water glass solutions in the ratio Na 2 O: SiO 2 = 1: 2.0 to 1: 3.5, potassium water glass, layered silicates or zeolite A. However, the silicates can also be added in the form of water glass, the use of potassium water glass being preferred.

Das Reinigungsmittel gemäß der Erfindung enthält mindestens Natrium- und/oder Kaliumhydroxid (wasserfrei oder als Monohydrat) sowie Natrium- oder Kaliumcarbonat.The cleaning agent according to the invention contains at least Sodium and / or potassium hydroxide (anhydrous or as Monohydrate) and sodium or potassium carbonate.

Als gasabspaltendes Mittel werden erfindungsgemäß Alkalihydrogencarbonate eingesetzt, die vermutlich durch Reaktion mit dem Phosphorsäurepartialester Kohlendioxid abspalten und so die Schaumbildung hauptsächlich hervorrufen.As a gas-releasing agent according to the invention Alkali hydrogen carbonates used, which are believed to be caused by Reaction with the phosphoric acid partial ester carbon dioxide split off and thus mainly cause foaming.

Das erfindungsgemäß Reinigungsmittel kann weiterhin Komplexbildner wie Phosphonate und/oder Natriumsalze der Ethylendiamintetraessigsäure oder der Nitrilotriessigsäure und der komplexierende Carbonsäuren wie Citronensäure oder Weinsäure in Mengen von 0,5 bis 5 Gew.% enthalten.The cleaning agent according to the invention can also Complexing agents such as phosphonates and / or sodium salts Ethylenediaminetetraacetic acid or nitrilotriacetic acid and the complexing carboxylic acids such as citric acid or Contain tartaric acid in amounts of 0.5 to 5% by weight.

Weiterhin kann das Reinigungsmittel gemäß der Erfindung Tenside enthalten, beispielsweise Fettalkoholpolyglykolether mit 12 bis 18 C-Atomen und 3 bis 25 Mol Ethylenoxid, Ethylendiamin-Ethylenoxid-Propylenoxid-Addukte, Fettalkohol-Ethylenoxid-Propylenoxid-Addukte oder Blockpolymerisate aus Propylenoxid und Ethylenoxid.Furthermore, the cleaning agent according to the invention Contain surfactants, for example fatty alcohol polyglycol ether with 12 to 18 carbon atoms and 3 to 25 moles of ethylene oxide, Ethylene diamine-ethylene oxide-propylene oxide adducts, fatty alcohol-ethylene oxide-propylene oxide adducts or block polymers Propylene oxide and ethylene oxide.

Schließlich können in dem erfindungsgemäßen Reinigungsmittel 0,1 bis 10 Gew.-% aktivsauerstoff- bzw. aktivchlorabspaltende Verbindungen wie Perborate, Persulfate, chlorierte Isocyanursäuren oder "Chloramin T" (N-Chlor-p-toluolsulfonsäureamid-Natrium) enthalten sein.Finally, in the cleaning agent according to the invention 0.1 to 10% by weight of active oxygen or active chlorine Compounds such as perborates, persulfates, chlorinated Isocyanuric acids or "chloramine T" (sodium N-chloro-p-toluenesulfonamide) be included.

Die vorliegende Erfindung wird anhand der folgenden Herstellungsbeispiele und dem Vergleichsbeispiel weiter veranschaulicht.The present invention is illustrated by the following Manufacturing examples and the comparative example further illustrated.

Herstellungsbeispiel 1Production Example 1

150 Gewichtsteile Natriummetasilikat in Pulverform wurden in einen Rührbehälter gegeben. Nach Zugabe von 50 Gewichtsteilen 70°C heißen Wassers wurde über 2 Minuten gerührt. Danach wurden 160 Gewichtsteile 45%ige Natronlauge hinzugegeben und gerührt. Nach 2 Minuten wurden 4 Gewichtsteile Phophorsäurepartialester hinzugemischt und gerührt. Nach einer weiteren Minute wurden 60 Gewichtsteile Natriumhydrogencarbonat als gasabspaltendes Mittel hinzugegeben. Nach der Zugabe von 260 Gewichtsteilen Natriumtripolyphosphat unter Rühren war eine starke Schaumentwicklung zu beobachten. Nach weiteren 5 Minuten wurden 65 Gewichtsteile Natriumsulfat und 35 Gewichtsteile Natriumcarbonat hinzugemischt. Nach einminütigem Rühren wurden 130 Gewichtsteile Kaliwasserglas, nach einer weiteren Minute 35 Gewichtsteile Natriumhydroxid in Perlenform untergemengt. Als letzte Komponente wurde 51 Gewichtsteile Chloramin T hinzugegeben und die Mischung kräftig gerührt. Nach zwei Minuten wurde die Mischung in Formen gegossen, und man ließ die Mischung in den Formen abbinden. Das erhaltene Produkt besaß eine Dichte von etwa 1,3 g/cm3. Die erhaltenen Formlinge besaßen eine hohe mechanische Festigkeit, die sich auch nach mehrwöchiger Lagerung an der Luft nicht verschlechterte.150 parts by weight of sodium metasilicate in powder form were placed in a stirred container. After adding 50 parts by weight of water at 70 ° C., the mixture was stirred for 2 minutes. Then 160 parts by weight of 45% sodium hydroxide solution were added and stirred. After 2 minutes, 4 parts by weight of partial phosphoric acid ester were mixed in and stirred. After another minute, 60 parts by weight of sodium hydrogen carbonate was added as a gas releasing agent. After the addition of 260 parts by weight of sodium tripolyphosphate with stirring, a strong foaming was observed. After a further 5 minutes, 65 parts by weight of sodium sulfate and 35 parts by weight of sodium carbonate were added. After stirring for one minute, 130 parts by weight of potassium water glass were mixed in, after another minute 35 parts by weight of sodium hydroxide in pearl form. The last component was added 51 parts by weight of chloramine T and the mixture was stirred vigorously. After two minutes the mixture was poured into molds and the mixture was allowed to set in the molds. The product obtained had a density of about 1.3 g / cm 3 . The moldings obtained had a high mechanical strength, which did not deteriorate even after storage in the air for several weeks.

Herstellungsbeispiel 2Production Example 2

Das in Beispiel 1 beschriebene Verfahren wurde nachgearbeitet, ausgenommen, daß anstelle von Natriumsulfat Natriumhydroxid in Perlenform in gleichen Gewichtsteilen untergemengt wurde. Das erhaltene Produkt besaß eine Dichte von etwa 1,3 g/cm3. Die erhaltenen Formlinge besaßen eine hohe mechanische Festigkeit, die sich auch nach mehrwöchiger Lagerung an der Luft nicht verschlechterte.The procedure described in Example 1 was followed except that sodium hydroxide in pearl form was mixed in in equal parts by weight instead of sodium sulfate. The product obtained had a density of about 1.3 g / cm 3 . The moldings obtained had a high mechanical strength, which did not deteriorate even after storage in the air for several weeks.

Herstellungsbeispiel 3Production Example 3

Das in Beispiel 1 beschriebene Verfahren wurde nachgearbeitet, ausgenommen, daß anstelle von Natriumsulfat in gleichen Gewichtsteilen Natriumhydroxid in Perlenform und anstelle von 30 Gewichtsteilen Wasserglas 30 Gewichtsteile Natriumhydroxid in Perlenform verwendet wurden. Das erhaltene Produkt besaß eine Dichte von etwa 1,3 g/cm3. Die erhaltenen Formlinge besaßen eine hohe mechanische Festigkeit, die sich auch nach mehrwöchiger Lagerung an der Luft nicht verschlechterte.The procedure described in Example 1 was followed except that instead of sodium sulfate in equal parts by weight sodium hydroxide in pearl form and instead of 30 parts by weight of water glass 30 parts by weight sodium hydroxide in pearl form were used. The product obtained had a density of about 1.3 g / cm 3 . The moldings obtained had a high mechanical strength, which did not deteriorate even after storage in the air for several weeks.

Herstellungsbeispiel 4Production Example 4

Es wurden die gleichen Herstellungsverbindungen wie in Beispiel 1 eingesetzt. Dabei wurden die gemäß der in Herstellungsbeispiel 1 in flüssiger Form eingesetzten Komponenten miteinander vermischt. Die gemäß der Rezeptur in Herstellungsbeispiel 1 verwendeten Komponenten in Pulverform wurden ebenfalls miteinander gemischt, und zu dieser Mischung wurde die Mischung der Flüssigkomponenten gegeben. Unter heftigem Rühren setzte eine kräftige Schaumentwicklung ein, und nach etwa 5 Minuten wurde die erhaltene schaumbreiartige Mischung in Formen gefüllt, und man ließ die Formlinge abbinden. Die in Herstellungsbeispiel 2 hergestellten Formlinge besaßen die gleichen Eigenschaften in Bezug auf Dichte und Lagerbeständigkeit wie die in Herstellungsbeispiel 1 hergestellten Formlinge.The same production connections as in Example 1 used. The were according to the in Production example 1 used in liquid form Components mixed together. The according to the recipe in Production Example 1 used components in powder form were also mixed together, and to this mixture the mixture of liquid components was given. Under vigorous stirring started a vigorous foaming, and after about 5 minutes, the foam paste obtained was Mix filled in molds, and the moldings were left tie off. Those prepared in Preparation Example 2 Moldings had the same properties in terms of Density and shelf life like those in manufacturing example 1 manufactured moldings.

Vergleichsbeispiel 1Comparative Example 1

Das Herstellungsbeispiel 1 der EP-0 297 273 wurde nachgearbeitet. Die Dichte des so hergestellten Formlings betrug unmittelbar nach der Herstellung 0,8 g/cm3. Nach mehrtägiger Lagerung an der Luft begann der Formling aufzuquellen und verlor seine ursprüngliche Festigkeit, die allerdings von vornherein nicht so hoch wie bei den erfindungsgemäß hergestellten Formlingen war, was durch einfache mechanische Bearbeitung festgestellt wurde.Manufacturing example 1 of EP-0 297 273 was reworked. The density of the molding thus produced was 0.8 g / cm 3 immediately after production. After being stored in air for several days, the molding began to swell and lost its original strength, which, however, was not as high from the outset as with the moldings produced according to the invention, which was determined by simple mechanical processing.

Claims (10)

  1. Method for producing cleaning agents in the form of foam blocks, at least consisting of 50 to 400 parts by weight of alkali silicates, 50 to 400 parts by weight of alkali hydroxides, alkali carbonates, alkali hydrogen carbonates, 10 to 400 parts by weight of alkali phosphates, 1 to 10 parts by weight of phosphoric acid partial ester and up to 150 parts by weight of water as well as optionally further ingredients commonly contained in cleaning agents, characterized in that the phosphoric acid partial ester is mixed with an aqueous solution of alkali silicate and alkali hydroxide and is foamed while adding by stirring and/or kneading alkali hydrogen carbonate and alkali phosphate as well as the rest of the components in powder form, the foamy mixture is processed into molded articles and is allowed to set.
  2. Process according to claim 1, characterized in that 1 to 10 parts by weight of phosphoric acid partial ester are combined with an aqueous solution consisting of 80 to 200 parts by weight of alkali silicate in powder form, 10 to 200 parts by weight of alkali hydroxide and 50 to 150 parts by weight of water, and is foamed while adding by stirring and/or kneading 50 to 100 parts by weights of alkali hydrogen carbonate, 15 to 350 parts by weight of alkali phosphate, up to 70 parts by weight of alkali sulfate, 10 to 100 parts by weight of alkali carbonate, 50 to 150 parts by weight of alkali water-glass, 10 to 100 parts by weight of alkali hydroxide as well as optionally up to 100 parts by weight of bleaching agent, the foamy mixture is processed into molded articles and is allowed to set.
  3. Method according to claim 1 or 2, characterized in that 1 to 10 parts by weight of phosphoric acid partial ester are combined with an aqueous solution consisting of 80 to 200 parts by weight of powdered alkali silicate, 10 to 200 parts by weight of alkali hydroxide and 50 to 150 parts by weight of water, are foamed while adding by stirring and/or kneading 50 to 100 parts by weight of alkali hydrogen carbonate, 15 to 300 parts by weight of alkali phosphate, up to 70 parts by weight of alkali sulfate, 10 to 100 parts by weight of alkali carbonate, 50 to 150 parts by weight of alkali water-glass, 10 to 50 parts by weight of alkali hydroxide as well as optionally up to 50 parts by weight of bleaching agent, the foamy mixture is processed into molded articles and is allowed to set.
  4. Method according to claim 1, 2 or 3, characterized in that the components employed in liquid form are mixed with one another and the components employed in powder form are sequentially worked into the liquid mixture by stirring.
  5. Method according to claim 1, 2 or 3, characterized in that the components employed in liquid form are mixed with one another and a mixture of the components employed in powdered form is worked into the liquid mixture by stirring.
  6. Method according to one of the previous claims, characterized in that the mixture is allowed to set as a molded article in the mixing container used.
  7. Method according to one of the claims 1 to 5, characterized in that the molded articles are obtained by extrusion of the mixture.
  8. Method according to claim 7, characterized in that the extruded strands are cut into pieces.
  9. Method according to one of the previous claims, characterized in that the molded articles are provided with a protective coating.
  10. Cleaning agent, produced according to one of the methods claimed in claims 1 to 8.
EP95117602A 1994-11-10 1995-11-08 Dimensionally stable dish cleaner Expired - Lifetime EP0711826B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4440142A DE4440142C2 (en) 1994-11-10 1994-11-10 Process for the production of cleaning agents in foam block form
DE4440142 1994-11-10

Publications (3)

Publication Number Publication Date
EP0711826A2 EP0711826A2 (en) 1996-05-15
EP0711826A3 EP0711826A3 (en) 1997-12-10
EP0711826B1 true EP0711826B1 (en) 2000-05-24

Family

ID=6532954

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95117602A Expired - Lifetime EP0711826B1 (en) 1994-11-10 1995-11-08 Dimensionally stable dish cleaner

Country Status (3)

Country Link
EP (1) EP0711826B1 (en)
AT (1) ATE193321T1 (en)
DE (2) DE4440142C2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50112692D1 (en) * 2000-05-17 2007-08-16 Henkel Kgaa WASHING OR CLEANING MOLDING BODY
US7153820B2 (en) 2001-08-13 2006-12-26 Ecolab Inc. Solid detergent composition and method for solidifying a detergent composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3391083A (en) * 1966-06-29 1968-07-02 Monsanto Co Surface active agents
DE2645211C2 (en) 1976-10-07 1982-02-11 Hoechst Ag, 6000 Frankfurt Process for the preparation of mixtures of acidic orthophosphoric acid esters
DE2806344C3 (en) * 1978-02-15 1980-12-11 Hoechst Ag, 6000 Frankfurt Process for the production of window cleaning agents
DE3519353A1 (en) 1985-05-30 1986-12-04 Henkel KGaA, 4000 Düsseldorf MELT BLOCK-SHAPED, ALKALINE HYDROXIDE-CONTAINING AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THE PRODUCTION THEREOF
DE3519355A1 (en) 1985-05-30 1986-12-04 Henkel KGaA, 4000 Düsseldorf MELT BLOCK-SHAPED, ALKALINE HYDROXIDE AND ACTIVE CHLORINE-CONTAINING AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THEIR PRODUCTION
DE3519354A1 (en) 1985-05-30 1986-12-04 Henkel KGaA, 4000 Düsseldorf MELT BLOCK-SHAPED ALKALINE HYDROXIDE-FREE AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THE PRODUCTION THEREOF
FR2609168A1 (en) 1986-12-24 1988-07-01 Nivarox Sa METHOD AND DEVICE FOR ASSAYING LIQUID SAMPLES
DE3721461A1 (en) * 1987-06-30 1989-01-12 Hoechst Ag STABLE AND SPECIFICALLY LIGHT ALKALINE CLEANING AGENTS AND A METHOD FOR THEIR PRODUCTION
AU605573B2 (en) * 1987-08-12 1991-01-17 Ecolab Inc. Solid cast warewashing composition

Also Published As

Publication number Publication date
ATE193321T1 (en) 2000-06-15
EP0711826A3 (en) 1997-12-10
EP0711826A2 (en) 1996-05-15
DE59508387D1 (en) 2000-06-29
DE4440142C2 (en) 1999-03-11
DE4440142A1 (en) 1996-05-15

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