EP0203526B1 - Compounds in melted block form containing alkaline hydroxide and active chlorine for machine dish-washing, and process for their preparation - Google Patents

Compounds in melted block form containing alkaline hydroxide and active chlorine for machine dish-washing, and process for their preparation Download PDF

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Publication number
EP0203526B1
EP0203526B1 EP86106948A EP86106948A EP0203526B1 EP 0203526 B1 EP0203526 B1 EP 0203526B1 EP 86106948 A EP86106948 A EP 86106948A EP 86106948 A EP86106948 A EP 86106948A EP 0203526 B1 EP0203526 B1 EP 0203526B1
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Prior art keywords
active chlorine
weight
detergents
water
blocks
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German (de)
French (fr)
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EP0203526A2 (en
EP0203526A3 (en
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Theodor Dr. Altenschöpfer
Jochen Dr. Jacobs
Peter Dr. Jeschke
Klaus Dr. Schumann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast detergent 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
    • C11D3/02—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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents

Definitions

  • Solid detergents for automatic dishwashing are mainly offered in powder or granular form (agglomerates).
  • the individual particles of these agents have a preferred diameter between 0.01 and 3 mm.
  • a serious disadvantage of this type of solid cleaning agents, especially those used in the field of large-scale commercial use with a content of 10 to 60% by weight of alkali metal hydroxides, is that, due to the hygroscopicity of individual raw materials, small amounts of moisture have a strong tendency to Baked or clumped.
  • a disadvantage is the use of cleaning agents that tend to clump or cake when exposed to moisture, especially in automatic, stocking dosing devices that are used in large numbers in the area of large-scale commercial use of single-tank and multi-tank dishwashers.
  • cleaning agents that tend to clump or cake when exposed to moisture
  • the only remedy is to prevent the entry of moisture into the storage container, but this cannot be guaranteed in a damp kitchen atmosphere or after cleaning the device with water without drying the parts of the storage container and the dosing device.
  • the clumping or caking of alkaline cleaning agents can be avoided, among other things, by producing them in block form from the outset and packing, distributing and using them in a moisture-proof manner.
  • EP-PS 3 769 describes detergent containers, in particular for machine dishwashing, which contain solid detergent blocks made from water and two solid constituents, at least one of which is an alkaline hydratable compound and which are only open at one point then the detergent through the water flow is washed out in the washing machine.
  • these cleaning agents are to contain active chlorine compounds in addition to alkali hydroxide, which are necessary for the removal of bleachable soiling, such as, for. B. tea, coffee, fruit juices, etc. are considered, these must preferably be introduced as pre-shaped kernels during the solidification of the heat-dissolved cleaning agent in the still soft mass.
  • the core should still be coated either with paraffin or with a wax-like mono- and dialkyl ester of polyphosphoric acid.
  • Example 13 Direct incorporation of compounds containing active chlorine, especially in the presence of high concentrations of alkali metal hydroxide, is not considered feasible.
  • Table 1 it is shown that a direct addition of the active chlorine-releasing compound to the dewaxing solution of the other cleaning components leads to a high loss of active chlorine within 24 hours.
  • the investigated chlorine carriers were Ca (OCl) 2, LiOCl and Na dichloroisocyanurate dihydrate. Depending on the chlorine carrier, residual chlorine activities between only 3.5 and 17.4% of the initial value were determined.
  • the object was therefore to find ways of introducing active chlorine carriers into block-shaped cleaning agents in the most homogeneous distribution possible in the presence of alkali metal hydroxides.
  • detergent formulations should be developed that correspond to the current state of common powder or granular products for commercial dishwashers.
  • alkali hydroxide-containing, melt-block-like agents for the mechanical cleaning of dishes have been described, which by mixing with all other alkaline-reacting active substances such as. B. sodium silicates and pentasodium triphosphate and optionally water, if the preferred water of hydration of the compounds mentioned is not sufficient, and then gentle heating of the mixture with stirring to 90 to 100 ° C until reaching a uniformly molten mass and its pouring into molds and solidification to a dense Crystal aggregate were manufactured.
  • active chlorine-containing compounds in these melt-block-shaped agents has not been mentioned there.
  • the invention now relates to melt block-shaped, alkali hydroxide-containing, homogeneous and storage-stable agents for the mechanical cleaning of dishes containing alkali silicates and water, preferably as water of crystallization, and optionally pentalkalitriphosphate and is characterized in that it is 0.2 to 4% by weight on the active chlorine content and the entire agent, on an active choir-releasing compound which has a hydrolysis constant of 3. 10 -4 or less.
  • alkali hydroxide potassium and, for reasons of price, preferably sodium hydroxide are suitable, which are preferably in solid form, ie. H. as flakes, flakes or prills, practically anhydrous or as a monohydrate.
  • the amounts that are used are in particular 2 to 70, preferably 5 to 50,% by weight, anhydrous, based on the total composition.
  • Alkali silicates in particular are alkali metal silicates, namely water-free, but advantageously in the form of sodium metasilicate. 9 H2O, sodium metasilicate. 6 H2O and sodium metasilicate. 5 H2O used.
  • the amounts used in the particular form are in particular 2 to 60, preferably 5 to 50,% by weight, based on the total composition.
  • pentaalkali metal triphosphate which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, so that a total water content of 5.5 moles is calculated.
  • pentaalkali metal triphosphate which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, so that a total water content of 5.5 moles is calculated.
  • pentaalkali metal triphosphate which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, so that a total water content of 5.5 moles is calculated.
  • pentaalkali metal triphosphate which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, so that a total water content of 5.5 moles is calculated.
  • They are in amounts of 0.2 to 4, preferably from 0.5 to 2 wt .-%, based on the active chlorine content, the z. B. to be determined by iodometric titration, and the entire mean used.
  • the total water content of the melt-block-shaped cleaning agents from dense crystal aggregates is 10 to 40, preferably 15 to 30% by weight. It is preferred by the crystal water content of the alkaline active substances, but possibly also introduced via water glass solutions. The calculations of the water content must therefore be based on these compounds.
  • the alkali silicate is first anhydrous, as a metasilicate hydrate and / or as a water glass solution, alone or together with solid alkali hydroxide or its monohydrate at 45 to 65 ° C until silum bie; warmed without affecting the automatic heating to 60 to 65 ° C, then with stirring or kneading all other, preferably hydrate-containing components, of which last, at temperatures from 50 to 65 ° C, preferably from 55 to 63 ° C, pentasodium triphosphate and / or whose hexahydrate and the active chlorine-releasing compound are stirred in, the still liquid melt is poured into arbitrarily shaped, preferably flexible, molds and solidifies into blocks therein.
  • the solidification process takes a few minutes to about an hour depending on the size of the mold.
  • the melting blocks are very hard, hard or less hard, but in any case consistently and thoroughly composed and quickly soluble when used.
  • the cast melting bodies had a weight of 25 to 30 g. They were stored in the laboratory and the active chlorine content (A-Cl) was determined in a known manner after appropriate times.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
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  • Coloring Foods And Improving Nutritive Qualities (AREA)

Abstract

Detergents for dishwashing machines in the form of fused blocks containing alkali metal hydroxides, alkali metal silicates, and from 0.2 to 4% by weight of active chlorine donors having a hydrolysis constant of 3x10-4 or lower (preferably Na- or K-dichloroisocyanurate, Na-dichloroisocyanurate dihydrate, Na-monochloroamido-sulfonate or Na-N-chloro-p-toluene sulfonic acid amide). The process of making the fused blocks comprises heating metasilicate or waterglass solution with or without solid alkali metal hydroxide to 45 DEG to 48 DEG C., allowing the reaction temperature to rise to 60 DEG to 65 DEG C., adding the remaining ingredients including the active chlorine donor at 50 DEG to 65 DEG C., pouring the still liquid melt into flexible molds and allowing it to solidify into blocks therein. The detergent blocks of the invention have good stability to storage and a high dissolving rate in use.

Description

Feste Reinigungsmittel für das maschinelle Geschirrspülen werden überwiegend in Pulver- bzw. Granulatform (Agglomerate) angeboten. Die Einzelpartikeln dieser Mittel haben dabei einen bevorzugten Durchmesser zwischen 0,01 bis 3 mm. Ein gravierender Nachteil dieser Art fester Reinigungsmittel, speziell der im Bereich des gewerblichen Großverbrauchs verwendeten mit einem Gehalt von 10 bis 60 Gew.-% an Alkalihydroxiden, besteht darin, daß wegen der Hygroskopizität einzelner Rohstoffe bei Zutritt von geringen Mengen an Feuchtigkeit eine starke Neigung zum Verbacken oder Verklumpen besteht.Solid detergents for automatic dishwashing are mainly offered in powder or granular form (agglomerates). The individual particles of these agents have a preferred diameter between 0.01 and 3 mm. A serious disadvantage of this type of solid cleaning agents, especially those used in the field of large-scale commercial use with a content of 10 to 60% by weight of alkali metal hydroxides, is that, due to the hygroscopicity of individual raw materials, small amounts of moisture have a strong tendency to Baked or clumped.

Durch Zusatz von sogenannten "Anticaking"-Mitteln, wie z. B. Paraffin, oder durch Umhüllen stark hygroskopischer Bestandteile, wie z. B. der Alkalihydroxide und des Natriummetasilikats, mit pulverförmigen Substanzen, wie z. B. Pentanatriumtriphosphat oder Natriumsulfat, werden leichte Verbesserungen des Verbackungs- bzw. Klumpverhaltens erzielt; größere Mengen an Feuchtigkeit in Form von Wasser oder Wasserdampf führen aber trotzdem zum Verbacken bzw. Verklumpen der pulverförmigen oder granulierten (agglomerierten) Reinigungsmittel.By adding so-called "anticaking" agents, such as. B. paraffin, or by enveloping strongly hygroscopic components, such as. B. the alkali metal hydroxides and sodium metasilicate, with powdery substances such. B. pentasodium triphosphate or sodium sulfate, slight improvements in caking or clumping behavior are achieved; Larger amounts of moisture in the form of water or water vapor nevertheless lead to caking or clumping of the powdery or granulated (agglomerated) cleaning agents.

Die Reinigungsmittel werden dadurch zwar nicht unbrauchbar, denn die Wirkung der Bestandteile bleibt auch nach dem Verklumpen bzw. Verbacken infolge von Feuchtigkeitszutritt erhalten. Für den Anwender erscheint die Qualität der Reinigungsmittel häufig jedoch allein schon aus optischen Gründen in den meisten Fällen gemindert oder schlecht, was zu Reklamationen führt.This does not make the cleaning agents unusable, because the effect of the components remains after Get clumped or caked as a result of moisture ingress. For the user, however, the quality of the cleaning agents often appears to be reduced or poor in most cases for optical reasons alone, which leads to complaints.

Nachteilig ist der Einsatz von Reinigungsmitteln, die bei Zutritt von Feuchtigkeit zum Verklumpen bzw. Verbacken neigen, insbesondere in automatischen, bevorratenden Dosiergeräten, die im Bereich des gewerblichen Großverbrauchs an Eintank- und Mehrtankspülmaschinen in großer Zahl Verwendung finden. Es kommt zu Dosierstörungen in der Art, daß zu wenig Reinigungsmittel ausgetragen wird oder sogar mechanische Beschädigungen des Dispensersystems auftreten, so daß dieses unbrauchbar wird. Abhilfe kann nur das Unterbinden des Zutritts von Feuchtigkeit in das Vorratsgefäß schaffen, was jedoch in feuchter Küchenatmosphäre oder nach Reinigung des Gerätes mit Wasser ohne besondere Trocknung der Teile des Vorratsgefäßes und der Dosiervorrichtung nicht gewährleistet werden kann.A disadvantage is the use of cleaning agents that tend to clump or cake when exposed to moisture, especially in automatic, stocking dosing devices that are used in large numbers in the area of large-scale commercial use of single-tank and multi-tank dishwashers. There are metering disorders in the way that too little cleaning agent is discharged or even mechanical damage to the dispenser system occurs, so that it becomes unusable. The only remedy is to prevent the entry of moisture into the storage container, but this cannot be guaranteed in a damp kitchen atmosphere or after cleaning the device with water without drying the parts of the storage container and the dosing device.

Das Verklumpen bzw. Verbacken von alkalischen Reinigungsmitteln kann unter anderem dadurch vermieden werden, daß man diese von vornherein in Blockform herstellt und in hohem Maße feuchtigkeitssicher verpackt, vertreibt und verwendet.The clumping or caking of alkaline cleaning agents can be avoided, among other things, by producing them in block form from the outset and packing, distributing and using them in a moisture-proof manner.

Damit sind jedoch keineswegs alle Probleme gelöst, denn die Einarbeitung aktivchlorhaltiger Verbindungen in stark alkalische Reinigungsmittel ist sehr schwierig.However, this does not solve all problems, because the incorporation of compounds containing active chlorine into strongly alkaline cleaning agents is very difficult.

So werden in der EP-PS 3 769 Waschmittelbehälter, insbesondere zum maschinellen Geschirreinigen, beschrieben, die feste Reinigungsmittelblöcke, hergestellt aus Wasser und zwei festen Bestandteilen, von denen mindestens einer eine alkalische hydratisierbare Verbindung ist, enthalten und nur an einer Stelle offen sind, aus der dann das Reinigungsmittel durch den Wasserstrom in der Waschmaschine herausgespült wird. Sofern diese Reinigungsmittel neben Alkalihydroxid noch Aktivchlorverbindungen enthalten sollen, die als notwendig für die Entfernung bleichbarer Anschmutzungen, wie z. B. Tee, Kaffee, Fruchtsäfte usw. angesehen werden, müssen diese vorzugsweise als vorgeformte Kerne während des Erstarrens der heißgelösten Reinigungsmittel in die noch weiche Masse eingebracht werden. Zum besseren Schutz des Chlorträgers soll der Kern noch entweder mit Paraffin oder mit einem wachsähnlichen Mono- und Dialkylester der Polyphosphorsäure umhüllt werden. Eine direkte Einarbeitung von aktivchlorhaltigen Verbindungen, speziell in Gegenwart hoher Konzentrationen an Alkalihydroxid, wird als nicht realisierbar angesehen. In Beispiel 13, Tabelle 1, wird aufgezeigt, daß eine direkte Zugabe der aktivchlorabspaltenden Verbindung zu der entanenden losung der übrigen Reinigunprinttel bestandteile innerhalb von 24 Stunden zu einem hohen Verlust an Aktivchlor führt. Die untersuchten Chlorträger waren Ca(OCl)₂, LiOCl und Na-dichlorisocyanurat-dihydrat. Es wurden je nach dem Chlorträger Restchloraktivitäten zwischen nur noch 3,5 und 17,4% des Ausgangswertes bestimmt.EP-PS 3 769 describes detergent containers, in particular for machine dishwashing, which contain solid detergent blocks made from water and two solid constituents, at least one of which is an alkaline hydratable compound and which are only open at one point then the detergent through the water flow is washed out in the washing machine. If these cleaning agents are to contain active chlorine compounds in addition to alkali hydroxide, which are necessary for the removal of bleachable soiling, such as, for. B. tea, coffee, fruit juices, etc. are considered, these must preferably be introduced as pre-shaped kernels during the solidification of the heat-dissolved cleaning agent in the still soft mass. To better protect the chlorine carrier, the core should still be coated either with paraffin or with a wax-like mono- and dialkyl ester of polyphosphoric acid. Direct incorporation of compounds containing active chlorine, especially in the presence of high concentrations of alkali metal hydroxide, is not considered feasible. In Example 13, Table 1, it is shown that a direct addition of the active chlorine-releasing compound to the dewaxing solution of the other cleaning components leads to a high loss of active chlorine within 24 hours. The investigated chlorine carriers were Ca (OCl) ₂, LiOCl and Na dichloroisocyanurate dihydrate. Depending on the chlorine carrier, residual chlorine activities between only 3.5 and 17.4% of the initial value were determined.

Das Einarbeiten vorgeformter Kerne mit aktivchlorabspaltenden Verbindungen ist zwar durchführbar, verursacht jedoch hohe Kosten durch arbeitsintensive Herstellung und die erforderlichen Rohstoffe. Außerdem kommt es naturgemäß zu differierenden Löslichkeiten von Reinigungsmittelblöcken und deren Kern.The incorporation of preformed cores with active chlorine-releasing compounds is feasible, but causes high costs due to labor-intensive production and the necessary raw materials. In addition, there are naturally different solubilities of detergent blocks and their core.

Es bestand daher die Aufgabe, Möglichkeiten zu finden, Aktivchlorträger in Gegenwart von Alkalihydroxiden in möglichst homogener Verteilung in blockförmige Reinigungsmittel einzubringen. Dabei sollten gleichzeitig auch Reinigungsmittelformulierungen entwickelt werden, die dem gegenwärtigen Stand heute üblicher pulver- oder granulatförmiger Produkte für gewerbliche Geschirrspülmaschinen entsprechen.The object was therefore to find ways of introducing active chlorine carriers into block-shaped cleaning agents in the most homogeneous distribution possible in the presence of alkali metal hydroxides. At the same time, detergent formulations should be developed that correspond to the current state of common powder or granular products for commercial dishwashers.

In der US-PS 2,412,819 sind schon alkalihydroxidhaltige, schmelzblockförmige Mittel für das maschinelle Reinigen von Geschirr beschrieben worden, die durch Zusammenmischen mit allen weiteren alkalisch reagierenden Aktivsubstanzen wie z. B. Natriumsilikaten und Pentanatriumtriphosphat sowie gegebenenfalls Wasser, falls das bevorzugte Hydratwasser der genannten Verbindungen nicht ausreicht, und anschließendes mildes Erwärmen der Mischung unter Rühren auf 90 bis 100°C bis zum Erreichen einer einheitlich geschmolzenen Masse sowie deren Vergießen in Formen und Erstarrenlassen zu einem dichten Kristallaggregat hergestellt wurden. Ein möglicher Gehalt dieser schmelzblockförmigen Mittel an aktivchlorhaltigen Verbindungen ist dort nicht erwähnt worden.In US Pat. No. 2,412,819, alkali hydroxide-containing, melt-block-like agents for the mechanical cleaning of dishes have been described, which by mixing with all other alkaline-reacting active substances such as. B. sodium silicates and pentasodium triphosphate and optionally water, if the preferred water of hydration of the compounds mentioned is not sufficient, and then gentle heating of the mixture with stirring to 90 to 100 ° C until reaching a uniformly molten mass and its pouring into molds and solidification to a dense Crystal aggregate were manufactured. A possible content of active chlorine-containing compounds in these melt-block-shaped agents has not been mentioned there.

Die Erfindung betrifft nun alkalihydroxidhaltige schmelzblockförmige, homogene und lagerstabile Mittel für das maschinelle Reinigen von Geschirr mit einem Gehalt an Alkalisilikaten und Wasser, vorzugsweise als Kristallwasser, sowie gegebenenfalls Pentaalkalitriphosphat und ist dadurch gekennzeichnet, daß sie 0,2 bis 4 Gew.-%, bezogen auf den Aktivchlorgehalt und das gesamte Mittel, an einer aktivchorabspaltenden Verbindung, die eine Hydrolysenkonstante von 3. 10-4 oder kleiner besitzt, enthalten.The invention now relates to melt block-shaped, alkali hydroxide-containing, homogeneous and storage-stable agents for the mechanical cleaning of dishes containing alkali silicates and water, preferably as water of crystallization, and optionally pentalkalitriphosphate and is characterized in that it is 0.2 to 4% by weight on the active chlorine content and the entire agent, on an active choir-releasing compound which has a hydrolysis constant of 3. 10 -4 or less.

Als Alkalihydroxid kommen Kalium- und aus Preisgründen vorzugsweise Natriumhydroxid in Betracht, die vorzugsweise in fester Form, d. h. als Schuppen, Flocken oder Prills, praktisch wasserfrei oder als Monohydrat, eingesetzt werden. Die Mengen, die eingesetzt werden, betragen insbesondene 2 bis 70, vorzugsweise 5 bis 50 Gew.-%, wasserfrei, bezogen auf das gesamte Mittel.As alkali hydroxide, potassium and, for reasons of price, preferably sodium hydroxide are suitable, which are preferably in solid form, ie. H. as flakes, flakes or prills, practically anhydrous or as a monohydrate. The amounts that are used are in particular 2 to 70, preferably 5 to 50,% by weight, anhydrous, based on the total composition.

Als Alkalisilikate werden besonders Alkalimetasilikate, und zwar wasserfrei, vorteilhaft aber in Form von Natriummetasilikat . 9 H₂O, Natriummetasilikat . 6 H₂O und Natriummetasilikat . 5 H₂O eingesetzt. Die Einsatzmengen in der jeweiligen Form betragen insbesondene 2 bis 60, vorzugsweise 5 bis 50 Gew.-%, bezogen auf das gesamte Mittel. Man kann aber die Alkalimetasilikate auch teilweise oder vollständig durch Wasserglaslösungen ersetzen, wobei das Verhältnis von Na₂O : SiO₂ 1 : 1 bis 1 : 4, vorzugsweise 1 : 2 bis 1 : 3,5 beträgt. Wegen des höheren Silikatgehaltes des Wasserglases werden dessen Lösungen in Mengen von 2 bis 30, vorzugsweise von 5 bis 15 Gew.-%, bezogen auf das gesamte Mittel, eingesetzt.Alkali silicates in particular are alkali metal silicates, namely water-free, but advantageously in the form of sodium metasilicate. 9 H₂O, sodium metasilicate. 6 H₂O and sodium metasilicate. 5 H₂O used. The amounts used in the particular form are in particular 2 to 60, preferably 5 to 50,% by weight, based on the total composition. But you can also partially or completely replace the alkali metal silicates with water glass solutions, which Ratio of Na₂O: SiO₂ is 1: 1 to 1: 4, preferably 1: 2 to 1: 3.5. Because of the higher silicate content of the water glass, its solutions are used in amounts of 2 to 30, preferably 5 to 15% by weight, based on the total agent.

Vorteilhaft hat sich auch ein Zusatz von insbesondene 2 bis 50, vorzugsweise 5 bis 45 Gew.-%, wasserfrei, bezogen auf das gesamte Mittel, an Pentaalkalitriphosphat erwiesen, das als Hexahydrat oder als Mischung von Hexahydrat mit geringen Mengen von wasserfreiem Pentanatriumtriphosphat eingesetzt wird, so daß sich ein Gesamtwassergehalt von 5,5 Mol errechnet. Es kann aber auch wasserfrei eingesetzt werden, was vom Gesamtwassergehalt der anderen Bestandteile abhängt.It has also proven advantageous to add in particular 2 to 50, preferably 5 to 45,% by weight, anhydrous, based on the total composition, of pentaalkali metal triphosphate, which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, so that a total water content of 5.5 moles is calculated. However, it can also be used without water, depending on the total water content of the other components.

Als aktivchlorabspaltende Verbindungen können die verschiedenen chlorierten Verbindungen der Isocyanursäure, wie Na/K-Di-chlorisocyanurat und Na-Dichlorisocyanurat-dihydrat (Na- DCC-2H₂O), Na-monochloramidosulfonat (= N-Chlorosulfamat), und N-Chlor-p-toluolsulfonsäureamid-Natrium ("Chloramin T") eingesetzt werden. Allen gemeinsam ist, daß sie eine Hydrolysenkonstante von etwa 3 10⁻⁴ oder kleiner besitzen (vergleiche hierzu W.G. Mizuno "Dishwashing", Kapitel 21, insbesondere Seite 875, Tabelle 7 in "Detergency, Theory and Test Methods", Teil 3 (1981), Verlag Marcel Dekker, N.Y.).The various chlorinated compounds of isocyanuric acid, such as Na / K-di-chloroisocyanurate and Na dichloroisocyanurate dihydrate (Na-DCC-2H₂O), Na-monochloramidosulfonate (= N-chlorosulfamate), and N-chloro-p- toluenesulfonamide sodium ("chloramine T") are used. Common to all is that they have a hydrolysis constant of about 3 10 etwa or less (compare WG Mizuno "Dishwashing", Chapter 21, in particular page 875, Table 7 in "Detergency, Theory and Test Methods", Part 3 (1981) , Publisher Marcel Dekker, NY).

Sie werden in Mengen von 0,2 bis 4, vorzugsweise von 0,5 bis 2 Gew.-%, bezogen auf den Aktivchlorgehalt, der z. B. durch jodometrische Titration zu bestimmen ist, und das gesamte Mittel, eingesetzt.They are in amounts of 0.2 to 4, preferably from 0.5 to 2 wt .-%, based on the active chlorine content, the z. B. to be determined by iodometric titration, and the entire mean used.

Der gesamte Wassergehalt der schmelzblockförmigen Reinigungsmittel aus dichten Kristallaggregaten beträgt 10 bis 40, vorzugsweise 15 bis 30 Gew.-%. Er wird bevorzugt durch den Kristallwassergehalt der alkalisch reagierenden Aktivsubstanzen, gegebenenfalls aber auch über Wasserglaslösungen, eingebracht. Die Berechnungen des Wassergehalts haben daher von diesen Verbindungen auszugehen.The total water content of the melt-block-shaped cleaning agents from dense crystal aggregates is 10 to 40, preferably 15 to 30% by weight. It is preferred by the crystal water content of the alkaline active substances, but possibly also introduced via water glass solutions. The calculations of the water content must therefore be based on these compounds.

Bekanntlich hydrolysiert Pentanatriumtriphosphat in Gegenwart von Alkalihydroxiden. Die Hydrolyse wird durch erhöhte Temperaturen noch gesteigert. Nach der in der US-PS 2,412,819 beschriebenen Vorgehensweise wird daher bei möglichst niedrigen Schmelztemperaturen von 90 bis 100°C gearbeitet.As is known, pentasodium triphosphate hydrolyzes in the presence of alkali metal hydroxides. The hydrolysis is increased by elevated temperatures. The procedure described in US Pat. No. 2,412,819 is therefore carried out at the lowest possible melting temperatures of 90 to 100.degree.

Es hat sich gezeigt, daß man bei weitaus niedrigeren und daher schonenderen Temperaturen von 45 bis 70°C, vorzugsweise von 45 bis 65°C arbeiten kann, wenn man erfindungsgemäß zuerst das Alkalisilikat, wasserfrei, als Metasilikathydrat und/oder als Wasserglaslösung allein oder zusammen mit festem Alkalihydroxid oder dessen Monohydrat auf 45 bis 65°C bis zur Silumebie; erwärmt, ohne das dabei auftretende selbsttätige Erwärmen auf 60 bis 65°C zu beeinflussen, anschließend unter Rühren oder Kneten alle weiteren, vorzugsweise hydratwasserhaltigen Bestandteile, davon zuletzt, bei Temperaturen von 50 bis 65°C, vorzugsweise von 55 bis 63°C, Pentanatriumtriphosphat und/oder dessen Hexahydrat und die aktivchlorabspaltende Verbindung einrührt, die noch flüssige Schmelze in beliebig gestaltete, vorzugsweise flexible Formen gießt und in diesen zu Blöcken erstarren läßt.It has been shown that it is possible to work at much lower and therefore gentler temperatures of 45 to 70 ° C., preferably 45 to 65 ° C., if, according to the invention, the alkali silicate is first anhydrous, as a metasilicate hydrate and / or as a water glass solution, alone or together with solid alkali hydroxide or its monohydrate at 45 to 65 ° C until silum bie; warmed without affecting the automatic heating to 60 to 65 ° C, then with stirring or kneading all other, preferably hydrate-containing components, of which last, at temperatures from 50 to 65 ° C, preferably from 55 to 63 ° C, pentasodium triphosphate and / or whose hexahydrate and the active chlorine-releasing compound are stirred in, the still liquid melt is poured into arbitrarily shaped, preferably flexible, molds and solidifies into blocks therein.

Der Erstarrungsprozeß dauert je nach Größe der Gußform wenige Minuten bis etwa eine Stunde. Die Schmelzblöcke sind je nach ihrer Zusammensetzung sehr hart, hart oder weniger hart, in jedem Fall aber durch und durch einheitlich zusammengesetzt und bei der Anwendung schnell löslich.The solidification process takes a few minutes to about an hour depending on the size of the mold. Depending on their composition, the melting blocks are very hard, hard or less hard, but in any case consistently and thoroughly composed and quickly soluble when used.

BeispieleExamples Beispiel 1:Example 1:

Ein Gemisch aus 50 Gewichtsteilen Na₂SiO₃ . 9 H₂O und 50 Gewichtsteilen Na0H-Prills wurde in einem Edelstahlgefäß unter Rühren mit einem Teflonrührwerk von außen auf 46 bis 47°C erwärmt, wobei die Abspaltung des Kristallwassers begann und gleichzeitig durch die Hydratisierung der Na0H ein Temperaturanstieg erfolgte (60 bis 65°C). Nach Abkühlung auf Temperaturen unterhalb 55°C wurde in die fließfähige Suspension der Chlorträger eingearbeitet und in Wachspappeformen vergossen. Als Chlorträger wurden Trichlorisocyanursäure (TICA), Na-di-chlorisocyanurat -dihydrat (NaDCC-2 H₂O) und Chloramin T (Cl-T) eingearbeitet. Dabei wurde die Menge an Chlorträger so gewählt, daß im fertigen Produkt gleiche Aktivchlorgehalte vorlagen. Daraus resultierten folgende Zusammensetzungen (Angaben in Gew.-%):

Figure imgb0001
A mixture of 50 parts by weight of Na₂SiO₃. 9 H₂O and 50 parts by weight of Na0H prills were heated in a stainless steel vessel with stirring using a Teflon stirrer from outside to 46 to 47 ° C, the elimination of the crystal water and at the same time a temperature increase (60 to 65 ° C) due to the hydration of the Na0H. . After cooling to temperatures below 55 ° C, the chlorine carrier was incorporated into the flowable suspension and poured into wax cardboard molds. Trichloroisocyanuric acid (TICA), sodium di-chloroisocyanurate dihydrate (NaDCC-2 H₂O) and chloramine T (Cl-T) were incorporated as chlorine carriers. The amount of chlorine carrier was chosen so that the same active chlorine content was present in the finished product. This resulted in the following compositions (data in% by weight):
Figure imgb0001

Die vergossenen Schmelzkörper hatten ein Gewicht von 25 bis 30 g. Sie wurden im Labor gelagert und nach entsprechenden Zeiten in bekannter Weise der Aktivchlorgehalt (A-Cl) bestimmt.

Figure imgb0002
The cast melting bodies had a weight of 25 to 30 g. They were stored in the laboratory and the active chlorine content (A-Cl) was determined in a known manner after appropriate times.
Figure imgb0002

Die Ergebnisse zeigen, daß für Chloramin T die günstigste Chlorstabilität mit nahezu vollständiger Aktivchlorerhaltung beobachtet wurde, während der Einsatz von TICA ungeeignet ist.The results show that the cheapest chlorine stability with almost complete retention of active chlorine was observed for chloramine T, while the use of TICA is unsuitable.

Beispiel 2:Example 2:

10 Gewichtsteile Wasserglaslösung wurden bei 50 bis 55°C mit 50 Gewichtsteilen NaOH . H₂O und 40 Gewichtsteilen wasserfreiem Pentanatriumtriphosphat sowie dem Aktivchlorträger vermischt. Die Suspension wurde in Formen vergossen, wo sie rasch erstarrte. Als Aktivchlorträger wurden TICA und Cl-T verwendet. Dabei wurde die Menge an Aktivchlorträger so gewählt, daß im fertigen Produkt gleiche Aktivchlorgehalte vorlagen. Daraus resultierten folgende Zusammensetzungen (Angaben in Gew.-%):

Figure imgb0003
10 parts by weight of water glass solution were at 50 to 55 ° C with 50 parts by weight of NaOH. H₂O and 40 parts by weight of anhydrous pentasodium triphosphate and the active chlorine carrier mixed. The suspension was poured into molds where it quickly solidified. TICA and Cl-T were used as active chlorine carriers. The amount of active chlorine carrier was chosen so that the same active chlorine contents were present in the finished product. This resulted in the following compositions (data in% by weight):
Figure imgb0003

Wie in Beispiel 1 beschrieben, wurden auch hier entsprechende Lagerversuche durchgeführt:

Figure imgb0004
As described in Example 1, corresponding storage tests were also carried out here:
Figure imgb0004

Auch hier wird für Chloramin T eine gute Lagerstabilität gefunden, während TICA für den Einsatz ebenfalls ungeeignet ist.Here too, good storage stability is found for chloramine T, while TICA is also unsuitable for use.

Beispiel 3:Example 3:

12 Gewichtsteile Wasserglaslösung wurden bei Raumtemperatur 55 Gewichtsteile mit NaOH-Prills vermischt, wobei die Temperatur auf ca. 65 bis 70°C anstieg. Nach Abkühlung auf ca. 50 bis 55°C wurden der Lösung die aktivchlorhaltige Komponente und 33 Gewichtsteile Pentanatriumtriphosphat hinzugemischt und die Schmelzmasse vergossen. Als Aktivchlorträger wurden das Natriumsalz der N-Monochloramidosulfonsäure (MCAS) als wäßrige Lösung (9,4% Aktivchlor) und Chlorlaugelösung (12,8% Aktivchlor) eingerührt. Die eingesetzten Mengen an Chlorträgern wurden dabei wieder so gewählt, daß vergleichbare Aktivchlorgehalte vorlagen. Daraus resultierten folgende Zusammensetzungen (Angaben in Gew.-%):

Figure imgb0005
12 parts by weight of water glass solution were mixed at room temperature with 55 parts by weight of NaOH prills, the temperature rising to about 65 to 70 ° C. After cooling to about 50 to 55 ° C., the active chlorine-containing component and 33 parts by weight of pentasodium triphosphate were mixed into the solution and the melt was poured in. The sodium salt of N-monochloramidosulfonic acid (MCAS) was stirred in as the active chlorine carrier as an aqueous solution (9.4% active chlorine) and chlorine solution (12.8% active chlorine). The amounts of chlorine carriers used were chosen so that comparable levels of active chlorine were available. This resulted in the following compositions (data in% by weight):
Figure imgb0005

Mit den hergestellten Reinigerblöcken wurden, wie im Beispiel 1 beschrieben, Lagerversuche durchgeführt. Rezeptur 3c konnte nicht mitgeprüft werden, da direkt nach der Herstellung Aktivchlorgehalte von weniger als 40% des Ausgangswertes gefunden wurden. Chlorlaugelösung ist also als Bestandteil der erfindungsgemäßen Mittel nicht geeignet.

Figure imgb0006
Storage tests were carried out with the cleaner blocks produced, as described in Example 1. Formulation 3c could not be checked as well, since active chlorine contents of less than 40% of the initial value were found immediately after production. Chlorine solution is therefore not suitable as a component of the agents according to the invention.
Figure imgb0006

Die Ergebnisse zeigen, daß der Chlorträger MCAS in homogener Verteilung ausreichend stabil eingearbeitet werden kann.The results show that the chlorine carrier MCAS can be incorporated in a sufficiently stable manner in a homogeneous distribution.

Beispiel 4:Example 4:

In einem Edelstahlgefäß wurden 10 Gewichtsteile Wasserglas-Lösung (34,5%ig, wie in Beispiel 2) mit 8 Gewichtsteilen einer 50%igen wäßrigen NaOH-Lösung vorgelegt und vermischt. In die Lösung wurden 35 Gewichtsteile festes NaOH in Form von Microprills eingerührt, die sich zunächst nur teilweise lösten. Nach Zugabe von 11 Gewichtsteilen einer MCAS-Chlorträgerlösung (vgl. Beispiel 3) wurde eine homogene Schmelze erhalten, deren Temperatur auf 63°C eingestellt wurde. In die Schmelze wurden dann zügig 36 Gewichtsteile Pentanatriumtriphosphat eingerührt. Die resultierende Masse wurde vergossen. Das Material erstarrte weitgehend innerhalb von 10 - 15 Minuten zu formstabilen Blöcken.10 parts by weight of water glass solution (34.5% as in Example 2) with 8 parts by weight of a 50% aqueous NaOH solution were placed in a stainless steel vessel and mixed. 35 parts by weight of solid NaOH in the form of microprills were stirred into the solution, which initially only partially dissolved. After adding 11 parts by weight of an MCAS chlorine carrier solution (cf. Example 3), a homogeneous melt was obtained, the temperature of which was set at 63 ° C. 36 parts by weight of pentasodium triphosphate were then rapidly stirred into the melt. The resulting mass was poured. The material solidified to form stable blocks within 10 - 15 minutes.

Claims (4)

1. Homogeneous and storable detergents for dishwashing machines in the form of fused blocks containing alkali hydroxides, alkali silicates and water, preferably as water of crystallization, and optionally pentaalkali triphos­phate, characterized in that they contain 0.2 to 4% by weight, based on the active chlorine content and on the detergent as a whole, of an active chlorine donor having a hydrolysis constant of 3.10-4 or lower.
2. Detergents as claimed in claim 1, characterized in that they contain Na- or K-dichloroisocyanurate,.Na-dichlo­roisocyanurate dihydrate, Na-N-monochloroamidosulfonic acid or Na-N-chloro-p-toluene sulfonic acid amide as active chlorine donor.
3. Detergents as claimed in claims 1 and 2, characterized in that they contain the active chlorine donor in quant­ities of from 0.5 to 2% by weight, based on the active chlorine content and on the detergent as a whole.
4. A process for producing the homogeneous, storable detergents in the form of fused blocks containing alkali hydroxides claimed in claim 1, characterized in that the alkali silicate, anhydrous, as metasilicate and/or as waterglass solution, is first heated either on its own or together with solid alkali hydroxide or its monohydrate to 45 to 65°C - without influencing the resulting spontaneous heating to 60 to 65°C - until a melt is formed, all the other constituents, preferably containing water of hydra­tion, including last of all - after the temperature of the melt has fallen to 50 to 65°C and preferably 55 to 63°C - pentasodium triphosphate and/or its hexahydrate, and the active chlorine donor are then introduced with stirring or kneading and the still liquid melt is poured into preferab­ly flexible moulds of any shape and allowed to solidify into blocks therein.
EP86106948A 1985-05-30 1986-05-22 Compounds in melted block form containing alkaline hydroxide and active chlorine for machine dish-washing, and process for their preparation Expired - Lifetime EP0203526B1 (en)

Priority Applications (1)

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AT86106948T ATE60355T1 (en) 1985-05-30 1986-05-22 MELT BLOCK, ALKALINE HYDROXIDE AND ACTIVE CHLORINE CONTAINING DETERGENTS FOR AUTOMATIC DISH WASHING AND PROCESS FOR THEIR MANUFACTURE.

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DE3519355 1985-05-30
DE19853519355 DE3519355A1 (en) 1985-05-30 1985-05-30 MELT BLOCK-SHAPED, ALKALINE HYDROXIDE AND ACTIVE CHLORINE-CONTAINING AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THEIR PRODUCTION

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US4729845A (en) 1988-03-08
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EP0203526A3 (en) 1988-03-23
DE3519355A1 (en) 1986-12-04
ATE60355T1 (en) 1991-02-15

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