EP0203526A2 - 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
EP0203526A2
EP0203526A2 EP86106948A EP86106948A EP0203526A2 EP 0203526 A2 EP0203526 A2 EP 0203526A2 EP 86106948 A EP86106948 A EP 86106948A EP 86106948 A EP86106948 A EP 86106948A EP 0203526 A2 EP0203526 A2 EP 0203526A2
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EP
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Prior art keywords
active chlorine
alkali metal
water
compounds
chlorine
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EP86106948A
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German (de)
French (fr)
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EP0203526B1 (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 used in powder or Granular form (agglomerates) offered.
  • 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 which tend to clump or cake when exposed to moisture, in particular in automatic, stocking dosing devices which are used in large numbers in the area of large-scale commercial use of single-tank and multi-tank dishwashers.
  • cleaning agents which tend to clump or cake when exposed to moisture
  • the only remedy is to prevent the entry of moisture into the storage container - which, however, cannot be guaranteed in a damp kitchen atmosphere or after cleaning the device with water without special drying of the parts of the storage container and the dosing device.
  • the clumping or caking of alkaline cleaning agents can be avoided, inter alia, by producing them in block form from the outset and packaging, 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 are only open at one point then the detergent is rinsed out by the water flow 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 preformed Keme during the solidification of the detergent in the still soft mass. In order 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.
  • Example 13 shows that a direct addition of the active chlorine-releasing compound to the melt mass leads to a high loss of active chlorine within 24 hours.
  • the chlorine carriers investigated were Ca (OCI)., LiOCI 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 also be developed which correspond to the current state of common powder or granular products for commercial dishwashers.
  • alkali hydroxide-containing, melt-block-like agents for machine cleaning of dishes have already 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 mildly heating the mixture with stirring to 90 to 100 ° C until reaching a uniformly molten mass and pouring it into molds and allowing it to solidify Crystal aggregate were manufactured.
  • a possible content of these - melt block-like agents in compounds containing active chlorine has not been mentioned there.
  • the invention now relates to alkali hydroxide-containing, melt-block-shaped, homogeneous and storage-stable agents for the mechanical cleaning of dishes containing alkali silicates and water, preferably as water of crystallization, and optionally pentaalkali nitride phosphate with a further content of active chlorine-releasing compounds.
  • alkali hydroxide potassium and, for reasons of price, preferably sodium hydroxide are suitable, which are preferably in solid form, i.e. H. as flakes, flakes or prills, practically anhydrous or as a monohydrate.
  • the amounts used are 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 H 2 0, sodium metasilicate. 6 H 2 0 and sodium metasilicate. 5 H 2 0 used.
  • the amounts used in the particular form are 2 to 60, preferably 5 to 50,% by weight, based on the total composition.
  • the alkali metal silicates can also be partially or completely replaced by water glass solutions, the ratio of Na 2 0: Si0 2 being 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.
  • An addition of 2 to 50, preferably 5 to 45% by weight, anhydrous, based on the total composition, of pentaalkali metal triphosphate, which is used as a hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, has also proven advantageous 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.
  • 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 wt .-%. It is preferably introduced by the crystal water content of the alkaline reacting substances, but possibly also 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 heated to 45 to 65 ° C with solid alkali metal hydroxide or its monohydrate, without influencing the automatic heating to 60 to 65 ° C which occurs, then with stirring or kneading, all other, preferably hydrate-containing constituents, of which lastly, at tempera doors from 50 to 65 ° C, preferably from 55 to 63 ° C, pentasodium triphosphate and / or its hexahydrate and the active chlorine-releasing compound, which still pours liquid melt into any shape, preferably flexible, and solidifies it into blocks.
  • 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)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Cleaning Or Drying Semiconductors (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 used in powder or Granular form (agglomerates) offered. 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. As pentasodium triphosphate or sodium sulfate, slight improvements in the baking or. Achieved clumping behavior; 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 is retained even after clumping or caking due to the ingress of moisture. 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 which tend to clump or cake when exposed to moisture, in particular in automatic, stocking dosing devices which 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 - which, however, cannot be guaranteed in a damp kitchen atmosphere or after cleaning the device with water without special drying of 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, inter alia, by producing them in block form from the outset and packaging, 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 Keme während des Erstarrens der 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 Schmelzmasse innerhalb von 24 Stunden zu einem hohen Verlust an Aktivchlor führt. Die untersuchten Chlorträger waren Ca(OCI)., LiOCI 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 are only open at one point then the detergent is rinsed out by the water flow 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 preformed Keme during the solidification of the detergent in the still soft mass. In order 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. Example 13, Table 1, shows that a direct addition of the active chlorine-releasing compound to the melt mass leads to a high loss of active chlorine within 24 hours. The chlorine carriers investigated were Ca (OCI)., LiOCI 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 also be developed which 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 machine cleaning of dishes have already 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 mildly heating the mixture with stirring to 90 to 100 ° C until reaching a uniformly molten mass and pouring it into molds and allowing it to solidify Crystal aggregate were manufactured. A possible content of these - melt block-like agents in compounds containing active chlorine 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 mit einem weiteren Gehalt an aktivchlorabspaltenden Verbindungen.The invention now relates to alkali hydroxide-containing, melt-block-shaped, homogeneous and storage-stable agents for the mechanical cleaning of dishes containing alkali silicates and water, preferably as water of crystallization, and optionally pentaalkali nitride phosphate with a further content of active chlorine-releasing compounds.

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 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, i.e. H. as flakes, flakes or prills, practically anhydrous or as a monohydrate. The amounts used are 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 H20, Natriummetasilikat . 6 H20 und Natriummetasilikat . 5 H20 eingesetzt. Die Einsatzmengen in der jeweiligen Form betragen 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 Na20 : Si02 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 H 2 0, sodium metasilicate. 6 H 2 0 and sodium metasilicate. 5 H 2 0 used. The amounts used in the particular form are 2 to 60, preferably 5 to 50,% by weight, based on the total composition. However, the alkali metal silicates can also be partially or completely replaced by water glass solutions, the ratio of Na 2 0: Si0 2 being 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 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.An addition of 2 to 50, preferably 5 to 45% by weight, anhydrous, based on the total composition, of pentaalkali metal triphosphate, which is used as a hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, has also proven advantageous 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-2 H20), 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-2 H 2 0), Na-monochloramidosulfonate (= N-chlorosulfamate), and N-chlorine can be used as active chlorine-releasing compounds -p-toluenesulfonamide sodium ("chloramine T") can be used. Common to all is that they have a hydrolysis constant of about 3 10-4 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 wt .-%. It is preferably introduced by the crystal water content of the alkaline reacting substances, but possibly also 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 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 heated to 45 to 65 ° C with solid alkali metal hydroxide or its monohydrate, without influencing the automatic heating to 60 to 65 ° C which occurs, then with stirring or kneading, all other, preferably hydrate-containing constituents, of which lastly, at tempera doors from 50 to 65 ° C, preferably from 55 to 63 ° C, pentasodium triphosphate and / or its hexahydrate and the active chlorine-releasing compound, which still pours liquid melt into any shape, preferably flexible, and solidifies it into blocks.

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 H20 und 50 Gewichtsteilen NaOH-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 NaOH ein Temperaturanstieg erfolgte (60 bis 65 °C). Nach Abkühlung auf Temperaturen unterhalb 55 °C wurde in die fließfähige Suspension der Chtorträger eingearbeitet und in Wachspappeformen vergossen. Als Chlorträger wurden Trichiorisocyanursäure (TICA), Na-di-chlorisocyanurt -dihydrat (NaDCC-2 H20) und Chloramin T (CI-T) eingearbeitet. Dabei wurde die Menge an Chlorträger so gewählt, daß im fertigen Produkt gleiche Aktivchlorgehalte vorlagen. Daraus resultierten folgende Zusammensetzungen (Angaben in Gew.-%):A mixture of 50 parts by weight of Na 2 SiO 3 . 9 H 2 0 and 50 parts by weight of NaOH prills were heated in a stainless steel vessel with stirring using a Teflon stirrer from outside to 46 to 47 ° C, with the elimination of the crystal water and at the same time a temperature increase (60 to 65 °.) By the hydration of the NaOH C). After cooling to temperatures below 55 ° C., the chlorine support was incorporated into the flowable suspension and cast in wax cardboard molds. Trichiorisocyanuric acid (TICA), Na di-chloroisocyanuric dihydrate (NaDCC-2 H20) and chloramine T (CI-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
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 . H20 und 40 Gewichtsteilen wasserfreiem Pentanatriumtriphosphat sowie dem Aktivchlorträger vermischt.10 parts by weight of water glass solution were at 50 to 55 ° C with 50 parts by weight of NaOH. H 2 0 and 40 parts by weight of anhydrous pentasodium triphosphate and the active chlorine carrier mixed.

Die Suspension wurde in Formen vergossen, wo sie rasch erstarrte. Als Aktivchlorträger wurden TICA und CI-T verwendet. Dabei wurde die Menge an Aktivchlorträger so gewählt, daß im fertigen Produkt gleiche Aktivchlorgehalte vorlagen. Daraus resultierten folgende Zusammensetzungen (Angaben in Gew.-%):The suspension was poured into molds where it quickly solidified. TICA and CI-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
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 added to the solution and the melt mass was poured in sen. 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, as 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 largely within 10 -15 minutes to form stable blocks.

Claims (5)

1. 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, mit einem weiteren Gehalt an aktivchlorabspaltenden Verbindungen.1. Alkali hydroxide-containing, melt-block-shaped, homogeneous and storage-stable agent for the mechanical cleaning of dishes containing alkali silicates and water, preferably as water of crystallization, and optionally pentaalkali metal phosphate, with a further content of active chlorine-releasing compounds. 2. Mittel nach Anspruch 1, deren aktivchlorabspaltende Verbindungen eine Hydrolysenkonstante von 3 9 10-4 oder kleiner besitzen.2. Composition according to claim 1, the active chlorine-releasing compounds have a hydrolysis constant of 3 9 10- 4 or less. 3. Mittel nach Anspruch 1 mit Na-oder K-Dichlorisocyanurat, Na-Dichlorisocyanurat-dihydrat, Na-N-monochloramidosulfonsäure oder Na-N-Chlor-p-toluolsulfonsäureamid als aktivchlorabspaltende Verbindungen.3. Composition according to claim 1 with Na or K-dichloroisocyanurate, Na-dichloroisocyanurate dihydrate, Na-N-monochloramidosulfonic acid or Na-N-chloro-p-toluenesulfonic acid amide as active chlorine-releasing compounds. 4. Mittel nach den Ansprüchen 1 bis 3, mit einem Gehalt an aktivchlorabspaltenden Verbindungen in Mengen von 0,2 bis 4, vorzugsweise 0,5 bis 2 Gew.-%, bezogen auf den Aktivchlorgehalt und das gesamte Mittel.4. Agent according to claims 1 to 3, with a content of active chlorine-releasing compounds in amounts of 0.2 to 4, preferably 0.5 to 2 wt .-%, based on the active chlorine content and the total agent. 5. Verfahren zur Herstellung von alkalihydroxidhaltigen schmelzblockförmigen homogenen und lagerstabilen Mitteln nach Anspruch 1, dadurch gekennzeichnet, daß man zuerst Alkalisilikat, wasserfrei, als Metasilikathydrat und/oder als Wasserglaslösung allein oder zusammen mit festem Alkalihydroxid oder dessen Monohydrat auf 45 bis 48 °C erwärmt, ohne das dabei auftretende selbsttätige Erwärmen auf 60 bis 65 °C zu beeinflussen, anschließend unter Rühren oder Kneten alle weiteren vorzugsweise hydratwasserhaltigen Bestandteile zusetzt, 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.5. A process for the preparation of alkali metal-containing melt-block-shaped homogeneous and storage-stable agents according to claim 1, characterized in that first alkali silicate, anhydrous, as a metasilicate hydrate and / or as a water glass solution, alone or together with solid alkali metal hydroxide or its monohydrate, is heated to 45 to 48 ° C, without influencing the automatic heating to 60 to 65 ° C that occurs, then adding with stirring or kneading all other preferably hydrate-containing constituents, of which lastly, at temperatures from 50 to 65 ° C, preferably from 55 to 63 ° C, pentasodium triphosphate and / or stirring its hexahydrate and the active chlorine-releasing compound, which still pours molten melt into any shape, preferably flexible, and solidifies it into blocks.
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)

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EP0245760A2 (en) * 1986-05-14 1987-11-19 Henkel Kommanditgesellschaft auf Aktien Stock supply of a cleaning agent for use in an industrial dish-washing machine
EP0297273A1 (en) * 1987-06-30 1989-01-04 Hoechst Aktiengesellschaft Formstable alkaline detergent with low specific weight and a process for its production
EP0361380A2 (en) * 1988-09-28 1990-04-04 Jörg-Peter Prof. Schür Process for the mechanical cleaning, disinfecting and rinsing of dishes, and means suited therefor
US5066416A (en) * 1987-08-31 1991-11-19 Olin Corporation Process for producing moldable detergents having a stable available chlorine concentration
DE4109921C1 (en) * 1991-03-26 1992-11-05 Woellner-Werke Gmbh & Co, 6700 Ludwigshafen, De Moulded solid, cleaning, disinfection and/or preservation agent - obtd. from mixt. of powdered agents and auxiliary materials which are put in shaped container
EP0711826A2 (en) 1994-11-10 1996-05-15 ISCON HYGIENE GmbH Dimensionally stable dish cleaner

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US5268002A (en) * 1989-03-10 1993-12-07 Ecolab Inc. Decolorizing dyed fabric or garments
US4997450A (en) * 1989-03-10 1991-03-05 Ecolab Inc. Decolorizing dyed fabric or garments
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
US5858299A (en) * 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
US6689305B1 (en) 1993-05-05 2004-02-10 Ecolab Inc. Process for consolidating particulate solids and cleaning products therefrom II
US5482641A (en) * 1993-09-02 1996-01-09 Fleisher; Howard Stratified solid cast detergent compositions and methods of making same
GB9423952D0 (en) * 1994-11-24 1995-01-11 Unilever Plc Cleaning compositions and their use
US6083895A (en) * 1995-03-11 2000-07-04 The Procter & Gamble Company Detergent compositions in tablet form
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Cited By (9)

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Publication number Priority date Publication date Assignee Title
EP0245760A2 (en) * 1986-05-14 1987-11-19 Henkel Kommanditgesellschaft auf Aktien Stock supply of a cleaning agent for use in an industrial dish-washing machine
EP0245760A3 (en) * 1986-05-14 1990-03-21 Henkel Kommanditgesellschaft auf Aktien Stock supply of a cleaning agent for use in an industrial dish-washing machine
EP0297273A1 (en) * 1987-06-30 1989-01-04 Hoechst Aktiengesellschaft Formstable alkaline detergent with low specific weight and a process for its production
US4915865A (en) * 1987-06-30 1990-04-10 Hoechst Aktiengesellschaft Dimensionally stable alkaline cleansing agents of low density, and a process for their preparation
US5066416A (en) * 1987-08-31 1991-11-19 Olin Corporation Process for producing moldable detergents having a stable available chlorine concentration
EP0361380A2 (en) * 1988-09-28 1990-04-04 Jörg-Peter Prof. Schür Process for the mechanical cleaning, disinfecting and rinsing of dishes, and means suited therefor
EP0361380A3 (en) * 1988-09-28 1991-10-16 Jörg-Peter Prof. Schür Process for the mechanical cleaning, disinfecting and rinsing of dishes, and means suited therefor
DE4109921C1 (en) * 1991-03-26 1992-11-05 Woellner-Werke Gmbh & Co, 6700 Ludwigshafen, De Moulded solid, cleaning, disinfection and/or preservation agent - obtd. from mixt. of powdered agents and auxiliary materials which are put in shaped container
EP0711826A2 (en) 1994-11-10 1996-05-15 ISCON HYGIENE GmbH Dimensionally stable dish cleaner

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DE3677058D1 (en) 1991-02-28
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EP0203526A3 (en) 1988-03-23
DE3519355A1 (en) 1986-12-04
ATE60355T1 (en) 1991-02-15

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