EP0203524A2 - Alkaline hydroxide-free compound in melted block form for machine dish-washing, and process for its preparation - Google Patents
Alkaline hydroxide-free compound in melted block form for machine dish-washing, and process for its preparation Download PDFInfo
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- EP0203524A2 EP0203524A2 EP86106943A EP86106943A EP0203524A2 EP 0203524 A2 EP0203524 A2 EP 0203524A2 EP 86106943 A EP86106943 A EP 86106943A EP 86106943 A EP86106943 A EP 86106943A EP 0203524 A2 EP0203524 A2 EP 0203524A2
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- active chlorine
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- alkali
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- sodium metasilicate
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- 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
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- 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
- C11D3/3958—Bleaching agents combined with phosphates
Definitions
- Powder, granule or tablet detergents for dishes in dishwashers essentially consist of! Pentasodium triphosphate, alkali silicate, predominantly alkali metasilicate and optionally from a low-foaming, preferably chlorine-stable, nonionic surfactant and bleaching agents, preferably those which release active chlorine in aqueous solution. They are mainly used to facilitate the removal of stains from tea, coffee or fruit juices.
- the agents are strongly alkaline because of their high content of alkali silicates and pentasodium triphosphate. Their ready-to-use solutions have a pH value of around 11 to 12. An addition of sodium hydroxide is not intended, because in the contact times customary in household dishwashers, porcelain, frosting decorations and glasses are then attacked by the high alkalinity. This attack is called corrosion. Silicate, on the other hand, synergistically supports the cleaning power of triphosphate and inhibits corrosion in certain concentrations in the total triphosphate / silicate mixture.
- the known agents are generally produced by customary production processes, such as mixing or granulating. They are also used in powder or granule form usual concentrations, ie in amounts of about 30 to 50 g per & 4 machine filling.
- a disadvantage of the production of a tablet on the basis of compressed individual substances is that mechanical strength and dissolution speed are in opposite directions. For this reason, it is necessary to add tableting aids and so-called "disintegrants". On the one hand, these bring about a homogeneity of the pulverulent or granulated raw materials during the pressing process, on the other hand the tablet is broken up by contact with water by swelling of the disintegrant, whereby a better solubility is achieved.
- both additives are useless for the cleaning process as such, so they represent dietary fiber, the incorporation of which is also time-consuming.
- melt-block detergents for machine dishwashing have already been described, which can be obtained by simply mixing together all the alkaline-reacting active substances, such as, for. B. up to 65 wt .-%, based on the total agent, of 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 it is reached a uniformly melted mass as well as its casting in molds and solidification to a dense crystal aggregate. Additions of active chlorine-releasing compounds were not mentioned there. This is understandable because the agents themselves are strongly alkaline and it was to be expected that, like many substances whose addition would be desirable, but which are sensitive to alkali, they would be rendered ineffective during the melting process.
- Example 8 Melting-block agents for machine dishwashing are also described in EP-PS 3,769. They mostly contain high proportions of alkali hydroxides. However, Example 8 also gives a composition that is free of alkali hydroxide. There the active chlorine carrier is stirred directly into the later solidifying aqueous solution of the components, but mostly the active chlorine carrier is added in the form of a separate core. In this example, the AS content is only 60% by weight, based on the total agent, which is too low for use in household dishwashers. Since the patent repeatedly refers to the known alkali sensitivity of the active chlorine carriers, also in comparative experiments, it could not be assumed that active chlorine carriers could be incorporated directly into strongly alkaline, alkali hydroxide-free melt block cleaners.
- melt block-shaped alkali hydroxide-free agents for the mechanical cleaning of dishes with a content of 65 to 85, preferably 70 to 80% by weight, based on the total agent, of a mixture of alkali silicates and Pentaalkalitriphosphaten and a homogeneous distributed content of preferably organic active chlorine-releasing compounds.
- the present invention thus relates to melt-block-shaped alkali hydroxide-free agents for the automatic cleaning of dishes with a content of 65 to 85, preferably 70 to 80% by weight, based on the total agent, of a mixture of alkali silicates and pentaalkali metal phosphates and a homogeneously distributed content of preferably organic active chlorine releasing compounds.
- Alkali silicates are preferably used as alkali silicates, advantageously in the form of sodium metasilicate 9 H 2 0, sodium metasilicate 6 H 2 0 and sodium metasilicate 5 H 2 0.
- the amounts used are 5 to 60% by weight, preferably 10 to 50% by weight, based on the total composition. But you can also replace some of the hydrate-containing alkali metal silicates with the anhydrous compound. This is even desirable because it enables high active substance contents to be set with an optimal ratio of alkali silicate to pentaalkali metal phosphate.
- the optimal ratio of pentasodium triphosphate to sodium metasilicate, each anhydrous, is 1: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
- inorganic active chlorine carriers such as. Chlorinated lime, lithium or calcium hypochlorite can be used. 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 is 11 to 34.8, preferably 18 to 29.5% by weight. It is preferably introduced by the crystal water content of the alkaline reacting active substances. The calculations of the water content must therefore be based on these compounds. Small amounts of free water for weight compensation can be added, but are not within the scope of the invention.
- 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 active substance content (AS) - according to the definition given - was:
- the active substance content (AS) was 72.5%.
- the active chlorine content was determined after 24 hours. It was 0.93% (theory 0.91%).
- the cleaner block was produced as described in Example 2.
- the composition was made using a combination of Na 2 Si0 3 . 9 H 2 0 and Na 2 Si0 3 . 5 H 2 0 selected so that a total of the same amounts of water as in Example 8 of EP-PS 3 769 were present. It was found that in order to produce the melt according to this example 8, the mixture had to be stirred at 55 to 60 ° C. for about 30 minutes until the suspension began to become viscous and could be poured. Such measures are expensive for technical processes and therefore disadvantageous. Storage at 25 ° C and 85% rel. Moisture resulted in the following active chlorine losses:
- Example 3 The results showed a clear advantage for Example 3 according to the invention. It must also be taken into account that compositions with a lower water content have even better stabilities.
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Abstract
Description
Pulver-, granulat- oder tablettenförmige Reinigungsmittel für Geschirr in Geschirrspülmaschinen bestehen im wesentlichen aus ! Pentanatriumtriphosphat, Alkalisilikat, vorwiegend Alkalimetasilikat und gegebenenfalls aus einem schwach schäumenden, vorzugsweise chlorstabilen, nichtionischen Tensid sowie Bleichmitteln, vorzugsweise solchen, die in wäßriger Lösung Aktivchlor abgeben. Sie dienen vor allem der Erleichterung der Entfernung von Flecken von Tee, Kaffee oder Obstsäften.Powder, granule or tablet detergents for dishes in dishwashers essentially consist of! Pentasodium triphosphate, alkali silicate, predominantly alkali metasilicate and optionally from a low-foaming, preferably chlorine-stable, nonionic surfactant and bleaching agents, preferably those which release active chlorine in aqueous solution. They are mainly used to facilitate the removal of stains from tea, coffee or fruit juices.
Die Mittel sind wegen ihres hohen Gehaltes an Alkalisilikaten und Pentanatriumtriphosphat stark alkalisch. Ihre Gebrauchslösungen haben einen pH-Wert von etwa 11 bis 12. Dabei ist ein Zusatz von Natriumhydroxid nicht vorgesehen, weil bei den in Haushaltsgeschirrspülmaschinen üblichen Kontaktzeiten dann durch die hohe Alkalinität Porzellan, Aufglasurdekors und Gläser angegriffen wird. Man bezeichnet diesen Angriff als Korrosion. Silikat dagegen unterstützt die Reinigungskraft des Triphosphats synergistisch und hemmt in bestimmten Konzentrationen im Gesamtgemisch Triphosphat/Silikat die Korrosion.The agents are strongly alkaline because of their high content of alkali silicates and pentasodium triphosphate. Their ready-to-use solutions have a pH value of around 11 to 12. An addition of sodium hydroxide is not intended, because in the contact times customary in household dishwashers, porcelain, frosting decorations and glasses are then attacked by the high alkalinity. This attack is called corrosion. Silicate, on the other hand, synergistically supports the cleaning power of triphosphate and inhibits corrosion in certain concentrations in the total triphosphate / silicate mixture.
Die Herstellung der bekannten Mittel erfolgt im allgemeinen nach üblichen Herstellungsverfahren, wie Mischen oder Granulieren. Die Anwendung erfolgt in Pulver- oder Granulatform in ebenfalls üblichen Konzentrationen, d. h. in Mengen von etwa 30 bis 50 g pro &4aschinenfüllung.The known agents are generally produced by customary production processes, such as mixing or granulating. They are also used in powder or granule form usual concentrations, ie in amounts of about 30 to 50 g per & 4 machine filling.
Derartige pulver- oder granulatförmige Mittel sind beispielsweise in den deutschen Offenlegungsschriften 23 50 295, 23 58 249 und 29 13 145 sowie in den deutschen Auslegeschriften 24 34 309 und 26 02 357 beschrieben.Such powdered or granular agents are described, for example, in German Offenlegungsschriften 23 50 295, 23 58 249 and 29 13 145 and in German patent specifications 24 34 309 and 26 02 357.
Nach der französischen Patentschrift 1 472 680 hat man aus einfachen Mischungen der bekannten Reinigungsmittelbestandteile unter Zusatz eines Tablettierungshilfsmittels scheibenähnliche Tabletten hergestellt.According to French patent specification 1,472,680, disk-like tablets have been produced from simple mixtures of the known detergent components with the addition of a tabletting aid.
Tabletten der vorstehend genannten Art sind auch in den deutschen Offenlegungsschriften 28 57 001 und 33 15 950 beschrieben. Der Gehalt der alkalischen Komponenten (im weiteren als Aktivsubstanz (AS) bezeichnet), worunter der Anteil an Alkalisilikaten und Pentaalkalitriphosphaten verstanden wird, liegt in der Größenordnung von 65 bis 95 Gew.-% der Tablette. Damit entsprechen solche Reinigungstabletten auf Basis verpreßter Rohstoffe in ihrer Zusammensetzung durchaus pulverförmigen oder granulierten Reinigungsmitteln.Tablets of the type mentioned above are also described in German Offenlegungsschriften 28 57 001 and 33 15 950. The content of the alkaline components (hereinafter referred to as active substance (AS)), which means the proportion of alkali silicates and pentaalkali metal triphosphates, is in the order of 65 to 95% by weight of the tablet. Such cleaning tablets based on compressed raw materials correspond in their composition to powdery or granular cleaning agents.
Nachteilig bei der Herstellung einer Tablette auf Basis verpreßter Einzelsubstanzen ist, daß mechanische Festigkeit und Auflösegeschwindigkeit gegenläufig sind. Aus diesem Grunde ist es notwendig, Tablettierhilfsstoffe und sogenannte "Sprengmittel" zuzusetzen. Diese bewirken einerseits eine Homogenität der pulverförmigen oder granulierten Rohstoffe beim Preßvorgang, andererseits wird beim Kontakt mit Wasser durch Quellung des Sprengmittels die Tablette zerteilt, wodurch eine bessere Löslichkeit erzielt wird. Beide Zusätze sind jedoch für den Reinigungsprozeß als solchen unbrauchbar, stellen also Ballaststoffe dar, deren Einarbeitung zudem zeitaufwendig ist.A disadvantage of the production of a tablet on the basis of compressed individual substances is that mechanical strength and dissolution speed are in opposite directions. For this reason, it is necessary to add tableting aids and so-called "disintegrants". On the one hand, these bring about a homogeneity of the pulverulent or granulated raw materials during the pressing process, on the other hand the tablet is broken up by contact with water by swelling of the disintegrant, whereby a better solubility is achieved. However, both additives are useless for the cleaning process as such, so they represent dietary fiber, the incorporation of which is also time-consuming.
In der US-PS 2,412,819 sind schon schmelzblockförmige Reinigungsmittel für das maschinelle Geschirrspülen beschrieben worden, die durch bloßes Zusammenmischen aller alkalisch reagierenden Aktivsubstanzen wie z. B. bis zu 65 Gew.-%, bezogen auf das gesamte Mittel, an 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. Zusätze an aktivchlorabspaltenden Verbindungen sind dort nicht genannt worden. Das ist verständlich, weil die Mittel selbst stark alkalisch sind und zu erwarten war, daß sie wie viele Substanzen, deren Zusatz erwünscht wäre, die aber alkaliempfindlich sind, bereits beim Schmelzprozeß unwirksam gemacht werden würden.In US Pat. No. 2,412,819, melt-block detergents for machine dishwashing have already been described, which can be obtained by simply mixing together all the alkaline-reacting active substances, such as, for. B. up to 65 wt .-%, based on the total agent, of 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 it is reached a uniformly melted mass as well as its casting in molds and solidification to a dense crystal aggregate. Additions of active chlorine-releasing compounds were not mentioned there. This is understandable because the agents themselves are strongly alkaline and it was to be expected that, like many substances whose addition would be desirable, but which are sensitive to alkali, they would be rendered ineffective during the melting process.
Schmelzblockförmige Mittel für die maschinelle Geschirreinigung werden auch in der EP-PS 3 769 beschrieben. Sie enthalten überwiegend hohe Anteile an Alkalihydroxiden. Beispiel 8 gibt aber auch eine Zusammensetzung an, die alkalihydroxidfrei ist. Dort wird der Aktivchlorträger zwar in die später erstarrende wäßrige Lösung der Bestandteile direkt eingerührt, meist aber wird der Aktivchlorträger in Form eines gesonderten Kerns zugegeben. Der AS-Gehalt liegt bei diesem Beispiel nur bei 60 Gew.-%, bezogen auf das gesamte Mittel, was für den Einsatz in Haushaltsgeschirrspülmaschinen zu gering ist. Da in der Patentschrift wiederholt, auch in Vergleichsversuchen, auf die bekannte Alkaliempfindlichkeit der Aktivchlorträger hingewiesen wird, war nicht davon auszugehen, daß sich Aktivchlorträger in stark alkalische, alkalihydroxidfreie Schmelzblockreiniger direkt einarbeiten lassen würden.Melting-block agents for machine dishwashing are also described in EP-PS 3,769. They mostly contain high proportions of alkali hydroxides. However, Example 8 also gives a composition that is free of alkali hydroxide. There the active chlorine carrier is stirred directly into the later solidifying aqueous solution of the components, but mostly the active chlorine carrier is added in the form of a separate core. In this example, the AS content is only 60% by weight, based on the total agent, which is too low for use in household dishwashers. Since the patent repeatedly refers to the known alkali sensitivity of the active chlorine carriers, also in comparative experiments, it could not be assumed that active chlorine carriers could be incorporated directly into strongly alkaline, alkali hydroxide-free melt block cleaners.
Es wurde nun überraschenderweise gefunden, daß man auf dem Wege des Schmelzprosses zu schmelzblockförmigen alkalihydroxidfreien Mitteln für das maschinelle Reinigen von Geschirr mit einem Gehalt an 65 bis 85, vorzugsweise 70 bis 80 Gew.-%, bezogen auf das gesamte Mittel, eines Gemisches aus Alkalisilikaten und Pentaalkalitriphosphaten und einem homogenen verteilten Gehalt an vorzugsweise organischen aktivchlorabspaltenden Verbindungen kommt.It has now surprisingly been found that, on the way to the melting process, melt block-shaped alkali hydroxide-free agents for the mechanical cleaning of dishes with a content of 65 to 85, preferably 70 to 80% by weight, based on the total agent, of a mixture of alkali silicates and Pentaalkalitriphosphaten and a homogeneous distributed content of preferably organic active chlorine-releasing compounds.
Die vorliegende Erfindung betrifft somit schmelzblockförmige alkalihydroxidfreie Mittel für das maschinelle Reinigen von Geschirr mit einem Gehalt an 65 bis 85, vorzugsweise 70 bis 80 Gew.-%, bezogen auf das gesamte Mittel, eines Gemisches aus Alkalisilikaten und Pentaalkalitriphosphaten und einem homogen verteilten Gehalt an vorzugsweise organischen aktivchlorabspaltenden Verbindungen.The present invention thus relates to melt-block-shaped alkali hydroxide-free agents for the automatic cleaning of dishes with a content of 65 to 85, preferably 70 to 80% by weight, based on the total agent, of a mixture of alkali silicates and pentaalkali metal phosphates and a homogeneously distributed content of preferably organic active chlorine releasing compounds.
Als Alkalisilikate werden bevorzugt Alkalimetasilikate, und zwar vorteilhaft in Form von Natriummetasilikat 9 H20, Natriummetasilikat · 6 H20 und Natriummetasilikat 5 H20 eingesetzt. Die Einsatzmengen betragen 5 bis 60, vorzugsweise 10 bis 50 Gew.-%, bezogen auf das gesamte Mittel. Man kann aber auch einen Teil der hydratwasserhaltigen Alkalimetasilikate durch die wasserfreie Verbindung ersetzen. Dies ist sogar wünschenswert, da dadurch hohe Aktivsubstanzgehalte bei optimalem Verhältnis von Alkalisilikat zu Pentaalkalitriphosphat eingestellt werden können.Alkali silicates are preferably used as alkali silicates, advantageously in the form of sodium metasilicate 9 H 2 0, sodium metasilicate 6 H 2 0 and sodium metasilicate 5 H 2 0. The amounts used are 5 to 60% by weight, preferably 10 to 50% by weight, based on the total composition. But you can also replace some of the hydrate-containing alkali metal silicates with the anhydrous compound. This is even desirable because it enables high active substance contents to be set with an optimal ratio of alkali silicate to pentaalkali metal phosphate.
Als Pentaalkalitriphosphat dient ein Zusatz von 5 bis 50 Gew.-%, vorzugsweise 5 bis 45 Gew.-%, bezogen auf das gesamte Mittel, an Pentaalkalitriphosphat erwiesen, das als Hexahydrat oder als Mischung von Hexahydrat mit geringen Mengen an wasserfreiem Pentanatriumtriphosphat eingesetzt wird, so daß sich ein Gesamtwassergehalt von 5,5 Mol errechnet. Auch hier können zur Erzielung optimaler Aktivsubstanzkombinationen und -gehalte wasserfreie Verbindungen eingesetzt werden.An addition of 5 to 50 wt.%, Preferably 5 to 45 wt. so that a total water content of 5.5 moles is calculated. Here too Achievement of optimal active substance combinations and contents of water-free compounds can be used.
Das optimale Verhältnis von Pentanatriumtriphosphat zu Natriummetasilikat, jeweils wasserfrei, beträgt 1 : 1 bis 1 : 2, vorzugsweise 1 : 1 bis 1 : 1,7.The optimal ratio of pentasodium triphosphate to sodium metasilicate, each anhydrous, is 1: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
Als organische aktivchlorabspaltende Verbindungen können die verschiedenen chlorierten Verbindungen der Isocyanursäure, wie Trichlorisocyanursäure (TICA), Na/K-Dichlorisocyanurat, Na-Dichlorisocyanurat-dihydrat (Na-DCC-2 H20), Na-monochloramidosulfonat (= N-Chlorosulfamat) und N-Chlor-p-toluolsulfonsäureamid-Natrium ("Chloramin T") eingesetzt werden. Auch anorganische Aktivchlorträger wie beispielsweise. Chlorkalk, Lithium-oder Calciumhypochlorit können Anwendung finden. 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.The various chlorinated compounds of isocyanuric acid, such as trichloroisocyanuric acid (TICA), Na / K dichloroisocyanurate, Na dichloroisocyanurate dihydrate (Na DCC-2 H 2 0), Na monochloramidosulfonate (= N-chlorosulfamate) and N-chloro-p-toluenesulfonamide sodium ("chloramine T") can be used. Also inorganic active chlorine carriers such as. Chlorinated lime, lithium or calcium hypochlorite can be used. 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 beträgt 11 bis 34,8, vorzugsweise 18 bis 29,5 Gew.-%. Er wird bevorzugt durch den Kristallwassergehalt der alkalisch reagierenden Aktivsubstanzen eingebracht. Die Berechnungen des Wassergehaltes haben daher von diesen Verbindungen auszugehen. Geringe Mengen freien Wassers zum Gewichtsausgleich können zwar zugesetzt werden, liegen aber nicht im Bereich der Erfindung.The total water content of the melt-block-shaped cleaning agents is 11 to 34.8, preferably 18 to 29.5% by weight. It is preferably introduced by the crystal water content of the alkaline reacting active substances. The calculations of the water content must therefore be based on these compounds. Small amounts of free water for weight compensation can be added, but are not within the scope of the invention.
Es hat sich gezeigt, daß man erfindungsgemäß bei niedrigeren und daher schonenderen Temperaturen als nach dem Stand der Technik, nämlich bei 45 bis 60 °C, vorzugsweise 50 bis 55 °C, arbeiten kann, wenn man zuerst Natriummetasilikat . 9 H20 auf 45 bis 55 °C erwärmt, unter Rühren oder Kneten alle weiteren, gegebenenfalls hydratwasserhaltigen Bestandteile, davon zuletzt Pentanatriumtriphosphatderivat und die aktivchlorabspaltenden Verbindungen, zugibt und die noch flüssige Schmelze in beliebig gestaltete, vorzugsweise flexible Formen gießt und in diesen zu Blöcken erstarren läßt.It has been shown that, according to the invention, it is possible to work at lower and therefore gentler temperatures than according to the prior art, namely at 45 to 60 ° C., preferably 50 to 55 ° C., if sodium metasilicate is used first. 9 H 2 0 heated to 45 to 55 ° C., with stirring or kneading, all other constituents which may contain water of hydration, of which lastly pentasodium triphosphate derivative and the active chlorine-releasing compounds Connections, admits and pours the still liquid melt into arbitrarily designed, preferably flexible molds and solidifies into blocks in these.
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.
Es wurden je 150 g Reinigungsmittel mit folgenden Zusammensetzungen hergestellt (Angaben in Gew.-%).
Dabei wurde so verfahren, daß zuerst Na2SiO3 . 9 H20 auf etwa 53 °C erwärmt wurde bis eine klare Schmelze entstand. Danach wurden die weiteren Wirkstoffe hinzugefügt, durchgerührt und vergossen. Die Schmelze erstarrte innerhalb weniger Minuten.The procedure was such that Na 2 SiO 3 . 9 H 2 0 was heated to about 53 ° C until a clear melt formed. Then the other active ingredients were added, stirred and poured. The melt solidified within a few minutes.
Der Aktivsubstanzgehalt (AS) - gemäß der angeführten Definition - betrug:
Nach 24 Stunden wurde der Aktivchlorgehalt (A-Cl) bestimmt, der für alle 3 Zusammensetzungen den theoretisch berechneten Wert ergab.
Es wurden 150 g Reinigungsmittel mit folgender Zusammensetzung hergestellt (Angaben in Gew.-%):
Analog wie bei Beispiel 1 wurde diesmal Na2SiO3 · 9 H20 zusammen mit Na2SiO3 · 5 H20 auf ca. 53 °C erwärmt bis eine klare Schmelze entstand. Die weiteren Komponenten wurden hinzugefügt, durchgerührt und vergossen. Die Schmelze erstarrte ebenfalls innerhalb weniger Minuten.Analogous to Example 1, this time Na 2 SiO 3 · 9 H 2 0 2 SiO 3 · 5 H 2 0 is heated together with Na to about 53 ° C was established until a clear melt. The other components were added, stirred and poured. The melt also solidified within a few minutes.
Der Aktivsubstanzgehalt (AS) betrug 72,5 %.The active substance content (AS) was 72.5%.
Nach 24 Stunden wurde der Aktivchlorgehalt bestimmt. Er betrug 0,93 % (Theorie 0,91 %).The active chlorine content was determined after 24 hours. It was 0.93% (theory 0.91%).
Um die Überlegenheit der erfindungsgemäßen Mittel gegenüber denen nach der EP-PS 3 769 zu demonstrieren, wurde ein Schmelzblock mit folgender Zusammensetzung hergestellt (Angaben in Gew.-%):
Der Reinigerblock wurde, wie im Beispiel 2 beschrieben, hergestellt. Die Zusammensetzung wurde durch Verwendung einer Kombination von Na2Si03 . 9 H20 und Na2Si03 . 5 H20 so gewählt, daß insgesamt gleiche Mengen Wasser wie in Beispiel 8 der EP-PS 3 769 vorlagen. Dabei zeigte sich, daß zur Herstellung der Schmelze nach diesem Beispiel 8 etwa 30 Minuten lang bei 55 bis 60 °C gerührt werden mußte, bis die Suspension begann, viskos zu werden und vergossen werden konnte. Solche Maßnahmen sind für technische Verfahren kostenintensiv und daher nachteilig. Die Lagerung bei 25 °C und 85 % rel. Feuchtigkeit ergab folgende Aktivchlorverluste:
Die Ergebnisse zeigten einen deutlichen Vorteil für das erfindungsgemäße Beispiel 3. Hierbei muß noch berücksichtigt werden, daß Zusammensetzungen mit geringerem Wasseranteil noch bessere Stabilitäten aufweisen.The results showed a clear advantage for Example 3 according to the invention. It must also be taken into account that compositions with a lower water content have even better stabilities.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86106943T ATE66246T1 (en) | 1985-05-30 | 1986-05-22 | MELTING BLOCK NON-ALKALINE HYDROXIDE AGENT FOR AUTOMATIC DISH WASHING AND PROCESS FOR ITS MANUFACTURE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3519354 | 1985-05-30 | ||
| DE19853519354 DE3519354A1 (en) | 1985-05-30 | 1985-05-30 | MELT BLOCK-SHAPED ALKALINE HYDROXIDE-FREE AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THE PRODUCTION THEREOF |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0203524A2 true EP0203524A2 (en) | 1986-12-03 |
| EP0203524A3 EP0203524A3 (en) | 1988-03-23 |
| EP0203524B1 EP0203524B1 (en) | 1991-08-14 |
Family
ID=6271985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86106943A Expired - Lifetime EP0203524B1 (en) | 1985-05-30 | 1986-05-22 | Alkaline hydroxide-free compound in melted block form for machine dish-washing, and process for its preparation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4690770A (en) |
| EP (1) | EP0203524B1 (en) |
| AT (1) | ATE66246T1 (en) |
| DE (2) | DE3519354A1 (en) |
Cited By (4)
| 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 |
| JPS6451498A (en) * | 1987-08-12 | 1989-02-27 | Ecolab Inc | Solid casting composition for washing instruments |
| 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 |
| CN1055494C (en) * | 1996-04-24 | 2000-08-16 | 中国人民解放军第二五一医院 | Agent for rust-proof, corrosion-proof and sterilization |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3541153A1 (en) * | 1985-11-21 | 1987-05-27 | Henkel Kgaa | MULTILAYER DETERGENT IN MELT BLOCK SHAPE |
| DE3634812A1 (en) * | 1986-10-13 | 1988-04-14 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF MELT BLOCK-SHAPED, ALKALI HYDROXIDE AND, IF NECESSARY, ALSO ACTIVE CHLORINE-BASED AGENTS FOR THE MACHINE CLEANING OF DISHES |
| DE3721461A1 (en) * | 1987-06-30 | 1989-01-12 | Hoechst Ag | STABLE AND SPECIFICALLY LIGHT ALKALINE CLEANING AGENTS AND A METHOD FOR THEIR PRODUCTION |
| US5066416A (en) * | 1987-08-31 | 1991-11-19 | Olin Corporation | Process for producing moldable detergents having a stable available chlorine concentration |
| US5133892A (en) * | 1990-10-17 | 1992-07-28 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing detergent tablets |
| NZ239112A (en) | 1991-01-29 | 1994-12-22 | Ecolab Inc | Solid alkaline compositions containing the reaction product in water of alkali metal hydroxide and alkali metal silicate; process of manufacture |
| US5407598A (en) * | 1993-02-26 | 1995-04-18 | Ecolab Inc. | Shaped solid bleach with encapsulate source of bleach |
| US6689305B1 (en) | 1993-05-05 | 2004-02-10 | Ecolab Inc. | Process for consolidating particulate solids and cleaning products therefrom II |
| US5858299A (en) * | 1993-05-05 | 1999-01-12 | Ecolab, Inc. | Process for consolidating particulate solids |
| DE4440142C2 (en) | 1994-11-10 | 1999-03-11 | Iscon Hygiene Gmbh | Process for the production of cleaning agents in foam block form |
| US6083895A (en) * | 1995-03-11 | 2000-07-04 | The Procter & Gamble Company | Detergent compositions in tablet form |
| US6007735A (en) * | 1997-04-30 | 1999-12-28 | Ecolab Inc. | Coated bleach tablet and method |
| US6471974B1 (en) | 1999-06-29 | 2002-10-29 | S.C. Johnson & Son, Inc. | N-chlorosulfamate compositions having enhanced antimicrobial efficacy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2412819A (en) * | 1945-07-21 | 1946-12-17 | Mathieson Alkali Works Inc | Detergent briquette |
| US3936386A (en) * | 1972-11-24 | 1976-02-03 | Fmc Corporation | Dishwashing compositions containing chlorinated isocyanurate |
| EP0003769A1 (en) * | 1978-02-07 | 1979-09-05 | Economics Laboratory, Inc. | Cast detergent-containing article and method of making and using |
| US4329246A (en) * | 1977-11-07 | 1982-05-11 | The Procter & Gamble Company | Alkaline dishwasher detergent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3390092A (en) * | 1965-03-30 | 1968-06-25 | Fmc Corp | Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate |
| IT1020170B (en) * | 1973-10-06 | 1977-12-20 | Benckiser Gmbh Joh A | STABLE CHLORINE DETERGENTS |
| US3933670A (en) * | 1973-11-12 | 1976-01-20 | Economic Laboratories, Inc. | Process for making agglomerated detergents |
| FR2298599A2 (en) * | 1975-01-24 | 1976-08-20 | Sifrance | NEW SOLID NON-CORROSIVE DETERGENT COMPOSITIONS |
| CA1120819A (en) * | 1977-06-01 | 1982-03-30 | Jurgen W.K. Gromer | Detergent tablet |
-
1985
- 1985-05-30 DE DE19853519354 patent/DE3519354A1/en not_active Withdrawn
-
1986
- 1986-05-22 AT AT86106943T patent/ATE66246T1/en not_active IP Right Cessation
- 1986-05-22 EP EP86106943A patent/EP0203524B1/en not_active Expired - Lifetime
- 1986-05-22 DE DE8686106943T patent/DE3680823D1/en not_active Expired - Fee Related
- 1986-05-29 US US06/868,913 patent/US4690770A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2412819A (en) * | 1945-07-21 | 1946-12-17 | Mathieson Alkali Works Inc | Detergent briquette |
| US3936386A (en) * | 1972-11-24 | 1976-02-03 | Fmc Corporation | Dishwashing compositions containing chlorinated isocyanurate |
| US4329246A (en) * | 1977-11-07 | 1982-05-11 | The Procter & Gamble Company | Alkaline dishwasher detergent |
| EP0003769A1 (en) * | 1978-02-07 | 1979-09-05 | Economics Laboratory, Inc. | Cast detergent-containing article and method of making and using |
Cited By (6)
| 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 |
| JPS6451498A (en) * | 1987-08-12 | 1989-02-27 | Ecolab Inc | Solid casting composition for washing instruments |
| 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 |
| CN1055494C (en) * | 1996-04-24 | 2000-08-16 | 中国人民解放军第二五一医院 | Agent for rust-proof, corrosion-proof and sterilization |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0203524B1 (en) | 1991-08-14 |
| EP0203524A3 (en) | 1988-03-23 |
| DE3519354A1 (en) | 1986-12-04 |
| ATE66246T1 (en) | 1991-08-15 |
| US4690770A (en) | 1987-09-01 |
| DE3680823D1 (en) | 1991-09-19 |
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