EP0636688A1 - Automatic dishwashing detergent - Google Patents

Automatic dishwashing detergent Download PDF

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Publication number
EP0636688A1
EP0636688A1 EP94111805A EP94111805A EP0636688A1 EP 0636688 A1 EP0636688 A1 EP 0636688A1 EP 94111805 A EP94111805 A EP 94111805A EP 94111805 A EP94111805 A EP 94111805A EP 0636688 A1 EP0636688 A1 EP 0636688A1
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EP
European Patent Office
Prior art keywords
detergent according
dishwasher detergent
taed
encapsulated
bleach
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EP94111805A
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German (de)
French (fr)
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EP0636688B1 (en
Inventor
Ludwig Hertling
Christa Deisinger
Guido Dr. Wäschenbach
Harald Dr. Magg
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Reckitt Benckiser NV
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Joh A Benckiser GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the invention relates to a mildly alkaline machine dishwashing detergent containing an oxygen-based bleach and other customary components.
  • the invention therefore relates to mildly alkaline machine dishwashing detergents which generally bring the pH of the washing liquor below 11 at the application concentration.
  • the pH of the washing liquor of such mildly alkaline machine dishwashing detergents should be 9-11, preferably 9.5-10.8.
  • the invention teaches to add additives to such a mildly alkaline machine dishwashing detergent, which ensure that the bleach content of the washing liquor is essentially completely degraded at the end of the cleaning cycle in an alkaline medium.
  • substantially completely degraded means an oxygen content that is completely or almost completely degraded.
  • Suitable as an additive is, for example, an encapsulated enzyme suitable for oxygen degradation, such as peroxidase, e.g. Catalase.
  • the additive can be an encapsulated reducing agent, for example thiosulfate.
  • an encapsulated heavy metal or its compound such as copper, iron, manganese, zinc or titanium, which is able to catalytically decompose the bleaching agent.
  • Suitable oxygen activators are TAED (tetraacetylethylenediamine), TAGU (tetraacetylglycoluril), GPA (glucose pentaacetate), NOBS (sodium nonaoylbenzenesulfonate), PAG (pentaacetylglucose), DADHT (diacetyldioxohexahydichydriazine).
  • TAED tetraacetylethylene diamine
  • TAED is a modern detergent additive, which leads to peracids by reaction with hydrogen peroxide. Two molecules of hydrogen peroxide react with one molecule of TAED. For all recipes, attention must therefore be paid to this in accordance with the manufacturer's instructions. that at least 2 moles of perborate are used per 1 mole of TAED. In practice, a significantly higher excess of perborate is used (see TAED brochure from Hoechst).
  • the oxygen activator is now preferably used in a stoichiometric excess over the bleaching agent.
  • Sodium perborate, sodium percarbonate and / or potassium monopersulfate or known stabilized qualities of these substances are suitable as oxygen-based bleaches.
  • Sodium perborate monohydrate is particularly preferred.
  • the stoichiometric ratio of TAED to bleach, such as sodium perborate, is 0.5: 1.
  • the oxygen activator is therefore preferably used in a molar ratio to the bleaching agent of more than 0.5: 1, preferably at least 0.65: 1.
  • a machine dishwashing detergent in which the activator is TAED and the bleaching agent is sodium perborate monohydrate is particularly preferred, the activator being present in a weight ratio to the bleaching agent of at least 1.14: 1, preferably of at least 1.5: 1.
  • a combination of one or more activators and encapsulated additives is used.
  • the table below shows that with a TAED / sodium perborate monohydrate ratio of 1.5, as is preferred according to the invention, a high amount of active oxygen is used and nevertheless only a very small amount of active oxygen is carried over into the first intermediate rinse cycle .
  • the active oxygen content used is therefore just as high as with a TAED / perborate ratio of 0.27, but the residual oxygen content at the end of the cleaning cycle and the oxygen content carried over into the first intermediate rinse cycle are only very low.
  • the mildly alkaline machine dishwashing detergents according to the invention also contain other conventional constituents. These include sodium carbonate, sodium or potassium silicates such as sodium disilicate, phosphates such as sodium tripolyphosphate, builders and buffering substances such as trisodium citrate, as well as surfactants, especially nonionic surfactants, in a total amount of up to 5, preferably up to 2% by weight. can be present.
  • the dishwashing detergents according to the invention preferably also contain the enzymes customary in such detergents, such as amylase and / or protease.
  • a household dishwasher was loaded with dishes and silver cutlery, which had the following contamination: 50 ml of a mixture of Ketchup 25 g mustard 25 g gravy 25 g Potato starch 5 g Benzoic acid 1 g egg yolk 3rd milk 500 g water 700 g 20 program sequences; Water hardness 18-20 ° d

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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)
  • Washing And Drying Of Tableware (AREA)

Abstract

The invention relates to a slightly alkaline automatic dishwashing detergent containing an oxygen-based bleach and further conventional ingredients, which is characterised in that it contains a combination of a) one or more activators and b) one or more encapsulated additives, which ensures that the bleach content of the washing liquor is essentially completely decomposed at the end of the cleaning cycle in the alkaline medium.

Description

Die Erfindung betrifft ein mildalkalisches Maschinengeschirrspülmittel enthaltend ein Bleichmittel auf sauerstoffbasis sowie weitere übliche Bestandteile.The invention relates to a mildly alkaline machine dishwashing detergent containing an oxygen-based bleach and other customary components.

Mildalkalische, chlorfreie Reiniger, die ein Bleichmittel auf Sauerstoffbasis enthalten, neigen unter bestimmten Bedingungen dazu Silber zu verfärben, insbesondere dann, wenn Aktivsauerstoff in den ersten Zwischenspülgang verschleppt wird (Laugenverschleppung) und gleichzeitig aufgrund der Verdünnung durch Frischwasser der pH-Wert herabgesetzt wird.Mildly alkaline, chlorine-free cleaners that contain an oxygen-based bleaching agent tend to discolour silver under certain conditions, especially if active oxygen is carried over into the first intermediate rinse cycle (carryover of lye) and, at the same time, the pH value is reduced due to dilution with fresh water.

Es wurde gefunden, daß insbesondere bei einem pH-Wert von 6-9 solche Silberverfärbungen gravierend sind. Bei einem Einsatz von mildalkalischen Reinigern, selbst wenn diese in der Spülflotte einen pH-Wert von über 10 einstellen, ergibt sich im ersten Zwischenspülgang ein pH-Wert von 8-9, der genau im kritischen Bereich liegt.It has been found that such silver discoloration is serious, especially at a pH of 6-9. When using mildly alkaline detergents, even if they set a pH value of over 10 in the washing liquor, the first intermediate rinse results in a pH value of 8-9, which is exactly in the critical range.

Das Problem der Silberverfärbung ist bekannt und wird insbesondere in der DE-OS 41 28 672 ausführlich behandelt. Nach der Lehre der DE-OS 41 28 672 wird dieses Problem dadurch gelöst, daß stark alkalische Mittel verwendet werden zur Verhinderung des Anlaufens von Silberbestecken. Als stark alkalische Mittel werden solche verstanden, die einen pH-Wert von oberhalb von 11 einstellen. Diese bekannten, stark alkalischen Reinigungsmittel besitzen einen Gehalt an Persäure oder von mit organischen Bleichaktivatoren versetzten Peroxyverbindungen. Bei einem Gehalt von 3-10 Gew.% an Peroxyverbindung, bezogen auf das gesamte Mittel, können diese bekannten Reinigungsmittel zusätzlich einen Gehalt von 0,5-5 Gew.% an organischen Bleichaktivatoren, bezogen auf das gesamte Mittel, enthalten.The problem of silver discoloration is known and is dealt with in detail in DE-OS 41 28 672 in particular. According to the teaching of DE-OS 41 28 672, this problem is solved in that strongly alkaline agents are used to prevent tarnishing of silver cutlery. Strongly alkaline agents are understood to be those which set a pH of above 11. These known, strongly alkaline cleaning agents contain peracid or peroxy compounds mixed with organic bleach activators. With a content of 3-10% by weight of peroxy compound, based on the total composition, these known cleaning agents can additionally contain 0.5-5% by weight of organic bleach activators, based on the total composition.

Diese aus der DE-OS 41 28 672 bekannten Reinigungsmittel besitzen jedoch den Nachteil, daß sie stark alkalisch sind, was gerade durch die moderne mildalkalische Reinigergeneration vermieden werden soll.However, these cleaning agents known from DE-OS 41 28 672 have the disadvantage that they are strongly alkaline, which should be avoided precisely by the modern mildly alkaline generation of detergents.

In weiteren Versuchen, die zu der vorliegenden Erfindung führten, wurde gefunden, daß es für die Vermeidung der Silberverfärbung darauf ankommt, daß wenn der pH-Wert der Spülflotte auf unter 9 absinkt, was bei Verwendung von mildalkalischen Reinigern bereits im ersten Zwischenspülgang der Fall ist, die Spülflotte keinen Aktivsauerstoffgehalt mehr besitzt. Durch Laugenverschleppung in den ersten Zwischenspülgang werden regelmäßig Aktivsauerstoffverbindungen übertragen. Bei einem mildalkalischen Produkt liegt der Aktivsauerstoffgehalt im allgemeinen bei 1-1,5 %, das heißt bei einer Dosierung von 20 g Reiniger liegen im Reinigungsgang 200-300 mg Aktivsauerstoff vor. Messungen ergaben, daß bei einem Ausgangswert von 225 mg Aktivsauerstoff am Ende des Reinigungsganges noch etwa 50 % der Ausgangsmenge vorhanden ist und im ersten Zwischenspülgang noch ca. 10 % des Aktivsauerstoffs vorliegt. Dies zeigt, daß bei Verwendung von mildalkalischen Maschinengeschirrspülmitteln im Zwischenspülgang ideale Bedingungen für eine Silberverfärbung vorliegen.In further experiments, which led to the present invention, it was found that in order to avoid silver discoloration, it is important that the pH of the washing liquor drops to below 9, which is already the case in the first intermediate rinse cycle when using mildly alkaline detergents , the wash liquor no longer has active oxygen content. Leaching of lye into the first intermediate rinse cycle regularly transfers active oxygen compounds. In the case of a mildly alkaline product, the active oxygen content is generally 1-1.5%, This means that with a dosage of 20 g of cleaner, 200-300 mg of active oxygen are present in the cleaning cycle. Measurements showed that with a starting value of 225 mg of active oxygen at the end of the cleaning cycle about 50% of the initial amount is still present and about 10% of the active oxygen is still present in the first intermediate rinse cycle. This shows that when mildly alkaline machine dishwashing detergents are used in the intermediate rinse cycle, there are ideal conditions for silver discoloration.

Die Erfindung bezieht sich also auf mildalkalische Maschinengeschirrspülmittel, die im allgemeinen bei Anwendungskonzentration einen pH-Wert der Spülflotte von unter 11 bewirken. Im allgemeinen soll der pH-Wert der Spülflotte solcher mildalkalischer Maschinengeschirrspülmittel bei 9-11, vorzugsweise bei 9,5-10,8 liegen.The invention therefore relates to mildly alkaline machine dishwashing detergents which generally bring the pH of the washing liquor below 11 at the application concentration. In general, the pH of the washing liquor of such mildly alkaline machine dishwashing detergents should be 9-11, preferably 9.5-10.8.

In ihrer allgemeinsten Form gibt die Erfindung die Lehre, einem solchen mildalkalischen Maschinengeschirrspülmittel Zusätze beizugeben, welche sicherstellen, daß am Ende des Reinigungsganges im alkalischen Milieu der Bleichmittelgehalt der Spülflotte im wesentlichen vollständig abgebaut ist. Unter im wesentlichen vollständig abgebaut versteht man einen Sauerstoffgehalt, der vollständig oder nahezu vollständig abgebaut ist.In its most general form, the invention teaches to add additives to such a mildly alkaline machine dishwashing detergent, which ensure that the bleach content of the washing liquor is essentially completely degraded at the end of the cleaning cycle in an alkaline medium. Substantially completely degraded means an oxygen content that is completely or almost completely degraded.

Die Zusätze, welche den Abbau des Sauerstoffgehaltes am Ende des Reinigungsganges bewirken, bestehen aus einer Kombination aus

  • a) einem oder mehreren Aktivatoren und
  • b) einem oder mehreren verkapselten Zusatzmitteln.
The additives that reduce the oxygen content at the end of the cleaning cycle consist of a combination of
  • a) one or more activators and
  • b) one or more encapsulated additives.

Als Zusatzmittel geeignet ist beispielsweise ein verkapseltes, für den Sauerstoffabbau geeignetes Enzym, wie beispielsweise Peroxydase, z.B. Katalase.Suitable as an additive is, for example, an encapsulated enzyme suitable for oxygen degradation, such as peroxidase, e.g. Catalase.

Oder das Zusatzmittel kann ein verkapseltes Reduktionsmittel, beispielsweise Thiosulfat, sein.Or the additive can be an encapsulated reducing agent, for example thiosulfate.

Auch geeignet als Zusatzmittel ist ein verkapseltes Schwermetall oder dessen Verbindung, wie beispielsweise Kupfer, Eisen, Mangan, Zink oder Titan, welches in der Lage ist, das Bleichmittel katalytisch zu zersetzen.Also suitable as an additive is an encapsulated heavy metal or its compound, such as copper, iron, manganese, zinc or titanium, which is able to catalytically decompose the bleaching agent.

Methoden zur Verkapselung solcher zusatzmittel sind bekannt. Geeignet ist ein Überzug, der sich erst allmählich löst, wie beispielsweise Paraffin. Es ist auch möglich, das Zusatzmittel in Form einer Tablette in einer größeren Tablette des Reinigungsmittels aufzunehmen.Methods for encapsulating such additives are known. A coating that is only gradually loosening, such as paraffin, is suitable. It is also possible to take up the additive in the form of a tablet in a larger tablet of the cleaning agent.

Eine weitgehende Zersetzung des Bleichmittels wird bereits erreicht, wenn der Sauerstoff-Aktivator in einer Menge von oberhalb des stöchiometrischen Verhältnisses zu dem Bleichmittel eingesetzt wird. Als Sauerstoff-Aktivatoren eignen sich TAED (Tetraacetylethylendiamin), TAGU (Tetraacetylglycoluril), GPA (Glucosepentaacetat), NOBS (Natriumnonaoylbenzolsulfonat), PAG (Pentaacetyl-glucose), DADHT (Diacetyldioxohexahydrotriazin), oder ISA (Isatosäureanhydrid). Besonders bevorzugt wird TAED (Tetraacetylethylendiamin).Extensive decomposition of the bleaching agent is already achieved when the oxygen activator is used in an amount above the stoichiometric ratio to the bleaching agent. Suitable oxygen activators are TAED (tetraacetylethylenediamine), TAGU (tetraacetylglycoluril), GPA (glucose pentaacetate), NOBS (sodium nonaoylbenzenesulfonate), PAG (pentaacetylglucose), DADHT (diacetyldioxohexahydichydriazine). TAED (tetraacetylethylene diamine) is particularly preferred.

TAED ist ein modernes Waschmitteladditiv, welches durch Umsetzung mit Wasserstoffperoxid zu Persäuren führt. Es setzen sich zwei Moleküle Wasserstoffperoxid mit einem Molekül TAED um. Bei allen Rezepturen ist deshalb nach der Herstellervorschrift darauf zu achten. daß mindestens 2 Mol Perborat auf 1 Mol TAED eingesetzt werden. In der Praxis setzt man einen deutlich höheren Überschuß an Perborat ein (vergl. TAED-Prospekt der Fa. Hoechst).TAED is a modern detergent additive, which leads to peracids by reaction with hydrogen peroxide. Two molecules of hydrogen peroxide react with one molecule of TAED. For all recipes, attention must therefore be paid to this in accordance with the manufacturer's instructions. that at least 2 moles of perborate are used per 1 mole of TAED. In practice, a significantly higher excess of perborate is used (see TAED brochure from Hoechst).

Vorzugsweise wird nun der Sauerstoff-Aktivator entgegen der bisherigen Anwendungsempfehlungen im stöchiometrischen Überschuß gegenüber dem Bleichmittel eingesetzt.Contrary to the previous application recommendations, the oxygen activator is now preferably used in a stoichiometric excess over the bleaching agent.

Als Bleichmittel auf Sauerstoffbasis eignet sich Natriumperborat, Natriumpercarbonat und/oder Kaliummonopersulfat oder bekannte stabilisierte Qualitäten dieser Stoffe. Besonders bevorzugt wird Natriumperborat-Monohydrat.Sodium perborate, sodium percarbonate and / or potassium monopersulfate or known stabilized qualities of these substances are suitable as oxygen-based bleaches. Sodium perborate monohydrate is particularly preferred.

Das stöchiometrische Verhältnis von TAED zum Bleichmittel wie beispielsweise Natriumperborat beträgt 0,5:1. Vorzugsweise wird also der Sauerstoff-Aktivator in einem Molverhältnis zum Bleichmittel von über 0,5:1, vorzugsweise von mindestens 0,65:1, eingesetzt.The stoichiometric ratio of TAED to bleach, such as sodium perborate, is 0.5: 1. The oxygen activator is therefore preferably used in a molar ratio to the bleaching agent of more than 0.5: 1, preferably at least 0.65: 1.

Besonders bevorzugt wird ein Maschinengeschirrspülmittel, bei dem der Aktivator TAED und das Bleichmittel Natriumperborat-Monohydrat ist, wobei der Aktivator in einem Gewichtsverhältnis zum Bleichmittel von mindestens 1,14:1, vorzugsweise von mindestens 1,5:1 vorliegt.A machine dishwashing detergent in which the activator is TAED and the bleaching agent is sodium perborate monohydrate is particularly preferred, the activator being present in a weight ratio to the bleaching agent of at least 1.14: 1, preferably of at least 1.5: 1.

Bei Einsatz anderer Aktivatoren und/oder anderer Bleichmittel werden die bevorzugten Mol- bzw. Gewichts-Verhältnisse entsprechend berechnet.If other activators and / or other bleaching agents are used, the preferred molar or weight ratios are calculated accordingly.

Erfindungsgemäß wird eine Kombination aus einem oder mehreren Aktivatoren und verkapselten Zusatzmitteln eingesetzt.According to the invention, a combination of one or more activators and encapsulated additives is used.

Aus der nachstehenden Tabelle geht hervor, daß bei einem TAED/Natriumperborat-Monohydrat-Verhältnis von 1,5, wie es erfindungsgemäß bevorzugt wird, eine hohe Menge an Aktivsauerstoff genutzt wird und dennoch nur eine sehr geringe Menge an Aktivsauerstoff in den ersten Zwischenspülgang verschleppt wird. Der genutzte Aktivsauerstoffgehalt ist also ebenso hoch wie bei einem TAED/Perborat-Vehältnis von 0,27, der Restsauerstoffgehalt am Ende des Reinigungsganges und der in den ersten Zwischenspulgang verschleppte Sauerstoffgehalt sind aber nur sehr gering. TAED/Perborat Gew.-Verhältnis Ausgangswert Oa Restsauerstoffgehalt Ende Reinigungsgang genutzter Oa in den 1. Zwischenspülgang verschleppt 0,27 225 mg 118 mg 107 mg 26 mg 0,53 225 mg 70 mg 155 mg 15 mg 1,0 120 mg 26 mg 94 mg 8 mg 1,5 120 mg 12 mg 108 mg 3 mg The table below shows that with a TAED / sodium perborate monohydrate ratio of 1.5, as is preferred according to the invention, a high amount of active oxygen is used and nevertheless only a very small amount of active oxygen is carried over into the first intermediate rinse cycle . The active oxygen content used is therefore just as high as with a TAED / perborate ratio of 0.27, but the residual oxygen content at the end of the cleaning cycle and the oxygen content carried over into the first intermediate rinse cycle are only very low. TAED / perborate weight ratio Initial value Oa Residual oxygen content at the end of the cleaning cycle used Oa dragged into the 1st intermediate rinse cycle 0.27 225 mg 118 mg 107 mg 26 mg 0.53 225 mg 70 mg 155 mg 15 mg 1.0 120 mg 26 mg 94 mg 8 mg 1.5 120 mg 12 mg 108 mg 3 mg

Die erfindungsgemäßen mildalkalischen Maschinengeschirrspülmittel enthalten ferner weitere übliche Bestandteile. Hierzu gehören Natriumcarbonat, Natrium- oder Kaliumsilikate, wie beispielsweise Natriumdisilikat, Phosphate, wie beispielsweise Natriumtripolyphosphat, Builder und puffernd wirkende Substanzen wie beispielsweise Trinatriumcitrat, sowie Tenside, insbesondere nichtionische Tenside, die in einer Gesamtmenge bis zu 5, vorzugsweise bis zu 2 Gew. % vorliegen können. Vorzugsweise enthalten die erfindungsgemäßen Geschirrspülmittel auch die in solchen Mitteln üblichen Enzyme, wie Amylase und/oder Protease.

Figure imgb0001
The mildly alkaline machine dishwashing detergents according to the invention also contain other conventional constituents. These include sodium carbonate, sodium or potassium silicates such as sodium disilicate, phosphates such as sodium tripolyphosphate, builders and buffering substances such as trisodium citrate, as well as surfactants, especially nonionic surfactants, in a total amount of up to 5, preferably up to 2% by weight. can be present. The dishwashing detergents according to the invention preferably also contain the enzymes customary in such detergents, such as amylase and / or protease.
Figure imgb0001

AnwendungstestApplication test

Die Maschinengeschirrspülmittel der Beispiele 1-3 und 5-7 Vergleichsbeispiele A und B wurden unter folgenden Versuchsbedingungen getestet:The machine dishwashing detergents of Examples 1-3 and 5-7 Comparative Examples A and B were tested under the following test conditions:

Eine Haushaltsgeschirrspülmaschine wurde mit Geschirr und Silberbesteck beladen, welches folgende Schmutzbelastung besaß: 50 ml einer Mischung aus Ketchup 25 g Senf 25 g Bratensoße 25 g Kartoffelstärke 5 g Benzoesäure 1 g Eigelb 3 Milch 500 g Wasser 700 g 20 Programmabläufe; Wasserhärte 18-20 °d A household dishwasher was loaded with dishes and silver cutlery, which had the following contamination: 50 ml of a mixture of Ketchup 25 g mustard 25 g gravy 25 g Potato starch 5 g Benzoic acid 1 g egg yolk 3rd milk 500 g water 700 g 20 program sequences; Water hardness 18-20 ° d

Ergebnisse:Results:

Bei Anwendung der Maschinengeschirrspülmittel der Beispiele 1-3 und 5-7 waren Silber, Geschirr und Maschine blank.When using the machine dishwashing detergents from Examples 1-3 and 5-7, silver, dishes and machine were bare.

Bei Anwendung der Maschinengeschirrspülmittel der Vergleichsbeispiele A und B war das Silber stark verfärbt.The silver was severely discolored when the machine dishwashing detergents from comparative examples A and B were used.

Claims (9)

1) Mildalkalisches Maschinengeschirrspülmittel enthaltend ein Bleichmittel auf Sauerstoffbasis sowie weitere übliche Bestandteile, dadurch gekennzeichnet, daß es eine Kombination aus a) einem oder mehreren Aktivatoren und b) einem oder mehreren verkapselten Zusatzmitteln enthält, welche sicherstellt, daß am Ende des Reinigungsganges im alkalischen Milieu, der Bleichmittelgehalt der Spülflotte im wesentlichen vollständig abgebaut ist. 1) Mildly alkaline machine dishwashing detergent containing an oxygen-based bleach and other common ingredients, characterized in that it is a combination of a) one or more activators and b) one or more encapsulated additives, which ensures that at the end of the cleaning cycle in an alkaline environment, the bleach content of the washing liquor is essentially completely degraded. 2) Maschinengeschirrspülmittel nach Anspruch 1, dadurch gekennzeichnet, daß das Zusatzmittel ein verkapseltes sauerstoffzersetzendes Enzym ist. 2) dishwasher detergent according to claim 1, characterized in that the additive is an encapsulated oxygen-decomposing enzyme. 3) Maschinengeschirrspülmittel nach Anspruch 1, dadurch gekennzeichnet, daß das Zusatzmittel ein verkapseltes Reduktionsmittel ist. 3) dishwasher detergent according to claim 1, characterized in that the additive is an encapsulated reducing agent. 4) Maschinengeschirrspülmittel nach Anspruch 1, dadurch gekennzeichnet, daß das Zusatzmittel ein verkapseltes Schwermetall oder dessen Verbindung ist, welches in der Lage ist das Bleichmittel katalytisch zu zersetzen. 4) dishwasher detergent according to claim 1, characterized in that the additive is an encapsulated heavy metal or its compound, which is able to catalytically decompose the bleach. 5) Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß als Aktivator TAED, TAGU, GPA, NOBS, DPDDA, PAG, DADHT oder ISA eingesetzt wird. 5) dishwasher detergent according to one of the preceding claims, characterized in that TAED, TAGU, GPA, NOBS, DPDDA, PAG, DADHT or ISA is used as activator. 6) Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß als Bleichmittel Natriumperborat, Natriumpercarbonat und/oder Kaliummonopersulfat oder stabilisierte Qualitäten dieser Stoffe eingesetzt wird. 6) Dishwasher detergent according to one of the preceding claims, characterized in that sodium perborate, sodium percarbonate and / or potassium monopersulfate or stabilized qualities of these substances are used as bleaching agents. 7) Maschinengeschirrspülmittel nach Anspruch 5 und 6, dadurch gekennzeichnet, daß der Aktivator TAED ist und in einem Molverhältnis zum Bleichmittel von über 0,5:1, vorzugsweise von mindestens 0,65:1 vorliegt. 7) dishwasher detergent according to claim 5 and 6, characterized in that the activator is TAED and is in a molar ratio to the bleaching agent of over 0.5: 1, preferably of at least 0.65: 1. 8) Maschinengeschirrspülmittel nach Anspruch 5 und 6, dadurch gekennzeichnet, daß der Aktivator TAED ist und in einem Gewichtsverhältnis zu Natriumperborat-monohydrat als Bleichmittel von mindestens 1,14:1, vorzugsweise mindestens 1,5:1 vorliegt. 8) dishwasher detergent according to claim 5 and 6, characterized in that the activator is TAED and is present in a weight ratio to sodium perborate monohydrate as a bleaching agent of at least 1.14: 1, preferably at least 1.5: 1. 9) Maschinengeschirrspülmittel nach Anspruch 4, dadurch gekennzeichnet, daß das Schwermetall Kupfer, Eisen, Mangan, Zink oder Titan ist. 9) dishwasher detergent according to claim 4, characterized in that the heavy metal is copper, iron, manganese, zinc or titanium.
EP94111805A 1993-07-26 1994-07-26 Automatic dishwashing detergent Revoked EP0636688B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4325039A DE4325039A1 (en) 1993-07-26 1993-07-26 Automatic dishwasher detergents
DE4325039 1993-07-26

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EP0636688A1 true EP0636688A1 (en) 1995-02-01
EP0636688B1 EP0636688B1 (en) 1999-02-03

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EP (1) EP0636688B1 (en)
AT (1) ATE176497T1 (en)
DE (2) DE4325039A1 (en)
DK (1) DK0636688T3 (en)
ES (1) ES2127856T3 (en)
GR (1) GR3029397T3 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023507A1 (en) * 1999-09-30 2001-04-05 Henkel Kommanditgesellschaft Auf Aktien Machine-based silver cleaning agents
US6281180B1 (en) 1997-07-23 2001-08-28 Lever Brothers Company, Division Of Conopco, Inc. Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
WO2005037976A2 (en) * 2003-10-16 2005-04-28 The Procter & Gamble Company Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances
US8107304B2 (en) 1994-12-23 2012-01-31 Round Rock Research, Llc Distributed write data drivers for burst access memories
US20220151456A1 (en) * 2020-11-17 2022-05-19 The Procter & Gamble Company Automatic dishwashing method with alkaline rinse

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202008011292U1 (en) * 2008-02-12 2008-11-06 Thurn, Adolf cleaning supplies

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128672A1 (en) * 1991-08-29 1993-03-04 Henkel Kgaa USE OF STRONG ALKALINE AGENTS TO PREVENT THE STARTING OF SILVER PICKLES IN DISHWASHING MACHINES
EP0541475A1 (en) * 1991-11-08 1993-05-12 Cleantabs A/S Automatic dishwashing composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8321923D0 (en) * 1983-08-15 1983-09-14 Unilever Plc Machine-dishwashing compositions
US4536183A (en) * 1984-04-09 1985-08-20 Lever Brothers Company Manganese bleach activators
DE4112075A1 (en) * 1991-04-12 1992-10-15 Henkel Kgaa METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128672A1 (en) * 1991-08-29 1993-03-04 Henkel Kgaa USE OF STRONG ALKALINE AGENTS TO PREVENT THE STARTING OF SILVER PICKLES IN DISHWASHING MACHINES
EP0541475A1 (en) * 1991-11-08 1993-05-12 Cleantabs A/S Automatic dishwashing composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8107304B2 (en) 1994-12-23 2012-01-31 Round Rock Research, Llc Distributed write data drivers for burst access memories
US8213244B2 (en) 1994-12-23 2012-07-03 Round Rock Research, Llc Distributed write data drivers for burst access memories
US6281180B1 (en) 1997-07-23 2001-08-28 Lever Brothers Company, Division Of Conopco, Inc. Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
WO2001023507A1 (en) * 1999-09-30 2001-04-05 Henkel Kommanditgesellschaft Auf Aktien Machine-based silver cleaning agents
WO2005037976A2 (en) * 2003-10-16 2005-04-28 The Procter & Gamble Company Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances
WO2005037976A3 (en) * 2003-10-16 2005-06-16 Procter & Gamble Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances
US20220151456A1 (en) * 2020-11-17 2022-05-19 The Procter & Gamble Company Automatic dishwashing method with alkaline rinse

Also Published As

Publication number Publication date
DE4325039A1 (en) 1995-02-02
ES2127856T3 (en) 1999-05-01
DE59407759D1 (en) 1999-03-18
ATE176497T1 (en) 1999-02-15
DK0636688T3 (en) 1999-09-20
EP0636688B1 (en) 1999-02-03
GR3029397T3 (en) 1999-05-28

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