EP0414197A2 - Dishwashing compositions for dishwasher - Google Patents

Dishwashing compositions for dishwasher Download PDF

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Publication number
EP0414197A2
EP0414197A2 EP90115943A EP90115943A EP0414197A2 EP 0414197 A2 EP0414197 A2 EP 0414197A2 EP 90115943 A EP90115943 A EP 90115943A EP 90115943 A EP90115943 A EP 90115943A EP 0414197 A2 EP0414197 A2 EP 0414197A2
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EP
European Patent Office
Prior art keywords
weight
sodium
dishwasher detergent
carbonate
detergent according
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Granted
Application number
EP90115943A
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German (de)
French (fr)
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EP0414197B1 (en
EP0414197A3 (en
Inventor
Guido Dr. Dipl.-Chem. Wäschenbach
Ludwig Hertling
Wolfgang Dr. Dipl.-Chem. Ussat
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present invention relates to a dishwasher detergent.
  • the invention is therefore based on the object of developing a machine dishwashing detergent which has a lower pH than conventional dishwashing detergents and in particular has a pH below 10.5 (in a 1% strength aqueous solution), yet has good cleaning performance and consists of the environment is not composed or components that have as little pollution as possible.
  • a dishwasher detergent is known from EP-A 135 227, which is only weakly alkaline and has a pH of approximately 9.3-10.8 (in 0.3% aqueous solution), 25-50% by weight. Contains sodium triphosphate, 7.5-40% by weight sodium carbonate, 2-15% by weight sodium silicate, and a peroxy compound and enzyme. It is found that the effectiveness and stability of such a mildly alkaline, enzymatic composition is a matter of choosing the right amount of ingredients.
  • sodium metasilicate can be completely dispensed with in an effective dishwasher detergent if a mixture of sodium carbonate and sodium hydrogen carbonate is used instead.
  • This mixture offers the possibility to vary the pH value of the final formulation in a larger pH range, while maintaining the high alkalinity reserve.
  • this high reserve of alkalinity makes it possible to keep the enzyme content and builder content of the formulation very low. According to the invention, it is even possible to completely dispense with phosphate builders.
  • the machine dishwashing detergents according to the invention generally contain 20-80% by weight, preferably 30-70% by weight and in particular 45-55% by weight of sodium carbonate and 5-50% by weight, preferably 10-40% by weight and in particular 15-36% by weight sodium hydrogen carbonate.
  • US-P 4,306,987 discloses strongly alkaline dishwashing detergents with special low-foaming nonionic detergents.
  • These known dishwashing detergents generally contain 20-80% by weight of an alkaline detergent salt such as e.g. Sodium carbonate, sodium hydrogen carbonate and mixtures thereof, di- and trisodium orthopiosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate, and as a bleaching agent 5 - 50% by weight chlorinated trisodium phosphate or instead a mixture of lithium hypochlorite or chlorinated cyanuric acid and trisodium phosphate.
  • the sodium silicate generally makes up 20-80%, preferably 20-40%.
  • the pH of the dishwasher detergents according to the invention is generally in the range from 9.0 to 10.5 or even less, preferably in the range from 9.9 to 10.4.
  • the ratio of sodium carbonate to sodium hydrogen carbonate is generally 4: 1 to 1: 1, preferably 3: 1 to 1: 1.
  • Preferred dishwashing detergents according to the invention with a pH of 9.0-10.5, preferably 9.9-10.4, contain 20-80% by weight sodium carbonate and 5-50% by weight sodium hydrogen carbonate, the combination of Sodium carbonate and sodium hydrogen carbonate make up at least 30 wt .-% of the total composition.
  • the dishwashing detergents according to the invention can contain a phosphate, conventionally sodium tripolyphosphate as a builder.
  • a suitable phosphate-containing dishwashing detergent contains 20-60% by weight sodium carbonate and 10-20% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 30-70% by weight, and 10-40% by weight, preferably 20 - 35 wt .-% phosphate, especially sodium tripolyphosphate.
  • dishwasher detergents that are free of phosphates are particularly preferred.
  • phosphate-free builder systems can be used which replace the phosphate in whole or in part.
  • An acrylic acid / maleic acid copolymer for example the product Sokalan CP 5 ex BASF
  • a polyacrylic acid for example Acrysol LMW 45 ND ex Rhom & Haas
  • a phosphonic acid for example 1-hydroxyethane-1,1-diphosphonic acid / HEDP /
  • a phosphonic acid for example 1-hydroxyethane-1,1-diphosphonic acid / HEDP /
  • the polymer serving as a phosphate substitute can be used in an amount of 0 to 15% by weight, preferably 3 to 10% by weight.
  • the phosphonic acid is used in an amount of 0-10, preferably 2-4% by weight.
  • a phosphate-free builder system can also contain small amounts of low molecular weight polymers based on maleic acid or acrylic acid, e.g. Sokalan PM10 ex BASF or Sokalan PA15 ex BASF included.
  • the phosphate-free builder system can also contain nitrilotriacetic acid instead of phosphonic acids or low molecular weight polymers.
  • a suitable phosphate-free dishwasher detergent contains 25-60% by weight sodium carbonate and 10-35% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 35-75% by weight, and 3-10% by weight of a phosphate-free polymeric builder.
  • the machine dishwashing detergents according to the invention are preferably free of silicates.
  • a small amount of disilicates or layered silicates can be advantageous as corrosion inhibitors. If such silicates are used as corrosion inhibitors, their amount should not exceed 15% by weight of the total composition, in general their proportion is 5-10% by weight.
  • the machine dishwashing detergents according to the invention preferably contain enzymes which, however, are already effective in very small amounts in the compositions according to the invention.
  • Proteases for example the product Savinase 4.0 T ex Novo
  • amylases for example the product Termamyl 60 T ex Novo
  • lipases can also be advantageous for certain types of soiling, especially at low washing temperatures.
  • the enzymes are generally used in amounts of 0-3% by weight, preferably 0.4-1% by weight.
  • Chlorine bleaches such as sodium dichloroisocyanurate
  • oxygen bleaches can advantageously be used, such as sodium perborate monohydrate, sodium perborate tetrahydrate, potassium monopersulfate, magnesium monoperoxyphthalate hexahydrate (H48), diperoxidodecanedioic acid (desensitized) and sodium percarbonate.
  • the machine dishwashing detergents according to the invention advantageously contain 3 to 15% by weight, preferably 3 to 10% by weight and in particular 5 to 8% by weight of sodium perborate monohydrate or sodium percarbonate.
  • a bleach activator such as e.g. TAED (tetraacetylethylenediamine), TAGU (tetraacetylglycoluril), GPA (glucose pentaacetate) and others be incorporated into the wording.
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetylglycoluril
  • GPA glucose pentaacetate
  • compositions according to the invention can contain small amounts of a surfactant, preferably a nonionic surfactant, advantageously in an amount of up to 5% by weight, preferably up to 3% by weight and in particular up to 1% by weight. In general, amounts in the range of 0.2-2% by weight of a nonionic surfactant are completely sufficient.
  • the surfactants used must be low-foaming, so non-ionic surfactants are the most suitable. Low-foaming nonionic surfactants with good biodegradability are preferably used. This is e.g. adducts of ethylene oxide and propylene oxide or ethylene oxide and higher alkylene oxides with native or synthetic fatty alcohols or oxo alcohols. Corresponding adducts which are end group-closed are also very suitable.
  • the machine dishwashing detergent according to the invention may also contain other conventional ingredients, such as dyes, perfume oils or other auxiliaries, such as e.g. Stabilizers for enzymes.
  • the fatty acids or hydrocarbons are used in amounts of 0-3% by weight, preferably 0.5-2% by weight and in particular 0.7-1.5% by weight, based on the overall composition.
  • Sodium sulfate has also proven to be suitable as an anticaking agent and can be used instead of the white oils. Sodium sulfate is also suitable as a diluent. If the alkalinity of the formulation is to be reduced, part of the amount of sodium carbonate / sodium hydrogen carbonate can be replaced by sodium sulfate, but the minimum content of 25% by weight, preferably 30% by weight, of the sodium carbonate / sodium hydrogen carbonate combination must be maintained .
  • the machine dishwashing detergents according to the invention can therefore contain 0-35% by weight sodium sulfate.
  • a suitable, phosphate-containing composition according to the invention consists of 20-35% by weight sodium tripolyphosphate 35-55% by weight sodium carbonate 10 - 20% by weight sodium hydrogen carbonate 5-8% by weight sodium perborate monohydrate 0.4-1 wt% protease 0.4-1 wt% amylase 0.2-2% by weight of nonionic surfactant part of the sodium carbonate / sodium hydrogen carbonate amount by 0-20% by weight sodium sulfate can be replaced; and has a pH (in 1% solution) of 10.2 - 10.4.
  • a particularly suitable, phosphate-free composition according to the invention consists of 35-55% by weight sodium carbonate 20-35% by weight sodium hydrogen carbonate 5-8% by weight sodium perborate monohydrate 0.4-1 wt% protease 0.4-1 wt% amylase 0.2-2% by weight of nonionic surfactant 3 - 10% by weight acrylic acid / maleic acid / copolymer 0 - 4 wt .-% phosphonic acid , a part of the sodium carbonate / sodium bicarbonate amount can be replaced by 0-35% by weight sodium sulfate, and has a pH (in 1% solution) of 10.2-10.4.
  • the cleaning performance of the dishwasher detergents according to the invention is comparable to conventional, strongly alkaline dishwasher detergents based on sodium metasilicate.
  • the formulations according to the invention are even superior.
  • compositions according to the invention are much lower than those of comparable known formulations.
  • the machine dishwashing detergents according to the invention are generally formulated as dry powders or granules in a conventional manner. Their use in the form of tablets, pouches, portion packs but also in the form of liquid concentrates is not excluded.
  • a machine dishwashing detergent of the following composition was formulated by dry mixing or granulation: Sodium tripolyphosphate 24.0% by weight sodium 49.0% by weight Sodium bicarbonate 18.0% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight Nonionic surfactant (Lutensol LF403) 1.0% by weight
  • This composition had a pH (in 1% aqueous solution) of 10.3.
  • a machine dishwashing detergent of the following composition was formulated by dry mixing or granulation: sodium 49.0% by weight Sodium bicarbonate 34.5% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight Nonionic surfactant (Lutensol LF403) 1.0% by weight Acrylic acid / maleic acid copolymer 5.0% by weight Phosphonic acid (HEDP) 2.5% by weight
  • This composition had a pH (in 1% aqueous solution) of 10.0.
  • Example 3 sodium 50.0% by weight Sodium bicarbonate 33.0% by weight Sodium perborate monohydrate 6.0% by weight TAED 1.5% by weight Acrylic acid / maleic acid copolymer 5.0% by weight Phosphonic acid (HEDP) 2.5% by weight Fatty acid (C12-C18) 1.0% by weight Protease 0.5% by weight Amylase 0.5% by weight
  • This composition had a pH (in 1% solution) of 10.1.
  • formulations according to the invention of Examples 1 and 2 were compared with regard to their cleaning performance with a formulation containing sodium metasilicate (formulation I).
  • the test was carried out in accordance with the DIN 44990 regulation, only with the difference that the evaluation of the cleaning performance for spinach, minced meat, oatmeal and tea was weighted as a percentage.
  • the comparison formulation I had the following composition: Sodium tripolyphosphate 36.1% by weight Sodium metasilicate 51.0% by weight sodium 9.65% by weight Sodium dichloroisocyanurate 2.25% by weight Surfactant (Dehypon LT104) 1.0 wt%.
  • formulation II a formulation according to EP-A 135 227 was examined as formulation II, which had the following composition: Rec .: 45% sodium tripolyphosphate, 15% sodium carbonate, 10% sodium perborate * 4H20, 4% TAED, 3% Thermamyl 60 T, 2% Savinase 4.0 T, 0.7% Dequest 2016, 5% sodium disilicate, 10% sodium sulfate, 1, 5% Lutensol LF 403, water ad 100%.

Abstract

The invention relates to a mildly alkaline dishwashing composition which a) contains at least 25% by weight of a combination of sodium carbonate and sodium bicarbonate; b) is free of metasilicates; c) is free of chlorine bleaches and d) has a mildly alkaline pH of less than 10.5 in 1% strength aqueous solution. n

Description

Die vorliegende Erfindung betrifft ein Maschinengeschirr­spülmittel.The present invention relates to a dishwasher detergent.

Herkömmliche Maschinengeschirrspülmittel basieren im wesentlichen auf Natriumtripolyphosphat, Natriummetasilikat und Natriumcarbonat und sind stark alkalisch. Der pH-Wert dieser Produkte liegt im allgemeinen bei 12 (in 1 %iger Lösung) und ist im wesentlichen auf den hohen Gehalt an Natriummetasilikat und Natriumcarbonat zurückzuführen. Bei diesen pH-Werten können Reizungen bzw. Verätzungen der Haut und der Schleimhäute, insbesondere beim Verschlucken (Kleinkinder) auftreten und dadurch sind diese Produkte zunehmend in die öffentliche Diskussion geraten. Es besteht daher ein Bedarf an Maschinengeschirrspülmitteln, die weni­ger alkalisch sind. Bei einer Verminderung der Alkalinität wurde aber eine Verminderung der Geschirrspülleistung er­wartet.Conventional machine dishwashing detergents are essentially based on sodium tripolyphosphate, sodium metasilicate and sodium carbonate and are strongly alkaline. The pH of these products is generally 12 (in a 1% solution) and is essentially due to the high content of sodium metasilicate and sodium carbonate. At these pH values, irritation or burns to the skin and mucous membranes can occur, especially when swallowed (small children) and as a result, these products have increasingly come into public discussion. There is therefore a need for machine dishwashing detergents that are less alkaline. If the alkalinity was reduced, however, a reduction in the dishwasher performance was expected.

Der Erfindung liegt also die Aufgabe zugrunde ein Maschi­nengeschirrspülmittel zu entwickeln, welches einen niedri­geren pH-Wert als die herkömmlichen Geschirrspülmittel besitzt und insbesondere einen pH-Wert unterhalb von 10,5 (in 1 %iger wäßriger Lösung), dennoch eine gute Reinigungs­leistung aufweist und aus die Umwelt nicht oder möglichst wenig belastenden Bestandteilen zusammengesetzt ist.The invention is therefore based on the object of developing a machine dishwashing detergent which has a lower pH than conventional dishwashing detergents and in particular has a pH below 10.5 (in a 1% strength aqueous solution), yet has good cleaning performance and consists of the environment is not composed or components that have as little pollution as possible.

Aus der EP-A 135 227 ist ein Maschinengeschirrspülmittel bekannt, welches nur schwach alkalisch ist und einen pH-­Wert von etwa 9,3 - 10,8 (in 0,3 %iger wäßriger Lösung) aufweist, 25 - 50 Gew.-% Natriumtriphosphat, 7,5 - 40 Gew.­% Natriumcarbonat, 2 - 15 Gew.-% Natriumsilikat, sowie eine Peroxyverbindung und Enzym enthält. Es wird festgestellt, daß die Wirksamkeit und Stabilität einer solchen mild-alka­lischen, enzymatischen Zusammensetzung eine Sache der Aus­wahl der Bestandteile in richtiger Menge ist.A dishwasher detergent is known from EP-A 135 227, which is only weakly alkaline and has a pH of approximately 9.3-10.8 (in 0.3% aqueous solution), 25-50% by weight. Contains sodium triphosphate, 7.5-40% by weight sodium carbonate, 2-15% by weight sodium silicate, and a peroxy compound and enzyme. It is found that the effectiveness and stability of such a mildly alkaline, enzymatic composition is a matter of choosing the right amount of ingredients.

Gemäß vorliegender Erfindung wurde festgestellt, daß auf Natriummetasilikat in einem wirksamen Maschinengeschirr­spülmittel vollständig verzichtet werden kann, wenn statt dessen ein Gemisch aus Natriumcarbonat und Natriumhydrogen­carbonat eingesetzt wird. Dieses Gemisch bietet die Mög­lichkeit, den pH-Wert cer Endrezeptur in einem größeren pH-Bereich zu variieren, wobei die hohe Alkalitätsreserve erhalten bleibt. Diese hohe Alkalitätsreserve andererseits erlaubt es, den Enzymgehalt und den Buildergehait der Re­zeptur sehr niedrig zu halten. Erfindungsgemäß ist es sogar möglich auf Phosphatbuilder vollständig zu verzichten.According to the present invention, it has been found that sodium metasilicate can be completely dispensed with in an effective dishwasher detergent if a mixture of sodium carbonate and sodium hydrogen carbonate is used instead. This mixture offers the possibility to vary the pH value of the final formulation in a larger pH range, while maintaining the high alkalinity reserve. On the other hand, this high reserve of alkalinity makes it possible to keep the enzyme content and builder content of the formulation very low. According to the invention, it is even possible to completely dispense with phosphate builders.

Die erfindungsgemäßen Maschinengeschirrspülmittel enthalten im allgemeinen 20 - 80 Gew.-%, vorzugsweise 30 - 70 Gew.-% und insbesondere 45 - 55 Gew.-% Natriumcarbonat sowie 5 - 50 Gew.-%, vorzugsweise 10 - 40 Gew.-% und insbesondere 15 - 36 Gew.-% Natriumhydrogencarbonat.The machine dishwashing detergents according to the invention generally contain 20-80% by weight, preferably 30-70% by weight and in particular 45-55% by weight of sodium carbonate and 5-50% by weight, preferably 10-40% by weight and in particular 15-36% by weight sodium hydrogen carbonate.

Die US-P 4 306 987 offenbart stark alkalische Geschirrspül­mittel mit speziellen niedrigschäumenden nichtionischen Detergentien. Diese bekannten Geschirrspülmittel enthalten im allgemeinen 20 - 80 Gew.-% eines alkalischen Detergens­salzes wie z.B. Natriumcarbonat, Natriumhydrogencarbonat und Mischungen davon, Di- und Trinatriumorthopiosphat, Natriummetasilikat, Natriumsesquisilikat, Borax und Natrium borat, sowie als Bleichmittel 5 - 50 Gew.-% chloriertes Tri­natriumphosphat oder statt dessen eine Mischung aus Li­thiumhypochlorit oder chlorierter Cyanursäure und Trina­triumphosphat. Das Natriumsilikat macht in diesen bekannten Geschirrspülmitteln im allgemeinen 20 - 80 %, vorzugsweise 20 - 40 % aus.US-P 4,306,987 discloses strongly alkaline dishwashing detergents with special low-foaming nonionic detergents. These known dishwashing detergents generally contain 20-80% by weight of an alkaline detergent salt such as e.g. Sodium carbonate, sodium hydrogen carbonate and mixtures thereof, di- and trisodium orthopiosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate, and as a bleaching agent 5 - 50% by weight chlorinated trisodium phosphate or instead a mixture of lithium hypochlorite or chlorinated cyanuric acid and trisodium phosphate. In these known dishwashing detergents, the sodium silicate generally makes up 20-80%, preferably 20-40%.

In ihrer allgemeinsten Form betrifft die Erfindung ein Maschinengeschirrspülmittel, welches

  • a) mindestens 25 Gew.-%, vorzugsweise mindestens 30 Gew.-%, einer Kombination aus Natriumcarbonat und Natriumhydrogencarbonat enthält;
  • b) frei ist von Metasilikaten;
  • c) frei ist von Chlorbleichmitteln und
  • d) in 1 %iger wäßriger Lösung einen mild-alkalischen pH-Wert von weniger als 10,5 aufweist.
In its most general form, the invention relates to a dishwasher detergent which
  • a) contains at least 25% by weight, preferably at least 30% by weight, of a combination of sodium carbonate and sodium hydrogen carbonate;
  • b) is free of metasilicates;
  • c) is free from chlorine bleach and
  • d) in 1% aqueous solution has a mildly alkaline pH of less than 10.5.

Der pH-Wert der erfindungsgemäßen Maschinengeschirrspülmit­tel liegt im allgemeinen im Bereich von 9,0 - 10,5 oder sogar darunter, vorzugsweise im Bereich von 9,9 - 10,4.The pH of the dishwasher detergents according to the invention is generally in the range from 9.0 to 10.5 or even less, preferably in the range from 9.9 to 10.4.

In der erfindungsgemäß eingesetzten Kombination aus Na­triumcarbonat und Natriumhydrogencarbonat beträgt das Ver­hältnis von Natriumcarbonat zu Natriumhydrogencarbonat im allgemeinen 4:1 bis 1:1, vorzugsweise 3:1 bis 1:1.In the combination of sodium carbonate and sodium hydrogen carbonate used according to the invention, the ratio of sodium carbonate to sodium hydrogen carbonate is generally 4: 1 to 1: 1, preferably 3: 1 to 1: 1.

Bevorzugte erfindungsgemäße Geschirrspülmittel mit einem pH-Wert von 9,0 - 10,5, vorzugsweise von 9,9 - 10,4, ent­halten 20 - 80 Gew.-% Natriumcarbonat und 5 - 50 Gew.-% Natriumhydrogencarbonat, wobei die Kombination aus Natrium­carbonat und Natriumhydrogencarbonat mindestens 30 Gew.-% der Gesamtzusammensetzung ausmacht.Preferred dishwashing detergents according to the invention with a pH of 9.0-10.5, preferably 9.9-10.4, contain 20-80% by weight sodium carbonate and 5-50% by weight sodium hydrogen carbonate, the combination of Sodium carbonate and sodium hydrogen carbonate make up at least 30 wt .-% of the total composition.

Die erfindungsgemäßen Geschirrspülmittel können ein Phos­phat, herkömmlicherweise Natriumtripolyphosphat als Builder enthalten. Ein geeignetes phosphathaltiges Geschirrspülmit­tel enthält 20 - 60 Gew.-% Natriumcarbonat und 10 - 20 Gew.-% Natriumhydrogencarbonat, wobei die Summe von Na­triumcarbonat und Natriumhydrogencarbonat 30 - 70 Gew.-% ausmacht, und 10 - 40 Gew.-%, vorzugsweise 20 - 35 Gew.-% Phosphat, insbesondere Natriumtripolyphosphat.The dishwashing detergents according to the invention can contain a phosphate, conventionally sodium tripolyphosphate as a builder. A suitable phosphate-containing dishwashing detergent contains 20-60% by weight sodium carbonate and 10-20% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 30-70% by weight, and 10-40% by weight, preferably 20 - 35 wt .-% phosphate, especially sodium tripolyphosphate.

Besonders bevorzugt werden jedoch Maschinengeschirrspülmit­tel, die frei von Phosphaten sind. Statt des Phosphats können phosphatfreie Buildersysteme eingesetzt werden, die das Phosphat ganz oder teilweise ersetzen. Für diesen Zweck sind verschiedene Systeme bekannt geworden. Als besonders geeignet für die Zwecke der vorliegenden Erfindung hat sich ein Acrylsäure/Maleinsäure-Copolymer (beispielsweise das Produkt Sokalan CP 5 ex BASF), oder eine Polyacrylsäure (beispielsweise Acrysol LMW 45 ND ex Rhom & Haas) erwiesen, welche gegebenenfalls zusammen mit geringen Mengen einer Phosphonsäure (beispielsweise 1-Hydroxyethan-1,1-diphos­phonsäure/HEDP/) eingesetzt werden können. Das als Phos­phatersatzstoff dienende Polymer kann in einer Menge von 0 - 15 Gew.-%, vorzugsweise 3 - 10 Gew.-% eingesetzt werden. Die Phosphonsäure wird in einer Menge von 0 - 10, vorzugs­weise 2 - 4 Gew.-% eingesetzt. Ein phosphatfreies Builder­system kann anstelle von geringen Mengen einer Phosphonsäu­re auch geringe Mengen niedrigmolekularer Polymerer auf Basis der Maleinsäure bzw. Acrylsäure z.B. Sokalan PM10 ex BASF oder Sokalan PA15 ex BASF enthalten.However, dishwasher detergents that are free of phosphates are particularly preferred. Instead of the phosphate, phosphate-free builder systems can be used which replace the phosphate in whole or in part. Various systems have become known for this purpose. An acrylic acid / maleic acid copolymer (for example the product Sokalan CP 5 ex BASF) or a polyacrylic acid (for example Acrysol LMW 45 ND ex Rhom & Haas), which optionally together with small amounts, has proven to be particularly suitable for the purposes of the present invention a phosphonic acid (for example 1-hydroxyethane-1,1-diphosphonic acid / HEDP /) can be used. The polymer serving as a phosphate substitute can be used in an amount of 0 to 15% by weight, preferably 3 to 10% by weight. The phosphonic acid is used in an amount of 0-10, preferably 2-4% by weight. Instead of small amounts of a phosphonic acid, a phosphate-free builder system can also contain small amounts of low molecular weight polymers based on maleic acid or acrylic acid, e.g. Sokalan PM10 ex BASF or Sokalan PA15 ex BASF included.

Das phosphatfreie Buildersystem kann anstelle von Phosphon­säuren oder niedrigmolekularer Polymerer auch Nitrilotri­essigsäure enthalten.The phosphate-free builder system can also contain nitrilotriacetic acid instead of phosphonic acids or low molecular weight polymers.

Ein geeignetes phosphatfreies Maschinengeschirrspülmittel enthält 25 - 60 Gew.-% Natriumcarbonat und 10 - 35 Gew.-% Natriumhydrogencarbonat, wobei die Summe von Natriumcarbo­nat und Natriumhydrogencarbonat 35 - 75 Gew.-% ausmacht, sowie 3 - 10 Gew.-% eines phosphatfreien polymeren Buil­ders.A suitable phosphate-free dishwasher detergent contains 25-60% by weight sodium carbonate and 10-35% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 35-75% by weight, and 3-10% by weight of a phosphate-free polymeric builder.

Die erfindungsgemäßen Maschinengeschirrspülmittel sind vorzugsweise frei von Siiikaten. Es hat sich jedoch heraus­gestellt, daß eine geringe Menge an Disilikaten oder Schichtsilikaten als Korrosionsinhibitoren vorteilhaft sein kann. Sofern solche Silikate als Korrosionsinhibitoren eingesetzt werden soll ihre Menge 15 Gew.-% der gesamten Zusammensetzung nicht überschreiten, im allgemeinen liegt ihr Anteil bei 5 - 10 Gew.-%.The machine dishwashing detergents according to the invention are preferably free of silicates. However, it has been found that a small amount of disilicates or layered silicates can be advantageous as corrosion inhibitors. If such silicates are used as corrosion inhibitors, their amount should not exceed 15% by weight of the total composition, in general their proportion is 5-10% by weight.

Vorzugsweise enthalten die erfindungsgemäßen Maschinenge­schirrspülmittel Enzyme, die jedoch in den erfindungsge­mäßen Zusammensetzungen bereits in sehr geringen Mengen wirksam sind.The machine dishwashing detergents according to the invention preferably contain enzymes which, however, are already effective in very small amounts in the compositions according to the invention.

Vorzugsweise verwendet man Proteasen (beispielsweise das Produkt Savinase 4.0 T ex Novo) und Amylasen (beispielswei­se das Produkt Termamyl 60 T ex Novo), jedoch können auch, insbesondere bei tiefen Waschtemperaturen, Lipasen für bestimmte Anschmutzungen vorteilnaft sein.Proteases (for example the product Savinase 4.0 T ex Novo) and amylases (for example the product Termamyl 60 T ex Novo) are preferably used, but lipases can also be advantageous for certain types of soiling, especially at low washing temperatures.

Die Enzyme werden im allgemeinen in Mengen von 0 - 3 Gew.­%, vorzugsweise 0,4 - 1 Gew.-% eingesetzt.The enzymes are generally used in amounts of 0-3% by weight, preferably 0.4-1% by weight.

Chlorbleichmittel, wie beispielsweise Natriumdichlorisocya­nurat werden erfindungsgemäß vermieden, so daß eine dadurch bedingte Beeinträchtigung der Enzymstabilität und -aktivi­tät entfällt und eine eventuell mögliche Bildung von chlo­rierten organischen Verbindungen als Folge solcher Chlor­bleichmittel vermieden wird. Stattdessen können vorteil­haft Sauerstoffbleichmittel eingesetzt werden, wie bei­spielsweise Natriumperborat-Monohydrat, Natriumperborat­tetrahydrat, Kaliummonopersulfat, Magnesium-Monoperoxyph­thalat Hexahydrat(H48), Diperoxidodecandisäure (phlegmati­siert) und Natriumpercarbonat. Die erfindungsgemäßen Ma­schinengeschirrspülmittel enthalten zweckmäßigerweise 3 - 15 Gew.-%, vorzugsweise 3 - 10 Gew.-% und insbesondere 5 - 8 Gew.-% Natriumperborat-Monohydrat oder Natriumpercarbo­nat.Chlorine bleaches, such as sodium dichloroisocyanurate, are avoided in accordance with the invention, so that there is no impairment of the enzyme stability and activity and a possible formation of chlorinated organic compounds as a result of such chlorine bleaches is avoided. Instead, oxygen bleaches can advantageously be used, such as sodium perborate monohydrate, sodium perborate tetrahydrate, potassium monopersulfate, magnesium monoperoxyphthalate hexahydrate (H48), diperoxidodecanedioic acid (desensitized) and sodium percarbonate. The machine dishwashing detergents according to the invention advantageously contain 3 to 15% by weight, preferably 3 to 10% by weight and in particular 5 to 8% by weight of sodium perborate monohydrate or sodium percarbonate.

Speziell bei tiefen Temperaturen kann zur Optimierung der Bleichleistung ein Bleichaktivator, wie z.B.
TAED (Tetraacetylethylendiamin),
TAGU (Tetraacetylglycoluril),
GPA (Glucosepentaacetat) und andere
in die Formulierung eingebaut werden.Especially at low temperatures, a bleach activator such as e.g.
TAED (tetraacetylethylenediamine),
TAGU (tetraacetylglycoluril),
GPA (glucose pentaacetate) and others
be incorporated into the wording.

Die erfindungsgemäßen Zusammensetzungen können geringe Mengen eines Tensids, vorzugsweise eines nichtionischen Tensids enthalten und zwar zweckmäßigerweise in einer Menge bis 5 Gew.-%, vorzugsweise bis 3 Gew.-% und insbesondere bis 1 Gew.-%. Im allgemeinen sind Mengen im Bereich von 0,2 - 2 Gew.-% eines nichtionischen Tensids voll ausreichend. Die eingesetzten Tenside müssen schwachschäumend sein, daher sind nichtionische Tenside am besten geeignet. Be­vorzugt werden schwach schäumende nichtionische Tenside mit guter biologischer Abbaubarkeit eingesetzt. Dabei handelt es sich z.B. um Addukte von Ethylenoxid und Propylenoxid oder Ethylenoxid und höheren Alkylenoxiden an native bzw. synth. Fettalkohole oder Oxoalkohole. Ebenfalls gut geeig­net sind entsprechende Addukte die endgruppenverschlossen sind.The compositions according to the invention can contain small amounts of a surfactant, preferably a nonionic surfactant, advantageously in an amount of up to 5% by weight, preferably up to 3% by weight and in particular up to 1% by weight. In general, amounts in the range of 0.2-2% by weight of a nonionic surfactant are completely sufficient. The surfactants used must be low-foaming, so non-ionic surfactants are the most suitable. Low-foaming nonionic surfactants with good biodegradability are preferably used. This is e.g. adducts of ethylene oxide and propylene oxide or ethylene oxide and higher alkylene oxides with native or synthetic fatty alcohols or oxo alcohols. Corresponding adducts which are end group-closed are also very suitable.

Das erfindungsgemäße Maschinengeschirrspülmittel kann noch weitere übliche Bestandteile enthalten, wie Farbstoffe, Parfümöle oder sonstige Hilfsstoffe, wie z.B. Stabilisato­ren für Enzyme.The machine dishwashing detergent according to the invention may also contain other conventional ingredients, such as dyes, perfume oils or other auxiliaries, such as e.g. Stabilizers for enzymes.

Der vor allem bei stark Natriumcarbonat/Natriumbicarbonat­haltigen Formulierungen zu beobachtende Effekt einer ver­minderten Einspülbarkeit kann durch den Einsatz von Fett­säuren und/oder Kohlenwasserstoffen (Weißölen) überwunden werden (Anticaking Mittel).The effect of reduced flushability, which can be observed especially in formulations containing high sodium carbonate / sodium bicarbonate, can be overcome by using fatty acids and / or hydrocarbons (white oils) (anticaking agents).

Bei den Fettsäuren haben sich solche mit Kohlenwasserstoff­ketten im Bereich C₁₂-C₁₈ als geeignet erwiesen.In the case of fatty acids, those with hydrocarbon chains in the range C₁₂-C₁₈ have proven to be suitable.

Bei den Kohlenwasserstoffen haben sich solche Gemische aus gesättigten geradkettigen und cyclischen Kohlenwasserstof­fen mit einem Flammpunkt oberhalb 150° C als geeignet er­wiesen.In the case of hydrocarbons, such mixtures of saturated straight-chain and cyclic hydrocarbons with a flash point above 150 ° C. have proven to be suitable.

Die Fettsäuren bzw. Kohlenwasserstoffe werden in Mengen von 0 - 3 Gew.-%, vorzugsweise 0,5 - 2 Gew.-% und insbesondere 0,7 - 1,5 Gew.-% bezogen auf die gesamte Zusammensetzung eingesetzt.The fatty acids or hydrocarbons are used in amounts of 0-3% by weight, preferably 0.5-2% by weight and in particular 0.7-1.5% by weight, based on the overall composition.

Auch Natriumsulfat hat sich als Anticaking Mittel geeignet erwiesen und kann anstelle der Weißöle verwendet werden. Natriumsulfat eignet sich ferner als Verdünnungsstoff. Wenn die Alkalinität der Rezeptur vermindert werden soll, kann ein Teil der Natriumcarbonat/Natriumhydrogencarbonat-Menge durch Natriumsulfat ersetzt werden, wobei jedoch der Min­destgehalt von 25 Gew.-%, vorzugsweise 30 Gew.-% an der Natriumcarbonat/Natriumhydrogencarbonat-Kombination erhal­ten bleiben muß. Die erfindungsgemäßen Maschinengeschirr­spülmittel können daher 0 - 35 Gew.-% Natriumsulfat enthal­ten.Sodium sulfate has also proven to be suitable as an anticaking agent and can be used instead of the white oils. Sodium sulfate is also suitable as a diluent. If the alkalinity of the formulation is to be reduced, part of the amount of sodium carbonate / sodium hydrogen carbonate can be replaced by sodium sulfate, but the minimum content of 25% by weight, preferably 30% by weight, of the sodium carbonate / sodium hydrogen carbonate combination must be maintained . The machine dishwashing detergents according to the invention can therefore contain 0-35% by weight sodium sulfate.

Eine geeignete, phosphathaltige erfindungsgemäße Zusammen­setzung besteht aus
20 - 35 Gew.-% Natriumtripolyphosphat
35 - 55 Gew.-% Natriumcarbonat
10 - 20 Gew.-% Natriumhydrogencarbonat
5 - 8 Gew.-% Natriumperborat-Monohydrat
0,4 - 1 Gew.-% Protease
0,4 - 1 Gew.-% Amylase
0,2 - 2 Gew.-% Nichtionisches Tensid
wobei ein Teil der Natriumcarbonat/Natriumhydrogen­carbonat-Menge durch
0 - 20 Gew.-% Natriumsulfat ersetzt werden kann; und weist einen pH-Wert (in 1 %iger Lösung) von 10,2 - 10,4 auf.A suitable, phosphate-containing composition according to the invention consists of
20-35% by weight sodium tripolyphosphate
35-55% by weight sodium carbonate
10 - 20% by weight sodium hydrogen carbonate
5-8% by weight sodium perborate monohydrate
0.4-1 wt% protease
0.4-1 wt% amylase
0.2-2% by weight of nonionic surfactant
part of the sodium carbonate / sodium hydrogen carbonate amount by
0-20% by weight sodium sulfate can be replaced; and has a pH (in 1% solution) of 10.2 - 10.4.

Eine besonders geeignete, phosphatfreie erfindungsgemäße Zusammensetzung besteht aus
35 - 55 Gew.-% Natriumcarbonat
20 - 35 Gew.-% Natriumhydrogencarbonat
5 - 8 Gew.-% Natriumperborat-Monohydrat
0,4 - 1 Gew.-% Protease
0,4 - 1 Gew.-% Amylase
0,2 - 2 Gew.-% Nichtionisches Tensid
3 - 10 Gew.-% Acrylsäure/Maleinsäure/Copolymerisat
0 - 4 Gew.-% Phosphonsäure
, wobei ein Teil der Natriumcarbonat/Natriumhydrogencarbonat-­Menge durch 0 - 35 Gew.-% Natriumsulfat ersetzt werden kann, und weist einen pH-Wert (in 1 %iger Lösung) von 10,2 - 10,4 auf.A particularly suitable, phosphate-free composition according to the invention consists of
35-55% by weight sodium carbonate
20-35% by weight sodium hydrogen carbonate
5-8% by weight sodium perborate monohydrate
0.4-1 wt% protease
0.4-1 wt% amylase
0.2-2% by weight of nonionic surfactant
3 - 10% by weight acrylic acid / maleic acid / copolymer
0 - 4 wt .-% phosphonic acid
, a part of the sodium carbonate / sodium bicarbonate amount can be replaced by 0-35% by weight sodium sulfate, and has a pH (in 1% solution) of 10.2-10.4.

Entgegen allen Erwartungen ist die Reinigungsleistung der erfindungsgemäßen Maschinengeschirrspülmittel vergleichbar mit herkömmlichen, stark alkalischen Maschinengeschirrspül­mitteln auf der Basis von Natriummetasilikat. Für spezielle Anschmutzungen, wie z.B. Haferflocken, sind die erfindungs­gemäßen Formulierungen sogar noch überlegen.Contrary to all expectations, the cleaning performance of the dishwasher detergents according to the invention is comparable to conventional, strongly alkaline dishwasher detergents based on sodium metasilicate. For special soiling, e.g. Oatmeal, the formulations according to the invention are even superior.

Des weiteren waren die Ergebnisse von Korrosionsversuchen an Glas, Porzellan und Besteckteilen überraschend positiv. Anstelle einer verstärkten Glaskorrosion, die durch die Verwendung von Natriumcarbonat anstelle von Natriumsilikat erwartet wurde, ist der Angriff aber äußerst gering. Das gleiche gilt im Vergleich zu marktüblichen metasilikathal­tigen Reinigern.Furthermore, the results of corrosion tests on glass, porcelain and cutlery were surprisingly positive. Instead of increased glass corrosion, which was expected by using sodium carbonate instead of sodium silicate, the attack is extremely low. The same applies in comparison to commercially available cleaners containing metasilicate.

Ein weiterer Vorteil der erfindungsgemäßen Zusammensetzun­gen ist der, daß wegen der geringen eingesetzten Enzym- und Phosphatmengen die Rohstoffkosten der erfindungsgemäßen Rezepturen viel niedriger sind als die vergleichbarer be­kannter Rezepturen.Another advantage of the compositions according to the invention is that because of the small amounts of enzyme and phosphate used, the raw material costs of the formulations according to the invention are much lower than those of comparable known formulations.

Die erfindungsgemäßen Maschinengeschirrspülmittel werden im allgemeinen als trockene Pulver oder Granulate in herkömm­licher Weise formuliert. Ihr Einsatz in Form von Tabletten, Pouches, Portionspackungen aber auch in Form flüssiger Konzentrate ist jedoch nicht ausgeschlossen.The machine dishwashing detergents according to the invention are generally formulated as dry powders or granules in a conventional manner. Their use in the form of tablets, pouches, portion packs but also in the form of liquid concentrates is not excluded.

Die Erfindung wird anhand der nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.

Beispiel 1example 1

Durch Trockenvermischung bzw. Granulieren wurde ein Maschi­nengeschirrspülmittel folgender Zusammensetzung formuliert: Natriumtripolyphosphat 24,0 Gew.-% Natriumcarbonat 49,0 Gew.-% Natriumhydrogencarbonat 18,0 Gew.-% Natriumperborat-Monohydrat 7,0 Gew.-% Protease 0,5 Gew.-% Amylase 0,5 Gew.-% Nichtionisches Tensid (Lutensol LF403) 1,0 Gew.-% A machine dishwashing detergent of the following composition was formulated by dry mixing or granulation: Sodium tripolyphosphate 24.0% by weight sodium 49.0% by weight Sodium bicarbonate 18.0% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight Nonionic surfactant (Lutensol LF403) 1.0% by weight

Diese Zusammensetzung besaß einen pH-Wert (in 1 %iger wäßriger Lösung) von 10,3.This composition had a pH (in 1% aqueous solution) of 10.3.

Beispiel 2Example 2

Durch Trockenvermischung bzw. Granulieren wurde ein Maschi­nengeschirrspülmittel folgender Zusammensetzung formuliert: Natriumcarbonat 49,0 Gew.-% Natriumhydrogencarbonat 34,5 Gew.-% Natriumperborat-Monohydrat 7,0 Gew.-% Protease 0,5 Gew.-% Amylase 0,5 Gew.-% Nichtionisches Tensid (Lutensol LF403) 1,0 Gew.-% Acrylsäure/Maleinsäure-Copolymer 5,0 Gew.-% Phosphonsäure (HEDP) 2,5 Gew.-% A machine dishwashing detergent of the following composition was formulated by dry mixing or granulation: sodium 49.0% by weight Sodium bicarbonate 34.5% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight Nonionic surfactant (Lutensol LF403) 1.0% by weight Acrylic acid / maleic acid copolymer 5.0% by weight Phosphonic acid (HEDP) 2.5% by weight

Diese Zusammensetzung besaß einen pH-Wert (in 1 %iger wäßriger Lösung) von 10,0.This composition had a pH (in 1% aqueous solution) of 10.0.

Beispiel 3Example 3

Beispiel 3Example 3 Natriumcarbonatsodium 50,0 Gew.-%50.0% by weight NatriumhydrogencarbonatSodium bicarbonate 33,0 Gew.-%33.0% by weight Natriumperborat-MonohydratSodium perborate monohydrate 6,0 Gew.-%6.0% by weight TAEDTAED 1,5 Gew.-%1.5% by weight Acrylsäure/Maleinsäure CopolymerAcrylic acid / maleic acid copolymer 5,0 Gew.-%5.0% by weight Phosponsäure (HEDP)Phosphonic acid (HEDP) 2,5 Gew.-%2.5% by weight Fettsäure (C₁₂-C₁₈)Fatty acid (C₁₂-C₁₈) 1,0 Gew.-%1.0% by weight ProteaseProtease 0,5 Gew.-%0.5% by weight AmylaseAmylase 0,5 Gew.-%0.5% by weight

Diese Zusammensetzung besaß einen pH-Wert (in 1 %iger Lösung) von 10,1.This composition had a pH (in 1% solution) of 10.1.

VergleichsversucheComparative tests

Die erfindungsgemäßen Formulierungen der Beispiele 1 und 2 wurden in Bezug auf ihre Reinigungsleistung mit einer natriummetasilikathaltigen Formulierung (Rezeptur I) ver­glichen. Die Abprüfung erfolgte in Anlehnung an die DIN 44990-Vorschrift, nur mit dem Unterschied, daß die Auswer­tung der Reinigungsleistung für Spinat, Hackfleisch, Hafer­flocken und Tee prozentual gewichtet wurde.The formulations according to the invention of Examples 1 and 2 were compared with regard to their cleaning performance with a formulation containing sodium metasilicate (formulation I). The test was carried out in accordance with the DIN 44990 regulation, only with the difference that the evaluation of the cleaning performance for spinach, minced meat, oatmeal and tea was weighted as a percentage.

Die Vergleichsrezeptur I hatte folgende Zusammensetzung: Natriumtripolyphosphat 36,1 Gew.-% Natriummetasilikat 51,0 Gew.-% Natriumcarbonat 9,65 Gew.-% Natriumdichloroisocyanurat 2,25 Gew.-% Tensid (Dehypon LT104) 1,0 Gew.-%. The comparison formulation I had the following composition: Sodium tripolyphosphate 36.1% by weight Sodium metasilicate 51.0% by weight sodium 9.65% by weight Sodium dichloroisocyanurate 2.25% by weight Surfactant (Dehypon LT104) 1.0 wt%.

Zum weiteren Vergleich ist als Rezeptur II eine Formulie­rung gemäß EP-A 135 227 untersucht worden, die folgende Zusammensetzung aufwies:
Rez.: 45 % Natriumtripolyphosphat, 15 % Natriumcarbonat, 10 % Natriumperborat * 4H20, 4 % TAED, 3 % Thermamyl 60 T, 2 % Savinase 4.0 T, 0,7 % Dequest 2016, 5 % Natriumdisilikat, 10 % Natriumsulfat, 1,5 % Lutensol LF 403, Wasser ad 100 %.For further comparison, a formulation according to EP-A 135 227 was examined as formulation II, which had the following composition:
Rec .: 45% sodium tripolyphosphate, 15% sodium carbonate, 10% sodium perborate * 4H20, 4% TAED, 3% Thermamyl 60 T, 2% Savinase 4.0 T, 0.7% Dequest 2016, 5% sodium disilicate, 10% sodium sulfate, 1, 5% Lutensol LF 403, water ad 100%.

Die Ergebnisse der Vergleichsversuche sind in der nachste­henden Tabelle I zusammengefaßt.The results of the comparative tests are summarized in Table I below.

Die Vergleichsversuche zeigen, daß die erfindungsgemäßen Formulierungen eine vergleichbare Reinigungsleistung er­bringen trotz der niedereren Alkalität gegenüber Rezeptur I und trotz der geringeren Enzymmenge und geringeren Phos­phatmenge gegenüber Rezeptur II. Tabelle I Anschmutzung Vergleich Rez. I Vergleich Rez. II Beisp. 1 Beisp. 2 Beisp. 1 jedoch ohne Enzyme Wasserhärte 4°d 20°d 20°d 4°d 20°d 4°d 20°d 20°d Eigelb 4,9 5,0 5,0 4,9 4,9 5,0 5,0 4,9 Spinat 4,4 3,6 4,4 4,3 3,2 3,8 3,7 3,5 Hackfleisch 5,0 4,9 5,0 5,0 5,0 4,9 4,9 3,1 Haferflocken 4,2 4,1 4,5 4,8 4,5 4,7 4,4 4,0 Tee 5,0 4,9 5,0 5,0 4,6 4,5 3,0 4,4 Margarine 5,0 5,0 5,0 5,0 5,0 5,0 4,6 5,0 Milch 3,8 3,2 2,4 3,7 4,2 4,0 3,9 3,4 Gesamt 4,6 4,5 4,6 4,8 4,6 4,6 4,3 4,3 The comparative experiments show that the formulations according to the invention perform a comparable cleaning performance despite the lower alkalinity compared to formulation I and despite the lower amount of enzyme and lower amount of phosphate compared to formulation II. Table I Pollution Comparison Rez. I Comparison rec. II Ex. 1 Ex. 2 Example 1 but without enzymes Water hardness 4 ° d 20 ° d 20 ° d 4 ° d 20 ° d 4 ° d 20 ° d 20 ° d egg yolk 4.9 5.0 5.0 4.9 4.9 5.0 5.0 4.9 spinach 4.4 3.6 4.4 4.3 3.2 3.8 3.7 3.5 Minced meat 5.0 4.9 5.0 5.0 5.0 4.9 4.9 3.1 oatmeal 4.2 4.1 4.5 4.8 4.5 4.7 4.4 4.0 tea 5.0 4.9 5.0 5.0 4.6 4.5 3.0 4.4 margarine 5.0 5.0 5.0 5.0 5.0 5.0 4.6 5.0 milk 3.8 3.2 2.4 3.7 4.2 4.0 3.9 3.4 total 4.6 4.5 4.6 4.8 4.6 4.6 4.3 4.3

Claims (19)

1. Maschinengeschirrspülmittel, welches a) mindestens 25 Gew.-% einer Kombination aus Natrium­carbonat und Natriumhydrogencarbonat enthält; b) frei ist von Metasilikaten; c) frei ist von Chlorbleichmitteln und d) in 1%iger wäßriger Lösung einen mild-alkalischen pH-Wert von weniger als 10,5 aufweist. 1. Dishwasher detergent, which a) contains at least 25% by weight of a combination of sodium carbonate and sodium hydrogen carbonate; b) is free of metasilicates; c) is free from chlorine bleach and d) in 1% aqueous solution has a mildly alkaline pH of less than 10.5. 2. Maschinengeschirrspülmittel gemäß Anspruch 1, dadurch gekennzeichnet, daß es mindestens 30 Gew.-% einer Kom­bination aus Natriumcarbonat und Natriumhydrogencar­bonat enthält.2. Dishwasher detergent according to claim 1, characterized in that it contains at least 30 wt .-% of a combination of sodium carbonate and sodium hydrogen carbonate. 3. Maschinengeschirrspülmittel gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß in der Kombination aus Natriumcarbonat und Natriumhydrogencarbonat das Ver­hältnis von Natriumcarbonat zu Natriumhydrogencarbonat 4:1 bis 1:1, vorzugsweise 3'1 bis 1:1 beträgt.3. dishwasher detergent according to claim 1 or 2, characterized in that in the combination of sodium carbonate and sodium hydrogen carbonate the ratio of sodium carbonate to sodium hydrogen carbonate is 4: 1 to 1: 1, preferably 3'1 to 1: 1. 4. Maschinengeschirrspülmittel gemäß einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es einen pH-Wert von 9,0 - 10,5, vorzugsweise von 9,9 - 10,4 aufweist und 20 - 80 Gew.-% Natriumcarbonat und 5 - 50 Gew.-% Natriumhydrogencarbonat enthält.4. dishwasher detergent according to one of the preceding claims, characterized in that it has a pH of 9.0-10.5, preferably 9.9-10.4 and 20-80 wt .-% sodium carbonate and 5-50 Wt .-% sodium bicarbonate contains. 5. Maschinengeschirrspülmittel gemäß einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es 20 - 60 Gew.-­% Natriumcarbonat und 10 - 20 Gew.-% Natriumhydrogen­carbonat enthält, wobei die Summe von Natriumcarbonat und Natriumhydrogencarbonat 30 - 70 Gew.-% ausmacht, und daß es 10 - 40 Gew.-%, vorzugsweise 20 - 35 Gew.-% Phosphat, vorzugsweise Natriumtripolyphosphat enthält.5. dishwasher detergent according to one of the preceding claims, characterized in that it contains 20 - 60 wt .-% sodium carbonate and 10 - 20 wt .-% sodium bicarbonate, the sum of sodium carbonate and sodium bicarbonate making up 30 - 70 wt .-%, and that it contains 10-40% by weight, preferably 20-35% by weight phosphate, preferably sodium tripolyphosphate. 6. Maschinengeschirrspülmittel gemäß einem der Ansprüche 1 - 4, dadurch gekennzeichnet, daß es frei von Phosphaten ist.6. Dishwasher detergent according to one of claims 1-4, characterized in that it is free of phosphates. 7. Maschinengeschirrspülmittel gemäß Anspruch 6, dadurch gekennzeichnet, daß es 25 - 60 Gew.-% Natriumcarbonat und 10 35 Gew.-% Natriumhydrogencarbonat enthält, wobei die Summe von Natriumcarbonat und Natriumhydro­gencarbonat 35 - 75 Gew.-% ausmacht, und daß es 3 - 10 Gew.-% eines phosphatfreien polymeren Builders enthält.7. dishwasher detergent according to claim 6, characterized in that it contains 25 - 60 wt .-% sodium carbonate and 10 35 wt .-% sodium bicarbonate, the sum of sodium carbonate and sodium bicarbonate making up 35 - 75 wt .-%, and that it 3 - Contains 10 wt .-% of a phosphate-free polymeric builder. 8. Maschinengeschirrspülmittel gemäß einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es bis 15 Gew.-­%, insbesondere 5 - 10 Gew.-% Disilikat enthält.8. dishwasher detergent according to one of the preceding claims, characterized in that it contains up to 15 wt .-%, in particular 5 - 10 wt .-% disilicate. 9. Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es ein oder mehrere Enzyme enthält.9. dishwasher detergent according to one of the preceding claims, characterized in that it contains one or more enzymes. 10. Maschinengeschirrspülmittel nach Anspruch 9, dadurch gekennzeichnet, daß es eine Protease und/oder eine Amylase und/oder eine Lipase enthält.10. Dishwasher detergent according to claim 9, characterized in that it contains a protease and / or an amylase and / or a lipase. 11. Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es ein Sauer­stoffbleichmittel enthält.11. Dishwasher detergent according to one of the preceding claims, characterized in that it contains an oxygen bleach. 12. Maschinengeschirrspülmittel nach Anspruch 11, dadurch gekennzeichnet, daß es 3 - 15 Gew.-%, vorzugsweise 3 - 10 Gew.-% Natriumperborat-Monohydrat oder Natriumper­carbonat enthält.12. dishwasher detergent according to claim 11, characterized in that it contains 3 - 15 wt .-%, preferably 3 - 10 wt .-% sodium perborate monohydrate or sodium percarbonate. 13. Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es 0 - 5 Gew.-%, vorzugsweise 0 - 1 Gew.-% eines nichtionischen Tensids enthält.13. Dishwasher detergent according to one of the preceding claims, characterized in that it contains 0 - 5 wt .-%, preferably 0 - 1 wt .-% of a nonionic surfactant. 14. Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es einen Zusatz von Fettsäuren (C₁₂-C₁₈) und/oder Weißölen in einer Menge bis 3 Gew.-% als Anticaking-Mittel enthält.14. Dishwasher detergent according to one of the preceding claims, characterized in that it contains an addition of fatty acids (C₁₂-C₁₈) and / or white oils in an amount up to 3 wt .-% as an anti-caking agent. 15. Maschinengeschirrspülmittel nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß es 0 - 35 Gew.-% Natriumsulfat enthält.15. Dishwasher detergent according to one of the preceding claims, characterized in that it contains 0 - 35 wt .-% sodium sulfate. 16. Maschinengeschirrspülmittel nach Anspruch 5, dadurch gekennzeichnet, daß es besteht aus
20 - 35 Gew.-% Natriumtripolyphosphat
35 - 55 Gew.-% Natriumcarbonat
10 - 20 Gew.-% Natriumhydrogencarbonat
5 - 8 Gew.-% Natriumperborat-Monohydrat
0,4 - 1 Gew.-% Protease
0,4 - 2 Gew.-% Amylase
0,2 - 2 Gew.-% Nichtionisches Tensid
wobei ein Teil der Natriumcarbonat/Natriumhydrogencar­bonat-Menge durch
0 - 20 Gew.-% Natriumsulfat ersetzt werden kann und einen pH-Wert (in 1 %iger Lösung) von 10,2 - 10,4 aufweist.16. Dishwasher detergent according to claim 5, characterized in that it consists of
20-35% by weight sodium tripolyphosphate
35-55% by weight sodium carbonate
10 - 20% by weight sodium hydrogen carbonate
5-8% by weight sodium perborate monohydrate
0.4-1 wt% protease
0.4-2% by weight amylase
0.2-2% by weight of nonionic surfactant
part of the sodium carbonate / sodium hydrogen carbonate amount by
0-20% by weight of sodium sulfate can be replaced and has a pH (in 1% solution) of 10.2-10.4. 17. Maschinengeschirrspülmittel nach Anspruch 6, dadurch gekennzeichnet, daß es besteht aus
35 - 55 Gew.-% Natriumcarbonat
20 - 35 Gew.-% Natriumhydrogencarbonat
5 - 8 Gew.-% Natriumperborat-Monohydrat
0,4 - 1 Gew.-% Protease
0,4 - 1 Gew.-% Amylase
0,2 - 2 Gew.-% Nichtionisches Tensid
3 - 10 Gew.-% Acrylsäure/Maleinsäure/Copolymerisat
0 - 4 Gew.-% Phosphonsäure,
wobei ein Teil der Natriumcarbonat/Natriumhydrogencarbonat-­Menge durch 0 - 35 Gew.-% Natriumsulfat ersetzt werden kann, und einen pH-Wert (in 1 %iger Lösung) von 10,2 - 10,4 aufweist.17. Dishwasher detergent according to claim 6, characterized in that it consists of
35-55% by weight sodium carbonate
20-35% by weight sodium hydrogen carbonate
5-8% by weight sodium perborate monohydrate
0.4-1 wt% protease
0.4-1 wt% amylase
0.2-2% by weight of nonionic surfactant
3 - 10% by weight acrylic acid / maleic acid / copolymer
0 - 4% by weight phosphonic acid,
part of the sodium carbonate / sodium hydrogen carbonate amount can be replaced by 0-35% by weight sodium sulfate, and has a pH (in 1% solution) of 10.2-10.4. 18. Maschinengeschirrspülmittel nach Anspruch 5, dadurch gekennzeichnet, daß es besteht aus
22 - 26 Gew.-% Natriumtripolyphosphat
47 - 52 Gew.-% Natriumcarbonat
16 - 20 Gew.-% Natriumhydrogencarbonat
6 - 8 Gew.-% Natriumperborat-Monohydrat
0,4 - 0,6 Gew.-% Protease
0,4 - 0,6 Gew.-% Amylase
0,5 - 2 Gew.-% Nichtionisches Tensid
und einen pH-Wert (in 1 %iger Lösung) von 10,2 - 10,4 aufweist.18. Dishwasher detergent according to claim 5, characterized in that it consists of
22-26% by weight sodium tripolyphosphate
47-52% by weight sodium carbonate
16-20% by weight sodium hydrogen carbonate
6-8% by weight sodium perborate monohydrate
0.4-0.6 wt% protease
0.4-0.6 wt% amylase
0.5-2% by weight of nonionic surfactant
and has a pH (in 1% solution) of 10.2-10.4. 19. Maschinengeschirrspülmittel nach Anspruch 6, dadurch gekennzeichnet, daß es besteht aus
47 - 52 Gew.-% Natriumcarbonat
32 - 36 Gew.-% Natriumhydrogencarbonat
6 - 8 Gew.-% Natriumperborat-Monohydrat
0,4 - 0,6 Gew.-% Protease
0,4 - 0,6 Gew.-% Amylase
0,5 - 2 Gew.-% Nichtionisches Tensid
3 - 7 Gew.-% Acrylsäure/Maleinsäure-Copolymer
2 - 4 Gew.-% Phosphonsäure
und einen pH-Wert von 9,9 - 10,2 aufweist.19. Dishwasher detergent according to claim 6, characterized in that it consists of
47-52% by weight sodium carbonate
32-36% by weight sodium hydrogen carbonate
6-8% by weight sodium perborate monohydrate
0.4-0.6 wt% protease
0.4-0.6 wt% amylase
0.5-2% by weight of nonionic surfactant
3-7% by weight acrylic acid / maleic acid copolymer
2-4% by weight of phosphonic acid
and has a pH of 9.9-10.2.
EP90115943A 1989-08-22 1990-08-20 Dishwashing compositions for dishwasher Revoked EP0414197B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3927714 1989-08-22
DE3927714 1989-08-22
DE3939494 1989-11-29
DE3939494 1989-11-29

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EP0414197A2 true EP0414197A2 (en) 1991-02-27
EP0414197A3 EP0414197A3 (en) 1992-03-04
EP0414197B1 EP0414197B1 (en) 1997-12-10

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JP (1) JPH03163199A (en)
AT (1) ATE161036T1 (en)
AU (1) AU6113190A (en)
CA (1) CA2023529A1 (en)
DE (1) DE59010780D1 (en)
DK (1) DK0414197T3 (en)
ES (1) ES2112247T3 (en)
FI (1) FI904155A0 (en)
NO (1) NO903682L (en)
PL (1) PL286561A1 (en)
PT (1) PT95049A (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0504091A1 (en) * 1991-03-15 1992-09-16 Cleantabs A/S A phosphate-free automatic dishwashing composition
WO1993018129A1 (en) * 1992-03-12 1993-09-16 The Procter & Gamble Company Low-dosage automatic dishwashing detergent with monopersulfate and enzymes
WO1994007981A1 (en) 1992-09-25 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Weakly alkaline washing-up agent
WO1995012653A1 (en) * 1993-11-03 1995-05-11 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
US5597789A (en) * 1993-04-27 1997-01-28 The Procter & Gamble Company Liquid or granular automatic dishwashing detergent compositions containing silicate and low molecular weight modified polyacrylate coploymers
EP0815192A1 (en) * 1995-03-11 1998-01-07 The Procter & Gamble Company Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme
US5786314A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium precipitation in automatic dishwashing
EP2117993A1 (en) * 2007-02-01 2009-11-18 JohnsonDiversey, Inc. Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
EP2428572A2 (en) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alkaliphilic Bacillus species alpha-amylase variants, compositions comprising alpha-amylase variants, and methods of use
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
CN113874485A (en) * 2019-04-19 2021-12-31 仅一居家品牌有限公司 Stable waterless dishwashing soap and manufacturing method thereof

Families Citing this family (2)

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JP3566015B2 (en) * 1997-02-17 2004-09-15 花王株式会社 Detergent composition for dishwashers
MX2010013123A (en) 2008-06-06 2011-01-14 Danisco Inc Variant alpha-amylases from bacillus subtilis and methods of use, thereof.

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0504091A1 (en) * 1991-03-15 1992-09-16 Cleantabs A/S A phosphate-free automatic dishwashing composition
WO1993018129A1 (en) * 1992-03-12 1993-09-16 The Procter & Gamble Company Low-dosage automatic dishwashing detergent with monopersulfate and enzymes
WO1994007981A1 (en) 1992-09-25 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Weakly alkaline washing-up agent
EP0662117B1 (en) * 1992-09-25 2000-06-21 Henkel Kommanditgesellschaft auf Aktien Weakly alkaline washing-up agent
US5597789A (en) * 1993-04-27 1997-01-28 The Procter & Gamble Company Liquid or granular automatic dishwashing detergent compositions containing silicate and low molecular weight modified polyacrylate coploymers
WO1995012653A1 (en) * 1993-11-03 1995-05-11 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
US5786314A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium precipitation in automatic dishwashing
US5786315A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
EP0815192A4 (en) * 1995-03-11 1999-09-22 Procter & Gamble Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme
EP0815192A1 (en) * 1995-03-11 1998-01-07 The Procter & Gamble Company Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme
EP2117993A1 (en) * 2007-02-01 2009-11-18 JohnsonDiversey, Inc. Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same
EP2117993A4 (en) * 2007-02-01 2012-06-06 Diversey Inc Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same
EP2428572A2 (en) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alkaliphilic Bacillus species alpha-amylase variants, compositions comprising alpha-amylase variants, and methods of use
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
CN113874485A (en) * 2019-04-19 2021-12-31 仅一居家品牌有限公司 Stable waterless dishwashing soap and manufacturing method thereof

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ATE161036T1 (en) 1997-12-15
FI904155A0 (en) 1990-08-22
AU6113190A (en) 1991-02-28
PL286561A1 (en) 1991-05-20
EP0414197B1 (en) 1997-12-10
ES2112247T3 (en) 1998-04-01
EP0414197A3 (en) 1992-03-04
PT95049A (en) 1991-04-18
DE59010780D1 (en) 1998-01-22
JPH03163199A (en) 1991-07-15
DK0414197T3 (en) 1998-02-02
NO903682D0 (en) 1990-08-21
CA2023529A1 (en) 1991-02-23
NO903682L (en) 1991-02-25

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