EP0095136B1 - Rinsing agents for use in mechanical dishwashing - Google Patents

Rinsing agents for use in mechanical dishwashing Download PDF

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Publication number
EP0095136B1
EP0095136B1 EP19830104888 EP83104888A EP0095136B1 EP 0095136 B1 EP0095136 B1 EP 0095136B1 EP 19830104888 EP19830104888 EP 19830104888 EP 83104888 A EP83104888 A EP 83104888A EP 0095136 B1 EP0095136 B1 EP 0095136B1
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Prior art keywords
weight
mol
rinse
ethylene oxide
gew
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EP19830104888
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German (de)
French (fr)
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EP0095136A3 (en
EP0095136A2 (en
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Erich P. Frieser
Alexander Jainschig
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to low-foaming rinse aid for machine dishwashing based on nonionic surfactants, which have a good wetting and draining effect on hard surfaces.
  • rinse aids should have a high wetting effect compared to all materials used for the production of dishes, such as glass, porcelain, metal and also plastics.
  • the surface tension of the rinse aid liquor should be reduced to such an extent that the rinse water remains on the dishes as long as possible as a closed film. The longer the time it takes for the water film on the dishes to tear open, the more water drains from the dishes, the less residues, such as lime from the water hardness, remain on the dishes and the better the clear dry effect. The dishes are practically given a brand new shine.
  • DE-AS 1 247 529 describes non-foaming detergents which contain mixtures of two different types of propylene oxide / ethylene oxide block polymers in conjunction with a low-ethoxylated alkylphenol.
  • DE-AS 1 106 907 mentions dishwashing detergents which contain a propylene oxide-ethylene oxide block polymer and a highly ethoxylated alkylphenol.
  • AT-PS 274 994 contains examples of rinse aid with a combination of a highly and a low ethoxylated polypropylene oxide and a highly ethoxylated propoxylated ethylenediamine with an ethoxylated and propoxylated fatty alcohol.
  • the claimed combinations can expediently be added to the rinse aid liquor as a concentrate in liquid or pasty form via conventional automatic metering devices.
  • the rinse aid combination is preferably added in the form of aqueous or aqueous-alcoholic concentrates with contents of 10 to 60 percent by weight of the sum of components A and B.
  • the use concentrations of the claimed combination in the rinse aid liquor are 0.05 to 1.0 g / l, preferably 0.15 to 0.25 g / l of the sum of components A and B.
  • the amount used in the rinse aid liquor depends to a certain extent on the type of dishes and on the degree of purity of the tap or process water. Plastic dishes and salt-rich water require a slightly higher dosage of rinse aid. They are particularly suitable for rinsing dishes after a previous cleaning cycle with strongly alkaline cleaning agents. At concentrations of approximately 0.1 g / l, a drip-free, film-like drain of the rinse aid liquor from the dishes is achieved. No disturbing foaming occurs at these concentrations.
  • an introduced rinse aid liquor with proportions of the claimed rinse aid even has a defoaming effect in the temperature range between 40 and 70 ° C.
  • Suitable group A surfactants are addition products of 14, 23 or 30 moles of ethylene oxide with nonylphenol, 15, 24 or 30 moles of ethylene oxide with octylphenol, 25 moles of ethylene oxide with hexylphenol and 20 moles of ethylene oxide with dodecylphenol.
  • Suitable group B surfactants are addition products of 12 mol of ethylene oxide with about 80 mol of propylene oxide or of 14 mol of ethylene oxide with ethylenediamine reacted with about 104 mol of propylene oxide.
  • Group B surfactants adducts may e.g. can be obtained in such a way that one also works in a known manner in two successive process steps, initially at 30-150 moles of propylene oxide and then 5-50 moles of ethylene oxide at elevated temperatures and pressures. It also works with known catalysts.
  • the adducts themselves are liquid or pasty, they can also be used as such, i.e. be used in solvent-free form.
  • the concentrates can also contain low molecular weight aliphatic alcohols with 2 to 3 carbon atoms and 1 to 2 hydroxyl groups in the molecule.
  • aryl sulfonates e.g. B. cumene or xylene sulfonates can be used as solubilizers.
  • the concentrates or rinse aid liquor can be used to avoid limescale deposits and limescale deposits on the washed dishes or the dishwasher itself 1 to 75% by weight of one or more low molecular weight organic carboxylic acids with 2 to 6 carbon atoms and / or one or more organic phosphonic acids can be added.
  • Acids which are physiologically harmless and which have complex-forming properties with respect to the hardness formers of water are preferred, such as tartaric acid, lactic acid or glycolic acid, but also acetic acid, glutaric acid, succinic acid and adipic acid; citric acid is preferably used.
  • Suitable organic phosphonic acids are phosphonobutane tricarboxylic acid, hydroxyethylenediphosphonic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid.
  • agents of the invention can of course also contain other conventional ingredients such as colors and fragrances.
  • Dirty canteen dishes were cleaned at 60 ° C. with 2.5 g / l of an alkaline cleaner of the composition given in Example 2 in a commercial dishwashing machine of the stand-alone type and then without intermediate rinsing at 80 ° C. with 0.3 g / l Rinse aid rinsed clear.
  • the water hardness was 8 ° d, the total program duration was 90 seconds.
  • the rinse aid liquor was returned to the cleaning cycle.
  • the application concentration was about 0.4 g / l, with a liquor temperature of about 55 ° C. being maintained. Even with hard water, the drainage effect was good and the dishes were stain-free after washing and drying.
  • This combination showed an excellent drainage effect in the range of 0.3-0.6 g / l.
  • the invention further comprises a method for machine washing dishes in machines with one or more cleaning and rinse cycles, an aqueous solution of 0.05-1.0 g / l of the agents according to the invention being added to the first rinse cycle.

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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)
  • Detergent Compositions (AREA)

Description

Die Erfindung betrifft schaumarme Klarspülmittel für die maschinelle Geschirreinigung auf Basis nichtionischer Tenside, die eine gute Benetzungs-und Ablaufwirkung gegenüber harten Oberflächen aufweisen.The invention relates to low-foaming rinse aid for machine dishwashing based on nonionic surfactants, which have a good wetting and draining effect on hard surfaces.

Beim maschinellen Geschirrspülen laufen aufeinander folgend, eventuell durch Zwischenspülgänge mit Leitungswasser getrennt, zwei verschiedene Spülgänge mit unterschiedlichem Produktzusatz ab. Im sogenannten Reinigungsgang kommen meist stärker alkalische Mittel zum Einsatz, die die Speisereste ablösen und emulgieren. Im sogenannten Klarspülgang werden dagegen Klarspülmittel verwendet, die der Erzielung eines klartrocknenden, glänzenden Geschirrs dienen.In automatic dishwashing, two different rinse cycles with different product additions take place in succession, possibly separated by intermediate rinse cycles with tap water. In the so-called cleaning cycle, more alkaline agents are used that detach and emulsify the food residues. In the so-called rinse cycle, on the other hand, rinse aid is used to achieve clear-drying, shiny dishes.

Diese Klarspülmittel sollen gegenüber allen für die Geschirrherstellung verwendeten Materialien wie Glas, Porzellan, Metall und auch Kunststoffen über eine hohe Benetzungswirkung verfügen. Die Oberflächenspannung der Klarspülflotte soll soweit herabgesetzt werden, dass das Nachspülwasser auf dem Geschirr möglichst lange Zeit als geschlossener Film verbleibt. Je länger die Zeit dauert, die der auf dem Geschirr vorhandene Wasserfilm bis zum Aufreissen benötigt, desto mehr Wasser läuft vom Geschirr ab, desto weniger Rückstände, wie etwa Kalk aus der Wasserhärte, verbleiben auf dem Geschirr und desto besser ist damit der Klartrockeneffekt. Das Geschirr erhält damit praktisch einen fabrikneuen Glanz.These rinse aids should have a high wetting effect compared to all materials used for the production of dishes, such as glass, porcelain, metal and also plastics. The surface tension of the rinse aid liquor should be reduced to such an extent that the rinse water remains on the dishes as long as possible as a closed film. The longer the time it takes for the water film on the dishes to tear open, the more water drains from the dishes, the less residues, such as lime from the water hardness, remain on the dishes and the better the clear dry effect. The dishes are practically given a brand new shine.

Besonders bei gewerblichen und industriellen Spülmaschinen wird mit verkürzten Spülzeiten, erhöhten Spültemperaturen und intensiverer Sprühmechanik, d.h. erhöhter Wasserumwälzung, gearbeitet. Bei diesen Spülmaschinen erfolgt in der Regel eine teilweise Rückführung der Klarspülflotte in die Reinigungsflotte. Beim Zusammentreffen der erhöhten Wasserumwälzung mit zum Schäumen neigenden Schmutzbelastungen wie Eiweiss, Seifen und gegebenenfalls Resten von manuellen Spülmitteln, kommt es zu starker Schaumbildung im Reinigungsgang, damit zur Beeinträchtigung der Sprühmechanik mit reduzierter Reinigungswirkung, und zum Überschäumen.Especially in commercial and industrial dishwashers, shorter washing times, increased washing temperatures and more intensive spray mechanics, i.e. increased water circulation, worked. With these dishwashers, the rinse aid liquor is usually partially returned to the cleaning liquor. When the increased water circulation coincides with dirt loads that tend to foam, such as protein, soaps and possibly residues of manual dishwashing detergents, there is strong foaming in the cleaning cycle, thus impairing the spray mechanics with reduced cleaning action, and causing excessive foaming.

Bekannte, gut netzende Verbindungen wie höhermolekulare Alkylbenzolsulfonate, Alkylsulfate oder Alkansulfonate zeigen bei Konzentrationen, bei denen sie einen guten Ablaufeffekt bewirken, ein zu starkes Schäumen. Ähnlich verhalten sich auch Ethylenoxidaddukte an gesättigte und ungesättigte aliphatische Alkohole mit 8 bis 20 C-Atomen und über 5 Mol Ethylenoxid. In der Praxis werden als Klarspülmitteltenisde meist sogenannte Propylenoxid-Ethylenoxid-Blockpolymere eingesetzt. Derartige Klarspülmittel besitzen aber eine ungenügende Benetzungswirkung und einen mangelhaften Klartrockeneffekt oder sie schäumen bei Rückführung in die belastete Reinigungsflotte zu stark.Known, well-wetting compounds such as higher molecular weight alkylbenzenesulfonates, alkylsulfates or alkanesulfonates show too much foaming at concentrations at which they have a good runoff effect. Ethylene oxide adducts with saturated and unsaturated aliphatic alcohols with 8 to 20 C atoms and over 5 moles of ethylene oxide behave in a similar manner. In practice, so-called propylene oxide-ethylene oxide block polymers are mostly used as rinse aid. Such rinse aids, however, have an insufficient wetting action and a poor clear drying effect, or they foam too much when returned to the contaminated cleaning liquor.

So werden in der DE-AS 1 247 529 nichtschäumende Spülmittel beschrieben, die Gemische aus zwei verschiedenartigen Propylenoxid-Ethylenoxid-Blockpolymeren in Verbindung mit einem niedrigethoxylierten Alkylphenol enthalten.For example, DE-AS 1 247 529 describes non-foaming detergents which contain mixtures of two different types of propylene oxide / ethylene oxide block polymers in conjunction with a low-ethoxylated alkylphenol.

In der DE-AS 1 106 907 werden Geschirrspülmittel genannt, die ein Propylenoxid-Ethylenoxid-Blockpolymeres und ein hochethoxyliertes Alkylphenol enthalten.DE-AS 1 106 907 mentions dishwashing detergents which contain a propylene oxide-ethylene oxide block polymer and a highly ethoxylated alkylphenol.

Schliesslich enthält die AT-PS 274 994 Beispiele für Klarspülmittel mit einer Kombination aus einem hoch- und einem niedrigethoxylierten Polypropylenoxid sowie aus einem hochethoxylierten propoxylierten Ethylendiamin mit einem ethoxylierten und propoxylierten Fettalkohol.Finally, AT-PS 274 994 contains examples of rinse aid with a combination of a highly and a low ethoxylated polypropylene oxide and a highly ethoxylated propoxylated ethylenediamine with an ethoxylated and propoxylated fatty alcohol.

Diese bekannten schaumarmen Klarspülmittel sind geeignet für den Einsatz in Haushaltsgeschirrspülmaschinen. Sie verursachen jedoch noch immer zu starkes Schäumen, wenn sie beim Einsatz in gewerblichen Geschirrspülmaschinen bedingt durch die Technik der Maschinen teilweise in die Reinigungsflotte eingeleitet werden.These known low-foaming rinse aids are suitable for use in household dishwashers. However, they still cause excessive foaming if they are partly introduced into the cleaning liquor when used in commercial dishwashers due to the technology of the machines.

Gegenstand der Erfindung sind die geschilderten Nachteile praktisch nicht aufweisende Klarspülmittel für die maschinelle Geschirreinigung auf Basis eines Gemisches nichtionischer Tenside mit einem Anteil an hochethoxylierten Alkylphenolen, die dadurch gekennzeichnet sind, dass sie als wesentlichen Bestandteil eine Tensidkombination aus

  • A) einem Addukt von 10 bis 50, vorzugsweise 12 bis 40 Mol Ethylenoxid an Cs-C12-Alkylphenole und
  • B) einem Addukt von 5 bis 50, vorzugsweise 7 bis 35 Mol Ethylenoxid an ein Umsetzungsprodukt aus 1 Mol aliphatisches Mono- oder Diamin u. 30 bis 150, vorzugsweise 30 bis 110 Mol Propylenoxid, enthalten, wobei das Gewichtsverhältnis von A: B zwischen 1:3 und 1:12, vorzugsweise zwischen 1:4 und 1:9 liegt.
The invention relates to the disadvantages described, which have practically no rinse aid for machine dishwashing based on a mixture of nonionic surfactants with a proportion of highly ethoxylated alkylphenols, which are characterized in that they comprise a surfactant combination as an essential component
  • A) an adduct of 10 to 50, preferably 12 to 40 moles of ethylene oxide with Cs-C12-alkylphenols and
  • B) an adduct of 5 to 50, preferably 7 to 35, moles of ethylene oxide to a reaction product of 1 mole of aliphatic mono- or diamine and the like. 30 to 150, preferably 30 to 110 moles of propylene oxide, the weight ratio of A: B being between 1: 3 and 1:12, preferably between 1: 4 and 1: 9.

Die beanspruchten Kombinationen können der Klarspülmittelflotte als Konzentrat in flüssiger oder pastöser Form zweckmässigerweise über gebräuchliche automatische Dosiergeräte zugesetzt werden.The claimed combinations can expediently be added to the rinse aid liquor as a concentrate in liquid or pasty form via conventional automatic metering devices.

Der Zusatz der Klarspülmittelkombination erfolgt aber vorzugsweise in Form wässriger oder wässrig-alkoholischer Konzentrate mit Gehalten von 10 bis 60 Gewichtsprozenten der Summe der Komponenten A und B. Die Anwendungskonzentrationen der beanspruchten Kombination in der Klarspülflotte betragen 0,05 bis 1,0 g/l, vorzugsweise 0,15 bis 0,25 g/I der Summe der Komponenten A und B. Die Anwendungsmenge in der Klarspülflotte richtet sich in gewissem Umfang nach der Geschirrart sowie nach dem Reinheitsgrad des Leitungs- oder Brauchwassers. Geschirr aus Kunststoff und salzreicheres Wasser erfordern eine etwas höhere Dosierung an Klarspülmitteln. Sie eignen sich in hervorragendem Masse zum Klarspülen von Geschirr nach einem vorausgegangenen Reinigungsgang mit stark alkalischen Reinigungsmitteln. Bei Konzentrationen von etwa 0,1 g/I wird dabei ein tropfenfreier filmartiger Ablauf der Klarspülflotte vom Geschirr erzielt. Eine störende Schaumbildung tritt bei diesen Konzentrationen nicht ein.However, the rinse aid combination is preferably added in the form of aqueous or aqueous-alcoholic concentrates with contents of 10 to 60 percent by weight of the sum of components A and B. The use concentrations of the claimed combination in the rinse aid liquor are 0.05 to 1.0 g / l, preferably 0.15 to 0.25 g / l of the sum of components A and B. The amount used in the rinse aid liquor depends to a certain extent on the type of dishes and on the degree of purity of the tap or process water. Plastic dishes and salt-rich water require a slightly higher dosage of rinse aid. They are particularly suitable for rinsing dishes after a previous cleaning cycle with strongly alkaline cleaning agents. At concentrations of approximately 0.1 g / l, a drip-free, film-like drain of the rinse aid liquor from the dishes is achieved. No disturbing foaming occurs at these concentrations.

In der Reinigungsflotte, auch bei deren Belastung mit zum Schäumen neigenden Verschmutzungen, wirkt eine eingebrachte Klarspülflotte mit Anteilen am beanspruchten Klarspülmittel im Temperaturbereich zwischen 40 und 70°C sogar entschäumend.In the cleaning liquor, even when it is loaded with soiling that tends to foam, an introduced rinse aid liquor with proportions of the claimed rinse aid even has a defoaming effect in the temperature range between 40 and 70 ° C.

Beispiele für geeignete Tenside der Gruppe A sind Anlagerungsprodukte von jeweils 14, 23 oder 30 Mol Ethylenoxid an Nonylphenol, 15, 24 oder 30 Mol Ethylenoxid an Octylphenol, 25 Mol Ethylenoxid an Hexylphenol sowie 20 Mol Ethylenoxid an Dodecylphenol.Examples of suitable group A surfactants are addition products of 14, 23 or 30 moles of ethylene oxide with nonylphenol, 15, 24 or 30 moles of ethylene oxide with octylphenol, 25 moles of ethylene oxide with hexylphenol and 20 moles of ethylene oxide with dodecylphenol.

Beispiele für geeignete Tenside der Gruppe B sind Anlagerungsprodukte von 12 Mol Ethylenoxid an mit etwa 80 Mol Propylenoxid oder von 14 Mol Ethylenoxid an mit etwa 104 Mol Propylenoxid umgesetztes Ethylendiamin.Examples of suitable group B surfactants are addition products of 12 mol of ethylene oxide with about 80 mol of propylene oxide or of 14 mol of ethylene oxide with ethylenediamine reacted with about 104 mol of propylene oxide.

Die Anlagerung von Ethylenoxid an die Phenole zur Herstellung der Tenside der Gruppe A erfolgt in bekannter Weise in Gegenwart von Katalysatoren, wobei vorzugsweise erhöhte Temperaturen und Drucke angewendet werden.The addition of ethylene oxide to the phenols for the preparation of the group A surfactants takes place in a known manner in the presence of catalysts, preferably at elevated temperatures and pressures.

Die Addukte der Tenside der Gruppe B können z.B. derart erhalten werden, dass man in ebenfalls bekannter Weise in zwei aufeinanderfolgenden Verfahrensstufen arbeitet, wobei bei erhöhten Temperaturen und Drucken zunächst 30-150 Mol Propylenoxid und anschliessend 5-50 Mol Ethylenoxid angelagert werden. Dabei wird mit ebenfalls bekannten Katalysatoren gearbeitet.Group B surfactants adducts may e.g. can be obtained in such a way that one also works in a known manner in two successive process steps, initially at 30-150 moles of propylene oxide and then 5-50 moles of ethylene oxide at elevated temperatures and pressures. It also works with known catalysts.

Soweit die Addukte selbst flüssig oder pastenförmig sind, können sie auch als solche, d.h. in lösungsmittelfreier Form verwendet werden. Die Konzentrate können jedoch auch niedermolekulare aliphatische Alkohole mit 2 bis 3 Kohlenstoffatomen und 1 bis 2 Hydroxylgruppen im Molekül enthalten. Auch Arylsulfonate, z. B. Cumol- oder Xylolsulfonate können als Lösungsvermittler eingesetzt werden. Sofern mit hartem Wasser gespült werden muss, können den Konzentraten bzw. der Klarspülflotte zur Vermeidung von Kalkverkrustungen und Kalkschleiern auf dem gespülten Geschirr oder der Geschirrspülmaschine selbst 1 bis 75 Gew.-% an einer oder mehreren niedermolekularen organischen Carbonsäuren mit 2 bis 6 Kohlenstoffatomen und/oder einer oder mehreren organischen Phosphonsäuren zugesetzt werden. Bevorzugt werden Säuren, die physiologisch unbedenklich sind und die gegenüber den Härtebildnern des Wassers komplexbildende Eigenschaften besitzen, wie beispielsweise Weinsäure, Milchsäure oder Glykolsäure, aber auch Essigsäure, Glutarsäure, Bernsteinsäure und Adipinsäure; vorzugsweise wird Zitronensäure verwendet.Insofar as the adducts themselves are liquid or pasty, they can also be used as such, i.e. be used in solvent-free form. However, the concentrates can also contain low molecular weight aliphatic alcohols with 2 to 3 carbon atoms and 1 to 2 hydroxyl groups in the molecule. Also aryl sulfonates, e.g. B. cumene or xylene sulfonates can be used as solubilizers. If it is necessary to rinse with hard water, the concentrates or rinse aid liquor can be used to avoid limescale deposits and limescale deposits on the washed dishes or the dishwasher itself 1 to 75% by weight of one or more low molecular weight organic carboxylic acids with 2 to 6 carbon atoms and / or one or more organic phosphonic acids can be added. Acids which are physiologically harmless and which have complex-forming properties with respect to the hardness formers of water are preferred, such as tartaric acid, lactic acid or glycolic acid, but also acetic acid, glutaric acid, succinic acid and adipic acid; citric acid is preferably used.

Als organische Phosphonsäuren (auch in Form der Na-Salze) eignen sich Phosphonobutantricarbonsäure, Hydroxyethylendiphosphonsäure, Aminotrimethylenphosphonsäure, Diethylentriaminpentamethylenphosphonsäure, Ethylendiamintetramethylenphosphonsäure.Suitable organic phosphonic acids (also in the form of the Na salts) are phosphonobutane tricarboxylic acid, hydroxyethylenediphosphonic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid.

In der Klarspülflotte können je nach Wasserhärte 0,1-0,6 Gewichtsprozent dieser Säuren oder 0,02-0,75 g/I mitverwendet werden. Die Mittel der Erfindung können selbstverständlich noch weitere übliche Bestandteile wie etwa Farb- und Duftstoffe enthalten.Depending on the water hardness, 0.1-0.6 percent by weight of these acids or 0.02-0.75 g / l can be used in the rinse aid liquor. The agents of the invention can of course also contain other conventional ingredients such as colors and fragrances.

Beispiel 1example 1

In einer gewerblichen Geschirrspülmaschine vom Typ Eintank-Standanlage wird normal verschmutztes Geschirr mit einer 55°C-heissen alkalischen Reinigerlösung, bestehend aus 2 g/I eines pulverförmigen Reinigers aus 60 Gew.-% Natriumtriphosphat, 26 Gew.-% Natriummetasilikat, wasserfrei, 13 Gew.-% Soda und 1 Gew.-% Kaliumdichlorisocyanurat, gespült und ohne Zwischenspülen anschliessend bei 70°C klargespült. Das zum Reinigen und Klarspülen verwendete Wasser wurde mittels Kationaustauscher auf eine Resthärte von 4°d enthärtet. Die Klarspülflotte wurde in die Reinigerlösung zurückgeführt. Die Dauer eines Gesamtprogrammes betrug 75 Sekunden. Im Klarspülgang wurde eine Klarspülflotte verwendet, die 0,15 g/I der nachstehenden Mischungen enthielt:

  • a) Erfindungsgemässes Klarspülmittel aus
    • 5 Gew.-% eines Adduktes von 23 Mol Ethylenoxid an 1 Mol Nonylphenol
    • 41 Gew.-% eines Adduktes von 7 Mol Ethylenoxid an ein Umsetzungsprodukt aus 1 Mol Ethylendiamin und etwa 50 Mol Propylenoxid
    • 39 Gew.-% Wasser 15 Gew.-% Ethanol, denat.
  • b) Handelsübliches Klarspülmittel aus
    • 11 Gew.-% eines Adduktes von 4,5 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 1750.
    • 28 Gew.-% eines Adduktes von 10 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 1750
    • 7 Gew.-% eines Adduktes von 9 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 4000
    • 39 Gew.-% Wasser
    • 15 Gew.-% Ethanol, denat.
      Figure imgb0001
In a commercial dishwashing machine of the one-tank stand type, normally soiled dishes are washed with a 55 ° C hot alkaline detergent solution, consisting of 2 g / l of a powdered detergent made of 60% by weight sodium triphosphate, 26% by weight sodium metasilicate, anhydrous, 13 % By weight of soda and 1% by weight of potassium dichloroisocyanurate, rinsed and then rinsed clear at 70 ° C. without intermediate rinsing. The water used for cleaning and rinsing was softened to a residual hardness of 4 ° d using a cation exchanger. The rinse aid liquor was returned to the detergent solution. The duration of an overall program was 75 seconds. A rinse aid liquor containing 0.15 g / l of the following mixtures was used in the rinse cycle:
  • a) Rinse aid according to the invention
    • 5% by weight of an adduct of 23 moles of ethylene oxide with 1 mole of nonylphenol
    • 41% by weight of an adduct of 7 moles of ethylene oxide with a reaction product of 1 mole of ethylenediamine and about 50 moles of propylene oxide
    • 39% by weight water 15% by weight ethanol, denat.
  • b) Commercial rinse aid
    • 11% by weight of an adduct of 4.5 mol of ethylene oxide with a polypropylene glycol with an average molecular weight of 1750.
    • 28% by weight of an adduct of 10 moles of ethylene oxide with a polypropylene glycol with an average molecular weight of 1750
    • 7% by weight of an adduct of 9 moles of ethylene oxide with a polypropylene glycol with an average molecular weight of 4000
    • 39% by weight water
    • 15% by weight ethanol, denat.
      Figure imgb0001

Klartrockeneffekt-Noten:

  • 1: annähernd geradliniger, rückstandsfreier Ablaufeffekt, optimaler Klartrockeneffekt
  • 3: unregelmässiges Aufreissen (Inselbildung)
  • 5: geringe Benetzung, mangelhafter Klartrockeneffekt.
Clear dry notes:
  • 1: almost straight, residue-free drainage effect, optimal clear drying effect
  • 3: irregular tearing (island formation)
  • 5: low wetting, poor clear drying effect.

Ein optimaler Klartrockeneffekt wird dann erzielt, wenn der Wasserfilm möglichst lange geschlossen bleibt und annähernd geradlinig von dem in der Spülmaschine senkrecht oder schräg stehend eingeordneten Geschirr nach unten abläuft.An optimal clear drying effect is achieved when the water film remains closed for as long as possible and runs almost straight down from the dishes arranged vertically or at an angle in the dishwasher.

Bei den handelsüblichen Klarspülmitteln auf Basis von Ethylenoxid-Propylenoxid-Blockpolymeren tritt dagegen durch zu geringe Benetzungswirkung ein rasches und unregelmässiges Aufreissen des Filmes (Inselbildung) ein und es kommt damit zu einem sichtbaren Auftrocknen von Wasserinhaltsstoffen, also zu einem mangelhaften Klartrockeneffekt.In the case of commercially available rinse aids based on ethylene oxide / propylene oxide block polymers, on the other hand, the wetting action, which is too low, causes the film to tear open quickly and irregularly (island formation), which leads to a visible drying of water constituents, that is to say a deficient clear drying effect.

Beispiel 2Example 2

In ein Intensiv-Schaumgerät wurden bei einer Schaumhärte von 8°d 2 g/I eines alkalischen Reinigers bestehend aus 50% Natriumtriphosphat, 25% Natriummetasilikat, wasserfrei, 23% Natriumhydroxid und 2% Kaliumdichlorisocyanuratzudosiert. Ausserdem wurde ein Vollei zugegeben. Die Menge an Klarspülmittel betrug 0,3 g/l.2 g / l of an alkaline cleaner consisting of 50% sodium triphosphate, 25% sodium metasilicate, anhydrous, 23% sodium hydroxide and 2% potassium dichloroisocyanurate were metered into an intensive foam device at a foam hardness of 8 ° d. A whole egg was also added. The amount of rinse aid was 0.3 g / l.

Zusammensetzung der geprüften Klarspülmittel:

  • a) Erfindungsgemässes Klarspülmittel aus
    • 4 Gew.-% eines Adduktes von 14 Mol Ethylenoxid an 1 Mol Nonylphenol 30 Gew.-% eines Adduktes an 14 Mol Ethylenoxid an ein Umsetzungsprodukt aus 1 Mol Ethylendiamin und etwa 105 Mol Propylenoxid
    • 51 Gew.-% Wasser
    • 15 Gew.-% Isopropanol
  • b) Handelsübliches Klarspülmittel aus:
    • 4 Gew.-% eines Adduktes von 9 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 4000
    • 30 Gew.-% eines Adduktes von 4,5 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 1750
    • 51 Gew.-% Wasser
    • 15 Gew.-% Isopropanol
      Figure imgb0002
Composition of the tested rinse aid:
  • a) Rinse aid according to the invention
    • 4% by weight of an adduct of 14 moles of ethylene oxide with 1 mole of nonylphenol 30% by weight of an adduct with 14 moles of ethylene oxide to a reaction product of 1 mole of ethylenediamine and about 105 moles of propylene oxide
    • 51 wt% water
    • 15% by weight isopropanol
  • b) Commercial rinse aid from:
    • 4% by weight of an adduct of 9 moles of ethylene oxide with a polypropylene glycol with an average molecular weight of 4000
    • 30% by weight of an adduct of 4.5 mol of ethylene oxide with a polypropylene glycol with an average molecular weight of 1750
    • 51 wt% water
    • 15% by weight isopropanol
      Figure imgb0002

Beispiel 3Example 3

In einer gewerblichen Geschirrspülmaschine, Typ Eintank-Standmaschine wurde normal verschmutzes Geschirr bei 60 °C mit 2 g/I eines alkalischen Reinigers in der in Beispiel 2 angegebenen Zusammensetzung gereinigt und ohne Zwischenspülung anschliessend bei 80°C mit 0,3 g/I Klarspülmittel klargespült. Die Wasserhärte betrug 8 °d. Die Gesamtprogrammdauer betrug 90 Sekunden.Normally soiled dishes were cleaned at 60 ° C. with 2 g / l of an alkaline detergent in the composition given in Example 2 in a commercial dishwasher, type stand-alone, and then rinsed with 0.3 g / l of rinse aid without intermediate rinsing at 80 ° C. . The water hardness was 8 ° d. The total program duration was 90 seconds.

Zusammensetzung der geprüften Klarspülmittel:

  • a) Erfindungsgemässes Klarspülmittel aus
    • 5 Gew.-% eines Adduktes von 15 Mol Ethylenoxid an 1 Mol Nonylphenol
    • 25 Gew.-% eines Adduktes von 35 Mol Ethylenoxid an ein Umsetzungsprodukt aus 1 Mol primäres aliphatisches Amin und etwa 45 Mol Propylenoxid 65 Gew.-% Wasser
    • 5 Gew.-% Natriumcumolsulfonat
  • b) Handelsübliches Klarspülmittel aus
    • 5 Gew.-% eines Adduktes von 16 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 2750
    • 25 Gew.-% eines Adduktes von 7 Mol Ethylenoxid an ein Polypropylenglykol mit einem mittleren Molgewicht 1200
    • 65 Gew.-% Wasser
    • 5 Gew.-% Natriumcumolsulfonat
      Figure imgb0003
      Klartrockeneffektbenotung siehe Beispiel 1.
Composition of the tested rinse aid:
  • a) Rinse aid according to the invention
    • 5% by weight of an adduct of 15 moles of ethylene oxide with 1 mole of nonylphenol
    • 25% by weight of an adduct of 35 moles of ethylene oxide with a reaction product of 1 mole of primary aliphatic amine and about 45 moles of propylene oxide and 65% by weight of water
    • 5% by weight sodium cumene sulfonate
  • b) Commercial rinse aid
    • 5% by weight of an adduct of 16 moles of ethylene oxide with a polypropylene glycol with an average molecular weight of 2750
    • 25% by weight of an adduct of 7 moles of ethylene oxide with a polypropylene glycol with an average molecular weight of 1200
    • 65% by weight water
    • 5% by weight sodium cumene sulfonate
      Figure imgb0003
      For clear dry effect grading, see example 1.

Beispiel 4Example 4

In einer gewerblichen Geschirrspülmaschine Typ Eintank-Standmaschine wurde verschmutztes Kantinengeschirr bei 60°C mit 2,5 g/I eines alkali- .schen Reinigers der im Beispiel 2 angegebenen Zusammensetzung gereinigt und ohne Zwischenspülen anschliessend bei 80°C mit 0,3 g/l Klarspülmittel klargespült. Die Wasserhärte betrug 8°d, die Gesamtprogrammdauer 90 Sekunden. Die Klarspülflotte wurde in den Reinigungsgang rückgeführt.Dirty canteen dishes were cleaned at 60 ° C. with 2.5 g / l of an alkaline cleaner of the composition given in Example 2 in a commercial dishwashing machine of the stand-alone type and then without intermediate rinsing at 80 ° C. with 0.3 g / l Rinse aid rinsed clear. The water hardness was 8 ° d, the total program duration was 90 seconds. The rinse aid liquor was returned to the cleaning cycle.

Zusammensetzung der geprüften Klarspülmittel:

  • a) Erfindungsgemässes Klarspülmittel aus
    • 5 Gew.-% eines Adduktes von 25 Mol Ethylenoxid an Hexylphenol
    • 25 Gew.-% eines Adduktes von 35 Mol Ethylenoxid an ein Umsetzungsprodukt von 1 Mol eines primären aliphatischen Amins mit etwa 45 Mol Propylenoxid
    • 55 Gew.-% Wasser
    • 15 Gew.-% Isopropanol
  • b) Herkömmliches Klarspülmittel
    • 10 Gew.-% eines Adduktes von 10 Mol Ethylenoxid an ein Umsetzungsprodukt von 1 Mol Ethylendiamin mit etwa 60 Mol Propylenoxid
    • 20 Gew.-% eines Adduktes von 10 Mol Ethylenoxid an ungesättigten Fettalkohol C16―C16
    • 55 Gew.-% Wasser
    • 15 Gew.-% Isopropanol
      Figure imgb0004
      Klartrockeneffekt- und Schaumbenotung siehe
Composition of the tested rinse aid:
  • a) Rinse aid according to the invention
    • 5% by weight of an adduct of 25 moles of ethylene oxide with hexylphenol
    • 25% by weight of an adduct of 35 moles of ethylene oxide with a reaction product of 1 mole of a primary aliphatic amine with about 45 moles of propylene oxide
    • 55% by weight of water
    • 15% by weight isopropanol
  • b) Conventional rinse aid
    • 10% by weight of an adduct of 10 moles of ethylene oxide with a reaction product of 1 mole of ethylenediamine with about 60 moles of propylene oxide
    • 20% by weight of an adduct of 10 moles of ethylene oxide with unsaturated fatty alcohol C 16 ―C 16
    • 55% by weight of water
    • 15% by weight isopropanol
      Figure imgb0004
      Clear dry effect and foam grade see

Beispiel 1.Example 1. Beispiel 5Example 5

Ein auch für den Einsatz in Haushaltsgeschirrspülmaschinen gut wirksames Klarspülmittel wurde durch folgende Zusammensetzung erhalten:

  • 4 Gew.-% eines Adduktes von 15 Mol Ethylenoxid an 1 Mol Dodecylphenol
  • 12 Gew.-% eines Adduktes von 14 Mol Ethylenoxid an ein Umsetzungsprodukt aus 1 Mol Ethylendiamin und etwa 104 Mol Propylenoxid
  • 25 Gew.-% Zitronensäure
  • 8 Gew.-% Isopropanol
  • 5 Gew.-% Propylenglykol - 1,2
  • 46 Gew.-% Wasser
A rinse aid which was also effective for use in household dishwashers was obtained by the following composition:
  • 4% by weight of an adduct of 15 moles of ethylene oxide with 1 mole of dodecylphenol
  • 12% by weight of an adduct of 14 moles of ethylene oxide with a reaction product of 1 mole of ethylenediamine and about 104 moles of propylene oxide
  • 25% by weight of citric acid
  • 8% by weight isopropanol
  • 5% by weight propylene glycol - 1.2
  • 46 wt% water

Die Anwendungskonzentration betrug etwa 0,4 g/I, wobei eine Flottentemperatur von etwa 55 °C eingehalten wurde. Auch bei hartem Wasser war der Ablaufeffekt gut und das Geschirr nach dem Spülen und Trocknen fleckenfrei.The application concentration was about 0.4 g / l, with a liquor temperature of about 55 ° C. being maintained. Even with hard water, the drainage effect was good and the dishes were stain-free after washing and drying.

Beispiel 6Example 6

Ein schaumarmes Klarspülmittel für den Einsatz in Haushaltsgeschirrspülmaschinen wurde auch durch folgende Zusammensetzung erhalten:

  • 5 Gew.-% eines Adduktes von 24 Mol Ethylenoxid an 1 Mol Octylphenol
  • 40 Gew.-% eines Adduktes von 14 Mol Ethylenoxid an ein Umsetzungsprodukt aus 1 Mol Ethylendiamin und etwa 104 Mol Propylenoxid
  • 15 Gew.-% Weinsäure
  • 20 Gew.-% Isopropanol
  • 20 Gew.-% Wasser
A low-foaming rinse aid for use in household dishwashers was also obtained from the following composition:
  • 5% by weight of an adduct of 24 moles of ethylene oxide with 1 mole of octylphenol
  • 40% by weight of an adduct of 14 moles of ethylene oxide with a reaction product of 1 mole of ethylenediamine and about 104 moles of propylene oxide
  • 15% by weight tartaric acid
  • 20% by weight isopropanol
  • 20% by weight water

Diese Kombination zeigte im Einsatzbereich von 0,3-0,6 g/I einen ausgezeichneten Ablaufeffekt.This combination showed an excellent drainage effect in the range of 0.3-0.6 g / l.

Die Erfindung umfasst weiterhin ein Verfahren zum maschinellen Spülen von Geschirr in Maschinen mit ein bis mehreren Reinigungs- und Klarspülgängen, wobei man dem ersten Klarspülgang eine wässrige Lösung von 0,05-1,0 g/I der erfindungsgemässen Mittel zusetzt.The invention further comprises a method for machine washing dishes in machines with one or more cleaning and rinse cycles, an aqueous solution of 0.05-1.0 g / l of the agents according to the invention being added to the first rinse cycle.

Claims (5)

1. Low-foaming rinse aids for dishwashing machines based on a mixture of nonionic surfactants containing a proportion of highly ethoxylated alkyl phenols, characterized in that they contain as principal constituents a surfactant combination of
A) an adduct of 10 to 50 and preferably 12 to 40 mol ethylene oxide with CS-C12 alkyl phenols and
B) an adduct of 5 to 50 and preferably 7 to 35 mol ethylene oxide with a reaction product of 1 mol aliphatic mono- or diamine and 30 to 150 and preferably 30 to 110 mol propylene oxide,
the ratio by weight of A to B being from 1:3 to 1: 12 and preferably from 1:4 to 1:9.
2. Rinse aids as claimed in claim 1, characterized in that they contain 10 to 60% by weight of the surfactant combination of A and B in aqueous or aqueous-alcoholic solution.
3. Rinse aids as claimed in claims 1 and 2, characterized in that they contain from 5 to 15% by weight of a low molecular weight aliphatic alcohol containing 2 to 3 carbon atoms and 1 to 2 hydroxyl groups in the molecule.
4. Rinse aids as claimed in claims 1 to 3, characterized in that they additionally contain from 1 to 75% by weight of one or more low molecular weight organic carboxylic acids containing 2 to 6 carbon atoms and/or one or more organic phosphonic acids.
5. A machine dishwashing process comprising one to several washing and rinse cycles, characterized in that an aqueous solution of 0.05 to 1.0 g/I of the rinse aid claimed in claims 1 to 4 is added to the first rinse cycle.
EP19830104888 1982-05-26 1983-05-18 Rinsing agents for use in mechanical dishwashing Expired EP0095136B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT2082/82 1982-05-26
AT0208282A AT376236B (en) 1982-05-26 1982-05-26 RINSE AID AND METHOD FOR MACHINE CLEANING

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EP0095136A2 EP0095136A2 (en) 1983-11-30
EP0095136A3 EP0095136A3 (en) 1986-11-20
EP0095136B1 true EP0095136B1 (en) 1988-11-17

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DE4323253C1 (en) * 1993-07-12 1995-01-05 Henkel Kgaa Use of fatty acid N-alkyl polyhydroxyalkylamides as rinse aid for machine cleaning hard surfaces
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ATA208282A (en) 1984-03-15

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