EP0197434B1 - Rinsing agents for use in mechanical dish washing - Google Patents

Rinsing agents for use in mechanical dish washing Download PDF

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Publication number
EP0197434B1
EP0197434B1 EP86104164A EP86104164A EP0197434B1 EP 0197434 B1 EP0197434 B1 EP 0197434B1 EP 86104164 A EP86104164 A EP 86104164A EP 86104164 A EP86104164 A EP 86104164A EP 0197434 B1 EP0197434 B1 EP 0197434B1
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weight
acid
alkyl
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carbon atoms
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German (de)
French (fr)
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EP0197434A3 (en
EP0197434A2 (en
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Horst Prühs
Theodor Dr. Altenschöpfer
Robert Dr. Piorr
Karl-Heinz Dr. Schmid
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to DE19853512120 priority patent/DE3512120A1/en
Priority to DE19853530303 priority patent/DE3530303A1/en
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Priority claimed from AT86104164T external-priority patent/AT44761T/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D1/721End blocked ethers

Description

  • Die Erfindung betrifft schaumarme und biologisch abbaubare Klarspülmittel für die maschinelle Geschirreinigung mit guter Benetzungs- und Ablaufwirkung gegenüber harten Oberflächen.The invention relates to low-foaming and biodegradable rinse aids for machine dishwashing with good wetting and draining effects on hard surfaces.
  • Beim maschinellen Geschirrspülen werden im allgemeinen zwei meist durch Zwischenspülgänge mit reinem Wasser getrennte Spülgänge mit verschiedenartigen Produkten angewendet. Im eigentlichen Reinigungsgang kommen zur Ablösung und Emulgierung der Speisereste alkalisch reagierende Mittel zum Einsatz. Im sogenannten Nach- oder auch Klarspülgang werden dagegen spezielle Klarspülmittel angewendet. Diese sind keine Reinigungsmittel, sondern sollen ein gutes Netzvermögen besitzen und die Oberflächenspannung des Nachspülwassers soweit herabsetzen, daß dieses filmartig vom Geschirr abläuft und keine sichtbaren Rückstände, wie Kalkflecken oder andere Verschmutzungen hinterläßt.In the case of automatic dishwashing, two rinse cycles with different types of products, usually separated by intermediate rinse cycles with pure water, are used. In the actual cleaning cycle, alkaline reacting agents are used to detach and emulsify the food residues. In the so-called rinse or rinse cycle, however, special rinse aid is used. These are not cleaning agents, but should have a good wetting ability and reduce the surface tension of the rinse water to such an extent that it runs off the dishes like a film and does not leave any visible residues, such as lime stains or other soiling.
  • Wegen der starken Flottenbewegung in Haushalts- und gewerblichen Geschirrspülmaschinen müssen die Klarspülmittel möglichst schaumarm sein. Da die üblichen anionaktiven Netzmittel, wie höhermolekulare Alkylsulfate bzw. Alkyl- oder Alkylarylsulfonate bekanntlich eine starke Schaumneigung aufweisen und daher für diesen Einsatz nicht brauchbar sind, zieht man in der Praxis nichtionogene Tenside auf der Basis von Ethylenoxidaddukten an Fettalkohole, Alkylphenole oder Polypropylenglykole höherer Molekulargewichte vor.Because of the strong movement of liquors in household and commercial dishwashers, the rinse aid must be as low-foaming as possible. Since the usual anionic surfactants, such as higher molecular weight alkyl sulfates or alkyl or alkyl aryl sulfonates, are known to have a strong tendency to foam and are therefore not suitable for this use, nonionic surfactants based on ethylene oxide adducts with fatty alcohols, alkylphenols or polypropylene glycols of relatively high molecular weights are preferred in practice .
  • In der Praxis hat sich jedoch gezeigt, daß auch diese Produkte in den für eine ausreichende Netzwirkung erforderlichen Konzentrationsbereichen meist noch nicht ausreichend schaumarm sind. Sie führen, insbesondere in gewerblichen Spülmaschinen mit sehr hoher Wasserumwälzung und der üblichen Rückführung der etwa 80 °C heißen Klarspülflotte in den Hauptreinigungsgang mit ca. 50 bis 70 °C und alkalischem Reinigungsmittel und in die nur 40 °C warme Schmutzvorabraumzone mit noch allen Nahrungsmittelanschmutzungen, leicht zu mechanischen Störungen durch übermäßige und stabile Schaumbildung. Die gleichen Schwierigkeiten können jedoch auch in Haushaltsgeschirrspülmaschinen auftreten. Man ist daher meist gezwungen, auch bei Verwendung relativ schaumarmer Ethylenoxidaddukte dem Klarspülmittel Schaumdrücker zuzusetzen. Als solche kommen nichtionogene Alkoxylierungsprodukte, die bei Spültemperaturen wenig wasserlöslich sind, in Betracht, wie zum Beispiel Ethylenoxidaddukte an höhere Alkohole, Alkylphenole oder Amine mit niedrigem Ethoxylierungsgrad oder entsprechende Addukte von Ethylenoxid und Propylenoxid oder Propylenoxid und Ethylenoxid. Derartige Produkte besitzen jedoch bei Anwendungstemperaturen keinerlei Netzwirkung und stellen daher eine Belastung des Klarspülmittels dar.In practice, however, it has been shown that these products are usually still not sufficiently low in foam in the concentration ranges required for a sufficient wetting effect. They lead, especially in commercial dishwashers with very high water circulation and the usual recirculation of the rinse liquor, which is around 80 ° C hot, into the main cleaning cycle with approx. 50 to 70 ° C and alkaline cleaning agent and into the dirt pre-cleaning zone, which is only 40 ° C warm, with all food soiling, easy to mechanical faults due to excessive and stable foaming. However, the same difficulties can also occur in household dishwashers. It is therefore usually necessary to add foam detergent to the rinse aid even when using relatively low-foaming ethylene oxide adducts. Such nonionic alkoxylation products which are sparingly water-soluble at rinsing temperatures are suitable, such as, for example, ethylene oxide adducts with higher alcohols, alkylphenols or amines with a low degree of ethoxylation or corresponding adducts of ethylene oxide and propylene oxide or propylene oxide and ethylene oxide. However, such products have no wetting effect at application temperatures and therefore represent a burden on the rinse aid.
  • Aus der deutschen Patentschrift 21 06 819 sind aber auch schon extrem schaumarme und biologisch abbaubare Klarspülmittel bekannt, die ausschließlich als Netzmittel wirksame Anteile enthalten und die Mitverwendung schaumdrückender Ballasttenside oder anderer Schaumdämpfer unnötig machen. Es handelt sich dabei um Klarspülmittel für die maschinelle Geschirreinigung auf der Basis von nichtionogenen schaumarmen Tensiden mit einem Gehalt an Addukten von 5 bis 20 Mol Ethylenoxid und 1 bis 10 Mol Propylenoxid an sekundäre aliphatische Alkohole mit linearer Alkylkette von 10 bis 20 C-Atomen, die nach den damaligen Anforderungen eine gute biologische Abbaubarkeit besaßen, die aber den heutigen Ansprüchen nicht mehr genügt.From the German patent specification 21 06 819, however, extremely low-foaming and biodegradable rinse aids are also known, which only contain active ingredients as wetting agents and make the use of foam-suppressing ballast surfactants or other foam dampers unnecessary. These are rinse aids for machine dishwashing based on nonionic low-foaming surfactants containing adducts of 5 to 20 moles of ethylene oxide and 1 to 10 moles of propylene oxide with secondary aliphatic alcohols with a linear alkyl chain of 10 to 20 carbon atoms had good biodegradability according to the requirements at the time, but no longer meets today's requirements.
  • Gegenüber dem üblichen Spülgut, wie Porzellantellem, Besteckteilen und insbesondere Gläsern, die in dieser Hinsicht als besonders schwierig gelten, zeigen die genannten Addukte einen hervorragenden Ablauf- und Klartrockeneffekt, sie sind aber wegen der vorstehend zitierten nicht mehr als ausreichend angesehenen biologischen Abbaubarkeit nicht mehr einsetzbar.Compared to the usual wash ware, such as porcelain dishes, cutlery and especially glasses, which are considered to be particularly difficult in this regard, the adducts mentioned show an excellent drainage and clear drying effect, but they can no longer be used because of the biodegradability which is no longer regarded as sufficient .
  • Wegen der unzureichenden biologischen Abbaubarkeit sind auch die aus der amerikanischen Patentschrift 3,255,117 bekannten, bevorzugt verwendeten Alkylphenolpolyethylenglykolphenylether nur noch beschränkt als nichtionische Tenside einsetzbar. Über die Eigenschaften der danach pauschal ebenfalls beanspruchten Alkylolpolyethylenglykolalkylether vermittelt diese Veröffentlichung keine Erkenntnisse, da damit nicht gearbeitet wurde.Because of the inadequate biodegradability, the alkylphenol polyethylene glycol phenyl ethers known from the US Pat. No. 3,255,117, which are preferably used, are only of limited use as nonionic surfactants. This publication does not convey any knowledge of the properties of the alkylol polyethylene glycol alkyl ethers which are also claimed as a whole since this has not been used.
  • Aus der deutschen Offenlegungsschrift 25 56 544 sind nun solche Alkylolpolyethylenglykolalkylether bekannt, die ausschließlich mit einem tert.-Butylrest verethert worden sind. Sie wurden als einzelne Verbindung neben anderen nichtionischen Tensiden unter anderem in Klarpülmitteln für das maschinelle Geschirrspülen verwendet.From the German published patent application 25 56 544 such alkylol polyethylene glycol alkyl ethers are now known which have been etherified exclusively with a tert-butyl radical. They were used as a single compound in addition to other nonionic surfactants, among others in rinse aids for automatic dishwashing.
  • Aus der deutschen Offenlegungsschrift 3315951 ist bereits die Verwendung der erfindungsgemäßen Verbindungen der Formel (I) als schaumdrückende Zusätze zu schaumarmen Reinigungsmitteln bekannt. Es ist von daher auch bekannt, daß es sich um Verbindungen mit guter Alkali- und Säurestabilität handelt, deren biologische Abbaubarkeit nach den gesetzlichen Bestimmungsmethoden bei über 80 % BiAS-Abnahme liegt. Dem Stand der Technik ist jedoch nicht zu entnehmen, daß eines spezifisches gemisch von endgruppenverschlossenen Alkylpolyethylenglykolether als alleinige Tensidkomponente in Klarspülmitteln, die ja nicht als Reinigungsmittel gelten, für das maschinelle Geschirrspülen im Haushalt und Gewerbe verwendet werden können und neben säure- und vor allem alkalibeständiger Schaumarmut einen guten Klartrockeneffekt bewirken.German patent application 3315951 already discloses the use of the compounds of the formula (I) according to the invention as foam-suppressing additives for low-foam cleaning agents. It is therefore also known that these are compounds with good alkali and acid stability, the biodegradability of which, according to the statutory methods of determination, is over 80% BiAS decrease. However, it is not apparent from the prior art that a specific mixture of end-capped alkyl polyethylene glycol ethers as the sole surfactant component in rinse aids, which are not considered cleaning agents, can be used for automatic dishwashing in the household and in commerce and, in addition to low-acid and, above all, alkali-resistant foam cause a good clear dry effect.
  • Überraschenderweise zeigte es sich nun, daß die Verwendung von endgruppenverschlossenen Alkylpolyethylenglykolethern der folgenden allgemeinen Formel
    Figure imgb0001
    in der R1 einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, R2 einen Alkylrest mit 4 bis 8 Kohlenstoffatomen und n eine Zahl von 7 bis 16 bedeuten, im Gemisch mit endgruppenverschlossenen Alkylpolyethylenglykolether der allgemeinen Formel
    Figure imgb0002
    in der R1 einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen und R2 einen Alkylrest mit 4 bis 8 Kohlenstoffatomen bedeuten, und m eine Zahl von 17 bis 23, vorzugsweise 18 bis 20 bedeutet, zu neuen schaumarmen Klarspülmitteln führt, die an sich keinen weiteren Tensidzusatz benötigen und qualitativ mit den bekannten oben genannten mindestens vergleichbar sind.
    Surprisingly, it has now been found that the use of end-capped alkyl polyethylene glycol ethers of the following general formula
    Figure imgb0001
    in which R1 is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 carbon atoms, R 2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 16, in a mixture with end-capped alkyl polyethylene glycol ethers of the general formula
    Figure imgb0002
    in which R 1 is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 carbon atoms and R 2 is an alkyl radical with 4 to 8 carbon atoms, and m is a number from 17 to 23, preferably 18 to 20, leads to new low-foaming rinse aid which do not require any further surfactant addition per se and are qualitatively at least comparable to the known ones mentioned above.
  • In einer speziellen Ausführungsform der Erfindung werden Polyglykolether der zuvor beschriebenen Formel eingesetzt, in der n eine Zahl von 8 bis 14, vorzugsweise 9 bis 12 und R2 einen n-Butylrest bedeuten.In a special embodiment of the invention, polyglycol ethers of the formula described above are used in which n is a number from 8 to 14, preferably 9 to 12 and R 2 is an n-butyl radical.
  • Wenngleich die Ether der Formel (II) ihre Schaumarmut auch erst oberhalb von 45 °C entfalten, so daß ihr alleiniger Einsatz in Klarspülmitteln wenig sinvoll wäre, so lassen sie sich jedoch hervorragend mit den erfindungsgemäß zu verwendenden niedriger ethoxylierten Ethern gemäß Formel (I) mischen und vermitteln den Klarspülmitteln bei guter Schaumarmut zusätzlich ein hohes Benetzungsvermögen, das insbesondere bei von Natur aus schwer benetzbarem Kunststoffgeschirr zum Tragen kommt. Das Mischungsverhältnis von höher- zu niedrigerethoxylierten Ethern ist so zu wählen, daß der Trübungspunkt des Gemisches nicht höher als 45 °C liegt.Although the ethers of the formula (II) only develop their low foaming above 45 ° C., so that their sole use in rinse aids would make little sense, they can, however, be excellently mixed with the lower ethoxylated ethers of the formula (I) to be used according to the invention and impart good wetting power to the rinse aid if there is little foam, which is particularly important for plastic dishes that are difficult to wet by nature. The mixing ratio of higher to lower ethoxylated ethers should be chosen so that the cloud point of the mixture is not higher than 45 ° C.
  • Die Erfindung betrifft daher die Verwendung von endgruppenverschlossenen Alkylpolyethylenglykolethern der Formel
    Figure imgb0003
    in der R1 einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, R2 einen Alkylrest mit 4 bis 8 Kohlenstoffatomen und n eine Zahl von 7 bis 16 bedeuten, im Gemisch mit endgruppenverschlossenen Alkylpolyethylenglykolethern der Formel
    Figure imgb0004
    in der R1 und R2 die für Formel angegebene Bedeutung haben und m eine Zahl von 17 bis 23 ist, wobei der Trübungspunkt des Gemisches aus Ethern der Formeln und II nicht höher als 45 °C liegt, als nichtionisches schaumarmes Tensiogemisch in Klarspülmitteln für die maschinelle Geschirreinigung in Haushalt und Gewerbe.
    The invention therefore relates to the use of end-capped alkyl polyethylene glycol ethers of the formula
    Figure imgb0003
    in which R 1 is a straight-chain or branched alkyl or alkenyl radical with 8 to 18 carbon atoms, R 2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 16, in a mixture with end-capped alkyl polyethylene glycol ethers of the formula
    Figure imgb0004
    in which R 1 and R 2 have the meaning given for formula and m is a number from 17 to 23, the cloud point of the mixture of ethers of the formulas and II being not higher than 45 ° C., as a nonionic low-foaming tensio mixture in rinse aid for mechanical dishwashing in the household and business.
  • Das erfindungsgemäß verwendete Alkylpolyethylenglykolethergemisch wird in den Klarspülmitteln vorzugsweise in einer Konzentration von 5 bis 80, insbesonder von 15 bis 50 Gew.-% und vorzugsweise in wäßriger Lösung eingesetzt.The alkyl polyethylene glycol ether mixture used according to the invention is preferably used in the rinse aids in a concentration of 5 to 80, in particular 15 to 50% by weight and preferably in aqueous solution.
  • Es ist natürlich aus möglich, die endgruppenverschlossenen Alkylpolyethylenglykolether, etwa zur Verbilligung der Rezeptur, mit geringen Mengen anderer nichtionischer Tenside zu verschneiden, wie z. B. mit ausreichend abbaubaren Ethylenoxidaddukten an Fettalkohole oder Anlagerungsprodukten von Propylenoxid oder Butylenoxid an Fettalkoholethoxylate. Dadurch erfährt die Qualität der erfindungsgemäßen Klarspülmittel keine wesentliche Änderung. Bevorzugt kann man aber Gemische zweier oder mehrerer verschiedener endgruppenverschlossener Alkylpolyethylenglykolether ohne Zusatz anderer nichtionischer Tenside verwenden.It is of course possible to blend the end-capped alkyl polyethylene glycol ethers with small amounts of other nonionic surfactants, for example to reduce the cost of the formulation, such as. B. with sufficiently degradable ethylene oxide adducts with fatty alcohols or adducts of propylene oxide or butylene oxide with fatty alcohol ethoxylates. As a result, the quality of the rinse aid according to the invention is not significantly changed. However, it is preferred to use mixtures of two or more different end-capped alkyl polyethylene glycol ethers without the addition of other nonionic surfactants.
  • Als Ausgangsmaterial für die Herstellung der Polyglykolether der Formel I und II können die Fettalkohole n-Octanol, n-Decanol, N-Dodecanol, n-Tetradecanol, n-Hexadecanol, n-Octadecanol, n-Octadecen-9,10-ol (Oleylalkohol) und Oxoalkohole der genannten Kohlenstoffzahl einzeln oder im Gemisch eingesetzt werden.The fatty alcohols n-octanol, n-decanol, N-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-octadecen-9,10-ol (oleyl alcohol) can be used as starting material for the preparation of the polyglycol ethers of the formula I and II ) and oxo alcohols of the stated carbon number can be used individually or in a mixture.
  • Zur Herstellung der erfindungsgemäß zu verwendenden Alkylpolyethylenglykolether setzt man zweckmäßigerweise die vorstehend beschriebenen Fettalkohole mit Ethylenoxid im Molverhältnis 1 :7 bis 1 :16 bzw. im Molverhältnis : 17 bis 1 : 23 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxylierungsbedingungen, vorzugsweise in Gegenwart von geeigneten alkalischen Katalysatoren. Die Veretherung der freien Hydroxylgruppen wird bevorzugt unter den bekannten Bedingungen der Williamsonschen Ethersynthese mit geradkettigen oder verzweigten C4-C8-Alkylhalogeniden durchgeführt, beispielsweise mit n-Butyljodid, sec.-Butylbromid, tert.-Butylchlorid, Amylchlorid, tert.-Amylbromid, n-Hexylchlorid, n-Heptylbromid und n-Octylchlorid. Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkali im stöchiometrischen Überschuß, beispielsweise von 100 bis 200 %, bezogen auf die Anzahl der zu verethernden Hydroxylgruppen, einzusetzen.To prepare the alkyl polyethylene glycol ethers to be used according to the invention, the fatty alcohols described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 7 to 1:16 or in a molar ratio: 17 to 1:23, and the hydroxyl groups present in the reaction product obtained are then etherified. The reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts. The etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with straight-chain or branched C 4 -C 8 -alkyl halides, for example with n-butyl iodide, sec-butyl bromide, tert-butyl chloride, amyl chloride, tert-amyl bromide, n-hexyl chloride, n-heptyl bromide and n-octyl chloride. It may be expedient to use a stoichiometric excess of alkyl halide and alkali, for example from 100 to 200%, based on the number of hydroxyl groups to be etherified.
  • Die Erfindung betrifft- daher auch ein Verfahren zur Herstellung von schaumarmen Klarspülmitteln, für die maschinelle Geschirreinigung in Haushalt und Gewerbe, das dadurch gekennzeichnet ist, daß man Alkanole oder Alkenole der Formel RL-OH, in der R1 einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen bedeutet, im Molverhältnis 1 :7 bis 1 : 16, vorzugsweise 1 :8 bis 1 : 14 und insbesondere 1 : 9 bis 1 : 12 bzw. im Molverhältnis 1 : 17 bis 1 : 23, vorzugsweise 1 : 18 bis 1 : 20 in Gegenwart von alkalischen Katalysatoren mit Ethylenoxid ethoxyliert, anschließend die freien Hydroxylgruppen mit geradkettigen oder verzweigten C4-C8-Alkylhalogeniden, vorzugsweise im Überschuß von 100 bis 200 %, bezogen auf die Anzahl der Hydroxylgruppen, verethert, 'die jeweiligen Reaktionsprodukte der allgemeinen Formel (I) und (II) miteinander mischt, ohne daß der Trübungspunkt des Gemisches 45 °C überschreitet und 5 bis 80, vorzugsweise 15 bis 50 Gew.-% des so erhaltenen Gemisches endgruppenverschlossener Alkylpolyethylenglykolether der allgemeinen Formel
    Figure imgb0005
    in der R1 einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, R2 einen Alkylrest mit 4 bis 8 Kohlenstoffatomen, n eine Zahl von 7 bis 16 und m eine Zahl von 17 bis 23 bedeuten, in 20 bis 95, vorzugsweise 50 bis 85 Gew.-% Wasser löst.
    The invention therefore also relates to a process for the production of low-foaming rinse aids, for machine dishwashing in the household and business, which is characterized in that Alkanols or alkenols of the formula R L- OH, in which R 1 is a straight-chain or branched alkyl or alkenyl radical having 8 to 18 carbon atoms, in a molar ratio of 1: 7 to 1:16, preferably 1: 8 to 1:14 and in particular 1 : 9 to 1:12 or in a molar ratio 1:17 to 1:23, preferably 1:18 to 1:20 in the presence of alkaline catalysts ethoxylated with ethylene oxide, then the free hydroxyl groups with straight-chain or branched C 4 -C 8 alkyl halides , preferably in an excess of 100 to 200%, based on the number of hydroxyl groups, etherified, the respective reaction products of the general formulas (I) and (II) are mixed with one another without the cloud point of the mixture exceeding 45 ° C. and 5 to 80 , preferably 15 to 50% by weight of the mixture thus obtained of end-capped alkyl polyethylene glycol ethers of the general formula
    Figure imgb0005
    in which R 1 is a straight-chain or branched alkyl or alkenyl radical with 8 to 18 carbon atoms, R 2 is an alkyl radical with 4 to 8 carbon atoms, n is a number from 7 to 16 and m is a number from 17 to 23, in 20 to 95, preferably 50 to 85 wt .-% water dissolves.
  • Zur Erzielung einer ausreichenden Temperaturstabilität kann es aber sinnvoll sein, noch lösungsvermittelnde Substanzen, wie zum Beispiel ein- oder mehrwertige Alkanole (zum Beispiel Ethanol, Propanol, Isopropanol, Ethylenglykol, Propylenglykol) einzuarbeiten.To achieve sufficient temperature stability, however, it may be useful to incorporate solubilizing substances, such as, for example, mono- or polyhydric alkanols (for example ethanol, propanol, isopropanol, ethylene glycol, propylene glycol).
  • Ebenfalls gut wirksam sind hydrotrope Substanzen, wie die Alkalisalze niedermolekularer Alkylbenzolsulfonsäuren, Na-Cumolsulfonat, Na-Xylolsulfonat oder Na-Toluolsulfonat.Hydrotropic substances, such as the alkali metal salts of low molecular weight alkylbenzenesulfonic acids, sodium cumene sulfonate, sodium xylene sulfonate or sodium toluenesulfonate, are also effective.
  • Die Einsatzmengen der lösungvermittelnden und/oder der hydrotropen Substanzen können, je nach dem Trübungspunkt des Tensidgemisches sowie der gewünschten Lagerstabilität zwischen 0 und 40 Gew.-%, bezogen auf das gesamte Klarspülmittel, liegen.Depending on the cloud point of the surfactant mixture and the desired storage stability, the amounts of the solubilizing and / or hydrotropic substances can be between 0 and 40% by weight, based on the total rinse aid.
  • Zusätzlich können zur Verhinderung von Kalkablagerungen auf dem Geschirr bei Benutzung von nicht enthärtetem Wasser im Klarspülgang zusätzlich bis 40, vorzugsweise von 10 bis 35 Gew.-%, bezogen auf das gesamte Klarspülmittel, Komplexbildner, wie beispielsweise Zitronensäure, Weinsäure, Glykolsäure und/oder ein handelsübliches technisches Gemisch aus Bernsteinsäure, Glutarsäure und Adipinsäure (Sokalan DCS (R) der BASF) eingesetzt werden.In addition, to prevent limescale deposits on the dishes when using non-softened water in the rinse cycle, up to 40, preferably from 10 to 35% by weight, based on the total rinse aid, of complexing agents, such as, for example, citric acid, tartaric acid, glycolic acid and / or commercial technical mixture of succinic acid, glutaric acid and adipic acid (Sokalan DCS (R) from BASF) can be used.
  • Ebenfalls einsetzbar sind Komplexbildner - sofern diese physiologisch unbedenklich sind -, die Threshold-wirksame Eigenschaften besitzen, wie zum Beispiel 2-Phosphonobutan-1,2,4-tricarbonsäure (Bayhibit AM(R)). Hierbei können die Einsatzkonzentrationen auch geringer sein und 0 bis 10, vorzugsweise 2 bis 7 Gew.-%, bezogen auf das gesamte Klarspülmittel, betragen.Complexing agents which have threshold-effective properties, such as 2-phosphonobutane-1,2,4-tricarboxylic acid (Bayhibit AM (R) ), can also be used, provided they are physiologically harmless. The use concentrations can also be lower and can be 0 to 10, preferably 2 to 7% by weight, based on the total rinse aid.
  • Weiterhin können in üblicher Weise für den Einsatz in Klarspülmitteln übliche Farb-, Duft- und Konservierungsmittel zugegeben werden.Furthermore, customary colorants, fragrances and preservatives can be added in the customary manner for use in rinse aids.
  • Einige der erfindungsgemäß verwendeten endgruppenverschlossenen Alkylpolyethylenglykolether sind in der folgenden Tabelle 1 aufgeführt :
    Figure imgb0006
    Some of the end-capped alkyl polyethylene glycol ethers used according to the invention are listed in Table 1 below:
    Figure imgb0006
  • Die Produkte sind, dargestelt am Produkt 1, nach der folgenden Arbeitsweise hergestellt worden.The products, shown on product 1, were produced according to the following procedure.
  • 676 g (1 Mol) Anlagerungsprodukt von 10 Mol Ethylenoxid an n-Dodecanol, 185 g (2 Mol) n-Butylchlorid und 320 g 75-gewichtsprozentiger Natronlauge (6 Mol NaOH) wurden 4 Stunden lang bei 120°C gerührt. Das abgekühlte Reaktionsgemisch wurde mit 300 ml Wasser versetzt. Anschließend wurde die wäßrige Phase abgetrennt. Die organische Phase wurde so lange mit Wasser von ca. 50 °C gewaschen, bis die Waschflüssigkeit neutral reagierte. Durch Erhitzen auf 50 °C im Wasserstrahlvakuum wurden nicht umgesetztes Butylchlorid und Wasser aus dem Reaktionsprodukt entfernt. Es wurden 680 g n-Dodecylethylenglykolbutylether (n-Dodecanol + 10 EO + Butyl) erhalten. Die Hydroxylzahl des Produktes betrug 3,5.676 g (1 mol) of adduct of 10 mol of ethylene oxide with n-dodecanol, 185 g (2 mol) of n-butyl chloride and 320 g of 75% strength by weight sodium hydroxide solution (6 mol of NaOH) were stirred at 120 ° C. for 4 hours. The cooled reaction mixture was mixed with 300 ml of water. The aqueous phase was then separated off. The organic phase was washed with water at approx. 50 ° C. until the washing liquid reacted neutrally. Unreacted butyl chloride and water were removed from the reaction product by heating to 50 ° C. in a water jet vacuum. 680 g of n-dodecylethylene glycol butyl ether (n-dodecanol + 10 EO + butyl) were obtained. The hydroxyl number of the product was 3.5.
  • SchaumverhaltenFoaming behavior
  • In einem Schaumstampftest (Handstampfmethode nach DIN 53902) wurde das Schaumverhalten der Klarspülertenside (0,2 g/I) in 200 ml einer wäßrigen, alkalischen Reinigerflotte aus Alkalitriphosphaten, Alkalisilikaten, Kaliumhydroxid und Chlorbleichlauge (3 g/I Perclin intensiv FlüssigreinigertR) der Henkel KGaA) bestimmt. Das Wasser war enthärtet, die Temperatur betrug 65 °C. Es wurde 20 mal in einem Meßzylinder gestampft und die Schaumhöhe nach 10, 30 und 60 Sekunden abgelesen.In a foam ramming test (hand tamping method according to DIN 53902), the foaming behavior of the rinse aid surfactants (0.2 g / l) in 200 ml of an aqueous, alkaline detergent liquor consisting of alkali metal triphosphates, alkali silicates, potassium hydroxide and chlorine bleach (3 g / l perclin intensive liquid cleaner R ) of Henkel KGaA). The water was softened, the temperature was 65 ° C. It was stamped 20 times in a measuring cylinder and the foam height was read after 10, 30 and 60 seconds.
  • Alkalität und Temperatur entsprechen den Bedingungen in einer gewerblichen Geschirrspülmaschine.Alkalinity and temperature correspond to the conditions in a commercial dishwasher.
  • Zusätzlich wurde diesen Gemischen noch 2 g/l frisch geschlagenes Frischei zugegeben, um die nahrungsmittelschaumdämpfende Wirkung zu prüfen. Die Ergebnisse des Tests sind der folgenden Tabelle 2 zu entnehmen :
    Figure imgb0007
    In addition, 2 g / l freshly beaten fresh egg was added to these mixtures in order to test the food foam-suppressing effect. The results of the test are shown in Table 2 below:
    Figure imgb0007
  • Diese Verbindungen waren also äußerst schaumarm und drückten den Nahrungsmittelschaum ohne weitere Zusätze schaumdämpfender Verbindungen gut.These compounds were therefore extremely low-foaming and pressed the food foam well without the addition of foam-suppressing compounds.
  • Biologische AbbaubarkeitBiodegradability
  • Die biologische Abbaubarkeit der beanspruchten Addukte wurde im OECD-Screening Test (RVO zum WM-Gesetz) überprüft und in der BiAS-Abnahme nach 19 Tagen angegeben.The biodegradability of the adducts claimed was checked in the OECD screening test (RVO to the WM Act) and stated in the BiAS acceptance after 19 days.
  • Ebenfalls gemessen wurde die Abbaubarkeit gemäß der im Chemikaliengesetz ausgewiesenen GF-Prüfmethode auf « ready biodegradability nach der GF/BSB-Test-Vorschrift (COD/Chemical Oxygen Demand).Degradability was also measured in accordance with the GF test method specified in the Chemicals Act for «ready biodegradability according to the GF / BSB test regulation (COD / Chemical Oxygen Demand).
  • Die ermittelten Abbauwerte nach beiden Methoden sind am folgenden Beispiel aufgeführt.
    Figure imgb0008
    The determined degradation values according to both methods are shown in the following example.
    Figure imgb0008
  • Die Abbaubarkeitsforderung nach EG-Richtlinie wird somit voll erfüllt.The degradability requirement according to the EC directive is thus fully met.
  • Beispiel 1example 1
  • Ein gut wirksames Klarspülmittel für gewerbliche Geschirrspülmaschinen hatte folgende Zusammensetzung (Gew.-%) :
    • 12,5 % c12-14-Fettalkohol + 17 EO + n-Butyl
    • 12,5 % c12-18-Fettalkohol + 10 EO + n-Butyl
    • 3 % Na-Cumolsulfonat
    • 72 % Wasser
    A highly effective rinse aid for commercial dishwashers had the following composition (% by weight):
    • 12.5% c 12-14 fatty alcohol + 17 EO + n-butyl
    • 12.5% c 12-18 fatty alcohol + 10 EO + n-butyl
    • 3% Na cumene sulfonate
    • 72% water
  • Das Trübungspunkt des Ethergemisches lag bei 38 °C. In einer gewerblichen Geschirrspülmaschine trat bei der vorhandenen Reinigerflottentemperatur von 65 °C kein störender Schaum auf. Der Klartrockeneffekt bei einer Dosierung von 0,1 bis 1,5 g/I war ausgezeichnet, insbesondere an an sich schwer benetzbarem Kunststoffgeschirr:The cloud point of the ether mixture was 38 ° C. In a commercial dishwasher, there was no disruptive foam at the existing detergent liquor temperature of 65 ° C. The clear dry effect at a dosage of 0.1 to 1.5 g / l was excellent, especially on plastic dishes that were difficult to wet:
  • Beispiel 2Example 2
    • 10 % c12-14-Fettalkohol + 20 EO + n-Butyl10% c 12-14 fatty alcohol + 20 EO + n-butyl
    • 15 % C12-18-Fettalkohol + 10 EO + n-Butyl15% C 12-18 fatty alcohol + 10 EO + n-butyl
    • 1 % Na-Cumolsulfonat1% Na cumene sulfonate
    • 74 % Wasser74% water
    • (alles in Gew.-%)(all in% by weight)
  • Bei einer Dosierung des Klarspülmittels von 0,1 bis 1,5 g/I zeigte sich sowohl bei der Verwendung in einer gewerblichen als auch in einer Haushaltsgeschirrspülmaschine ein guter Klartrockeneffekt, insbesondere an Kunststoffgeschirr. Das Klarspülmittel ist oberhalb von 44 °C schaumarm und zeigt auch bei der Verschleppung in den Reinigungsgang von gewerblichen Geschirrspülmaschinen bei geringer Schaumbelastung bei Temperaturen um 60 °C Schaumarmut.With a dosage of the rinse aid of 0.1 to 1.5 g / l, a good clear drying effect, in particular on plastic dishes, was found both when used in a commercial and in a domestic dishwasher. The rinse aid is low-foaming above 44 ° C and also shows little foam when carried into the cleaning cycle of commercial dishwashers with low foam load at temperatures around 60 ° C.

Claims (10)

1. The use of terminated alkyl polyethylene glycol ethers corresponding to the following general formula
Figure imgb0012
in which R1 is a linear or branched alkyl radical or alkenyl radical containing from 8 to 18 carbon atoms, R2 is an alkyl radical containing 4 to 8 carbon atoms and n is a number of from 7 to 16, in admixture with terminated alkyl polyethylene glycol ethers corresponding to the following formula
Figure imgb0013
in which R1 and R2 have the meanings defined for formula I and m is a number of from 17 to 23, the cloud point of the mixture of ethers corresponding to formulae I and II being no higher than 45 °C, as a low-foaming nonionic surfactant mixture in rinse aids for domestic and institutional dishwashing machines.
2. The use of ether mixtures as claimed in claim 1 with the formulae I and II shown therein, in which R2 is an n-butyl radical, n is a number of 8 to 14, preferably 9 to 12, and m is a number of 18 to 20.
3. The use of ether mixtures as claimed in claim 1 or 2 in quantities of from 5 to 80 % by weight and preferably in quantities of from 15 to 50 % by weight in aqueous solution.
4. The use of ether mixtures as claimed in any of claims 1 to 3 with addition of solubilizing and/or hydrotropic substances.
5. The use of ether mixtures as claimed in any of claims 1 to 4 with addition of complexing agents, such as citric acid, tartaric acid, glycolic acid and/or technical mixtures of succinic acid, glutaric acid and adipic acid in quantities of up to 40 % by weight and preferably in quantities of from 10 to 35 % by weight, based on the rinse aid as a whole.
6. The use of ether mixtures as claimed in any of claims 1 to 6 with addition of threshold-active complexing agents, such as 2-phosphonobutane-1,2,4-tricarboxylic acid in quantities of up to 10 % by weight and preferably in quantities of from 2 to 7 % by weight, based on the rinse aid as a whole.
7. A process for the production of low-foaming rinse aids for domestic and institutional dishwashing machines according to claim 1, characterized in that alkanols or alkenols corresponding to the formula R'-OH, in which R1 is a linear or banched alkyl or alkenyl radical containing 8 to 18 carbon atoms, are ethoxylated with ethylene oxide in a molar ratio of from 1 : 7 to 1 : 16, preferably in a molar ratio of from 1 : 8 to 1 : 14 and more preferably in a molar ratio of from 1 : 9 to 1 : 12 or in a molar ratio of from 1 : 17 to 1 : 23 and preferably in a molar ratio of from 1 : 18 to 1 : 20 in the presence of alkaline catalysts, the free hydroxyl groups are then etherified with linear or branched C4-CB alkyl halides, preferably in an excess of from 100 to 200 %, based on the number of hydroxyl groups, the respective reaction products are mixed with one another without the cloud point of the mixture exceeding 45 °C and from 5 to 80 and preferably from 15 to 50 % by weight of the resulting mixture of terminated alkyl polyethylene glycol ethers corresponding to the general formula
Figure imgb0014
in which R1 is a linear or branched alkyl or alkenyl radical containing 8 to 18 carbon atoms, R2 is an alkyl radical containing 4 to 8 carbon atoms, n is a number of from 7 to 16 and m is a number of from 17 to 23, are dissolved in 20 to 95 % by weight and preferably in 50 to 85 % weight water.
8. A process as claimed in claim 7, characterized in that the water is partially replaced by solubilizing and/or hydrotropic substances.
9. A process as claimed in claims 7 and 8, characterized in that the water is partially replaced by up to 40 % by weight and preferably by 10 to 35 % by weight, based on the rinse aid as a whole, of complexing agents, such as citric acid, tartaric acid, glycolic acid and/or a technical mixture of succinic acid, glutaric acid and adipic acid.
10. A process as claimed in claims 7 to 9, characterized in that the water is partially replaced by up to 10 % by weight and preferably by 2 to 7 % by weight, based on the rinse aid as a whole, of threshold-active complexing agents, such as 2-phosphonobutane-1,2,4-tricarboxyiic acid.
EP86104164A 1985-04-03 1986-03-26 Rinsing agents for use in mechanical dish washing Expired EP0197434B1 (en)

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DE3512120 1985-04-03
DE19853512120 DE3512120A1 (en) 1985-04-03 1985-04-03 Clear rinsing agent for mechanical dishwashing
DE19853530303 DE3530303A1 (en) 1985-08-24 1985-08-24 Final rinse compositions for mechanical dish-cleaning
DE3530303 1985-08-24

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AT86104164T AT44761T (en) 1985-04-03 1986-03-26 Rinse aid for machine cleaning.

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DE4323252A1 (en) * 1993-07-12 1995-01-19 Henkel Kgaa Rinse aid for machine cleaning hard surfaces
WO2005075621A1 (en) 2004-02-04 2005-08-18 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent
US6962898B2 (en) 2000-07-07 2005-11-08 Henkel Kommanditgesellschaft Auf Aktien Machine dishwasher rinsing agent
US7871971B1 (en) 1998-11-09 2011-01-18 Cognis Ip Management Gmbh Machine dishwashing rinse agents and methods of using the same
US8276756B2 (en) 2010-01-29 2012-10-02 The Procter & Gamble Company Water-soluble film having improved dissolution and stress properties, and packets made therefrom
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DE3818062A1 (en) * 1988-05-27 1989-12-07 Henkel Kgaa FOAMING ALKYL POLYGLYCOLETHER FOR CLEANING AGENT (I)
GB2219596A (en) * 1988-06-09 1989-12-13 Procter & Gamble Liquid automatic dishwashing compositions having enhanced stability
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US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
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WO1994016045A1 (en) * 1993-01-18 1994-07-21 Unilever N.V. Machine dishwashing composition containing a corrosion inhibitor
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