EP0197434A2 - Rinsing agents for use in mechanical dish washing - Google Patents
Rinsing agents for use in mechanical dish washing Download PDFInfo
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- EP0197434A2 EP0197434A2 EP86104164A EP86104164A EP0197434A2 EP 0197434 A2 EP0197434 A2 EP 0197434A2 EP 86104164 A EP86104164 A EP 86104164A EP 86104164 A EP86104164 A EP 86104164A EP 0197434 A2 EP0197434 A2 EP 0197434A2
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- acid
- ethers
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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
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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
- 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
- C11D1/721—End blocked ethers
Definitions
- the invention relates to low-foaming and biodegradable rinse aids for machine dishwashing with good wetting and draining effects on hard surfaces.
- 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 alkylarylsulfonates, are known to have a strong tendency to foam and are therefore not suitable for this use, Practice non-ionic surfactants based on ethylene oxide adducts on fatty alcohols, alkylphenols or polypropylene glycols of higher molecular weights.
- nonionic alkoxylation products which are sparingly water-soluble at rinse 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 ethyl oxide and propylene oxide or propylene oxide and ethylene oxide.
- ethylene oxide adducts with higher alcohols, alkylphenols or amines with a low degree of ethoxylation or corresponding adducts of ethyl oxide and propylene oxide or propylene oxide and ethylene oxide have no wetting effect at application temperatures and therefore represent a burden on the rinse aid.
- 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 .
- the invention therefore relates to the use of end-capped alkyl polyethylene glycol ethers of the following general formula in which R '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 3 carbon atoms and n is a number from 7 to 16, as a nonionic low-foaming surfactant in rinse aid for machine dishwashing in the home and Business.
- 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.
- the alkyl polyethylene glycol ethers used according to the invention are used in the rinse aid in a concentration of 5 to 80, preferably 15 to 50% by weight and preferably in aqueous solution.
- these ethers only develop their low foam level above 45 ° C, so that their sole use in rinse aid would make little sense, they can, however, be excellently mixed with the lower ethoxylated ethers to be used according to the invention and additionally impart a high level of rinse aid with good low foam content Wetting ability, 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.
- the invention therefore also relates in particular to the use of end-capped alkyl polyethylene glycol ethers of the formula in which R 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 in which R 1 and R 2 have the meaning given for formula I and m is a number from 17 to 23, the cloud point of the mixture of ethers of the formulas I and II being not higher than 45 ° C., as a nonionic low-foaming surfactant mixture in rinse aid for automatic dishwashing in the home and business.
- fatty alcohols n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-octadecen-9,10-ol (oleyl alcohol ) and oxo alcohols of the stated carbon number can be used individually or in a mixture.
- 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 of 1:17 to 1:23, and the ether 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 are 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.
- the invention therefore also relates to a process for the production of low-foaming rinse aids for machine dishwashing in household and commercial use, which is characterized in that alkanols or alkenols of the formula R 1- OH, in which R 1 is a straight-chain or branched alkyl or Alkenyl radical having 8 to 18 carbon atoms means 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 etherifying 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, the respective reaction products mixes with one another without the cloud point of the mixture exceeding 45 ° C.
- the alkyl polyethylene glycol ether mixture used according to the invention is used in the rinse aids in a concentration of 5 to 80, preferably 15 to 50% by weight and preferably in aqueous solution.
- solubilizing substances such as, for example, mono- or polyhydric alkanols (for example ethanol, propanol, isopropanol, ethylene glycol, propylene glycol).
- 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.
- the amounts of the solvents and / or the hydrotropes can be between 0 and 40% by weight, based on the total rinse aid.
- 0 to 40 preferably 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 a commercial technical mixture of succinic acid, glutaric acid and adipic acid (Sokalan DCS (R) from BASF) can be used.
- complexing agents such as, for example, citric acid, tartaric acid, glycolic acid and / or a commercial technical mixture of succinic acid, glutaric acid and adipic acid (Sokalan DCS (R) from BASF
- Binc AM 2-phosphonobutane-1,2,4-tricarboxylic acid
- concentrations can also be lower and can be 0 to 10% by weight, preferably 2 to 7% by weight, based on the total rinse aid.
- customary colorants, fragrances and preservatives can be added in the customary manner for use in rinse aids.
- Alkalinity and temperature correspond to the conditions in a commercial dishwasher.
- Degradability was also measured according to the GF test method specified in the Chemicals Act for "ready biodegradability" according to the GFIBSB test regulation (C0D / Chemical Oxygen Demand).
- a highly effective rinse aid for dishwashers had the following composition (wt. 5):
- the solutions were clear between -2 ° and + 50 ° C and stable in storage. In a commercial dishwasher, there was no disruptive foam at the existing detergent liquor temperature of 60 ° C. The clear dry effect at a dosage of 0.2 to 1.0 g / l was excellent.
- the following rinse aid formulation resulted in a household dishwasher: when used in a rinse cycle with a liquor at 65 ° C at a dosage of 0.1 to 0.8 g / l, especially on glasses, a good clear drying effect:
- a rinse aid with a mixture of two of the surfactants used according to the invention was used in a commercial 1-tank dishwasher.
- Suitable rinse aids can also be packaged in a mixture with small amounts of other low-foaming nonionic surfactants.
- a highly effective rinse aid for commercial dishwashers had the following composition (% by weight):
- the cloud point of the ether mixture was 38 ° 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.
- the rinse aid 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 household 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.
- the clear dry effect of two of the surfactants used according to the invention was compared to the less readily degradable surfactant sec-C 11-15 alcohol + 8 EO + 5 PO (according to DE-PS 21 06 819) with a similar cloud point.
- the tests were carried out in a household dishwasher (softened water; 300 mg salt load) with one cleaning and one rinse cycle, with grades from 1 (very poor) to 10 (optimal rinse; highest possible grade).
- the dosage of the surfactants in the rinse aid was 0.02 to 0.1 g / l.
- Drinking glasses served as items to be washed, as they are most sensitive to stains, streaks and streaks. That grade 10 was not achieved here is due to the very critical grading and the fact that the water used was softened but not desalinated. Note 10 is only possible if demineralized water is used.
Abstract
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 alkylarylsulfonates, are known to have a strong tendency to foam and are therefore not suitable for this use, Practice non-ionic surfactants based on ethylene oxide adducts on fatty alcohols, alkylphenols or polypropylene glycols of higher molecular weights.
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 Ethytenoxid 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 rinse 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 ethyl 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 Klarspüimittel für die maschinelle Geschirreinigung auf der Basis von nlchtlonogenen 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 the use of foam-suppressing ballast surfactants or others Make foam silencers unnecessary. These are rinse aids for machine dishwashing based on non-ionogenic 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 Porzellantellern, 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 plates, 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 .
Überraschenderweise zeigte es sich nun, daß die Verwendung von endgruppenverschlossenen Alkylpolyethylenglykolethern der folgenden allgemeinen Formel
Aus der deutschen Offenlegungsschrift 33 15 951 ist bereits die Verwendung der vorstehend genannten Verbindungen 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 die 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 alkalibeständige Schaumarmut einen guten Klartrockeneffekt bewirken.From the German patent application 33 15 951 the use of the above-mentioned compounds as foam-suppressing additives to low-foam cleaning agents is already known. It is therefore also known that these are compounds with good alkali and acid stability, whose biodegradability according to the statutory methods of determination is over 80% BiAS decrease. However, it is not apparent from the prior art that the end-capped alkyl polyethylene glycol ethers can be used as the sole surfactant component in rinse aids, which are not considered detergents, for machine dishwashing in the household and in trade and, in addition to low-acid and, above all, alkali-resistant foam, a good clear drying effect cause.
Die Erfindung betrifft daher die Verwendung von endgruppenverschlossenen Alkylpolyethylenglykolethern der folaenden allaemeinen Formel
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.
Die erfindungsgemäß verwendeten Alkylpolyethylenglykolether werden in den Klarspülmittein in einer Konzentration von 5 bis 80, vorzugsweise 15 bis 50 Gew.-% und vorzugsweise in wäßriger Lösung eingesetzt.The alkyl polyethylene glycol ethers used according to the invention are used in the rinse aid in a concentration of 5 to 80, preferably 15 to 50% by weight and preferably in aqueous solution.
Es ist natürlich auch 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 also possible to use small amounts of the end-capped alkyl polyethylene glycol ethers, for example to reduce the cost of the formulation to blend nonionic surfactants 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.
In diesem Zusammenhang wurde weiterhin gefunden, daß auch solche endgruppenverschlossenen Alkylpolyethylenglykolether der allgemeinen Formel
Wenngleich diese Ether ihre Schaumarmut auch erst oberhalb von 45 °C entfalten, so daß ihr alleiniger Einsatz in Klarspülmittein wenig sinnvoll wäre, so lassen sie sich jedoch hervorragend mit den erfindungsgemäß zu verwendenden niedriger ethoxylierten Ethern mischen und vermitteln den Klarspülmittein 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 these ethers only develop their low foam level above 45 ° C, so that their sole use in rinse aid would make little sense, they can, however, be excellently mixed with the lower ethoxylated ethers to be used according to the invention and additionally impart a high level of rinse aid with good low foam content Wetting ability, 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 insbesondere auch die Verwendung von endgruppenverschlossenen Alkylpolyethylenglykolethern der Formel
Als Ausgangsmaterial für die Herstellung der Polyglykolether der Formeln 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 ) 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 1 : 17 bis 1 : 23 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxygruppen. 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.-Bu- tylbromid, tert.-Butylchlorid, Amylchlorid, tert.-Amyl- bromid, 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 of 1:17 to 1:23, and the ether 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 are 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 Geschirreiniguhg in Haushalt und Gewerbe, das dadurch gekennzeichnet ist, daß man Alkanole oder Alkenole der Formel R1-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 Reaktionsprödukte 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
Das erfindungsgemäß verwendete Alkylpolyethylenglykolethergemisch wird in den Klarspülmitteln in einer Konzentration von 5 bis 80, vorzugsweise 15 bis 50 Gew.-% und vorzugsweise in wäßriger Lösung eingesetzt.The alkyl polyethylene glycol ether mixture used according to the invention is used in the rinse aids in a concentration of 5 to 80, preferably 15 to 50% by weight and preferably in aqueous solution.
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.In order 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 lösunasvermitteinden 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 solvents and / or the hydrotropes 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 0 bis 40, vorzugsweise 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, in order to prevent limescale deposits on the dishes when using non-softened water in the rinse cycle, 0 to 40, preferably 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 a 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 KlarspüJmittel, betragen.Complexing agents which have threshold-effective properties, such as, for example, 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% by weight, 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.
Die erfindungsgemäß verwendeten endgruppenverschlossenen Alkylpolyethylenglykolether sind in der folgenden Tabelle 1 aufgeführt:
Die Produkte sind, dargestellt 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.
In einem Schaumstampftest (Handstampfmethode nach DIN 53902) wurde das Schaumverhalten der Klarspülertenside (0,2 g/l) in 200 ml einer wäßrigen, alkalischen Reinigerflotte aus Alkalitriphosphaten, Alkalisilikaten, Kaliumhydroxid und Chlorbleichlauge (3 g/l Perclin intensiv Flüssigreiniger (R) 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 tamping test (hand tamping method according to DIN 53902), the foam behavior of the rinse aid surfactants (0.2 g / l) in 200 ml of an aqueous, alkaline detergent liquor composed of alkali metal triphosphates, alkali silicates, potassium hydroxide and chlorine bleaching solution (3 g / l percline intensive liquid detergent (R)) 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:
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.
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 claimed adducts 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 GFIBSB-Test-Vorschrift (C0D/Chemical Oxygen Demand).Degradability was also measured according to the GF test method specified in the Chemicals Act for "ready biodegradability" according to the GFIBSB test regulation (C0D / Chemical Oxygen Demand).
Die ermittelten Abbauwerte nach beiden Methoden sind am folgenden Beispiel aufgeführt.
Die Abbaubarkeitsforderung nach EG-Richtlinie wird somit voll erfüllt.The degradability requirement according to the EC directive is thus fully met.
Ein gut wirksames Klarspülmittel für Geschirrspülmaschinen hatte folgende Zusammensetzung (Gew.-5):
Die Lösungen waren zwischen -2 ° und + 50 °C klar und lagerstabil. In einer gewerblichen Geschirrspülmaschine trat bei der verhandenen Reinigerflottentemperatur von 60 °C kein störender Schaum auf. Der Klartrockeneffekt bei einer Dosierung von 0,2 bis 1,0 g/l war ausgezeichnet.The solutions were clear between -2 ° and + 50 ° C and stable in storage. In a commercial dishwasher, there was no disruptive foam at the existing detergent liquor temperature of 60 ° C. The clear dry effect at a dosage of 0.2 to 1.0 g / l was excellent.
In einer Haushaltsgeschirrspülmaschine bewirkte folgende Klarspülmittelrezeptur:
Ein Klarspülmittel mit einem Gemisch aus zwei der erfindungsgemäß verwendeten Tenside wurde in einer gewerblichen 1-Tank-Spülmaschine eingesetzt.
Bei 50 °C und bei einer Dosierung von Q,2 bis 1,0 g/l war keine Schaumentwicklung zu beobachten. Der Klartrockeneffekt war gut.At 50 ° C and at a dosage of Q, 2 to 1.0 g / l no foaming was observed. The clear dry effect was good.
Ein gut wirksames Klarspülmittel für gewerbliche Geschirrspülmaschinen hatte folgende Zusammensetzung (Gew.-%):
Bei einer Dosierung des Klarspülmittels von 0,1 bis 1,5 g/l zeigte sich sowohl bei der Verwendung in einer gewerblichen als auch in einer Haushaltsgeschirrspülnaschine 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 household 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.
Als Vergleich wurde der Klartrockeneffekt von zwei der erfindungsgemäß verwendeten Tenside dem weniger gut abbaubaren Tensid sek.-C11-15-Alkohol + 8 EO + 5 PO (gemäß DE-PS 21 06 819) mit ähnlichem Trübungspunkt gegenübergestellt. Die Versuche erfolgten in einer Haushaltsgeschirrspülmaschine (enthärtetes Wasser; 300 mg Salzbelastung) mit einem Reinigungs- und einem Klarspülgang, wobei Noten von 1 (sehr schlecht) bis 10 (optimale Klarspülung; höchst mögliche Note) vergeben wurden. Die Dosierung der Tenside im Klarspülgang lag bei 0,02 bis 0,1 g/l. Als Spülgut dienten Trinkgläser, da diese in bezug auf Flecken, Schlieren und Streifen am empfindlichsten sind. Daß die Note 10 hierbei nicht erreicht wurde, liegt an der sehr kritischen Benotung sowie an dem Umstand, daß das verwendete Wasser enthärtet, jedoch nicht entsalzt war. Note 10 ist nur bei Verwendung von vollentsalztem Wasser möglich.As a comparison, the clear dry effect of two of the surfactants used according to the invention was compared to the less readily degradable surfactant sec-C 11-15 alcohol + 8 EO + 5 PO (according to DE-PS 21 06 819) with a similar cloud point. The tests were carried out in a household dishwasher (softened water; 300 mg salt load) with one cleaning and one rinse cycle, with grades from 1 (very poor) to 10 (optimal rinse; highest possible grade). The dosage of the surfactants in the rinse aid was 0.02 to 0.1 g / l. Drinking glasses served as items to be washed, as they are most sensitive to stains, streaks and streaks. That grade 10 was not achieved here is due to the very critical grading and the fact that the water used was softened but not desalinated. Note 10 is only possible if demineralized water is used.
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86104164T ATE44761T1 (en) | 1985-04-03 | 1986-03-26 | RINSE AID FOR AUTOMATIC DISH WASHING. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3512120 | 1985-04-03 | ||
DE19853512120 DE3512120A1 (en) | 1985-04-03 | 1985-04-03 | Clear rinsing agent for mechanical dishwashing |
DE3530303 | 1985-08-24 | ||
DE19853530303 DE3530303A1 (en) | 1985-08-24 | 1985-08-24 | Final rinse compositions for mechanical dish-cleaning |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0197434A2 true EP0197434A2 (en) | 1986-10-15 |
EP0197434A3 EP0197434A3 (en) | 1987-03-18 |
EP0197434B1 EP0197434B1 (en) | 1989-07-19 |
Family
ID=25831023
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86104164A Expired EP0197434B1 (en) | 1985-04-03 | 1986-03-26 | Rinsing agents for use in mechanical dish washing |
Country Status (2)
Country | Link |
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EP (1) | EP0197434B1 (en) |
DE (1) | DE3664480D1 (en) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0326795A2 (en) * | 1988-01-11 | 1989-08-09 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as anti-foaming agents in detergents |
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 |
EP0343503A1 (en) * | 1988-05-27 | 1989-11-29 | Henkel Kommanditgesellschaft auf Aktien | Foam-depressing polyglycol ethers for cleaning products |
EP0389157A2 (en) * | 1989-03-23 | 1990-09-26 | Imperial Chemical Industries Plc | Novel chemical compounds and their use as low foam surfactants and antifoaming agents |
US4988452A (en) * | 1988-06-09 | 1991-01-29 | The Procter & Gamble Company | Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant |
US5130043A (en) * | 1988-06-09 | 1992-07-14 | The Procter & Gamble Company | Liquid automatic dishwashing compositions having enhanced stability |
WO1994016045A1 (en) * | 1993-01-18 | 1994-07-21 | Unilever N.V. | Machine dishwashing composition containing a corrosion inhibitor |
WO1995002668A1 (en) * | 1993-07-12 | 1995-01-26 | Henkel Kommanditgesellschaft Auf Aktien | Hard surface cleaning agent |
WO1995016015A1 (en) * | 1993-12-10 | 1995-06-15 | Henkel Kommanditgesellschaft Auf Aktien | Non-ionic detergent mixtures |
WO2001092450A1 (en) * | 2000-05-31 | 2001-12-06 | Unilever Plc | Rinse aid compositions |
WO2005097957A1 (en) * | 2004-03-26 | 2005-10-20 | Henkel Kommanditgesellschaft Auf Aktien | Dishwasher rinse aid |
US7462588B2 (en) | 2003-09-15 | 2008-12-09 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Dishwasher detergents comprising a specific polymer mixture |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3255117A (en) * | 1963-10-08 | 1966-06-07 | Fmc Corp | Low-foaming dishwashing composition |
FR2118698A5 (en) * | 1970-12-16 | 1972-07-28 | Bayer Ag | |
FR2207983A1 (en) * | 1972-11-29 | 1974-06-21 | Henkel & Cie Gmbh | |
DE2524260A1 (en) * | 1975-05-31 | 1976-12-09 | Hoechst Ag | Cleaning compsn. contg. 1,3,5-tricaboxy pentane 3-phosphonic acid - esp. for washing glassware, avoiding use of hydratable colloids |
DE2556544A1 (en) * | 1975-12-16 | 1977-06-30 | Hoechst Ag | Detergent for dish washing machine - contains alkali-stable, low-foam nonionic polyglycol tert. butyl ether |
EP0036550A1 (en) * | 1980-03-22 | 1981-09-30 | BASF Aktiengesellschaft | Use of oxyalkylated fatty alcohols having a propylene terminal group, as low foaming alkali and acid stable tensides |
DE3315951A1 (en) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
-
1986
- 1986-03-26 EP EP86104164A patent/EP0197434B1/en not_active Expired
- 1986-03-26 DE DE8686104164T patent/DE3664480D1/en not_active Expired
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3255117A (en) * | 1963-10-08 | 1966-06-07 | Fmc Corp | Low-foaming dishwashing composition |
FR2118698A5 (en) * | 1970-12-16 | 1972-07-28 | Bayer Ag | |
FR2207983A1 (en) * | 1972-11-29 | 1974-06-21 | Henkel & Cie Gmbh | |
DE2524260A1 (en) * | 1975-05-31 | 1976-12-09 | Hoechst Ag | Cleaning compsn. contg. 1,3,5-tricaboxy pentane 3-phosphonic acid - esp. for washing glassware, avoiding use of hydratable colloids |
DE2556544A1 (en) * | 1975-12-16 | 1977-06-30 | Hoechst Ag | Detergent for dish washing machine - contains alkali-stable, low-foam nonionic polyglycol tert. butyl ether |
EP0036550A1 (en) * | 1980-03-22 | 1981-09-30 | BASF Aktiengesellschaft | Use of oxyalkylated fatty alcohols having a propylene terminal group, as low foaming alkali and acid stable tensides |
DE3315951A1 (en) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0326795A3 (en) * | 1988-01-11 | 1990-08-22 | Henkel Kommanditgesellschaft Auf Aktien | Use of polyglycol ethers as anti-foaming agents in detergents |
EP0326795A2 (en) * | 1988-01-11 | 1989-08-09 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as anti-foaming agents in detergents |
EP0343503A1 (en) * | 1988-05-27 | 1989-11-29 | Henkel Kommanditgesellschaft auf Aktien | Foam-depressing polyglycol ethers for cleaning products |
WO1989011525A1 (en) * | 1988-05-27 | 1989-11-30 | Henkel Kommanditgesellschaft Auf Aktien | Anti-froth alkyl polyglycol ethers for detergents (i) |
US4988452A (en) * | 1988-06-09 | 1991-01-29 | The Procter & Gamble Company | Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant |
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 |
US5130043A (en) * | 1988-06-09 | 1992-07-14 | The Procter & Gamble Company | Liquid automatic dishwashing compositions having enhanced stability |
EP0389157A2 (en) * | 1989-03-23 | 1990-09-26 | Imperial Chemical Industries Plc | Novel chemical compounds and their use as low foam surfactants and antifoaming agents |
EP0389157A3 (en) * | 1989-03-23 | 1991-03-20 | Imperial Chemical Industries Plc | Novel chemical compounds and their use as low foam surfactants and antifoaming agents |
WO1994016045A1 (en) * | 1993-01-18 | 1994-07-21 | Unilever N.V. | Machine dishwashing composition containing a corrosion inhibitor |
WO1995002668A1 (en) * | 1993-07-12 | 1995-01-26 | Henkel Kommanditgesellschaft Auf Aktien | Hard surface cleaning agent |
US5759987A (en) * | 1993-07-12 | 1998-06-02 | Haerer; Juergen | Mixtures of nonionic ethers for use as rinse aids and/or cleaning hard surfaces |
WO1995016015A1 (en) * | 1993-12-10 | 1995-06-15 | Henkel Kommanditgesellschaft Auf Aktien | Non-ionic detergent mixtures |
US5707956A (en) * | 1993-12-10 | 1998-01-13 | Henkel Kommanditgesellschaft Auf Aktien | Nonionic detergent mixtures based on specific mixed ethers |
WO2001092450A1 (en) * | 2000-05-31 | 2001-12-06 | Unilever Plc | Rinse aid compositions |
US7462588B2 (en) | 2003-09-15 | 2008-12-09 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Dishwasher detergents comprising a specific polymer mixture |
US7514395B2 (en) | 2003-09-15 | 2009-04-07 | Henkel Kommanditgesellschaft Auf Aktien | Dishwasher detergents comprising specific polymers |
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Also Published As
Publication number | Publication date |
---|---|
EP0197434A3 (en) | 1987-03-18 |
EP0197434B1 (en) | 1989-07-19 |
DE3664480D1 (en) | 1989-08-24 |
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