EP0268064A2 - Aqueous composition for the pretreatment of dishes - Google Patents

Aqueous composition for the pretreatment of dishes Download PDF

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Publication number
EP0268064A2
EP0268064A2 EP87114813A EP87114813A EP0268064A2 EP 0268064 A2 EP0268064 A2 EP 0268064A2 EP 87114813 A EP87114813 A EP 87114813A EP 87114813 A EP87114813 A EP 87114813A EP 0268064 A2 EP0268064 A2 EP 0268064A2
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EP
European Patent Office
Prior art keywords
weight
percent
dishes
viscosity
pretreatment
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87114813A
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German (de)
French (fr)
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EP0268064A3 (en
EP0268064B1 (en
Inventor
Theodor Dr. Altenschöpfer
Peter Dr. Jeschke
Klaus-Dieter Dr. Wisotzki
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT87114813T priority Critical patent/ATE103321T1/en
Publication of EP0268064A2 publication Critical patent/EP0268064A2/en
Publication of EP0268064A3 publication Critical patent/EP0268064A3/en
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Publication of EP0268064B1 publication Critical patent/EP0268064B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear

Definitions

  • alkaline cleaning agent mixtures are used for the automatic cleaning of dishes, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates and compounds which release active chlorine and which, if necessary, contain small amounts of a low-foaming nonionic surfactant to improve wetting.
  • inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates and compounds which release active chlorine and which, if necessary, contain small amounts of a low-foaming nonionic surfactant to improve wetting.
  • these mixtures At normal cleaning temperatures of 55 ° C to 65 ° C, these mixtures generally have good cleaning properties against all types of soiling.
  • the invention was therefore based on the object of finding a pretreatment or soaking agent which is easy to use and leads to the complete, automatic removal of problem soils in the mechanical cleaning process.
  • a pretreatment or soaking agent which is easy to use and leads to the complete, automatic removal of problem soils in the mechanical cleaning process.
  • strongly alkaline pot cleaning agents are known, which contain various thickening agents and active chlorine compounds, the agents being applied to the material to be cleaned and coated with water for a long time due to their gel structure the contact point remain and therefore have a particularly sustainable effect.
  • agents as described in the preceding invention would be suitable as pretreatment or cleaning agents for use in dishwashers.
  • the exposure time of the desired agent should on the one hand be kept as short as possible so as not to delay work processes, but on the other hand, even after treatment with this agent, even if the items to be washed have been in the dishwasher for a longer period of time, they should be prevented from drying out again with the agent will.
  • the agent according to the invention should be used in such a way that the user brings the food residues, which are difficult to remove, for example in a saucepan or in a frying pan, into contact with the agent, for example by spray pumps, brushes, foam guns, spray cans, and then the dishes immediately in a convenient position in the dishwasher, ie with the pot opening down in the direction of the water spray, the viscous product essentially adhering to the pot surface and starting the cleaning process as required. It should not be necessary to rinse out the pretreatment or soaking agent before the cleaning process.
  • Such pretreatment and soaking agents according to the invention for stubbornly soiled dishes for the complete, automatic removal of problem soils in the mechanical cleaning process are characterized in that they 0.5 to 20, preferably 1 to 15% by weight of nonionic, especially low-foaming, surfactants, 0.5 to 25, preferably 1 to 20% by weight of polyhydric aliphatic alcohols and / or glycol ethers, 0.5 to 10 preferably 1 to 8% by weight of a hydrotropic compound and 0.01 to 6, preferably 0.05 to 5 wt .-% viscosity regulators contained in aqueous suspension or solution and adjusted to a viscosity of at least 5, preferably at least 20 mPas.
  • Suitable nonionic, preferably low-foaming surfactants include ethylene oxide adducts with higher molecular weight propylene glycols with a molecular weight of 900 to 4000 and adducts with 1 to 10 mol ethylene oxide, or 1 to 10 mol ethylene oxide and 1 to 7 mol propylene oxide with higher molecular weight fatty alcohols with 8 to 22, preferably 10 up to 16 carbon atoms in the molecule or their naturally occurring mixtures and synthetic alcohols, for example those prepared by oxosynthesis, of the chain length C12-C18 and corresponding alkylene oxide adducts with nonylphenols.
  • Suitable humectants which are added to the formulations according to the invention in order to avoid re-drying together with the stubborn stains are the polyhydric aliphatic alcohols or glycol ethers or mixtures thereof, such as e.g. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or diethylene glycol monobutyl ether.
  • the preferred humectant is glycerin.
  • Short-chain monohydric alcohols with 2 to 4 carbon atoms in the molecule e.g. Ethanol, propanol, butanol or preferably isopropanol or hydrotrope e.g. Octyl sulfate, benzene, xylene, toluene or cumene sulfonate or polydiols with molecular weights up to 1000 can be used.
  • Suitable thickeners are added to adjust the viscosity of the composition according to the invention.
  • It is e.g. B. water-soluble polyethylene glycols with molecular weights between 105 and 4. 106, preferably between 4. 105 and 9. 105.
  • Such raw materials are available, for example, under the name Polyox® from Union Carbide.
  • Also suitable are, for. B. Efacos GT 282® from Akzo, a nonionic polymer (dialkyl polyglycols) with an average molecular weight of approximately 3000, e.g. B. different Carbopol® types from BF Goodrich as representatives of the polycarboxylates, layered silicates such as Laponite RD® from Laporte Ind.
  • Attapulgite clays such as e.g. B. Attagel 40® from Chemie-Mineralien KG, polysaccharides such as e.g. B. Kelzan® from Kelco or Rhodopol 23® from Rhône-Poulenc Ind., Cellulose derivatives such as Tylose H200YP® from Hoechst AG, C12 to C20 fatty alcohol ethoxylates from about 40 to 150 EO units.
  • compositions according to the invention In order to adjust the compositions according to the invention to the preferred pH range from 3 to 6, small amounts of an acid or a salt are added if necessary. Preferred substances for this are acetic acid, citric acid, lactic acid, tartaric acid. To set an exact pH, small amounts of e.g. As sodium hydroxide, sodium hydrogen carbonate or sodium carbonate may be required. Depending on the recipe, the formulations according to the invention are clear, cloudy or opaque solutions.
  • the invention further relates to a method for cleaning stubbornly soiled dishes, which is characterized in that the soiled areas are coated with an agent according to claims 1 to 3, the dishes with the coated surface in the direction against the jet of water circulation in a crockery basket classifies the dishwasher and, after any exposure time, preferably after at least 30 minutes, initiates the normal machine cleaning process and allows it to run.
  • test results listed below show the advantages of the pretreatment or soaking agents according to the invention.
  • the household dishwasher type Miele G 520 was used.
  • the pots with the test soils described later were cleaned in the cleaning cycle at 55 ° C and for the purpose of better comparability without the subsequent use of rinse aid.
  • 4 pots - opening against the spray jet, down here - were placed in the lower dishwasher basket.
  • the effect of the pretreatment or soaking agent according to the invention was compared with the cleaning performance which results from the use of 30 g of a conventional standard cleaning agent alone, consisting of: 40% by weight pentasodium triphosphate, anhydrous 45% by weight sodium metasilicate, anhydrous 5% by weight sodium carbonate, anhydrous 1% by weight of trichloroisocyanuric acid 1 wt .-% of an adduct of 5 moles of ethylene oxide (E0) and 4 moles of propylene oxide (P0) to a C12-C14 fatty alcohol Rest of water.
  • a conventional standard cleaning agent alone consisting of: 40% by weight pentasodium triphosphate, anhydrous 45% by weight sodium metasilicate, anhydrous 5% by weight sodium carbonate, anhydrous 1% by weight of trichloroisocyanuric acid 1 wt .-% of an adduct of 5 moles of ethylene oxide (E0) and 4 moles of prop
  • test soils were mainly produced in enamel pots from Silit, diameter 16 cm and height 8 cm. Tests were also carried out in stainless steel pots, diameter 16 cm and height 16 cm.
  • the mean value of the cleaning performance rating for the soiling was from 1 to 3.
  • Mixture 2 was placed in a saucepan and heated on an oil bath (200 ° C.) for 1 minute. The pot was removed from the heat source and Mix 1 mixed in with a wooden spoon. The The stirred pudding was then allowed to burn on the oil bath for 10 minutes without stirring.

Abstract

Die Vorbehandlungsmittel in Form einer wäßrigen Lösung oder Dispersion aus: 0,5-20Gew.-% nichtionische, schwachschäumende Tenside, 0,5 - 25 Gew.-% mehrwertige aliphatische Alkohole oder Glykolether als Feuchthaltemittel, z. B. Glycerin, 0,5 - 10 Gew.-% hydrophobe Verbindung als Lösungsvermittler, z. B. Cumolsulfonat, 0,01 - 6 Gew.-% Viskositätsregulatoren, z. B. wasserlösliche Polyethylenglykole (Viskositätseinstellung auf mindestens 5-20 mPas), mit pH = 2 - 7 entfernen selbsttätig Problemanschmutzungen. Dabei werden die angeschmutzten Stellen mit dem Mittel beschichtet, das Geschirr mit der beschichteten Fläche gegen den Wasserstrahl der Spülmaschine eingeordnet. Nach beliebiger Einwirkunszeit läßt man den üblichen Reinigungsprozeß ablaufen.The pretreatment agents in the form of an aqueous solution or dispersion of: 0.5-20% by weight nonionic, low-foaming surfactants, 0.5-25% by weight polyhydric aliphatic alcohols or glycol ethers as humectants, e.g. B. glycerin, 0.5 - 10 wt .-% hydrophobic compound as a solubilizer, for. B. cumene sulfonate, 0.01 - 6 wt .-% viscosity regulators, e.g. B. water-soluble polyethylene glycols (viscosity setting to at least 5-20 mPas), with pH = 2 - 7 automatically remove problem soiling. The soiled areas are coated with the agent, the dishes with the coated surface are placed against the water jet of the dishwasher. After any exposure time, the usual cleaning process is allowed to run.

Description

Zum maschinellen Reinigen von Geschirr werden bekanntlich al­kalisch eingestellte Reinigungsmittelgemische verwendet, die im wesentlichen aus anorganischen Salzen wie Alkaliphosphaten, Alkalisilikaten und Alkalicarbonaten und aktivchlorabspaltenden Verbindungen bestehen und die zur Verbesserung der Benetzung gegebenenfalls noch geringe Zusätze eines schwachschäumenden nichtionischen Tensids enthalten. Diese Gemische besitzen bei üblichen Reinigungstemperaturen von 55 °C bis 65 °C im allge­meinen ein gutes Reinigungsvermögen gegenüber allen Anschmut­zungen. Schwierigkeiten bei der Reinigung werden allerdings dann beobachtet, wenn es sich bei den Anschmutzungen um ange­brannte oder stark angetrocknete, eiweiß- und/oder stärkehaltige Speisereste sowie um weiße beziehungsweise graue Beläge auf dem Spülgut handelt, die im wesentlichen auf alkaliunlösliche, anorganische Calciumsalze zurückzuführen sind und zum einen aus den Speisen selbst, zum anderen aus dem bei der Zubereitung der Speisen verwendeten Wasser stammen. Diese Anschmutzungen wer­den beim maschinellen Reinigungsprozeß nicht immer vollständig beseitigt, was zu Reklamationen seitens der Anwender führen kann, oder diese dazu veranlaßt, dieses Spülgut nicht in der Maschine zu reinigen.As is known, alkaline cleaning agent mixtures are used for the automatic cleaning of dishes, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates and compounds which release active chlorine and which, if necessary, contain small amounts of a low-foaming nonionic surfactant to improve wetting. At normal cleaning temperatures of 55 ° C to 65 ° C, these mixtures generally have good cleaning properties against all types of soiling. Difficulties with cleaning are observed, however, if the soiling is burnt or heavily dried, protein and / or starchy food residues as well as white or gray deposits on the wash ware, which are essentially due to alkali-insoluble, inorganic calcium salts and on the one hand come from the food itself, on the other hand from the water used in the preparation of the food. These stains are not always completely removed in the machine cleaning process, which can lead to complaints from the user or cause them not to wash these items in the machine.

Der Erfindung lag daher die Aufgabe zugrunde, ein Vorbehand­lungs- oder Einweichmittel aufzufinden, das leicht anwendbar ist und zur vollständigen, selbsttätigen Entfernung von Probleman­schmutzungen im maschinellen Reinigungsprozeß führt. Aus der Us-amerikanischen Patentschrift 4 116 851 sind zwar pastöse thixotrope, stark alkalische Topfreinigungsmittel bekannt, die verschiedene Verdickungsmittel sowie Aktivchlorverbindungen enthalten, wobei die Mittel bei der Anwendung auf das zu reini­gende Gut aufgetragen und mit Wasser überschichtet werden, aufgrund ihrer Gelstruktur längere Zeit auf der Kontaktstelle verbleiben und daher besonders nachhaltig wirken. Dieser Pa­tentschrift war jedoch nicht zu entnehmen, daß sich Mittel, wie sie in der vorstehenden Erfindung beschrieben sind, als Vorbe­handlungs- oder Reinigungsmittel bei der Anwendung in Geschirr­spülmaschinen eignen würden.The invention was therefore based on the object of finding a pretreatment or soaking agent which is easy to use and leads to the complete, automatic removal of problem soils in the mechanical cleaning process. From the US Pat. No. 4,116,851 pasty thixotropic, strongly alkaline pot cleaning agents are known, which contain various thickening agents and active chlorine compounds, the agents being applied to the material to be cleaned and coated with water for a long time due to their gel structure the contact point remain and therefore have a particularly sustainable effect. However, it was not apparent from this patent that agents as described in the preceding invention would be suitable as pretreatment or cleaning agents for use in dishwashers.

Die Einwirkzeit des gewünschten Mittels sollte einerseits möglichst kurz gehalten werden, um Arbeitsabläufe nicht zu verzögern, andererseits sollte aber auch nach Behandlung mit diesem Mittel selbst bei längeren Standzeiten des Spülgutes während des Sam­melns in der Geschirrspülmaschine, ein erneutes Eintrocknen der Speisereste zusammen mit dem Mittel verhindert werden. Der Ein­satz des erfindungsgemäßen Mittels sollte in der Weise erfolgen, daß der Anwender die schwierig zu entfernenden Speisereste, z.B. in einem Kochtopf oder in einer Bratpfanne, mit dem Mittel, etwa durch Sprühpumpen, Pinsel, Schaumpistolen, Spraydosen, in Kontakt bringt, dann das Spülgut sofort in zweckmäßiger Position in die Spülmaschine stellt, d.h. mit der Topföffnung nach unten in die Richtung des Wassersprühstrahles, wobei das viskose Produkt im wesentlichen auf der Topfoberfläche haften bleibt, und nach Bedarf den Reinigungsprozeß startet. Ein Ausspülen des Vorbe­handlungs- oder Einweichmittels vor dem Reinigungsprozeß sollte nicht erforderlich sein.The exposure time of the desired agent should on the one hand be kept as short as possible so as not to delay work processes, but on the other hand, even after treatment with this agent, even if the items to be washed have been in the dishwasher for a longer period of time, they should be prevented from drying out again with the agent will. The agent according to the invention should be used in such a way that the user brings the food residues, which are difficult to remove, for example in a saucepan or in a frying pan, into contact with the agent, for example by spray pumps, brushes, foam guns, spray cans, and then the dishes immediately in a convenient position in the dishwasher, ie with the pot opening down in the direction of the water spray, the viscous product essentially adhering to the pot surface and starting the cleaning process as required. It should not be necessary to rinse out the pretreatment or soaking agent before the cleaning process.

Solche erfindungsgemäßen Vorbehandlungs- und Einweichmittel für hartnäckig angeschmutztes Geschirr zur vollständigen, selbst­tätigen Entfernung von Problemanschmutzungen im maschinellen Reinigungsprozeß sind dadurch gekennzeichnet, daß sie

0,5 bis 20, vorzugsweise 1 bis 15 Gew.-%       nichtionische insbesondere schwachschäumende Tenside,
0,5 bis 25, vorzugsweise 1 bis 20 Gew.-%       mehrwertige ali­phatische Alkohole und/oder Glykol­ether,
0,5 bis 10 vorzugsweise 1 bis 8 Gew.-%       einer hydrotropen Verbindung und
0,01 bis 6, vorzugsweise 0,05 bis 5 Gew.-%       Viskosi­tätsregulatoren

in wäßriger Suspension oder Lösung enthalten und auf eine Viskosität von mindestens 5, vorzugsweise mindestens 20 mPas eingestellt sind.Such pretreatment and soaking agents according to the invention for stubbornly soiled dishes for the complete, automatic removal of problem soils in the mechanical cleaning process are characterized in that they

0.5 to 20, preferably 1 to 15% by weight of nonionic, especially low-foaming, surfactants,
0.5 to 25, preferably 1 to 20% by weight of polyhydric aliphatic alcohols and / or glycol ethers,
0.5 to 10 preferably 1 to 8% by weight of a hydrotropic compound and
0.01 to 6, preferably 0.05 to 5 wt .-% viscosity regulators

contained in aqueous suspension or solution and adjusted to a viscosity of at least 5, preferably at least 20 mPas.

Gegebenenfalls können noch sonstige übliche Reinigungsmittel­hilfsstoffe, insbesondere Duft- und Farbstoffe, Konservierungs­mittel sowie geringste Mengen saurer oder alkalischer Mittel zur gewünschten pH-Wert-Einstellung zwischen 2 und 7, bevorzugt aber pH 3 bis 6, zugesetzt werden, wobei sich der Wasseranteil des gesamten Mittels entsprechend reduziert.If necessary, other customary detergent auxiliaries, in particular fragrances and colorants, preservatives and very small amounts of acidic or alkaline agents for the desired pH value between 2 and 7, but preferably pH 3 to 6, can be added, the water content of the total agent reduced accordingly.

Zu den geeigneten nichtionischen, vorzugsweise schwachschäu­menden Tensiden gehören die Ethylenoxidaddukte an höhermole­kulare Propylenglykole der Molgewichte 900 bis 4000 sowie Addukte von 1 bis 10 Mol Ethylenoxid, beziehungsweise 1 bis 10 Mol Ethylenoxid und 1 bis 7 Mol Propylenoxid an höhermolekulare Fettalkohole mit 8 bis 22, vorzugsweise 10 bis 16 Kohlenstoff­ atomen im Molekül oder deren natürlich vorkommende Gemische sowie synthetische, beispielsweise durch Oxosynthese hergestellte Alkohole der Kettenlänge C₁₂-C₁₈ und entsprechende Alkylenoxid­addukte an Nonylphenole in Betracht. Bevorzugt eingesetzt werden die biologisch weitestgehend abbaubaren Addukte von Ethylenoxid und Propylenoxid an höhermolekulare Fettalkohole, insbesondere das Anlagerungsprodukt von 2 bis 5 Mol Ethylenoxid und 2 bis 5 Mol Propylenoxid an ein Gemisch von C₁₂-C₁₈-Fett­alkoholen. Die endständigen Hydroxygruppen der Addukte können auch durch Umsetzung von einem Mol eines Aldehyds oder Ketons mit jeweils zwei Mol eines Addukts in Acetale oder Ketale umge­wandelt, "endgruppenverschlossen", werden. Auch ethoxilierte Diole mit bis zu 18 Kohlenstoffatomen und endständigen oder innenständigen vicinalen Hydroxylgruppen sowie die entsprechen­den Monoglycoletherdiole kommen in Betracht.Suitable nonionic, preferably low-foaming surfactants include ethylene oxide adducts with higher molecular weight propylene glycols with a molecular weight of 900 to 4000 and adducts with 1 to 10 mol ethylene oxide, or 1 to 10 mol ethylene oxide and 1 to 7 mol propylene oxide with higher molecular weight fatty alcohols with 8 to 22, preferably 10 up to 16 carbon atoms in the molecule or their naturally occurring mixtures and synthetic alcohols, for example those prepared by oxosynthesis, of the chain length C₁₂-C₁₈ and corresponding alkylene oxide adducts with nonylphenols. Preference is given to using the largely biodegradable adducts of ethylene oxide and propylene oxide with higher molecular weight fatty alcohols, in particular the adduct of 2 to 5 moles of ethylene oxide and 2 to 5 moles of propylene oxide with a mixture of C₁₂-C₁₈ fatty alcohols. The terminal hydroxyl groups of the adducts can also be converted into acetals or ketals, "end group-capped", by reacting one mole of an aldehyde or ketone with two moles of each adduct. Ethoxylated diols with up to 18 carbon atoms and terminal or internal vicinal hydroxyl groups and the corresponding monoglycol ether diols are also suitable.

Geeignete Feuchthaltemittel, die den erfindungsgemäßen Formulie­rungen zugesetzt werden, um eine Wiedereintrocknung zusammen mit den hartnäckigen Anschmutzungen zu vermeiden, sind die mehrwertigen aliphatischen Alkohole oder Glykolether beziehungs­weise Gemische davon, wie z.B. Ethylenglykol, Diethylenglykol, Propylenglykol, Dipropylenglykol oder Diethylenglykolmonobutyl­ether. Bevorzugtes Feuchthaltemittel ist Glycerin.Suitable humectants which are added to the formulations according to the invention in order to avoid re-drying together with the stubborn stains are the polyhydric aliphatic alcohols or glycol ethers or mixtures thereof, such as e.g. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or diethylene glycol monobutyl ether. The preferred humectant is glycerin.

Als Lösungsvermittler können kurzkettige einwertige Alkohole, mit 2 bis 4 Kohlenstoffatomen im Molekül, z.B. Ethanol, Propanol, Butanol oder vorzugsweise Isopropanol oder Hydrotrope, z.B. Octylsulfat, Benzol-, Xylol-, Toluol- oder Cumolsulfonat oder Polydiole mit Molgewichten bis 1000 eingesetzt werden.Short-chain monohydric alcohols with 2 to 4 carbon atoms in the molecule, e.g. Ethanol, propanol, butanol or preferably isopropanol or hydrotrope e.g. Octyl sulfate, benzene, xylene, toluene or cumene sulfonate or polydiols with molecular weights up to 1000 can be used.

Zur Einstellung einer gewünschten Viskosität der erfindungs­gemäßen Zusammensetzung werden geeignete Verdickungsmittel zugesetzt. Es handelt sich dabei z. B. um wasserlösliche Poly­ethylenglycole mit Molgewichten zwischen 10⁵ und 4 . 10⁶, vor­zugsweise zwischen 4 . 10⁵ und 9 . 10⁵. Derartige Rohstoffe sind beispielsweise unter dem Namen Polyox® von Union Carbide er­hältlich. Weiterhin geeignet sind z. B. Efacos GT 282® der Akzo, ein nichtionogenes Polymer (Dialkylpolyglycole) mit einer mittleren Molmasse von ungefähr 3000, z. B. verschiedene Carbopol®-Typen der B. F. Goodrich als Vertreter der Polycarb­oxylate, Schichtsilikate wie beispielsweise Laponite RD® der Laporte Ind. Ltd., Attapulgit-Tone wie z. B. Attagel 40® der Chemie-Mineralien KG, Polysaccharide wie z. B. Kelzan® der Kelco oder Rhodopol 23® der Rhône-Poulenc Ind., Cellulosederi­vate wie beispielsweise Tylose H200YP® der Hoechst AG, C₁₂ bis C₂₀-Fettalkoholethoxylate ab ungefähr 40 bis 150 EO-Einheiten.Suitable thickeners are added to adjust the viscosity of the composition according to the invention. It is e.g. B. water-soluble polyethylene glycols with molecular weights between 10⁵ and 4. 10⁶, preferably between 4. 10⁵ and 9. 10⁵. Such raw materials are available, for example, under the name Polyox® from Union Carbide. Also suitable are, for. B. Efacos GT 282® from Akzo, a nonionic polymer (dialkyl polyglycols) with an average molecular weight of approximately 3000, e.g. B. different Carbopol® types from BF Goodrich as representatives of the polycarboxylates, layered silicates such as Laponite RD® from Laporte Ind. Ltd., attapulgite clays such as e.g. B. Attagel 40® from Chemie-Mineralien KG, polysaccharides such as e.g. B. Kelzan® from Kelco or Rhodopol 23® from Rhône-Poulenc Ind., Cellulose derivatives such as Tylose H200YP® from Hoechst AG, C₁₂ to C₂₀ fatty alcohol ethoxylates from about 40 to 150 EO units.

Um die erfindungsgemäß zusammengesetzten Mittel auf den bevor­zugten pH-Bereich von 3 bis 6 einzustellen, werden bei Bedarf kleine Mengen einer Säure oder eines Salzes hinzugefügt. Be­vorzugte Substanzen hierfür sind Essigsäure, Zitronensäure, Milchsäure, Weinsäure. Zur Einstellung eines exakten pH-Wertes können gegebenenfalls auch kleine Mengen von z. B. Natrium­hydroxid, Natriumhydrogencarbonat oder Natriumcarbonat erfor­derlich sein. Bei den erfindungsgemäßen Formulierungen handelt es sich je nach Rezeptur um klare, trübe oder opake Lösungen.In order to adjust the compositions according to the invention to the preferred pH range from 3 to 6, small amounts of an acid or a salt are added if necessary. Preferred substances for this are acetic acid, citric acid, lactic acid, tartaric acid. To set an exact pH, small amounts of e.g. As sodium hydroxide, sodium hydrogen carbonate or sodium carbonate may be required. Depending on the recipe, the formulations according to the invention are clear, cloudy or opaque solutions.

Die Erfindung betrifft ferner ein Verfahren zum Reinigen von hartnäckig angeschmutztem Geschirr, das dadurch gekennzeichnet ist, daß man die angeschmutzten Stellen mit einem Mittel nach den Ansprüchen 1 bis 3 beschichtet, das Geschirr mit der beschich­teten Fläche in Richtung gegen den Strahl der Wasserumwälzung in einen Geschirrkorb der Geschirrspülmaschine einordnet und nach einer beliebigen Einwirkzeit, vorzugsweise nach wenig­stens 30 Minuten, den üblichen maschinellen Reinigungsprozeß einleitet und ablaufen läßt.The invention further relates to a method for cleaning stubbornly soiled dishes, which is characterized in that the soiled areas are coated with an agent according to claims 1 to 3, the dishes with the coated surface in the direction against the jet of water circulation in a crockery basket classifies the dishwasher and, after any exposure time, preferably after at least 30 minutes, initiates the normal machine cleaning process and allows it to run.

Die im folgenden aufgeführten Untersuchungsergebnisse zeigen die Vorteile der erfindungsgemäßen Vorbehandlungs- oder Einweich­mittel.The test results listed below show the advantages of the pretreatment or soaking agents according to the invention.

UntersuchungsergebnisseInvestigation results

Es wurden mit der Haushalts-Geschirrspülmaschine vom Typ Miele G 520 gearbeitet. Die Reinigung der Töpfe mit den später be­schriebenen Testanschmutzungen erfolgte im Reinigungsgang bei 55 °C und zwecks besserer Vergleichbarkeit ohne nachfolgende Klarspüleranwendung. Pro Reinigungsgang wurden 4 Töpfe - Öff­nung gegen den Sprühstrahl, hier nach unten - in den unteren Geschirrkorb der Spülmaschine gestellt.The household dishwasher type Miele G 520 was used. The pots with the test soils described later were cleaned in the cleaning cycle at 55 ° C and for the purpose of better comparability without the subsequent use of rinse aid. For each cleaning cycle, 4 pots - opening against the spray jet, down here - were placed in the lower dishwasher basket.

Die Wirkung des erfindungsgemäßen Vorbehandlungs- oder Ein­weichmittels wurde mit der Reinigungsleistung verglichen, die sich bei der Anwendung von 30 g eines üblichen Standardreinigungs­mittels allein ergibt, bestehend aus:

40 Gew.-% Pentannatriumtriphosphat, wasserfrei
45 Gew.-% Natriummetasilikat, wasserfrei
5 Gew.-% Natriumcarbonat, wasserfrei
1 Gew.-% Trichlorisocyanursäure
1 Gew.-% eines Adduktes von 5 Mol Ethylenoxid (E0) und 4 Mol Propylenoxid (P0) an einen C₁₂-C₁₄-Fettalkohol
Rest Wasser.The effect of the pretreatment or soaking agent according to the invention was compared with the cleaning performance which results from the use of 30 g of a conventional standard cleaning agent alone, consisting of:

40% by weight pentasodium triphosphate, anhydrous
45% by weight sodium metasilicate, anhydrous
5% by weight sodium carbonate, anhydrous
1% by weight of trichloroisocyanuric acid
1 wt .-% of an adduct of 5 moles of ethylene oxide (E0) and 4 moles of propylene oxide (P0) to a C₁₂-C₁₄ fatty alcohol
Rest of water.

Nach dem Ablauf des Reinigungsprozesses mit diesem Reinigungs­mittel allein verblieben noch Speisereste in den nicht vorbe­handelten Töpfen. Wurden die Testanschmutzungen vor dem Ein­bringen der Töpfe in die Spülmaschine mit einem der erfindungs­gemäßen Einweichmittel überstrichen und die Töpfe mit der Öffnung gegen den zulaufenden Wasserstrahl in den unteren Geschirrkorb der Spülmaschine gestellt und der Reinigungsprozeß nach einer Einwirkzeit des erfindungsgemäßen Mittels von min­destens ca. 1/2 Stunde oder über Nacht durchgeführt, so wurde die Reinigungsleistung gegenüber der der Standardreinigungs­mittelrezeptur allein deutlich gesteigert.After the cleaning process with this cleaning agent alone, food residues remained in the non-pretreated pots. Were the test soils coated with one of the soaking agents according to the invention before the pots were placed in the dishwasher and the pots with the opening against the incoming water jet were placed in the lower dish rack of the dishwasher and the cleaning process after an exposure time of the agent according to the invention of at least approx. 1/2 Hour or overnight, the cleaning performance compared to that of the standard cleaning agent formulation alone was significantly increased.

Die vorbehandelten, gereinigten Töpfe wurden danach mit den unbehandelten, gereinigten Töpfen (Blindwert) von 5 Testper­sonen visuell verglichen und die Ergebnisse einer Notenskala zugeordnet. Folgende Noten wurden vergeben:

  • 0 gleich dem Blindwert (Standardreiniger)
  • 1 besser als der Blindwert
  • 2 deutlich besser als der Blindwert
  • 3 extrem besser als der Blindwert
The pretreated, cleaned pots were then compared visually with the untreated, cleaned pots (blank value) from 5 test subjects and the results were assigned to a grading scale. The following grades were awarded:
  • 0 equal to the blank value (standard cleaner)
  • 1 better than the blank value
  • 2 significantly better than the blank value
  • 3 extremely better than the blank value

Die Testanschmutzungen wurden hauptsächlich in Emaille-Töpfen, Fa. Silit, Durchmesser 16 cm und Höhe 8 cm, hergestellt. Wei­terhin wurden Versuche in Edelstahltöpfen, Durchmesser 16 cm und Höhe 16 cm, durchgeführt.The test soils were mainly produced in enamel pots from Silit, diameter 16 cm and height 8 cm. Tests were also carried out in stainless steel pots, diameter 16 cm and height 16 cm.

Mit allen in der Tabelle 1 angegebenen Formulierungen lag der Mittelwert der Benotung der Reinigungsleistung bei den An­schmutzungen bei Note 1 bis Note 3.With all of the formulations given in Table 1, the mean value of the cleaning performance rating for the soiling was from 1 to 3.

Herstellung der TestanschmutzungenProduction of the test soiling Schokoladenpuddingchocolate pudding Mischung 1Mix 1

2,7 g Schokoladenpuddingpulver Dr. Oetker
2g Kristallzucker
6 ml Wasser

2.7 g chocolate pudding powder Dr. Oetker
2g granulated sugar
6 ml water

Mischung 2Mix 2

17,5 ml destilliertes Wasser
20 ml Milch (3,5 % Fett)
17.5 ml distilled water
20 ml milk (3.5% fat)

Mischung 2 wurde im Kochtopf vorgelegt und 1 Minute lang auf dem Ölbad (200 °C) erhitzt. Der Topf wurde von der Heizquelle genommen und Mischung 1 mit einem Holzlöffel untergerührt. Den angerührten Pudding ließ man dann 10 Minuten lang auf dem Ölbad ohne Umrühren anbrennen.Mixture 2 was placed in a saucepan and heated on an oil bath (200 ° C.) for 1 minute. The pot was removed from the heat source and Mix 1 mixed in with a wooden spoon. The The stirred pudding was then allowed to burn on the oil bath for 10 minutes without stirring.

HackfleischMinced meat

150 g fettfreies Rindergehacktes
1 Ei
50 ml destilliertes Wasser
150 g fat-free minced beef
1 egg
50 ml distilled water

Alle Zutaten wurden vermischt und davon 20 g pro Kochtopf ein­gewogen und gleichmäßig auf dem Topfboden verteilt. Die Hack­fleischanschmutzung wurde 12 Minuten lang bei 200 °C auf dem Ölbad angebrannt.All ingredients were mixed and 20 g of each saucepan were weighed in and evenly distributed on the bottom of the pot. The minced meat was burned on the oil bath at 200 ° C for 12 minutes.

KäseanschmutzungCheese soiling

1 Ei
10 g Käse (gerieben, Mischung Emmenthaler/Gouda ca. 40 % Fett)
1 egg
10 g cheese (grated, Emmenthaler / Gouda mixture approx. 40% fat)

Ei und Käse wurden miteinander verquirlt, je Topf 20 g der Mischung eingewogen und gleichmäßig auf dem Topfboden verteilt. Die Einbrennzeit auf dem Ölbad (200 °C) betrug 15 Minuten.Egg and cheese were whisked together, 20 g of the mixture was weighed into each pot and evenly distributed on the bottom of the pot. The burn-in time on the oil bath (200 ° C) was 15 minutes.

BeispieleExamples

Beispiele mit den erfindungsgemäßen Zusammensetzungen werden in der nachfolgenden Tabelle 1 angegeben. Die Handelsnamen bedeuten:

Dehypon LS 54® (Henkel/Dehydag) = Umsetzungsprodukt von 4 Mol Propylenoxid an ein Addukt von 5 Mol Ethylenoxid an einem C₁₂ - ­C₁₈-Fettalkohol

Dehypon LT 104® (Henkel/Dehydag) = Mit Butylalkohol endverethertes Anlagerungsprodukt von 10 Mol Ethylenoxid an einen C₁₂ - ­C₁₈-Fettalkohol

Laponite RD® (Laporte Ind. Ltd.) = Gelbildendes Natriummagnesiumsi­likat mit starkem Thixotropie­rungseffekt; pH-Wert einer 2 %igen Dispersion in Wasser: 8,2

Carbopol 941® (B.F. Goodrich) = Hochmolekulares Carboxyvinyl­polymeres

Dapral GT 282 S® (Akzo Chemie) = Hydrolyseempfindlicher Verdicker aus Polyalkylenglykol, Molmasse ∼3000

Kelzan® (Kelco) = Polysaccharid (Xanthangummi)

Polyox WSR 205® (Union Carbide) = Polyethylenglykol, mittleres MG 600,000

Tylose H 200 YP® (Hoechst AG) = Hydroxyethylcellulose

Figure imgb0001
Figure imgb0002
Figure imgb0003
 Examples with the compositions according to the invention are given in Table 1 below. The trade names mean:

Dehypon LS 54® (Henkel / Dehydag) = reaction product of 4 moles of propylene oxide with an adduct of 5 moles of ethylene oxide with a C₁₂ - C₁₈ fatty alcohol

Dehypon LT 104® (Henkel / Dehydag) = addition product of 10 moles of ethylene oxide, end etherified with butyl alcohol, to a C₁₂ - C₁₈ fatty alcohol

Laponite RD® (Laporte Ind. Ltd.) = gel-forming sodium magnesium silicate with strong thixotropic effect; pH of a 2% dispersion in water: 8.2

Carbopol 941® (BF Goodrich) = high molecular weight carboxyvinyl polymer

Dapral GT 282 S® (Akzo Chemie) = hydrolysis-sensitive thickener made of polyalkylene glycol, molecular weight ∼3000

Kelzan® (Kelco) = polysaccharide (xanthan gum)

Polyox WSR 205® (Union Carbide) = polyethylene glycol, medium MG 600,000

Tylose H 200 YP® (Hoechst AG) = hydroxyethyl cellulose
Figure imgb0001
Figure imgb0002
Figure imgb0003

Claims (3)

1. Vorbehandlungs- oder Einweichmittel für hartnäckig ange­schmutztes Geschirr im maschinellen Reinigungsprozeß, da­durch gekennzeichnet, daß sie 0,5 bis 20 Gewichtsprozent nichtionische, insbesondere schwachschäumende Tenside, 0,5 bis 25 Gewichtsprozent mehrwertige aliphatische Alkohole und/oder Glykolether, 0,5 bis 10 Gewichtsprozent einer hydrotropen Verbindung und 0,01 bis 6 Gewichtsprozent Vis­kositätsregulatoren in wäßriger Lösung oder Suspension ent­halten und auf eine Viskosität von mindestens 5 mPas sowie auf einen pH-Wert von 2 bis 7 eingestellt sind.1. pretreatment or soaking agent for stubbornly soiled dishes in the machine cleaning process, characterized in that they contain 0.5 to 20 percent by weight of nonionic, especially low-foaming surfactants, 0.5 to 25 percent by weight of polyhydric aliphatic alcohols and / or glycol ethers, 0.5 to 10 % By weight of a hydrotropic compound and 0.01 to 6% by weight of viscosity regulators in aqueous solution or suspension and are adjusted to a viscosity of at least 5 mPas and to a pH of 2 to 7. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß sie 1 bis 15 Gewichtsprozent nichtionische, insbesondere schwach­schäumende Tenside, 1 bis 20 Gewichtsprozent mehrwertige aliphatische Alkohole und/oder Glykolether, 1 bis 8 Ge­wichtsprozent einer hydrotropen Verbindung und 0,05 bis 5 Gewichtsprozent Viskositätsregulatoren in wäßriger Suspension oder Lösung enthalten und auf eine Viskosität von mindestens 20 mPas sowie auf einen pH-Wert von 3 bis 6 eingestellt sind.2. Composition according to claim 1, characterized in that they contain 1 to 15 percent by weight of nonionic, especially low-foaming surfactants, 1 to 20 percent by weight of polyhydric aliphatic alcohols and / or glycol ethers, 1 to 8 percent by weight of a hydrotropic compound and 0.05 to 5 percent by weight of viscosity regulators Contain aqueous suspension or solution and are adjusted to a viscosity of at least 20 mPas and a pH of 3 to 6. 3. Verfahren zum Reinigen von hartnäckig angeschmutztem Ge­schirr, dadurch gekennzeichnet, daß man die angeschmutzten Stellen mit einem Mittel nach den Ansprüchen 1 und 2 be­schichtet, das Geschirr mit der beschichteten Fläche in Richtung gegen den Strahl der Wasserumwälzung der Spülma­schine in einen Geschirrkorb einordnet und nach einer be­liebigen Einwirkzeit, vorzugsweise nach wenigstens 30 Mi­nuten, den üblichen maschinellen Reinigungsprozeß einleitet und ablaufen läßt.3. A method for cleaning stubbornly soiled dishes, characterized in that the soiled areas are coated with a composition according to claims 1 and 2, the dishes with the coated surface in the direction against the jet of water circulation of the dishwasher in a crockery basket and after any exposure time, preferably after at least 30 minutes, initiates the usual mechanical cleaning process and allows it to run.
EP87114813A 1986-10-18 1987-10-10 Aqueous composition for the pretreatment of dishes Expired - Lifetime EP0268064B1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5575864A (en) * 1994-03-23 1996-11-19 Haley; Kalliopi S. Method for cleaning a hard surface with an all-purpose liquid cleaning composition
WO2000029533A1 (en) * 1998-11-12 2000-05-25 Henkel Kommanditgesellschaft Auf Aktien Aqueous detergents for dishwasher
EP1010421A1 (en) * 1998-12-17 2000-06-21 Henkel Kommanditgesellschaft auf Aktien Thickened composition of watersoluble surfactants
WO2012073007A2 (en) 2010-11-30 2012-06-07 Reckitt Benckiser N.V. Method of cleaning
WO2016057623A1 (en) * 2014-10-07 2016-04-14 The Procter & Gamble Company Method of pre-treating articles to be washed in a dishwashing machine
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9000329A (en) * 1990-02-12 1991-09-02 Stork Friesland Bv HYDROFILE MEMBRANE, METHOD FOR MANUFACTURING A HYDROFILE MEMBRANE.
US5464477A (en) * 1992-09-18 1995-11-07 Crest Ultrasonics Corporation Process for cleaning and drying ferrous surfaces without causing flash rusting
US5851979A (en) * 1992-11-16 1998-12-22 The Procter & Gamble Company Pseudoplastic and thixotropic cleaning compositions with specifically defined viscosity profile
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AU7932094A (en) * 1993-11-03 1995-05-23 Procter & Gamble Company, The Control of calcium carbonate precipitation in automatic dishwashing
AU8015094A (en) * 1993-11-03 1995-05-23 Procter & Gamble Company, The Control of calcium carbonate precipitation in automatic dishwashing
US5474713A (en) * 1994-03-23 1995-12-12 Amway Corporation High actives cleaning compositions and methods of use
US5510052A (en) * 1994-08-25 1996-04-23 Colgate-Palmolive Co. Enzymatic aqueous pretreatment composition for dishware
DE19962883A1 (en) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Detergent tablets
DE19962859A1 (en) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Solid detergent
US20020142931A1 (en) * 2000-07-19 2002-10-03 The Procter & Gamble Company Gel form automatic dishwashing compositions, methods of preparation and use thereof
US8940676B2 (en) 2000-11-27 2015-01-27 The Procter & Gamble Company Detergent products, methods and manufacture
US8658585B2 (en) 2000-11-27 2014-02-25 Tanguy Marie Louise Alexandre Catlin Detergent products, methods and manufacture
DE60123463T2 (en) * 2000-11-27 2007-08-02 The Procter & Gamble Company, Cincinnati dishwashing
US7125828B2 (en) 2000-11-27 2006-10-24 The Procter & Gamble Company Detergent products, methods and manufacture
JP4965057B2 (en) 2000-11-27 2012-07-04 ザ プロクター アンド ギャンブル カンパニー Dishwashing method
DE10137925A1 (en) * 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Mixtures for improving hard surface wettability especially in machine dish washing comprise Gemini surfactant and polyethylene glycol
US6786223B2 (en) 2001-10-11 2004-09-07 S. C. Johnson & Son, Inc. Hard surface cleaners which provide improved fragrance retention properties to hard surfaces
US7468040B2 (en) * 2003-09-18 2008-12-23 Cardiac Pacemakers, Inc. Methods and systems for implantably monitoring external breathing therapy
GB2581142A (en) * 2019-01-23 2020-08-12 Linkage Tech Switzerland Sa Compositions and their use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2343145A1 (en) * 1973-08-27 1975-03-13 Henkel & Cie Gmbh Low-foaming clear-rinsing compsns for dish-washing machines - contg. propoxylated and ethoxylated derivs of 1,2-diols
US3882038A (en) * 1968-06-07 1975-05-06 Union Carbide Corp Cleaner compositions
CA1031229A (en) * 1974-07-22 1978-05-16 William G. Bush Dishwashing detergent gel composition
EP0017149A1 (en) * 1979-03-31 1980-10-15 Henkel Kommanditgesellschaft auf Aktien Use of a liquid composition for cleaning hard surfaces

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB975605A (en) * 1962-10-05 1964-11-18 Allied Chem Improvements relating to the production of foams
US3592774A (en) * 1968-05-03 1971-07-13 Henkel & Cie Gmbh Novel rinsing agents
US4116851A (en) * 1977-06-20 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
DE3133529A1 (en) * 1980-08-30 1982-04-01 Basf Ag, 6700 Ludwigshafen Phosphate- and silicate-free low-foaming dishwashing compositions and aqueous concentrates thereof
DE3302465C2 (en) * 1982-03-03 1984-10-11 Akzo Gmbh, 5600 Wuppertal Thickening agents based on polyether derivatives
DE3240688A1 (en) * 1982-11-04 1984-05-30 Henkel KGaA, 4000 Düsseldorf USE OF ALKYLMONOPHOSPHONIC ACIDS AS A KILLING SUBSTANCE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882038A (en) * 1968-06-07 1975-05-06 Union Carbide Corp Cleaner compositions
DE2343145A1 (en) * 1973-08-27 1975-03-13 Henkel & Cie Gmbh Low-foaming clear-rinsing compsns for dish-washing machines - contg. propoxylated and ethoxylated derivs of 1,2-diols
CA1031229A (en) * 1974-07-22 1978-05-16 William G. Bush Dishwashing detergent gel composition
EP0017149A1 (en) * 1979-03-31 1980-10-15 Henkel Kommanditgesellschaft auf Aktien Use of a liquid composition for cleaning hard surfaces

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5575864A (en) * 1994-03-23 1996-11-19 Haley; Kalliopi S. Method for cleaning a hard surface with an all-purpose liquid cleaning composition
US5837065A (en) * 1994-03-23 1998-11-17 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
WO2000029533A1 (en) * 1998-11-12 2000-05-25 Henkel Kommanditgesellschaft Auf Aktien Aqueous detergents for dishwasher
EP1010421A1 (en) * 1998-12-17 2000-06-21 Henkel Kommanditgesellschaft auf Aktien Thickened composition of watersoluble surfactants
EP3196281B1 (en) 2000-06-29 2018-11-21 Ecolab Inc. Rinse agent composition and method for rinsing a substrate surface
EP3196281B2 (en) † 2000-06-29 2022-05-25 Ecolab USA Inc. Use of a rinse agent composition and method for rinsing a substrate surface
WO2012073007A2 (en) 2010-11-30 2012-06-07 Reckitt Benckiser N.V. Method of cleaning
WO2016057623A1 (en) * 2014-10-07 2016-04-14 The Procter & Gamble Company Method of pre-treating articles to be washed in a dishwashing machine
JP2017537672A (en) * 2014-10-07 2017-12-21 ザ プロクター アンド ギャンブル カンパニー Method for pre-processing articles to be cleaned in a dishwasher

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DE3635535C2 (en) 1995-05-18
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DE3789421D1 (en) 1994-04-28

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