EP0033111A1 - Liquid cleaning and caring agent and its use - Google Patents

Liquid cleaning and caring agent and its use Download PDF

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Publication number
EP0033111A1
EP0033111A1 EP81100354A EP81100354A EP0033111A1 EP 0033111 A1 EP0033111 A1 EP 0033111A1 EP 81100354 A EP81100354 A EP 81100354A EP 81100354 A EP81100354 A EP 81100354A EP 0033111 A1 EP0033111 A1 EP 0033111A1
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Prior art keywords
weight
moles
aqueous
water
cleaning
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EP81100354A
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German (de)
French (fr)
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EP0033111B1 (en
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Theodor Dr. Altenschöpfer
Klaus Dr. Schumann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C11D2111/20—
    • 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

  • the commercially available powdery alkaline or acidic dishwashing detergents or rinse aids are not or only insufficiently suitable for cleaning the so-called "problem areas" of the dishwashers which are at risk of contamination, since they can be metered in and dissolved in the cleaning or rinse cycle of the dishwashing machines, but the soiled ones Do not touch areas at all or touch them too briefly. Therefore, one has so far only relied on manual cleaning of such zones.
  • the agents used for cleaning the dishes are unsuitable for such cleaning because they attack the skin too strongly.
  • Commercial cleaning agents for hard surfaces are also unsuitable for this special application, since they generally contain highly foaming surfactants, the residues of which in dishwashers can lead to various types of faults.
  • the agents can contain up to 30, preferably 15 to 20 percent by weight of a monohydric alcohol having 2 to 4 carbon atoms, such as ethanol, propanol, butanol and preferably isopropanol.
  • a monohydric alcohol having 2 to 4 carbon atoms such as ethanol, propanol, butanol and preferably isopropanol.
  • bonic acids with 2 to 6 carbon atoms in the molecule can preferably be used those polyvalent acids which, based on the first dissociation stage, have a K c value of> 10 -6 .
  • these are, for example, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid and preferably citric acid. Mixtures of such acids can also be used.
  • Ethylene glycol, propylene glycol and preferably glycerin are used as water-soluble polyhydric alcohols.
  • ethylene oxide adducts with higher molecular weight propylene glycols with a molecular weight of 900 to 4000 as well as adducts of 1 to 10 moles of ethylene oxide, or 1 to 10 moles of ethylene oxide and 1 to 7 moles of propylene oxide with higher molecular weight fatty alcohols with 10 to 20, preferably 12 to 18 carbon atoms in the molecule or their Mixtures and synthetic, for example by oxosynthesis considered alcohols of chain length C 12 -C 18 and corresponding alkylene oxide adducts with nonylphenols.
  • the biologically largely degradable adducts of ethylene oxide and propylene oxide to higher molecular weight fatty alcohols in particular the addition product of 2 to 5 moles of ethylene oxide and 2 to 5 moles of propylene oxide to a mixture of C12-C 18 fatty alcohols are preferably used.
  • the agents can also contain small amounts of about 0.1 to 4.5 percent by weight of solubilizers for the surfactants and / or fragrances, for example dipropylene glycol, and corrosion inhibitors, for example one under the name Rodine 58® from Gerhard Collardin GmbH , Cologne, known condensation product made from aldehydes and amines prepared in an acid medium.
  • solubilizers for the surfactants and / or fragrances for example dipropylene glycol
  • corrosion inhibitors for example one under the name Rodine 58® from Gerhard Collardin GmbH , Cologne, known condensation product made from aldehydes and amines prepared in an acid medium.
  • the products according to the invention can be added to the dishwashers in concentrations of 5 to 40, preferably 10 to 25 g / l at certain time intervals, about once or twice a month, in the cleaning or rinse cycle and there at an elevated temperature of about 35 ° to 60 ° C for at least about 5 minutes.
  • they can also advantageously be applied manually in concentrated form.
  • the liquid, acidic cleaning and care agents according to the invention dissolve and remove both the fatty food residues as well as lime and cleaning agent residues in the dishwashers.
  • the tarnish also disappears when rubbed off. Due to the content of polyhydric alcohols, the premature drying out of the agents is prevented.
  • not only rubber and plastic seals or connections in the Machine area is kept soft and elastic, but stubborn dirt is softened and easy to wipe off due to the delay in re-drying.
  • an artificial soiling consisting of a mixture of carbon black, machine oil, triglycerides of saturated fatty acids and low-boiling aliphatic hydrocarbons were uniformly applied to a plastic test plate measuring 26 ⁇ 28 cm using a surface brush.
  • a plastic sponge was impregnated with 12 ml of the cleaning agent solution to be tested according to Examples 1 to 3 and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed.
  • the cleaning mixture i.e. the whiteness of the plastic surface cleaned in this way area was measured with a photoelectric color measuring device LF 90 (Dr. B. Lange).
  • the original, clean, white plastic surface served as the white standard. During the measurement, this clean surface was set to 100 percent and the soiled area to 0 percent.
  • the stated values of the cleaned plastic surfaces are to be regarded as percent cleaning capacity (% RV). They are averages from a 4-fold determination. An average% RV of 21 was obtained with tap water.
  • the result of the machine application of the agent according to the invention for cleaning the interior of the dishwashers was determined in the form of the descaling capacity and the cleaning performance.
  • a water content of the machine of 10.0 ⁇ 0.5 1
  • 250 ml of one of the agents according to Examples 1 to 3 were added to the cleaning cycle of a commercially available Miele G 540 dishwasher; the maximum rinse temperature was 55 ° C ⁇ 3 ° C.

Abstract

Die wäßrige oder wäßrig-alkoholische, saure Lösung enthält: 5-50 (12 - 25) Gew.-% einer wasserlöslichen organischen ein/oder mehrbasischen, ggf. durch OH-Gruppen substituierten Carbonsäure (C2-6), bevorzugt Essigsäure und solche mehrwertigen Säuren, deren 1. Dissoziationsstufe einen Kc-Wert >10<-><6> besitzen, z.B. Zitronensäure; 3-20 (5 - 12) Gew.-% eines wasserlöslichen mehrwertigen Alkohols, wie Ethylenglykol, Propylenglykol, bevorzugt Glycerin; 0.1-10 (1-5) Gew.-% eines schwach schäumenden nichtionischen Tensids, vorzugsweise Addukte von 1-10 Mol Ethylenoxid bzw. 1-10 (2-5) Mol Ethylenoxid + 1-7 (2-5) Mol Propylenoxid an Fettalkoholgemische (C10-20), besonders (C12-18); 0-5 (0.1 - 4,5) Gew.-% an Duftstoffen, Farbstoffen, Lösungvermittlern, bevorzugt Dipropylenglykol, und/oder Korrosionsinhibitoren. Die Mittel können neben Wasser vorzugsweise bis zu 30 (15 - 20) Gew.-% eines niederen einwertigen Alkohols wie Isopropanol enthalten. Sie werden den Maschinen in Mengen von 5 - 40 (10 - 25) g/l in gewissen Zeitabständen im Reinigungs -oder Klarspülgang zugesetzt oder manuell in konzentrierter Form angewandt. Der Gehalt an mehrwertigen Alkoholen verhindert die Austrocknung der Mittel, wodurch Gummi- und Kunststoffdichtungen im Maschinenbereich elastisch bleiben und hartnäckige Verschmutzungen abwischbar aufgeweicht werden.The aqueous or aqueous-alcoholic, acidic solution contains: 5-50 (12-25)% by weight of a water-soluble organic mono- or polybasic carboxylic acid (C2-6) which is optionally substituted by OH groups, preferably acetic acid and such polyvalent Acids whose 1st dissociation level has a Kc value> 10 <-> <6>, e.g. Citric acid; 3-20 (5-12)% by weight of a water-soluble polyhydric alcohol, such as ethylene glycol, propylene glycol, preferably glycerol; 0.1-10 (1-5)% by weight of a low-foaming nonionic surfactant, preferably adducts of 1-10 moles of ethylene oxide or 1-10 (2-5) moles of ethylene oxide + 1-7 (2-5) moles of propylene oxide Fatty alcohol mixtures (C10-20), especially (C12-18); 0-5 (0.1 - 4.5)% by weight of fragrances, dyes, solubilizers, preferably dipropylene glycol, and / or corrosion inhibitors. In addition to water, the agents can preferably contain up to 30 (15-20)% by weight of a lower monohydric alcohol such as isopropanol. They are added to the machines in quantities of 5 - 40 (10 - 25) g / l at certain intervals in the cleaning or rinse cycle or applied manually in concentrated form. The content of polyhydric alcohols prevents the agents from drying out, which means that rubber and plastic seals in the machine area remain elastic and stubborn dirt is softened so that it can be wiped off.

Description

Im Bereich der Türdichtungen, Schlauchanschlüsse und strömungsarmen Zonen von Geschirrspülmaschinen, also dort, wo die Oberflächen des Geschirrspülmaschineninnenraums nicht dem direkten und intensiven Betriebsdruck der Reinigungsflotte ausgesetzt sind, kommt es im Laufe der Zeit zu Ablagerungen von Schmutz, der im wesentlichen aus feinteiligen, fetthaltigen Speiseresten besteht.In the area of door seals, hose connections and low-flow zones of dishwashers, i.e. where the surfaces of the interior of the dishwasher are not exposed to the direct and intensive operating pressure of the cleaning liquor, dirt builds up over time, which essentially consists of fine-particle, fatty food residues consists.

Auch durch gelegentliche, unvermeidliche, technische Störungen der Ionenaustauscheranlage von Geschirrspülmaschinen, die der Enthärtung des verwendeten Wassers dienen, oder durch andauerndes Unterdosieren der Reinigungsmittel durch die Anwender bilden sich, allmählich zunehmend, auf den inneren Oberflächen der Maschinen, gegebenenfalls auch auf dem darin behandelten Reinigungsgüt, Ablagerungen aus einem Gemisch von-Kalk aus hartem Wasser und Reinigungsmittelrückständen. Zum Teil bilden sich auch sogenannte "Anlauffarben", wie die regenbogenfarbenen Verfärbungen von Edelstahlteilen der Geschirrspülmaschinen oder auch Geschirrteilen aus Edelstahl genannt werden.Occasional, unavoidable, technical faults in the ion exchange system of dishwashers, which serve to soften the water used, or due to continuous underdosing of the cleaning agents by the users, gradually, increasingly, on the inner surfaces of the machines, possibly also on the cleaning goods treated therein , Deposits from a mixture of lime from hard water and detergent residues. In some cases so-called "tarnish colors" are formed, as the rainbow-colored discolorations of stainless steel parts of the dishwashers or also parts made of stainless steel are called.

Diese Schmutzablagerungen bieten einen unerwünschten Nährboden für Fäulnisprozesse, die sich durch eine unangenehme Geruchsbildung, besonders beim Öffnen der Spülmaschinen nach längerem Nichtgebrauch, bemerkbar macht. Darüber hinaus werden aber auch die Schlauch- und Dichtungsmaterialien, vor allem an den Türen, durch Langzeiteinwirkung dieser Schmutzablagerungen geschädigt.These dirt deposits provide an undesirable breeding ground for putrefaction processes, which is noticeable through an unpleasant smell, especially when the dishwasher is opened after a long period of non-use. In addition, the hose and sealing materials, especially on the doors, are damaged by long-term exposure to these dirt deposits.

Die handelsüblichen pulverförmigen alkalischen oder sauren Geschirr-, Reinigungs- beziehungsweise Klarspülmittel eignen sich nicht oder nur unzureichend zur Reinigung der verschmutzungsgefährdeten sogenannten "Problemzonen" der Geschirrspülmaschinen, da sie zwar in den Reinigungs- beziehungsweise Klarspülgang der Geschirrspülmaschinen eindosiert und gelöst werden können, jedoch die verschmutzten Bereiche entweder gar nicht oder zu kurzzeitig berühren. Daher ist man bisher ausschließlich auf die manuelle Reinigung derartiger Zonen angewiesen. Die zur Geschirreinigung verwendeten Mittel sind für eine derartige Reinigung ungeeignet, da sie die Haut zu stark angreifen. Auch handelsübliche Reinigungsmittel für harte Oberflächen sind für diese spezielle Anwendung nicht geeignet, da sie im allgemeinen stark schäumende Tenside enthalten, deren Rückstände in den Spülmaschinen zu Störungen vielfältiger Art führen können.The commercially available powdery alkaline or acidic dishwashing detergents or rinse aids are not or only insufficiently suitable for cleaning the so-called "problem areas" of the dishwashers which are at risk of contamination, since they can be metered in and dissolved in the cleaning or rinse cycle of the dishwashing machines, but the soiled ones Do not touch areas at all or touch them too briefly. Therefore, one has so far only relied on manual cleaning of such zones. The agents used for cleaning the dishes are unsuitable for such cleaning because they attack the skin too strongly. Commercial cleaning agents for hard surfaces are also unsuitable for this special application, since they generally contain highly foaming surfactants, the residues of which in dishwashers can lead to various types of faults.

Die vorliegende Erfindung betrifft ein flüssiges, wäßriges oder wäßrig-alkoholisches Reinigungs- und Pflegemittel, dadurch gekennzeichnet, daß es, bezogen auf das Gesamtgewicht der wäßrigen oder wäßrig-alkoholischen Lösung,

  • 5 bis 50, vorzugsweise 12 bis 25 Gewichtsprozent einer wasserlöslichen organischen einoder mehrbasigen, gegebenenfalls durch Hydroxygruppen substituierten Carbonsäure mit 2 bis 6 Kohlenstoffatomen im Molekül,
  • 3 bis 20, vorzugsweise 5 bis 12 Gewichtsprozent eines wasserlöslichen mehrwertigen Alkohols,
  • 0,1 bis 10, vorzugsweise 1 bis 5 Gewichtsprozent eines schwachschäumenden nichtionischen Tensids sowie
  • 0 bis 5, vorzugsweise 0,1 bis 4,5 Gewichtsprozent an Duftstoffen, Farbstoffen, Lösungsvermittlern und/oder Korrosionsinhibitoren

enthält.The present invention relates to a liquid, aqueous or aqueous-alcoholic cleaning and care agent, characterized in that it, based on the total weight of the aqueous or aqueous-alcoholic solution,
  • 5 to 50, preferably 12 to 25 percent by weight of a water-soluble organic mono- or polybasic, optionally substituted by hydroxy groups, carboxylic acid with 2 to 6 carbon atoms in the molecule,
  • 3 to 20, preferably 5 to 12 percent by weight of a water-soluble polyhydric alcohol,
  • 0.1 to 10, preferably 1 to 5 percent by weight of a low-foaming nonionic surfactant and
  • 0 to 5, preferably 0.1 to 4.5 percent by weight of fragrances, dyes, solubilizers and / or corrosion inhibitors

contains.

Neben Wasser können die Mittel bis zu 30, vorzugsweise 15 bis 20 Gewichtsprozent eines einwertigen Alkohols mit 2 bis 4 Kohlenstoffatomen wie Ethanol, Propanol, Butanol und vorzugsweise Isopropanol enthalten.In addition to water, the agents can contain up to 30, preferably 15 to 20 percent by weight of a monohydric alcohol having 2 to 4 carbon atoms, such as ethanol, propanol, butanol and preferably isopropanol.

Als wasserlösliche organische ein- oder mehrbasige, gegebenenfalls durch Hydroxygruppen substituierte Car- . bonsäuren mit 2 bis 6 Kohlenstoffatomen im Molekül können neben Essigsäure bevorzugt solche mehrwertigen Säuren verwendet werden, die bezogen auf die erste Dissoziationsstufe, einen Kc-Wert von>10-6 besitzen. Das sind beispielsweise Adipinsäure, Bernsteinsäure, Weinsäure, Äpfelsäure, Glutarsäure und bevorzugt Zitronensäure. Man kann auch Gemische derartiger Säuren einsetzen.As water-soluble organic mono- or polybasic, optionally substituted by hydroxyl groups Car-. In addition to acetic acid, bonic acids with 2 to 6 carbon atoms in the molecule can preferably be used those polyvalent acids which, based on the first dissociation stage, have a K c value of> 10 -6 . These are, for example, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid and preferably citric acid. Mixtures of such acids can also be used.

Als wasserlösliche mehrwertige Alkohole dienen Ethylenglykol, Propylenglykol und vorzugsweise Glycerin.Ethylene glycol, propylene glycol and preferably glycerin are used as water-soluble polyhydric alcohols.

Zur Steigerung der Reinigungsleistung werden schwachschäumende, nichtionische Tenside eingesetzt. Als solche kommen 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 10 bis 20, vorzugsweise 12 bis 18 Kohlenstoffatomen im Molekül oder deren 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.Low-foaming, nonionic surfactants are used to increase cleaning performance. As such come ethylene oxide adducts with higher molecular weight propylene glycols with a molecular weight of 900 to 4000 as well as adducts of 1 to 10 moles of ethylene oxide, or 1 to 10 moles of ethylene oxide and 1 to 7 moles of propylene oxide with higher molecular weight fatty alcohols with 10 to 20, preferably 12 to 18 carbon atoms in the molecule or their Mixtures and synthetic, for example by oxosynthesis considered alcohols of chain length C 12 -C 18 and corresponding alkylene oxide adducts with nonylphenols. The biologically largely degradable adducts of ethylene oxide and propylene oxide to higher molecular weight fatty alcohols, in particular the addition product of 2 to 5 moles of ethylene oxide and 2 to 5 moles of propylene oxide to a mixture of C12-C 18 fatty alcohols are preferably used.

Außer Farbstoffen und Duftstoffen können den Mitteln auch noch geringe Mengen von etwa 0,1 bis 4,5 Gewichtsprozent an Lösungsvermittlern für die Tenside und/oder Duftstoffe, beispielsweise Dipropylenglykol, sowie Korrosionsinhibitoren, beispielsweise ein unter dem Namen Rodine 58 ® der Firma Gerhard Collardin GmbH, Köln, bekanntes, in saurem Medium hergestelltes Kondensationsprodukt aus Aldehyden und Aminen zugesetzt werden.In addition to dyes and fragrances, the agents can also contain small amounts of about 0.1 to 4.5 percent by weight of solubilizers for the surfactants and / or fragrances, for example dipropylene glycol, and corrosion inhibitors, for example one under the name Rodine 58® from Gerhard Collardin GmbH , Cologne, known condensation product made from aldehydes and amines prepared in an acid medium.

Die erfindungsgemäßen Produkte können den Geschirrspülmaschinen in Konzentrationen von 5 bis 40, vorzugsweise 10 bis 25 g/l in gewissen Zeitabständen, etwa ein- bis zweimal monatlich, im Reinigungs- oder Klarspülgang zugesetzt werden und dort bei einer erhöhten Temperatur von etwa 35° bis 60 °C wenigstens etwa 5 Minuten lang zur Einwirkung gebracht werden. Sie können jedoch auch vorteilhaft in konzentrierter Form manuell angewendet werden.The products according to the invention can be added to the dishwashers in concentrations of 5 to 40, preferably 10 to 25 g / l at certain time intervals, about once or twice a month, in the cleaning or rinse cycle and there at an elevated temperature of about 35 ° to 60 ° C for at least about 5 minutes. However, they can also advantageously be applied manually in concentrated form.

Die erfindungsgemäßen flüssigen, sauren Reinigungs- und Pflegemittel lösen und entfernen sowohl die fetthaltigen Speiserestanschmutzungen als auch Kalk- und Reinigungsmittelrückstände in den Geschirrspülmaschinen. Auch die Anlauffarben verschwinden beim Abreiben. Infolge des Gehaltes an mehrwertigen Alkoholen wird die vorzeitige Austrocknung der Mittel verhindert. Dadurch werden nicht nur Gummi- und Kunststoffdichtungen oder -anschlüsse im Maschinenbereich weich und elastisch gehalten, sondern hartnäckige Verschmutzungen werden dadurch aufgeweicht und wegen der Verzögerung des Wiederantrocknens leicht abwischbar.The liquid, acidic cleaning and care agents according to the invention dissolve and remove both the fatty food residues as well as lime and cleaning agent residues in the dishwashers. The tarnish also disappears when rubbed off. Due to the content of polyhydric alcohols, the premature drying out of the agents is prevented. As a result, not only rubber and plastic seals or connections in the Machine area is kept soft and elastic, but stubborn dirt is softened and easy to wipe off due to the delay in re-drying.

B e i s p i e l eExample Beispiel 1example 1

Figure imgb0001
Figure imgb0001

Beispiel 2Example 2

Figure imgb0002
Figure imgb0002

Beispiel 3Example 3

Figure imgb0003
Figure imgb0003

ReinigungsvernögenCleaning powers

Zur Bestimmung des Reinigungsvermögens der manuell angewendeten erfindungsgemäßen Mittel von Gummi- und Kunststoffteilen einer Geschirrspülmaschine wurde folgende Versuchsanwendung benutzt:The following test application was used to determine the cleaning power of the manually applied agents according to the invention of rubber and plastic parts in a dishwasher:

Auf eine Kunststofftestplatte von 26 x 28 cm wurden mit Hilfe eines Flächenstreichers gleichmäßig 2 g einer aus einem Gemisch aus Ruß, Maschinenöl, Triglyceriden gesättigter Fettsäuren und niedrigsiedenden aliphatischen Kohlenwasserstoffen bestehenden künstlichen Anschmutzung aufgetragen.2 g of an artificial soiling consisting of a mixture of carbon black, machine oil, triglycerides of saturated fatty acids and low-boiling aliphatic hydrocarbons were uniformly applied to a plastic test plate measuring 26 × 28 cm using a surface brush.

Ein Kunststoffschwamm wurde jeweils mit 12 ml der zu prüfenden Reinigungsmittellösung gemäß den Beispielen 1 bis 3 getränkt und maschinell auf der Testfläche bewegt. Nach 6 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungsmischung, das heißt der Weißgrad der so gereinigten Kunststoffoberfläche wurde mit einem photoelektrischen Farbmeßgerät LF 90 (Dr. B. Lange) gemessen. Als Weiß-Standard diente die ursprüngliche, saubere, weiße Kunststoffoberfläche. Bei der Messung wurde diese saubere Oberfläche auf 100 Prozent und die angeschmutzte Fläche auf 0 Prozent eingestellt. Die angegebenen Werte der gereinigten Kunststofflächen sind als Prozent Reinigungsvermögen (% RV) anzusehen. Es sind gemittelte Werte aus einer 4fach-Bestimmung. Mit Leitungswasser wurde ein gemittelter Wert % RV von 21 erhalten.A plastic sponge was impregnated with 12 ml of the cleaning agent solution to be tested according to Examples 1 to 3 and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning mixture, i.e. the whiteness of the plastic surface cleaned in this way area was measured with a photoelectric color measuring device LF 90 (Dr. B. Lange). The original, clean, white plastic surface served as the white standard. During the measurement, this clean surface was set to 100 percent and the soiled area to 0 percent. The stated values of the cleaned plastic surfaces are to be regarded as percent cleaning capacity (% RV). They are averages from a 4-fold determination. An average% RV of 21 was obtained with tap water.

Figure imgb0004
Das Ergebnis der maschinellen Anwendung des erfindungsgemäßen Mittels zur Innenraumreinigung der Geschirrspülmaschinen wurde in Form des Kalklösevermögens und der Reinigungsleistung ermittelt. Hierzu wurden bei einem Wasserinhalt der Maschine von 10,0 ± 0,5 1 je 250 ml eines der Mittel nach den Beispielen 1 bis 3 in den Reinigungsgang einer handelsüblichen Geschirrspülmaschine vom Typ Miele G 540 gegeben; die maximale Spültemperatur betrug 55 °C ± 3 °C.
Figure imgb0004
 The result of the machine application of the agent according to the invention for cleaning the interior of the dishwashers was determined in the form of the descaling capacity and the cleaning performance. For this purpose, with a water content of the machine of 10.0 ± 0.5 1, 250 ml of one of the agents according to Examples 1 to 3 were added to the cleaning cycle of a commercially available Miele G 540 dishwasher; the maximum rinse temperature was 55 ° C ± 3 ° C.

KalklösevermögenDescaling power

Glasplatten der Größe 6 x 12 cm wurden gleichmäßig mit einer Schicht von 5 g einer Mischung aus

Figure imgb0005
belegt und 1,5 Stunden lang bei 80 °C getrocknet. Daraus resultierte ein stabiler "Kalkbelag". Jeweils 4 Glasplatten wurden mit je einem der Mittel gemäß den Beispielen 1 bis 3 behandelt. Durch titrimetrische Bestimmung der Restmengen an Ca++- und Mg++-Ionen auf den Glasplatten wurde die mittlere prozentuale Entfernung des Kalkbelags (Kalklösevermögen) festgestellt. Das lediglich mit Wasser bei 55 °C durch mechanischen Abtrag bewirkte Kalklösevermögen betrug 30 Prozent.
Figure imgb0006
 Glass plates of size 6 x 12 cm were evenly coated with a layer of 5 g of a mixture
Figure imgb0005
 occupied and dried at 80 ° C for 1.5 hours. This resulted in a stable "lime scale". In each case 4 glass plates were treated with one of the agents according to Examples 1 to 3. The mean percentage removal of the lime deposit (descaling capacity) was determined by titrimetric determination of the residual amounts of Ca ++ and Mg ++ ions on the glass plates. The descaling capacity caused by mechanical removal only with water at 55 ° C was 30 percent.
Figure imgb0006

ReinigungsleistungCleaning performance

Auf Edelstahloberflächen des Geschirrspülmaschineninnenraumes von 3 Maschinen vom Typ Miele G 540 wurden je 30 g einer Anschmutzung, bestehend aus

Figure imgb0007
. mittels eines Pinsels in Streifenform aufgetragen und 20 Stunden lang bei Raumtemperatur antrocknen gelassen. Dann wurden je ein Mittel gemäß den Beispielen 1 bis 3 in den Reinigungsgang der Geschirrspülmaschinen gegeben und dieser wie üblich in Gang gesetzt; anschließend wurde das Ergebnis von drei Versuchspersonen beurteilt. Die ursprüngliche neüwertige Edelstahlinnenoberfläche wurde dabei mit 10 (absolut sauber) und die nach dem Antrocknen der Anschmutzungen erhaltenen Edelstahloberflächen mit 0 benotet. Mit reiner wasserbehandlung wurde die Reinigungsnote 5,5 erreicht.
Figure imgb0008
 On stainless steel surfaces of the interior of 3 dishwashers of the Miele G 540 type, 30 g of soiling each consisted of
Figure imgb0007
 . applied in strip form with a brush and left to dry for 20 hours at room temperature. Then an agent according to Examples 1 to 3 was added to the cleaning cycle of the dishwashers and this was started as usual; the result was then assessed by three test subjects. The The original new stainless steel interior surface was rated 10 (absolutely clean) and the stainless steel surfaces obtained after the soiling had dried on with 0. The cleaning grade 5.5 was achieved with pure water treatment.
Figure imgb0008

Claims (6)

1. Flüssiges, wäßriges oder wäßrig-alkoholisches Reinigungs- und Pflegemittel, insbesondere für Geschirrspülmaschinen, dadurch gekennzeichnet, daß es, bezogen auf das Gesamtgewicht der wäßrigen oder wäßrig-alkoholischen Lösung,
Figure imgb0009
enthält.1. Liquid, aqueous or aqueous-alcoholic cleaning and care agent, in particular for dishwashers, characterized in that, based on the total weight of the aqueous or aqueous-alcoholic solution,
Figure imgb0009
 contains. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es bis zu 30, vorzugsweise 15 bis 20 Gewichtsprozent eines einwertigen Alkohols mit 2 bis 4 Kohlenstoffatomen, vorzugsweise Isopropanol enthält.2. Composition according to claim 1, characterized in that it contains up to 30, preferably 15 to 20 percent by weight of a monohydric alcohol having 2 to 4 carbon atoms, preferably isopropanol. 3 Mittel nach Anspruch 1 und 2, dadurch gekennzeichnet, daß es Essigsäure oder mehrwretige organische Carbonsäuren, deren erste Dissoziationsstufe einen Kc-Wert von >10-6 besitzen, vorzugsweise Zitronensäure oder Gemische derartiger Säuren enthält.3 Means according to claim 1 and 2, characterized in that it contains acetic acid or multi-carbon organic carboxylic acids, the first dissociation stage of which has a K c value of> 10 -6 , preferably citric acid or mixtures of such acids. 4. Mittel nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß es als wasserlösliche mehrwertige Alkohole Ethylenglykol, Propylenglykol und vorzugsweise Glycerin enthält.4. Composition according to claim 1 to 3, characterized in that it contains ethylene glycol, propylene glycol and preferably glycerol as water-soluble polyhydric alcohols. 5. Mittel nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß es als schwachschäumende nichtionische Tenside Addukte von 1 bis 10 Mol Ethylenoxid, beziehungsweise 1 bis 10, vorzugsweise 2 bis 5 Mol Ethylenoxid und 1 bis 7, vorzugsweise 2 bis 5 Mol Propylenoxid an Fettalkoholgemische mit 10 bis 20, vorzugsweise 12 bis 18 Kohlenstoffatomen im Molekül enthält.5. Composition according to claim 1 to 4, characterized in that it contains low-foaming nonionic surfactants adducts of 1 to 10 moles of ethylene oxide, or 1 to 10, preferably 2 to 5 moles of ethylene oxide and 1 to 7, preferably 2 to 5 moles of propylene oxide to fatty alcohol mixtures with 10 to 20, preferably 12 to 18 carbon atoms in the molecule. 6. Mittel nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es als Lösungsvermittler Dipropylenglykol enthält.6. Composition according to claim 1 to 5, characterized in that it contains dipropylene glycol as a solubilizer.
EP81100354A 1980-01-26 1981-01-19 Liquid cleaning and caring agent and its use Expired EP0033111B1 (en)

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DE19803002789 DE3002789A1 (en) 1980-01-26 1980-01-26 LIQUID CLEANING AND CARE PRODUCT

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EP0235774A2 (en) * 1986-03-05 1987-09-09 Henkel Kommanditgesellschaft auf Aktien Liquid surface-active mixtures
EP0286167A2 (en) * 1987-04-06 1988-10-12 The Procter & Gamble Company Hard-surface cleaning compositions
GR1000619B (en) * 1991-04-12 1992-08-31 Nikolaos Lazanas Novel compositions for liquid detergent
WO1992019711A1 (en) * 1991-05-03 1992-11-12 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agent
WO1994007991A1 (en) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Machine care stick
WO1994007982A1 (en) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Liquid cleaning and maintenance agent for household dish washers
WO1995019417A1 (en) * 1994-01-17 1995-07-20 Henkel Kommanditgesellschaft Auf Aktien Hard surface cleaning and care liquid aqueous agents
WO1996011572A1 (en) * 1994-10-14 1996-04-25 Sven Moberg Antimicrobial composition
DE102006009138A1 (en) * 2006-02-24 2007-08-30 Henkel Kgaa Detergent for removing greasy or oily soil and cleaning and conditioning hard surface, e.g. washing machine or automatic dishwasher contains nonionic surfactant mixture of (poly)alkylene oxide mono- or di-ether and amine oxide
WO2015144607A1 (en) * 2014-03-26 2015-10-01 Henkel Ag & Co. Kgaa Care product for automatic dishwashers having an optimised surfactant combination
EP3353273B1 (en) 2015-09-25 2021-02-24 Henkel AG & Co. KGaA Method for the care and cleaning of an automatic dishwasher

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US4501680A (en) * 1983-11-09 1985-02-26 Colgate-Palmolive Company Acidic liquid detergent composition for cleaning ceramic tiles without eroding grout
US4581161A (en) * 1984-01-17 1986-04-08 Lever Brothers Company Aqueous liquid detergent composition with dicarboxylic acids and organic solvent
DE4311713C1 (en) * 1993-04-08 1994-05-05 Dorothee Roesling Cleaning lime-scale from glass, plastics and tiled surfaces - using cleaning fluid comprising citric or tartaric acid in glycerine, ethylene glycol, propylene glycol and polyethylene:glycol]
US5925606A (en) * 1996-11-01 1999-07-20 Amway Corporation Concentrated acidic liquid detergent composition
WO2000015749A1 (en) * 1998-09-16 2000-03-23 The Procter & Gamble Company Process and composition for removing lycopene stains from plastic surfaces
EP1061123B2 (en) * 1999-05-28 2007-02-14 Unilever Plc Automatic dish-washing machine cleaning process and compositions relating thereto
FR2831181A1 (en) * 2001-10-23 2003-04-25 Rhodia Polyamide Intermediates Scale inhibitor composition in tablet form for prewashing dishes in automatic dishwashers
WO2005023971A1 (en) * 2003-09-03 2005-03-17 Johnsondiversey, Inc. Cleaning composition
EP1690924A1 (en) * 2005-02-11 2006-08-16 The Procter & Gamble Company Method of cleaning a washing machine or a dishwasher
DE102005034752A1 (en) 2005-07-21 2007-01-25 Henkel Kgaa Cleaning and care products with improved emulsifying ability
GB0525314D0 (en) * 2005-12-13 2006-01-18 Reckitt Benckiser Nv Method and composition
ES2729417T3 (en) * 2009-02-19 2019-11-04 Budich Int Gmbh Combined water softener and rinse aid for application in appliances and installations with metal, ceramic, glass or synthetic material surfaces

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0235774A2 (en) * 1986-03-05 1987-09-09 Henkel Kommanditgesellschaft auf Aktien Liquid surface-active mixtures
EP0235774A3 (en) * 1986-03-05 1990-05-23 Henkel Kommanditgesellschaft Auf Aktien Liquid surface-active mixtures
EP0286167A2 (en) * 1987-04-06 1988-10-12 The Procter & Gamble Company Hard-surface cleaning compositions
EP0286167A3 (en) * 1987-04-06 1989-08-30 The Procter & Gamble Company Hard-surface cleaning compositions
GR1000619B (en) * 1991-04-12 1992-08-31 Nikolaos Lazanas Novel compositions for liquid detergent
WO1992018595A1 (en) * 1991-04-12 1992-10-29 Nikolaos Lazanas Liquid detergent compositions containing natural vinegar
US5520836A (en) * 1991-05-03 1996-05-28 Henkel Kommanditgesellschaft Auf Aktien Liquid detergent
US5441662A (en) * 1991-05-03 1995-08-15 Henkel Kommanditgesellschaft Auf Aktien Liquid detergent
WO1992019711A1 (en) * 1991-05-03 1992-11-12 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agent
WO1994007991A1 (en) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Machine care stick
WO1994007982A1 (en) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Liquid cleaning and maintenance agent for household dish washers
WO1995019417A1 (en) * 1994-01-17 1995-07-20 Henkel Kommanditgesellschaft Auf Aktien Hard surface cleaning and care liquid aqueous agents
WO1996011572A1 (en) * 1994-10-14 1996-04-25 Sven Moberg Antimicrobial composition
DE102006009138A1 (en) * 2006-02-24 2007-08-30 Henkel Kgaa Detergent for removing greasy or oily soil and cleaning and conditioning hard surface, e.g. washing machine or automatic dishwasher contains nonionic surfactant mixture of (poly)alkylene oxide mono- or di-ether and amine oxide
WO2007098831A1 (en) * 2006-02-24 2007-09-07 Henkel Ag & Co. Kgaa Washing or cleaning compositions
WO2015144607A1 (en) * 2014-03-26 2015-10-01 Henkel Ag & Co. Kgaa Care product for automatic dishwashers having an optimised surfactant combination
EP3353273B1 (en) 2015-09-25 2021-02-24 Henkel AG & Co. KGaA Method for the care and cleaning of an automatic dishwasher

Also Published As

Publication number Publication date
ATE7709T1 (en) 1984-06-15
EP0033111B1 (en) 1984-05-30
DE3002789A1 (en) 1981-07-30
DE3163783D1 (en) 1984-07-05
US4392977A (en) 1983-07-12

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