EP0708816B1 - Use of mixed ethers in rinsing agents - Google Patents

Use of mixed ethers in rinsing agents Download PDF

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Publication number
EP0708816B1
EP0708816B1 EP94901884A EP94901884A EP0708816B1 EP 0708816 B1 EP0708816 B1 EP 0708816B1 EP 94901884 A EP94901884 A EP 94901884A EP 94901884 A EP94901884 A EP 94901884A EP 0708816 B1 EP0708816 B1 EP 0708816B1
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EP
European Patent Office
Prior art keywords
rinse aid
fatty alcohol
rinse
mixed ethers
acid
Prior art date
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.)
Expired - Lifetime
Application number
EP94901884A
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German (de)
French (fr)
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EP0708816A1 (en
Inventor
Jürgen Härer
Peter Jeschke
Karl Schmid
Karin Koren
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/2082—Polycarboxylic 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
    • C11D3/2086—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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to new agents for machine cleaning hard surfaces, especially rinse aid containing Mixed ethers and special fatty alcohol polyglycol ethers and the use of these mixtures for the production of mentioned means.
  • rinse aids are mixtures of low-foaming fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (for example cumene sulfonate), organic acids (for example citric acid) and solvents (for example ethanol).
  • solubilizers for example cumene sulfonate
  • organic acids for example citric acid
  • solvents for example ethanol
  • Rinse aid is known from EP-B1 0 197 434 (Henkel) Contain mixed ethers as surfactants.
  • a variety of different materials glass, metal, Silver, plastic, porcelain
  • This variety of materials must be wetted as well as possible in the rinse cycle.
  • Rinse aid formulations that act exclusively as a surfactant component Containing mixed ethers meet these requirements not or only to a small extent, so that the rinse aid or drying effect, especially with plastic surfaces is not satisfactory.
  • the object of the present invention was therefore to new ecological and toxicologically perfect formulations to be provided with regard to the application technology Properties deliver the same results as commercially available cleaning agents and the aforementioned Do not have disadvantages.
  • detergents especially rinse aid containing mixed ethers and Fatty alcohol polypropylene / polyethylene glycol ethers not only have a high ecotoxicological tolerance, but the requirements for a branded product also with regard to fully meet the application properties.
  • rinse aid Another benefit, which is preferably on rinse aid relates to the fact that to produce their homogeneous, low viscosity and therefore easy to dose solutions no further, mostly inert and therefore for drying and the rinse aid ineffective solubilizers such.
  • Mixed ethers are to be understood as meaning known end group-capped fatty alcohol polyglycol ethers which can be obtained by the relevant methods of preparative organic chemistry.
  • Fatty alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride, in the presence of bases.
  • Typical examples are mixed ethers of the formula (I) in which R 1 for an industrial C 12/18 or. C 12/14 cocoalkyl radical, ml for 0, nl for 5 to 10 and R 2 for a butyl group (Dehypon (R) LS-54, LS-104, LT-54, LS-104, Henkel KGaA, Duesseldorf / FRG ).
  • R 1 for an industrial C 12/18 or. C 12/14 cocoalkyl radical
  • ml for 0, nl for 5 to 10
  • R 2 for a butyl group
  • the polyglycol ethers which form component b) are known nonionic surfactants which are obtained by adding initially propylene oxide and then ethylene oxide or exclusively ethylene oxide to fatty alcohols.
  • Typical examples are polyglycol ethers of the formula (II) in which R 3 represents an alkyl radical having 12 to 14 carbon atoms, m2 represents 0 or 1 and n2 represents numbers from 2 to 5 (dehydol (R) LS-2, LS-4, LS-5, Henkel KGaA, Düsseldorf / FRG).
  • the polyglycol ethers can preferably have a narrow homolog distribution; in these cases, formulations with particularly advantageous physical properties are obtained.
  • the agents according to the invention can contain components a) and b) in a weight ratio of 10:90 to 80:20, preferably 30: 70 to 70: 30 and in particular 30: 70 to 40: 60 included.
  • the agents according to the invention can be used as further surfactants non-ionic substances of the alkyl oligoglucoside type and / or Contain fatty acid N-alkylglucamides.
  • carboxylic acids preferably Hydroxycarboxylic acids into consideration. Typical examples are malic acid (Monohydroxysuccinic acid), tartaric acid (dihydroxysuccinic acid); saturated aliphatic dicarboxylic acids such as Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; Gluconic acid (hexane-pentahydroxy-1-carboxylic acid), preferably however, anhydrous citric acid. You can in Amounts from about 1 to 50, preferably from about 1 to 30 % By weight are used. There are other additives all colors and fragrances in question.
  • Typical formulations of the agents according to the invention can for example have the following composition (ad 100% by weight water): 0.5 to 20% by weight Mixed ether, 0.5 to 20% by weight Fatty alcohol polypropylene glycol / polyethylene glycol ether and 1 to 50% by weight Carboxylic acids.
  • Recipes containing are particularly advantageous 3 to 10% by weight Mixed ether 3 to 10% by weight Fatty alcohol polyethylene glycol ether and 1 to 30% by weight Citric acid.
  • the agents according to the invention particularly contain ecotoxicologically compatible ingredients, can be solvent-free formulate and show excellent network assets against different materials.
  • Another object of the invention therefore relates to the use of mixtures of mixed ethers and fatty alcohol polypropylene glycol / polyethylene glycol ethers for production of Agents for cleaning hard surfaces, in particular Dishes in which they are used in quantities of 0.5 to 20, preferably 1 to 10 wt .-% - based on the agent - be included can.
  • Typical examples are rinse aid, All-purpose cleaner, hygiene cleaner, bottle cleaner as well generally agents in which usually low-foaming surfactants Find application.
  • the composition of the surfactant component of the rinse aid formulations tested is shown in Table 1.
  • Mixtures M1 to M6 are according to the invention, and mixtures M7 to M10 are used for comparison.
  • Rinse aid test results Percentages as% by weight ad 100% by weight water E.g. M c (surfactant)% CS% DS% St. ° C Out.
  • S 1 M1 17.5 3.0 0.5 > 70 clear 0 2nd M2 17.5 3.0 0.5 > 70 clear 0 3rd M5 17.5 3.0 0.5 > 70 clear 0 V1 M6 17.5 3.0 0.5 > 75 clear 1 V2 M7 17.5 3.0 0.5 > 75 clear 1 V3 M8 17.5 3.0 0.5 > 75 clear 1 V4 M9 17.5 3.0 0.5 > 75 clear 1

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft neue Mittel für die maschinelle Reinigung harter Oberflächen, insbesondere Klarspülmittel, enthaltend Mischether und spezielle Fettalkoholpolyglycolether sowie die Verwendung dieser Mischungen zur Herstellung der genannten Mittel.The invention relates to new agents for machine cleaning hard surfaces, especially rinse aid containing Mixed ethers and special fatty alcohol polyglycol ethers and the use of these mixtures for the production of mentioned means.

Stand der TechnikState of the art

Marktübliche Klarspülmittel stellen Gemische aus schwachschäumenden Fettalkoholpolyethylen/polypropylenglycolethern, Lösungsvermittlern (z. B. Cumolsulfonat), organischen Säuren (z.B. Citronensäure) und Lösungsmitteln (z.B. Ethanol) dar. Die Aufgabe dieser Mittel besteht darin, die Grenzflächenspannung des Wassers so zu beeinflussen, daß es in einem möglichst dünnen, zusammenhängenden Film vom Spülgut ablaufen kann, so daß beim anschließenden Trocknungsvorgang keine Wassertropfen, Streifen oder Filme zurückbleiben. Eine Übersicht über die Zusammensetzung von Klarspülern und Methoden zur Leistungsüberprüfung findet sich von W.Schirmer et al. in Tens. Surf. Det. 28, 313 (1991). Commercial rinse aids are mixtures of low-foaming fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (for example cumene sulfonate), organic acids (for example citric acid) and solvents (for example ethanol). The task of these agents is to influence the interfacial tension of the water so that it can run off the wash ware in as thin a coherent film as possible, so that no water drops, streaks or films remain during the subsequent drying process. An overview of the composition of rinse aids and methods for checking performance can be found by W. Schirmer et al. in tens. Surf. Det. 28, 313 (1991).

Bei der Verwendung moderner phosphatfreier und niederalkalischer Reiniger für das maschinelle Geschirrspülen kann es ferner zur Bildung von Kalk- bzw. Silicatbelägen auf dem Spülgut und im Maschineninnenraum kommen kann, da das Calciumbindevermögen dieser Reiniger geringer ist, als das der klassischen phosphathaltigen Produkte. Störende Kalk- bzw. Silicatbeläge treten insbesondere dann auf, wenn das Spülwasser der Geschirrspülmaschine nicht oder nicht ausreichend enthärtet wird und eine Wasserhärte von 4°d überschritten wird. In solchen Fällen lassen sich Kalk- bzw. Silicatbeläge wirksam vermeiden, wenn über den Klarspüler Citronensäure in den Klarspülgang dosiert wird. Da jedoch die normalerweise während des Klarspülgangs zugegebenen Klarspülermengen mit 3 ml - 6 ml sehr gering sind, muß zur Erreichung einer ausreichenden Säure- bzw. Komplexierkapazität der Citronensäuregehalt in Klarspülerformulierungen, die eine effektive Belagsinhibierung gewährleisten sollen, relativ hoch sein. Solche hohen Citronensäuregehalte unterstützen die Wirkung der Phosphatersatzstoffe und gewährleisten fleckenloses Geschirr.When using modern phosphate-free and lower alkaline Machine dishwashing detergents can also for the formation of lime or silicate deposits on the Washware and inside the machine can come because the calcium binding ability this cleaner is less than that of classic products containing phosphates. Disturbing lime or Silicate deposits occur particularly when the rinse water the dishwasher is insufficient or not sufficient is softened and a water hardness of 4 ° d is exceeded becomes. In such cases, lime or silicate coverings can be used effectively avoid citric acid in the rinse aid the rinse aid is dosed. However, since that is usually Amounts of rinse aid added during the rinse cycle with 3 ml - 6 ml are very low, must be sufficient to achieve an adequate level Acidity or complexing capacity of the citric acid content in rinse aid formulations that effectively inhibit fouling should ensure be relatively high. Such high citric acid levels support the effect of the phosphate substitutes and ensure spotless dishes.

Aus der EP-B1 0 197 434 (Henkel) sind Klarspüler bekannt, die als Tenside Mischether enthalten. In der Geschirrspülmaschine wird eine Vielzahl unterschiedlicher Materialien (Glas, Metall, Silber, Kunststoff, Porzellan) gereinigt. Diese Materialvielfalt muß im Klarspülgang möglichst gut benetzt werden. Klarspülerformulierungen, die als Tensidkomponente ausschließlich Mischether enthalten, erfüllen diese Anforderungen nicht oder nur in geringem Umfang, so daß der Klarspül- bzw. Trocknungseffekt insbesondere bei Kunststoffoberflächen nicht zufriedenstellend ist. Rinse aid is known from EP-B1 0 197 434 (Henkel) Contain mixed ethers as surfactants. In the dishwasher a variety of different materials (glass, metal, Silver, plastic, porcelain) cleaned. This variety of materials must be wetted as well as possible in the rinse cycle. Rinse aid formulations that act exclusively as a surfactant component Containing mixed ethers meet these requirements not or only to a small extent, so that the rinse aid or drying effect, especially with plastic surfaces is not satisfactory.

Für den Einsatz in Reinigungsmitteln, also auch in Klarspülerformulierungen, kommen ferner heute nur noch Rezepturbestandteile in Frage, die biologisch vollständig abbaubar und toxikologisch unbedenklich sind. Ein besonderes Interesse kommt dabei lösungsmittelfreien Produkten zu.For use in detergents, including rinse aid formulations, only recipe components come today in question that are completely biodegradable and are toxicologically safe. A special interest solvent-free products.

Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, neue ökologische und toxikologisch einwandfreie Formulierungen bereitzustellen, die bezüglich der anwendungstechnischen Eigenschaften gleiche Resultate liefern, wie marktgängige Reinigungsmittel und die vorstehend genannten Nachteile nicht aufweisen.The object of the present invention was therefore to new ecological and toxicologically perfect formulations to be provided with regard to the application technology Properties deliver the same results as commercially available cleaning agents and the aforementioned Do not have disadvantages.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist die Verwendung von Mischungen, enthaltend

  • a) Mischether der Formel (I),
    Figure 00030001
    in der R1 für einen linearen Alkyl- rest mit 12 bis 18 Kohlenstoffatomen, R2 für einen n-Butyltert m1 für 0 oder Zahlen von 1 bis 2 und n1 für Zahlen von 5 bis 10 steht, und
  • b) Fettalkoholpolypropylenglycol/polyethylenglycolether der Formel (II),
    Figure 00040001
    in der R3 für einen linearen Alkyl- rest mit 12 bis 14 Kohlenstoffatomen, m2 für 0 oder Zahlen von 1 bis 3 und n2 für Zahlen von 2 bis 5 steht,
    • im Gewichtsverhältnis 10:90 bis 80:20 zur Herstellung von KlarspülmittelnThe invention relates to the use of mixtures containing
  • a) mixed ethers of the formula (I),
    Figure 00030001
    in which R 1 is a linear alkyl radical having 12 to 18 carbon atoms, R 2 is an n-butyl tert m1 is 0 or numbers from 1 to 2 and n1 is numbers from 5 to 10, and
  • b) fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (II),
    Figure 00040001
    in which R 3 stands for a linear alkyl radical with 12 to 14 carbon atoms, m2 for 0 or numbers from 1 to 3 and n2 for numbers from 2 to 5,
    • in a weight ratio of 10:90 to 80:20 for the production of rinse aid

    Überraschenderweise wurde gefunden, daß Reinigungsmittel, insbesondere Klarspüler mit einem Gehalt an Mischethern und Fettalkoholpolypropylen/polyethylenglycolethern nicht nur eine hohe ökotoxikologische Verträglichkeit aufweisen, sondern die Anforderungen an ein Markenprodukt auch im Hinblick auf die anwendungstechnischen Eigenschaften voll erfüllen.Surprisingly, it was found that detergents, especially rinse aid containing mixed ethers and Fatty alcohol polypropylene / polyethylene glycol ethers not only have a high ecotoxicological tolerance, but the requirements for a branded product also with regard to fully meet the application properties.

    Ein weiterer Vorteil, der sich vorzugsweise auf Klarspüler bezieht, besteht darin, daß zur Herstellung ihrer homogenen, niedrigviskosen und daher leicht zu dosierenden Lösungen keine weiteren, meist inerten und daher für die Trocknung und den Klarspüleffekt uneffektiven Lösungsvermittler wie z. B. Natriumcumolsulfonat, Ethanol oder Glucosesirup benötigt werden, es sei denn, sie werden in geringen Mengen für die Einarbeitung von Farb- und/oder Duftstoffen erforderlich. Another benefit, which is preferably on rinse aid relates to the fact that to produce their homogeneous, low viscosity and therefore easy to dose solutions no further, mostly inert and therefore for drying and the rinse aid ineffective solubilizers such. B. Sodium cumene sulfonate, ethanol or glucose syrup required unless they are in small quantities for the Incorporation of dyes and / or fragrances required.

    MischetherMixed ether

    Unter Mischethern sind bekannte endgruppenverschlossene Fettalkoholpolyglycolether zu verstehen, die man nach einschlägigen Methoden der präparativen organischen Chemie erhalten kann. Vorzugsweise werden Fettalkoholpolyglycolether in Gegenwart von Basen mit Alkylhalogeniden, insbesondere Butyl- oder Benzylchlorid umgesetzt. Typische Beispiele sind Mischether der Formel (I), in der R1 für einen technischen C12/18-bzw. C12/14-Kokosalkylrest, ml für 0, nl für 5 bis 10 und R2 für eine Butylgruppe steht (Dehypon(R) LS-54, LS-104, LT-54, LS-104, Henkel KGaA, Düsseldorf/FRG). Die Verwendung von butyl- bzw. benzylgruppenverschlossenen Mischethern ist aus anwendungstechnischen Gründen besonders bevorzugt.Mixed ethers are to be understood as meaning known end group-capped fatty alcohol polyglycol ethers which can be obtained by the relevant methods of preparative organic chemistry. Fatty alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride, in the presence of bases. Typical examples are mixed ethers of the formula (I) in which R 1 for an industrial C 12/18 or. C 12/14 cocoalkyl radical, ml for 0, nl for 5 to 10 and R 2 for a butyl group (Dehypon (R) LS-54, LS-104, LT-54, LS-104, Henkel KGaA, Duesseldorf / FRG ). The use of mixed ethers which are closed with butyl or benzyl groups is particularly preferred for technical reasons.

    Fettalkoholpolypropylen/polyethylenglycoletherFatty alcohol polypropylene / polyethylene glycol ether

    Bei den Polyglycolethern, die die Komponente b) bilden, handelt es sich um bekannte nichtionische Tenside, die man durch Anlagerung von zunächst Propylenoxid und dann Ethylenoxid bzw. ausschließlich Ethylenoxid an Fettalkohole erhält. Typische Beispiele sind Polyglycolether der Formel (II), in der R3 für einen Alkylrest mit 12 bis 14 Kohlenstoffatomen, m2 für 0 oder 1 und n2 für Zahlen von 2 bis 5 steht (Dehydol(R) LS-2, LS-4, LS-5, Fa.Henkel KGaA, Düsseldorf/FRG). Vorzugsweise können die Polyglycolether eine eingeengte Homologenverteilung aufweisen; in diesen Fällen werden Formulierungen mit besonders vorteilhaften physikalischen Eigenschaften erhalten. The polyglycol ethers which form component b) are known nonionic surfactants which are obtained by adding initially propylene oxide and then ethylene oxide or exclusively ethylene oxide to fatty alcohols. Typical examples are polyglycol ethers of the formula (II) in which R 3 represents an alkyl radical having 12 to 14 carbon atoms, m2 represents 0 or 1 and n2 represents numbers from 2 to 5 (dehydol (R) LS-2, LS-4, LS-5, Henkel KGaA, Düsseldorf / FRG). The polyglycol ethers can preferably have a narrow homolog distribution; in these cases, formulations with particularly advantageous physical properties are obtained.

    Die erfindungsgemäßen Mittel können die Komponenten a) und b) im Gewichtsverhältnis 10 : 90 bis 80 : 20, vorzugsweise 30 : 70 bis 70 : 30 und insbesondere 30 : 70 bis 40 : 60 enthalten.The agents according to the invention can contain components a) and b) in a weight ratio of 10:90 to 80:20, preferably 30: 70 to 70: 30 and in particular 30: 70 to 40: 60 included.

    Tenside, Hilfs- und ZusatzstoffeSurfactants, auxiliaries and additives

    Als weitere Tenside können die erfindungsgemäßen Mittel nichtionische Stoffe vom Typ der Alkyloligoglucoside und/oder Fettsäure-N-alkylglucamide enthalten. Als wichtigste Zusatzstoffe kommen ein- und mehrwertige Carbonsäuren, vorzugsweise Hydroxycarbonsäuren in Betracht. Typische Beispiele sind Äpfelsäure (Monohydroxybernsteinsäure), Weinsäure (Dihydroxybernsteinsäure); gesättigte aliphatische Dicarbonsäuren wie Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure; Gluconsäure (Hexan-Pentahydroxy-1- Carbonsäure), vorzugsweise jedoch wasserfreie Citronensäure. Sie können in Mengen von etwa 1 bis 50, vorzugsweise von etwa 1 bis 30 Gew.-% eingesetzt werden. Als weitere Zusatzstoffe kommen vor allem Farb- und Duftstoffe in Frage.The agents according to the invention can be used as further surfactants non-ionic substances of the alkyl oligoglucoside type and / or Contain fatty acid N-alkylglucamides. As the most important additives come mono- and polyvalent carboxylic acids, preferably Hydroxycarboxylic acids into consideration. Typical examples are malic acid (Monohydroxysuccinic acid), tartaric acid (dihydroxysuccinic acid); saturated aliphatic dicarboxylic acids such as Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; Gluconic acid (hexane-pentahydroxy-1-carboxylic acid), preferably however, anhydrous citric acid. You can in Amounts from about 1 to 50, preferably from about 1 to 30 % By weight are used. There are other additives all colors and fragrances in question.

    Klarspüler-FormulierungenRinse aid formulations

    Typische Formulierungen der erfindungsgemäßen Mittel, sofern es sich dabei um Klarspüler handelt, können beispielsweise folgende Zusammensetzung aufweisen (ad 100 Gew.-% Wasser): 0,5 bis 20 Gew.-% Mischether, 0,5 bis 20 Gew.-% Fettalkoholpolypropylenglycol/ polyethylenglycolether und 1 bis 50 Gew.-% Carbonsäuren. Typical formulations of the agents according to the invention, provided that they are rinse aids, can for example have the following composition (ad 100% by weight water): 0.5 to 20% by weight Mixed ether, 0.5 to 20% by weight Fatty alcohol polypropylene glycol / polyethylene glycol ether and 1 to 50% by weight Carboxylic acids.

    Besonders vorteilhaft sind Rezepturen enthaltend 3 bis 10 Gew.-% Mischether 3 bis 10 Gew.-% Fettalkoholpolyethylenglycolether und 1 bis 30 Gew.-% Citronensäure. Recipes containing are particularly advantageous 3 to 10% by weight Mixed ether 3 to 10% by weight Fatty alcohol polyethylene glycol ether and 1 to 30% by weight Citric acid.

    Gewerbliche AnwendbarkeitIndustrial applicability

    Die erfindungsgemäßen Mittel enthalten ökotoxikologisch besonders verträgliche Inhaltsstoffe, lassen sich lösungsmittelfrei formulieren und zeigen ein ausgezeichnetes Netzvermögen gegenüber unterschiedlichsten Materialien.The agents according to the invention particularly contain ecotoxicologically compatible ingredients, can be solvent-free formulate and show excellent network assets against different materials.

    Ein weiterer Gegenstand der Erfindung betrifft daher die Verwendung von Mischungen aus Mischethern und Fettalkoholpolypropylenglycol/polyethylenglycolethern zur Herstellung von Mitteln für die Reinigung harter Oberflächen, insbesondere Geschirr, in denen sie in Mengen von 0,5 bis 20, vorzugsweise 1 bis 10 Gew.-% - bezogen auf die Mittel - enthalten sein können. Typische Beispiele hierfür sind vor allem Klarspüler, Allzweckreiniger, Hygienereiniger, Flaschenreiniger sowie generell Mittel, in denen üblicherweise schaumarme Tenside Anwendung finden. Another object of the invention therefore relates to the use of mixtures of mixed ethers and fatty alcohol polypropylene glycol / polyethylene glycol ethers for production of Agents for cleaning hard surfaces, in particular Dishes in which they are used in quantities of 0.5 to 20, preferably 1 to 10 wt .-% - based on the agent - be included can. Typical examples are rinse aid, All-purpose cleaner, hygiene cleaner, bottle cleaner as well generally agents in which usually low-foaming surfactants Find application.

    Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to be the subject of the invention explain in more detail without restricting it.

    BeispieleExamples I. Eingesetzte Tenside I. Surfactants

  • A1) C12/14-Kokosfettalkohol-5 EO-butylether Dehypon(R) LS-54A1) C 12/14 coconut fatty alcohol-5 EO-butyl ether dehypon (R) LS-54
  • A2) C12/14-Kokosfettalkohol-10 EO-butylether Dehypon(R) LS-104A2) C 12/14 coconut fatty alcohol-10 EO-butyl ether dehypon (R) LS-104
  • A3) C12/18-Kokosfettalkohol-10 EO-butyletherA3) C 12/18 coconut fatty alcohol-10 EO-butyl ether
  • B1) C12/14-Kokosfettalkohol-2 EO-Addukt Dehydol(R) LS-2B1) C 12/14 coconut fatty alcohol-2 EO adduct dehydol (R) LS-2
  • B2) C12/14-Kokosfettalkohol-4 EO-Addukt Dehydol(R) LS-4B2) C 12/14 coconut fatty alcohol-4 EO adduct dehydol (R) LS-4
  • B3) C12/14-Kokosfettalkohol-5 EO-Addukt Dehydol(R) LS-5B3) C 12/14 coconut fatty alcohol-5 EO adduct dehydol (R) LS-5
  • B5) 2-Ethylhexylalkohol-2 EO-AdduktB5) 2-ethylhexyl alcohol-2 EO adduct
  • B6) C12/14-Kokosfettalkohol-3 EO-Addukt-NRE*B6) C 12/14 coconut fatty alcohol-3 EO adduct NRE *
  • C1) C12/14-Kokosfettalkohol-5EO-4PO-Addukt Dehydol(R) LS-54C1) C 12/14 coconut fatty alcohol 5EO-4PO adduct dehydol (R) LS-54
  • C2) C12/14-Kokosfettalkohol-4EO-5PO-Addukt Dehydol(R) LS-45C2) C 12/14 coconut fatty alcohol 4EO-5PO adduct dehydol (R) LS-45

    • Alle Tenside sind Verkaufsprodukte der Henkel KGaA, Düsseldorf/FRG. Die Komponenten A und B sind erfindungsgemäß, die Komponenten C wurden zu Vergleichszwecken eingesetzt. All surfactants are sales products from Henkel KGaA, Düsseldorf / FRG. Components A and B are according to the invention, components C were used for comparison purposes.

    II. Anwendungstechnische Prüfung der Klarspüler II . Application test of rinse aid

    Die Zusammensetzung der Tensidkomponente der getesteten Klarspülerrezepturen ist in Tab.1 widergegeben. Die Mischungen M1 bis M6 sind erfindungsgemäß, die Mischungen M7 bis M10 dienen dem Vergleich. Klarspüler Tensidzusammensetzung Prozentangaben als Gew.-% M A1 % A2 % A3 % B1 % B2 % B3 % B4 % B5 % B6 % M1 30 70 M2 50 20 30 M5 50 40 10 M6 35 65 M A1 % A2 % B1 % B2 % B3 % B4 % B5 % C1 % C2 % M7 100 M8 100 M9 100 M10 30 70 Legende: M = Mischung The composition of the surfactant component of the rinse aid formulations tested is shown in Table 1. Mixtures M1 to M6 are according to the invention, and mixtures M7 to M10 are used for comparison. Rinse aid surfactant composition Percentages as% by weight M A1% A2% A3% B1% B2% B3% B4% B5% B6% M1 30th 70 M2 50 20th 30th M5 50 40 10th M6 35 65 M A1% A2% B1% B2% B3% B4% B5% C1% C2% M7 100 M8 100 M9 100 M10 30th 70 Legend : M = mixture

    a) Schaumverhalten der Tensidmischungen a) Foaming behavior of the surfactant mixtures

    Zur Bestimmung des Schaumverhaltens der Tensidmischungen wurden 2 Eier (ca. 100 bis 110 g) in einem elektrischen Mixgerät im Verhältnis 1:1 mit Wasser von 16°d verdünnt und 2 min verrührt. 100 g der resultierenden Emulsion wurden dann in einem doppelwandigen Meßzylinder von 2000 ml auf 500 ml mit Wasser von 16°d aufgefüllt und auf 50°C temperiert. Nach Erreichen der Prüftemperatur wurden dieser Mischung 20 g der Tensidmischungen M1 bis M9 zugesetzt. Mit Hilfe einer Labor-Schlauchpumpe wurde die Lösung mit einem Glasrohr vom Boden des Meßzylinders angesaugt. Die Rückführung erfolgte über ein zweites Rohr, dessen unteres Ende in der Höhe der 2000-ml-Markierung des Meßzylinders endete. Die Flüssigkeit wurde mit einer Geschwindigkeit von 4 l/min umgepumpt. Nach 5, 10, 20 und 30 min wurde das Volumen aus dem entstandenen Schaum und der Flüssigkeit abgelesen. Die Ergebnisse sind in Tab.2 zusammengefaßt: Schaumverhalten der Tensidmischungen Mischung Volumen in ml nach min 5 10 20 30 M1 750 850 1030 1060 M2 720 825 1000 1020 M5 600 750 1020 1040 M6 700 840 900 1000 M7 760 900 1100 1120 M8 600 700 1040 1060 M9 600 700 900 1000 M10 750 920 1100 1120 To determine the foaming behavior of the surfactant mixtures, 2 eggs (approx. 100 to 110 g) were diluted 1: 1 with water at 16 ° d in an electric mixer and stirred for 2 min. 100 g of the resulting emulsion were then made up in a double-walled measuring cylinder from 2000 ml to 500 ml with water at 16 ° C. and the temperature was raised to 50 ° C. After the test temperature had been reached, 20 g of the surfactant mixtures M1 to M9 were added to this mixture. With the help of a laboratory peristaltic pump, the solution was sucked from the bottom of the measuring cylinder with a glass tube. The return was carried out via a second tube, the lower end of which ended at the level of the 2000 ml mark on the measuring cylinder. The liquid was pumped around at a rate of 4 l / min. After 5, 10, 20 and 30 min the volume was read from the foam and the liquid. The results are summarized in Tab. 2: Foaming behavior of the surfactant mixtures mixture Volume in ml after min 5 10th 20th 30th M1 750 850 1030 1060 M2 720 825 1000 1020 M5 600 750 1020 1040 M6 700 840 900 1000 M7 760 900 1100 1120 M8 600 700 1040 1060 M9 600 700 900 1000 M10 750 920 1100 1120

    b) Schaumverhalten der Klarspülerrezepturen b) Foaming behavior of the rinse aid formulations

    Die Schaumentwicklung des Klarspülers wurde mit Hilfe eines Umwälzdruck-Meßgeräts ermittelt. Der Klarspüler (3 ml) wurde hierbei im Klarspülgang bei 50 °C von Hand dosiert. Dabei bedeuten:

  • 0 Punkte = keine Schaumentwicklung
  • 1 Punkt = schwache Schaumentwicklung
  • 2 Punkte = mittlere Schaumentwicklung (noch akzeptabel)
  • 3 Punkte = starke Schaumentwicklung
    • The foam development of the rinse aid was determined with the aid of a circulating pressure measuring device. The rinse aid (3 ml) was dosed by hand in the rinse aid at 50 ° C. Here mean:
  • 0 points = no foam development
  • 1 point = weak foaming
  • 2 points = medium foam development (still acceptable)
  • 3 points = strong foaming

    • c) Trocknung: c) drying:

    15 Minuten nach Beendigung des Spülprogramms wurde die Tür der Geschirrspülmaschine vollständig geöffnet. Nach 5 Minuten wurde die Trocknung durch Auszählen der Resttropfen auf den unten aufgeführten Geschirrteilen bestimmt. Bewertung:

  • 0 Punkte = mehr als 5 Tropfen
  • 1 Punkt = 5 Tropfen
  • 2 Punkte = 4 Tropfen
  • 3 Punkte = 3 Tropfen
  • 4 Punkte = 2 Tropfen
  • 5 Punkte = 1 Tropfen
  • 6 Punkte = 0 Tropfen (optimale Trocknung)
    • The dishwasher door was fully opened 15 minutes after the end of the washing program. After 5 minutes the drying was determined by counting the remaining drops on the dishes listed below. Rating:
  • 0 points = more than 5 drops
  • 1 point = 5 drops
  • 2 points = 4 drops
  • 3 points = 3 drops
  • 4 points = 2 drops
  • 5 points = 1 drop
  • 6 points = 0 drops (optimal drying)

    • d) Klarspüleffekt: d) rinse aid effect:

    Nach Beurteilung der Trocknung wurden die Geschirrteile außerhalb der Geschirrspülmaschine 30 Minuten zum Abkühlen abgestellt und dann unter Beleuchtung in einem schwarzen Kasten visuell abgemustert. Beurteilt wurden die auf dem Geschirr und Besteck verbliebenen eingetrockneten Resttropfen, Schlieren, Beläge, trüben Filme usw. Bewertung:

  • 0 Punkte = schlechter Klarspüleffekt
  • 8 Punkte = optimaler Klarspüleffekt
    • After the drying had been assessed, the dishes were placed outside the dishwasher for 30 minutes to cool and then visually checked under lighting in a black box. The dried residual drops, streaks, deposits, cloudy films etc. remaining on the dishes and cutlery were assessed.
  • 0 points = poor rinse aid effect
  • 8 points = optimal rinse aid effect

    • e) Für die Leistungsprüfungen c) und d) wurden die Versuche in der Geschirrspülmaschine Bauknecht GSF 1162 mit enthärtetem Wasser durchgeführt. Dazu wurde das 65°C Normalprogramm gewählt. Im Reinigungsgang wurden 40 ml Somat(R) Reiniger (Henkel) dosiert. Die Klarspülermenge betrug 3 ml und wurde von Hand bei 50°C im Klarspülgang dosiert. Die Salzbelastung des Wassers lag zwischen 600 und 700 mg/l. Pro Klarspülerrezeptur wurden 3 Spülgänge durchgeführt. Zur Beurteilung der Trocknung sowie des Klarspüleffekts wurden folgende Geschirrteile eingesetzt:

    • Gläser "Neckar-Becher" (Fa. Schott-Zwiesel), 6 Stück
    • Edelstahlmesser "Brasilia" (Fa. WMF), 3 Stück
    • weiße Prozellan-Eßteller (Fa. Arzberg), 3 Stück
    • rote Kunststoffteller "Valon-Eßteller" (Fa. Haßmann), 3 Stück
    e) For the performance tests c) and d), the tests were carried out in the Bauknecht GSF 1162 dishwasher with softened water. The 65 ° C normal program was selected for this. 40 ml of Somat (R) cleaner (Henkel) were dosed into the cleaning cycle. The amount of rinse aid was 3 ml and was dosed manually at 50 ° C in the rinse aid. The salt load in the water was between 600 and 700 mg / l. 3 rinse cycles were carried out for each rinse aid formulation. The following dishes were used to assess the drying and rinse aid effects:
    • "Neckar-Becher" glasses (Schott-Zwiesel), 6 pieces
    • Stainless steel knife "Brasilia" (from WMF), 3 pieces
    • white Prozellan dinner plates (from Arzberg), 3 pieces
    • red plastic plate "Valon-Eßteller" (Fa. Haßmann), 3 pieces

    Beispiele 1 bis 5, Vergleichsbeispiele V1 bis V4:Examples 1 to 5, Comparative Examples V1 to V4:

    Klarspüler-Testergebnisse Prozentangaben als Gew.-% ad 100 Gew.-% WasserRinse aid test results Percentages as% by weight ad 100% by weight water Bsp.E.g. MM c(Tensid) %c (surfactant)% CS %CS% DS %DS% St. °CSt. ° C Aus.Out. SS 11 M1M1 17,517.5 3,03.0 0,50.5 >70> 70 klarclear 00 22nd M2M2 17,517.5 3,03.0 0,50.5 >70> 70 klarclear 00 33rd M5M5 17,517.5 3,03.0 0,50.5 >70> 70 klarclear 00 V1V1 M6M6 17,517.5 3,03.0 0,50.5 >75> 75 klarclear 11 V2V2 M7M7 17,517.5 3,03.0 0,50.5 >75> 75 klarclear 11 V3V3 M8M8 17,517.5 3,03.0 0,50.5 >75> 75 klarclear 11 V4V4 M9M9 17,517.5 3,03.0 0,50.5 >75> 75 klarclear 11

    Beispiele 6 bis 10, Vergleichsbeispiele V5 bis V9:Examples 6 to 10, Comparative Examples V5 to V9:

    Trocknung der Geschirrteile/Klarspüleffekt Bsp. M. Gläser Messer Porzellan Kunstst. T KSE T KSE T KSE T KSE 4 M1 3,7 6,2 4,1 3,0 5,0 6,3 4,0 5,3 5 M2 3,5 6,1 4,2 2,9 5,1 6,3 3,9 5,5 6 M5 3,3 6,0 4,5 3,1 4,8 6,3 4,0 5,3 V5 * 4,8 6,0 4,8 6,6 5,0 8,0 5,0 6,8 V6 M6 2,7 5,7 4,1 2,0 4,9 6,0 4,0 5,3 V7 M7 2,5 5,8 4,2 1,9 4,0 6,0 4,0 5,1 V8 M8 1,3 5,3 2,3 1,7 4,0 4,3 2,7 4,5 V9 M9 2,4 5,8 4,4 2,2 4,9 6,4 4,1 5,1 Legende: T = Trocknung
       KSE = Klarspüleffekt
       * = Marktgängiger Klarspüler     Drying of the dishes / rinse aid effect E.g. M. Glasses knife porcelain Plastic T KSE T KSE T KSE T KSE 4th M1 3.7 6.2 4.1 3.0 5.0 6.3 4.0 5.3 5 M2 3.5 6.1 4.2 2.9 5.1 6.3 3.9 5.5 6 M5 3.3 6.0 4.5 3.1 4.8 6.3 4.0 5.3 V5 * 4.8 6.0 4.8 6.6 5.0 8.0 5.0 6.8 V6 M6 2.7 5.7 4.1 2.0 4.9 6.0 4.0 5.3 V7 M7 2.5 5.8 4.2 1.9 4.0 6.0 4.0 5.1 V8 M8 1.3 5.3 2.3 1.7 4.0 4.3 2.7 4.5 V9 M9 2.4 5.8 4.4 2.2 4.9 6.4 4.1 5.1 Legend: T = drying
    KSE = rinse aid effect
    * = Commercial rinse aid

    Claims (1)

    1. The use of mixtures containing
      a) mixed ethers corresponding to formula (I):
      Figure 00180001
      in which R1 is a linear alkyl group containing 12 to 18 carbon atoms, R2 is an n-butyl group, m1 has a value of 0 or 1 to 2 and n1 has a value of 5 to 10, and
      b) fatty alcohol polypropylene glycol/polyethylene glycol ethers corresponding to formula (II):
      Figure 00180002
      in which R3 is a linear alkyl group containing 12 to 14 carbon atoms, m2 has a value of 0 or 1 to 3 and n2 has a value of 2 to 5,
      in a ratio by weight of 10:90 to 80:20 for the production of rinse aids.
    EP94901884A 1993-07-12 1993-11-26 Use of mixed ethers in rinsing agents Expired - Lifetime EP0708816B1 (en)

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    DE4323252 1993-07-12
    DE4323252A DE4323252C2 (en) 1993-07-12 1993-07-12 Rinse aid for machine cleaning hard surfaces
    PCT/EP1993/003317 WO1995002668A1 (en) 1993-07-12 1993-11-26 Hard surface cleaning agent

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    EP0708816A1 EP0708816A1 (en) 1996-05-01
    EP0708816B1 true EP0708816B1 (en) 1998-10-14

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    Families Citing this family (28)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US5876514A (en) 1997-01-23 1999-03-02 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
    EP0894849A1 (en) * 1997-07-29 1999-02-03 Basf Corporation Aqueous based solvent free cleaner compositions containing two nonionic surfactants
    US6133218A (en) * 1997-07-29 2000-10-17 Basf Corporation Aqueous based solvent free cleaner compositions containing two nonionic surfactants
    DE19738866A1 (en) * 1997-09-05 1999-03-11 Henkel Kgaa Low-foaming surfactant mixtures with hydroxy mixed ethers
    DE19851453A1 (en) 1998-11-09 2000-05-11 Cognis Deutschland Gmbh Rinse aid for automatic dishwashing
    DE19856727A1 (en) 1998-12-09 2000-06-15 Cognis Deutschland Gmbh All-purpose cleaner
    BR0008014A (en) * 1999-02-05 2001-11-20 Unilever Nv Process for washing articles in a machine for mechanical washing, uses of citric acid bicarbonate, and a chelating agent, and set of parts for use in an automatic dish washing machine
    DE19962859A1 (en) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Solid detergent
    DE19962883A1 (en) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Detergent tablets
    DE10003809A1 (en) 2000-01-28 2001-08-02 Cognis Deutschland Gmbh Rinse aid
    US20030158071A1 (en) * 2000-01-28 2003-08-21 Joerg Kahre Rinsing and cleaning agents
    DE10004677A1 (en) * 2000-02-03 2001-08-09 Cognis Deutschland Gmbh Surfactant mixture used in detergent and rinse agents, comprises anionic surfactants and plant-based fatty alcohol ethoxylate of specific iodine number and conjugate content
    DE10004678A1 (en) * 2000-02-03 2001-08-09 Cognis Deutschland Gmbh Surfactant granules
    DE50200978D1 (en) 2001-02-01 2004-10-21 Cognis Deutschland Gmbh Dishwashing and cleaning agents
    US6921744B2 (en) 2001-02-01 2005-07-26 Cognis Deutschland Gmbh & Co. Kg Hydroxy mixed ethers having a high degree of ethoxylation, compositions containing the same and anti-foam uses therefor
    DE10121723A1 (en) 2001-05-04 2002-11-07 Cognis Deutschland Gmbh gemini
    DE10121724A1 (en) 2001-05-04 2002-11-07 Cognis Deutschland Gmbh gemini
    DE10121722A1 (en) 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Gemini surfactants in rinse aid
    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
    DE10152142A1 (en) * 2001-10-23 2003-04-30 Cognis Deutschland Gmbh Solid washing, rinsing and cleaning agents
    DE10153768A1 (en) 2001-11-02 2003-05-15 Cognis Deutschland Gmbh Hydroxy mixed ethers with polymers
    DE10162023A1 (en) * 2001-12-18 2003-07-03 Cognis Deutschland Gmbh Mixtures of gemini surfactants and fatty alcohol alkoxylates in rinse aid
    US20030166488A1 (en) * 2001-12-19 2003-09-04 Michael Elsner Dishwashing and cleaning compositions
    DE102004047553A1 (en) * 2004-06-16 2006-01-05 Cognis Ip Management Gmbh Rinse aid containing polyol alkyl ethers
    DE102004043657A1 (en) * 2004-09-07 2006-03-23 Miele & Cie. Kg Method for carrying out a rinse program section in a program-controlled dishwasher
    US7741265B2 (en) * 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
    DE102008060471A1 (en) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Machine dishwashing detergent
    WO2014095793A1 (en) * 2012-12-19 2014-06-26 Akzo Nobel Chemicals International B.V. The use of an ethoxylated alcohol as a hydrotrope for an alkylene oxide adduct of an alcohol

    Family Cites Families (16)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CA794805A (en) * 1965-06-25 1968-09-17 Henkel And Cie. G.M.B.H. Low-foaming washing and cleansing agents
    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
    DE3013923A1 (en) * 1980-04-11 1981-10-15 Bayer Ag, 5090 Leverkusen ORGANOPOLYSILOXANE-BASED DEFOAMER PREPARATION
    DE3315951A1 (en) * 1983-05-02 1984-11-08 Henkel KGaA, 4000 Düsseldorf USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS
    EP0197434B1 (en) * 1985-04-03 1989-07-19 Henkel Kommanditgesellschaft auf Aktien Rinsing agents for use in mechanical dish washing
    DE3773781D1 (en) * 1986-07-24 1991-11-21 Henkel Kgaa LOW-FOAM AND / OR FOAM-ABSORBING SURFACTANT MIXTURES AND THEIR USE.
    DE3643934A1 (en) * 1986-12-22 1988-06-23 Henkel Kgaa USE OF SELECTED ALKYL AND / OR ALKENYL DIETHANOLAMINE COMPOUNDS AS SOLUTIONS FOR LOW-FOAM SURFACES
    DE3727378A1 (en) * 1987-08-17 1989-03-02 Henkel Kgaa FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS
    DE3800492A1 (en) * 1988-01-11 1989-07-20 Henkel Kgaa FOAM CONTROL AGENT FOR THE PRODUCTION AND PROCESSING OF FOODSTUFFS OR FOR FERMENTATION PROCESSES
    DE3800490A1 (en) * 1988-01-11 1989-07-20 Henkel Kgaa USE OF SELECTED END-GROUP-CONTAINED FAT ALCOHOL ETHHOXYLATES FOR FOAM ARMS, COLD-FRYABLE CLEANING AGENTS
    DE3818062A1 (en) * 1988-05-27 1989-12-07 Henkel Kgaa FOAMING ALKYL POLYGLYCOLETHER FOR CLEANING AGENT (I)
    US5008030A (en) * 1989-01-17 1991-04-16 Colgate-Palmolive Co. Acidic disinfectant all-purpose liquid cleaning composition
    DE3928602A1 (en) * 1989-08-30 1991-03-07 Henkel Kgaa ALKALISTABLE AND STRONG ALKALINE-MOLDABLE ANTI-FOAM AGENTS FOR COMMERCIAL CLEANING, ESPECIALLY FOR BOTTLE AND CIP CLEANING
    DE3928600A1 (en) * 1989-08-30 1991-03-07 Henkel Kgaa FOAM-ABSORBING MULTI-MATERIAL MIXTURES WITH TENSIDE CHARACTER FOR MACHINE CLEANING AND BOTTLE CLEANING
    DE4014859A1 (en) * 1990-05-09 1991-11-14 Henkel Kgaa USE OF A COMBINATION OF IONIC AND NON-IONIC SURFACES
    DE4243643C1 (en) * 1992-12-22 1993-08-26 Henkel Kgaa, 4000 Duesseldorf, De

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