EP0303928B1 - Foam depressing additives in cleaning agents producing little foam - Google Patents

Foam depressing additives in cleaning agents producing little foam Download PDF

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Publication number
EP0303928B1
EP0303928B1 EP88112874A EP88112874A EP0303928B1 EP 0303928 B1 EP0303928 B1 EP 0303928B1 EP 88112874 A EP88112874 A EP 88112874A EP 88112874 A EP88112874 A EP 88112874A EP 0303928 B1 EP0303928 B1 EP 0303928B1
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EP
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Prior art keywords
foam
polyethylene glycol
cleaning agents
glycol ethers
cleaning
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EP88112874A
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German (de)
French (fr)
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EP0303928A1 (en
Inventor
Jürgen Dr. Geke
Erich Boebers
Gilbert Dr. Schenker
Robert Dr. Piorr
Karl-Heinz Dr. Schmid
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the invention relates to the use of short-chain end-capped alkyl polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents.
  • Aqueous cleaning agents intended for use in trade and industry in particular those for cleaning metal, glass, ceramic and plastic surfaces, generally contain substances which are able to counteract undesirable foam development.
  • foam-suppressing additives is due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents.
  • anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves contain constituents which give rise to undesirable foaming under the given working conditions, for example anionic surfactants or nonionic surfactants foaming at working temperature.
  • the present invention was therefore based on the object of finding foam-suppressing substances whose application properties are superior to those of the prior art at temperatures below 20 to 25 ° C. and which at the same time have the required biodegradability.
  • the solution to this problem is based on the knowledge that certain short-chain end group-capped adducts of ethylene oxide with longer-chain aliphatic alcohols, which are defined below, are able to meet the requirements, both with regard to the usability in terms of application (foam inhibition) and with regard to the biodegradability.
  • shorter-chain polyethylene glycol ethers have an excellent antifoam action even at temperatures of less than 20 to 25 ° C.
  • DE-A-25 56 544 describes a machine dishwashing detergent which contains compounds of the general formula (II) wherein R is an alkyl or alkenyl radical having 6 to 22 carbon atoms, X is an alkylene radical having 2 to 3 carbon atoms and n is 5 to 50.
  • Such polyglycol tert-butyl ethers are, because of their good compatibility with alkali and because of their foam-suppressing properties, advantageously for the production of detergents and cleaning agents, particularly for cleaning glass, dishes, bottles and the like. They can suitably be used in the detergent and cleaning agent formulations in combination with other customary nonionic, cationic or anionic surface-active substances, builders and other additives or auxiliaries.
  • the present invention relates to the use of polyethylene glycol ethers of the formula (I) R1 - O - (CH2CH2O) n - R2 in which R1 is octyl and / or decyl, R2 is n-butyl and n is 3 or 4, as foam-suppressing additives for low-foam detergents.
  • the fatty alcohols n-octanol, n-decanol, and their isomers branched on the alkyl radical and their isomers with OH groups on internal C atoms and oxo alcohols of the stated carbon number can be used individually or in a mixture . Individual compounds or mixtures from the group of the straight-chain alkanols from the above group are preferred.
  • the preparation of the alkyl polyethylene glycol ethers to be used according to the invention is advantageously carried out one or more of the above-described fatty alcohols with ethylene oxide in a molar ratio of 1: 2 to 1: 6 ⁇ m and then etherifies the hydroxyl groups present in the reaction product obtained.
  • the reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts.
  • the etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with straight-chain C4-alkyl halides, for example with n-butyl iodide. It may be expedient to use alkyl halide and alkali compound in a stoichiometric excess, for example from 100 to 200%, over the hydroxyl groups to be etherified.
  • biodegradability of the end group-capped alkyl polyethylene glycol ethers of the general formula (I) to be used according to the invention according to the statutory methods of determination is over 80% BiAS decrease (RVO to the Detergent Act).
  • the end group-capped polyethylene glycol ethers of the formula I to be used according to the invention are notable for their alkali and acid stability.
  • the foam-preventing action of the compounds of the formula I at temperatures of less than 20 to 25 ° C. in alkaline to weakly acidic cleaning liquors is superior to known foam inhibitors.
  • the cleaning agents in which the end group capped polyethylene glycol ethers (I) are used according to the invention can be used, the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and optionally also antimicrobial agents and / or organic solvents.
  • the surfactants used are nonionic surface-active substances, such as polyglycol ethers, which are obtained by the addition of ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants, such as alkali metal, amine and alkanolamine salts of fatty acids, alkylsulfonic acids, alkylsulfonic acids and alkylbenzenesulfonic acids Consider.
  • nonionic surface-active substances such as polyglycol ethers, which are obtained by the addition of ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides
  • anionic surfactants such as alkali metal, amine and alkanolamine salts of fatty acids, alkylsulfonic acids, alkylsulfonic acids and alkylbenzenesulfonic acids
  • the builders can include alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates, as well as citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane-1,1-diphosphonic acidphosphonic acid, amine and ethylenediaminetetra- (methylenephosphonic acid), phosphonoalkane polycarboxylic acids, e.g. Contain phosphonobutane tricarboxylic acid, and alkali metal salts and / or amine salts of these acids.
  • citric acid nitriloacetic acid
  • ethylenediaminetetraacetic acid 1-hydroxyalkane-1,1-diphosphonic acidphosphonic acid
  • phosphonoalkane polycarboxylic acids e.g. Contain phosphonobutane
  • the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons, and free alkanolamines.
  • detergents include the aqueous solutions intended for direct application to the substrates to be cleaned Roger that.
  • cleaning agents also includes the concentrates and solid mixtures intended for the preparation of the application solutions.
  • the ready-to-use solutions can be slightly acidic to strongly alkaline.
  • the end group-capped polyethylene glycol ethers to be used according to the invention are preferably added to the cleaning agents in amounts such that their concentration in the ready-to-use application solutions makes up 10 to 2500 ppm, particularly preferably 50 to 500 ppm.
  • the antifoam effect was tested in a practical 10 l continuous spray system at a spray pressure of 3 to 10 bar (30 mm smooth jet nozzle).
  • the circulation volume was about 10 to 19 l / min.
  • the cleaning solutions were designated at the application temperatures indicated in each case as sprayable in terms of application technology with minimal foam exposure, which had only a small foam blanket ( ⁇ 1 cm height) in continuous operation with otherwise rapid foam disintegration.
  • polyethylene glycol ethers of the formula (I) were tested in which R 1 is one C8 ⁇ 10-n-alkyl radical, R2 is a C4-alkyl radical and n is 3 or 4.
  • polyethylene glycol ethers (Ia) were tested in accordance with DE-A-33 15 951, in which R1 is C8 ⁇ 18-n-alkyl, R2 is C4-alkyl and n is 10.
  • Iron and steel sheets were treated at 15 ° C. with an aqueous solution of this surfactant. With a good cleaning effect, no disruptive foaming was observed.
  • Example 1 an analog short-chain PE glycol ether was used and foam-free sprayability was also achieved at temperatures ⁇ 15 ° C.
  • Example 3 a polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. The solution was not sprayable at a temperature of 15 ° C. In terms of application technology, this system was only sprayable at temperatures> 30 ° C.
  • Iron and steel sheets were treated at 15 ° C. with an aqueous solution of this cleaner (pH 9.0). With a good cleaning effect, no disruptive foam development occurred.
  • Example 4 In comparison to Example 4, a longer-chain polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. In terms of application technology, this system was only sprayable at temperatures> 40 ° C.
  • Iron sheets were treated at 15 ° C. with an aqueous solution of this cleaner (pH 3.5). With a good cleaning effect, no disruptive foaming was observed.
  • Example 5 In comparison to Example 5, a longer-chain polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. The system over-foamed at a temperature of 15 ° C; In terms of application technology, this system was only sprayable at temperatures> 30 ° C.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

Short-chain polyethlene glycol ethers corresponding to the formula: R1-O-(CH2CH2O)n-R2 wherein: R1 is a linear or branched C6-C18 alkyl or alkenyl radical, R2 is a C4-C8 alkyl radical, and N is an integer of from 2 to 6, are used as foam-inhibiting additives for low-foam cleaning compositions.

Description

Die Erfindung betrifft die Verwendung von kurzkettigen endgruppenverschlossenen Alkylpolyethylenglykolethern als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln.The invention relates to the use of short-chain end-capped alkyl polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents.

Für die Verwendung in Gewerbe und Industrie bestimmte wäßrige Reinigungsmittel, insbesondere solche für die Reinigung von Metall-, Glas-, Keramik- und Kunststoffoberflächen, enthalten in der Regel Substanzen, die in der Lage sind, einer unerwünschten Schaumentwicklung entgegenzuwirken. Der Einsatz von schaumdrückenden Zusätzen ist in den meisten Fällen dadurch bedingt, daß die von den Substraten abgelösten und in den Reinigungsbädern sich ansammelnden Verunreinigungen als Schaumbildner wirken. Daneben kann die Verwendung von Antischaummitteln auch aufrund der Tatsache erforderlich sein, daß die Reinigungsmittel selbst Bestandteile enthalten, die unter den vorgegebenen Arbeitsbedingungen zu unerwünschter Schaumbildung Anlaß geben, beispielsweise Aniontenside oder bei Arbeitstemperatur schäumende nichtionisch Tenside.Aqueous cleaning agents intended for use in trade and industry, in particular those for cleaning metal, glass, ceramic and plastic surfaces, generally contain substances which are able to counteract undesirable foam development. In most cases, the use of foam-suppressing additives is due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents. In addition, the use of anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves contain constituents which give rise to undesirable foaming under the given working conditions, for example anionic surfactants or nonionic surfactants foaming at working temperature.

Die DE-A-33 15 951 beschreibt die Verwendung von Polyethylenglykolethern der allgemeinen Formel (Ia)



        R¹-O-(CH₂CH₂O)n-R²   (Ia)



in der

R¹
einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 8 bis 18 C-Atomen,
R²
einen Alkylrest mit 4 bis 8 C-Atomen und
n
eine Zahl von 7 bis 12
bedeuten, als schaumdrückende Zusätze in Reinigungsmitteln. Diese Verbindungen zeigen jedoch unterhalb von 20 bis 25 °C keine Antischaumwirkung. Eine Schauminhibierung bei niedrigen Temperaturen ist jedoch angestrebt.DE-A-33 15 951 describes the use of polyethylene glycol ethers of the general formula (Ia)



R¹-O- (CH₂CH₂O) n -R² (Ia)



in the
R¹
a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 carbon atoms,
R²
an alkyl radical with 4 to 8 carbon atoms and
n
a number from 7 to 12
mean as foam-suppressing additives in cleaning agents. However, these compounds show no anti-foaming action below 20 to 25 ° C. Foam inhibition at low temperatures is, however, desirable.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, schaumdrückende Substanzen aufzufinden, deren anwendungstechnische Eigenschaften denen der Mittel des Standes der Technik bei Temperaturen auch unterhalb von 20 bis 25 °C überlegen sind und die gleichzeitig die geforderte biologische Abbaubarkeit besitzen. Die Lösung dieser Aufgabe geht von der Erkenntnis aus, daß bestimmte, im folgenden definierte, kurzkettige endgruppenverschlossene Anlagerungsprodukte des Ethylenoxids an längerkettige aliphatische Alkohole in der Lage sind, die gestellten Anforderungen, sowohl im Hinblick auf die anwendungstechnische Brauchbarkeit (Schauminhibierung) als auch im Hinblick auf die biologische Abbaubarkeit, zu erfüllen.The present invention was therefore based on the object of finding foam-suppressing substances whose application properties are superior to those of the prior art at temperatures below 20 to 25 ° C. and which at the same time have the required biodegradability. The solution to this problem is based on the knowledge that certain short-chain end group-capped adducts of ethylene oxide with longer-chain aliphatic alcohols, which are defined below, are able to meet the requirements, both with regard to the usability in terms of application (foam inhibition) and with regard to the biodegradability.

Überraschenderweise wurde gefunden, daß kürzerkettige Polyethylenglykolether im Gegensatz zu den bekannten längerkettigen der DE-A-33 15 951 auch bei Temperaturen von weniger als 20 bis 25 °C eine ausgezeichnete Antischaumwirkung aufweisen.Surprisingly, it was found that, in contrast to the known longer-chain DE-A-33 15 951, shorter-chain polyethylene glycol ethers have an excellent antifoam action even at temperatures of less than 20 to 25 ° C.

Ferner wird in der DE-A-25 56 544 ein Maschinengeschirrspülmittel beschrieben, das einen Gehalt an Verbindungen der allgemeinen Formel (II) aufweist

Figure imgb0001

worin R einen Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen, X einen Alkylenrest mit 2 bis 3 C-Atomen und n 5 bis 50 bedeuten. Derartige Polyglykol-tert.-butylether eignen sich wegen ihrer guten Alkaliverträglichkeit und wegen ihrer schaumdämpfenden Eigenschaften mit Vorteil zur Herstellung von Spül- und Reinigungsmitteln, besonders zur Reinigung von Glas, Geschirr, Flaschen und dergleichen. Sie können zweckmäßig in Kombination mit anderen üblichen nichtionischen, kationischen oder anionischen oberflächenaktiven Substanzen, Gerüstsubstanzen und anderen Zusatz- oder Hilfsstoffen in den Wasch- und Reinigungsmittelformulierungen zur Verwendung kommen.Furthermore, DE-A-25 56 544 describes a machine dishwashing detergent which contains compounds of the general formula (II)
Figure imgb0001
wherein R is an alkyl or alkenyl radical having 6 to 22 carbon atoms, X is an alkylene radical having 2 to 3 carbon atoms and n is 5 to 50. Such polyglycol tert-butyl ethers are, because of their good compatibility with alkali and because of their foam-suppressing properties, advantageously for the production of detergents and cleaning agents, particularly for cleaning glass, dishes, bottles and the like. They can suitably be used in the detergent and cleaning agent formulations in combination with other customary nonionic, cationic or anionic surface-active substances, builders and other additives or auxiliaries.

Die vorliegende Erfindung betrifft demgegenüber die Verwendung von Polyethylenglykolethern der Formel (I)



        R¹ - O - (CH₂CH₂O)n - R²



in der R¹ gleich Octyl und/oder Decyl, R² gleich n-Butyl und n gleich 3 oder 4 ist, als schaumdrückende Zusätze für schaumarme Reinigungsmittel.In contrast, the present invention relates to the use of polyethylene glycol ethers of the formula (I)



R¹ - O - (CH₂CH₂O) n - R²



in which R¹ is octyl and / or decyl, R² is n-butyl and n is 3 or 4, as foam-suppressing additives for low-foam detergents.

Als Ausgangsmaterial für die Herstellung der Polyglykolether der Formel I können die Fettalkohole n-Octanol, n-Decanol, sowie deren am Alkylrest verzweigte Isomere und deren Isomere mit OH-Gruppen an innenständigen C-Atomen und Oxoalkohole der genannten Kohlenstoffzahl einzeln oder im Gemisch eingesetzt werden. Bevorzugt sind Einzelverbindungen oder Gemische aus der Gruppe der geradkettigen Alkanole aus der obigen Gruppe.As the starting material for the preparation of the polyglycol ethers of the formula I, the fatty alcohols n-octanol, n-decanol, and their isomers branched on the alkyl radical and their isomers with OH groups on internal C atoms and oxo alcohols of the stated carbon number can be used individually or in a mixture . Individual compounds or mixtures from the group of the straight-chain alkanols from the above group are preferred.

Zur Herstellung der erfindungsgemäß zu verwendenden Alkylpolyethylenglykolether setzt man zweckmäßigerweise einen oder mehrere der vorstehend beschriebenen Fettalkohole mit Ethylenoxid im Molverhältnis von 1 : 2 bis 1 : 6 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxylierungsbedingungen, vorzugsweise in Gegenwart von geeigneten alkalischen Katalysatoren. Die Veretherung der freien Hydroxylgruppen wird bevorzugt unter den bekannten Bedingungen der Williamsonschen Ethersynthese mit geradkettigen C₄-Alkylhalogeniden durchgeführt, beispielsweise mit n-Butyliodid. Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkaliverbindung im stöchiometrischen Überschuß, beispielsweise von 100 bis 200 %, über die zu verethernden Hydroxylgruppen einzusetzen.The preparation of the alkyl polyethylene glycol ethers to be used according to the invention is advantageously carried out one or more of the above-described fatty alcohols with ethylene oxide in a molar ratio of 1: 2 to 1: 6 µm and then etherifies the hydroxyl groups present in the reaction product obtained. The reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts. The etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with straight-chain C₄-alkyl halides, for example with n-butyl iodide. It may be expedient to use alkyl halide and alkali compound in a stoichiometric excess, for example from 100 to 200%, over the hydroxyl groups to be etherified.

Die biologische Abbaubarkeit der erfindungsgemäß zu verwendenden endgruppenverschlossenen Alkylpolyethylenglykolether der allgemeinen Formel (I) nach den gesetzlichen Bestimmungsmethoden liegt bei über 80 % BiAS-Abnahme (RVO zum Waschmittelgesetz).The biodegradability of the end group-capped alkyl polyethylene glycol ethers of the general formula (I) to be used according to the invention according to the statutory methods of determination is over 80% BiAS decrease (RVO to the Detergent Act).

Die erfindungsgemäß zu verwendenden endgruppenverschlossenen Polyethylenglykolether der Formel I zeichnen sich durch ihre Alkali- und Säurestabilität aus. Die schaumverhindernde Wirkung der Verbindungen der Formel I bei Temperaturen von weniger als 20 bis 25 °C in alkalischen bis schwach sauren Reinigungsflotten ist bekannten Schauminhibitoren überlegen.The end group-capped polyethylene glycol ethers of the formula I to be used according to the invention are notable for their alkali and acid stability. The foam-preventing action of the compounds of the formula I at temperatures of less than 20 to 25 ° C. in alkaline to weakly acidic cleaning liquors is superior to known foam inhibitors.

Die Reinigungmittel, in denen die endgruppenverschlossenen Polyethylenglykolether (I) erfindungsgemäß zur Anwendung kommen, können die in solchen Mitteln üblichen Bestandteile, wie Netzmittel, Gerüstsubstanzen und Komplexbildner, Alkalien oder Säuren, Korrosionsinhibitoren und gegebenenfalls auch antimikrobielle Wirkstoffe und/oder organische Lösungsmittel enthalten.The cleaning agents in which the end group capped polyethylene glycol ethers (I) are used according to the invention Can be used, the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and optionally also antimicrobial agents and / or organic solvents.

Als Netzmittel kommen nichtionogene oberflächenaktive Substanzen, wie Polyglykolether, die durch Anlagerung von Ethylenoxid an Alkohole, insbesondere Fettalkohole, Alkylphenole, Fettamine und Carbonsäureamide erhalten werden, und anionaktive Netzmittel, wie Alkalimetall-, Amin- und Alkanolaminsalze von Fettsäuren, Alkylschwefelsäuren, Alkylsulfonsäuren und Alkylbenzolsulfonsäuren in Betracht. An Gerüstsubstanzen und Komplexbildnern können die Reinigungsmittel vor allem Alkalimetallorthophosphate, -polyphosphate, -silikate, -borate, -carbonate, -polyacrylate und -glukonate sowie Citronensäure, Nitriloessigsäure, Ethylendiamintetraessigsäure, 1-Hydroxyalkan-1,1-diphosphonsäuren, Aminotri-(methylenphosphonsäure) und Ethylendiamintetra-(methylenphosphonsäure), Phosphonoalkanpolycarbonsäuren, z.B. Phosphonobutantricarbonsäure, und Alkalimetallsalze und/oder Aminsalze dieser Säuren enthalten. Hochalkalische Reinigungsmittel, insbesondere solche für die Flaschenreinigung, enthalten beträchtliche Mengen Ätzalkali in Form von Natrium- und Kaliumhydroxid. Wenn besondere Reinigungseffekte gewünscht werden, können die Reinigungsmittel organische Lösungsmittel, beispielsweise Alkohole, Benzinfraktionen und chlorierte Kohlenwasserstoffe, und freie Alkanolamine enthalten.The surfactants used are nonionic surface-active substances, such as polyglycol ethers, which are obtained by the addition of ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants, such as alkali metal, amine and alkanolamine salts of fatty acids, alkylsulfonic acids, alkylsulfonic acids and alkylbenzenesulfonic acids Consider. The builders can include alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates, as well as citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane-1,1-diphosphonic acidphosphonic acid, amine and ethylenediaminetetra- (methylenephosphonic acid), phosphonoalkane polycarboxylic acids, e.g. Contain phosphonobutane tricarboxylic acid, and alkali metal salts and / or amine salts of these acids. Highly alkaline cleaning agents, especially those for bottle cleaning, contain considerable amounts of caustic alkali in the form of sodium and potassium hydroxide. If special cleaning effects are desired, the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons, and free alkanolamines.

Unter Reinigungsmittel werden im Zusammenhang mit der Erfindung einmal die zur direkten Anwendung auf die zu reinigenden Substrate bestimmten wäßrigen Lösungen verstanden. Daneben umfaßt der Begriff Reinigungsmittel auch die zur Herstellung der Anwendungslösungen bestimmten Konzentrate und festen Mischungen.In connection with the invention, detergents include the aqueous solutions intended for direct application to the substrates to be cleaned Roger that. In addition, the term cleaning agents also includes the concentrates and solid mixtures intended for the preparation of the application solutions.

Die gebrauchsfertigen Lösungen können schwach sauer bis stark alkalisch sein.The ready-to-use solutions can be slightly acidic to strongly alkaline.

Die erfindungsgemäß zu verwendenden endgruppenverschlossenen Polyethylenglykolether werden den Reinigungsmitteln vorzugsweise in solchen Mengen zugesetzt, daß ihre Konzentration in den gebrauchsfertigen Anwendungslösungen 10 bis 2500 ppm, besonders bevorzugt 50 bis 500 ppm, ausmacht.The end group-capped polyethylene glycol ethers to be used according to the invention are preferably added to the cleaning agents in amounts such that their concentration in the ready-to-use application solutions makes up 10 to 2500 ppm, particularly preferably 50 to 500 ppm.

Die Erfindung wird durch die folgenden Beispiele näher erläutert.The invention is illustrated by the following examples.

Allgemeine Vorgehensweise bei der Prüfung der AntischaumwirkungGeneral procedure for testing the anti-foam effect

Die Prüfung der Antischaumwirkung wurde in einer praxisnahen 10 l-Durchlauf-Spritzanlage bei einem Spritzdruck von 3 bis 10 bar (30 mm Glattstrahldüse) durchgeführt. Das Umlaufvolumen belief sich dabei auf ca. 10 bis 19 l/min.The antifoam effect was tested in a practical 10 l continuous spray system at a spray pressure of 3 to 10 bar (30 mm smooth jet nozzle). The circulation volume was about 10 to 19 l / min.

In den folgenden Beispielen wurden bei den jeweils angegebenen Einsatztemperaturen als anwendungstechnisch spritzfähig bei minimaler Schaumbelastung die Reinigungslösungen bezeichnet, die im Dauerbetrieb bei ansonsten schnellem Schaumzerfall nur eine geringe Schaumdecke (< 1 cm Höhe) aufwiesen.In the following examples, the cleaning solutions were designated at the application temperatures indicated in each case as sprayable in terms of application technology with minimal foam exposure, which had only a small foam blanket (<1 cm height) in continuous operation with otherwise rapid foam disintegration.

In den Beispielen 1 bis 5 wurden Polyethylenglykolether der Formel (I) getestet, in denen R¹ einen C₈₋₁₀-n-Alkylrest, R² einen C₄-Alkylrest und n 3 bzw. 4 bedeuten. In den Vergleichsbeispielen 1 bis 4 wurden Polyethylenglykolether (Ia) gemäß der DE-A-33 15 951 getestet, in denen R¹ für C₈₋₁₈-n-Alkylreste, R² für einen C₄-Alkylrest und n für 10 stehen.In Examples 1 to 5, polyethylene glycol ethers of the formula (I) were tested in which R 1 is one C₈₋₁₀-n-alkyl radical, R² is a C₄-alkyl radical and n is 3 or 4. In comparative examples 1 to 4, polyethylene glycol ethers (Ia) were tested in accordance with DE-A-33 15 951, in which R¹ is C₈₋₁₈-n-alkyl, R² is C₄-alkyl and n is 10.

Die im einzelnen eingesetzten Verbindungen sind der nachfolgenden Tabelle I zu entnehmen.

Figure imgb0002
The individual compounds used can be found in Table I below.
Figure imgb0002

Beispiel 1example 1 400 ppm Tensid A400 ppm surfactant A

Mit einer wäßrigen Lösung dieses Tensids wurden Eisen-und Stahlbleche bei 15 °C behandelt. Bei guter Reinigungswirkung wurde keine störende Schaumentwicklung beobachtet.Iron and steel sheets were treated at 15 ° C. with an aqueous solution of this surfactant. With a good cleaning effect, no disruptive foaming was observed.

Beispiel 2Example 2 400 ppm Tensid B400 ppm surfactant B

Entsprechend Beispiel 1 wurde ein analoger kurzkettiger PE-Glykolether eingesetzt und schaumfreie Spritzfähigkeit ebenfalls bei Temperaturen ≧ 15 °C erreicht.According to Example 1, an analog short-chain PE glycol ether was used and foam-free sprayability was also achieved at temperatures ≧ 15 ° C.

Vergleichsbeispiel 1Comparative Example 1 400 ppm Tensid C400 ppm surfactant C

Im Vergleich zu den Beispielen 1 und 2 wurde ein langkettiger Polyethylenglykolether (Ia) gemäß DE-A-33 15 951 getestet. Anwendungstechnisch spritzfähig war diese Tensidlösung erst bei Temperaturen > 35 °C.In comparison to Examples 1 and 2, a long-chain polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. In terms of application technology, this surfactant solution was only sprayable at temperatures> 35 ° C.

Beispiel 3Example 3

Figure imgb0003
Figure imgb0003

Mit einer wäßrigen Lösung dieses Reinigers (pH 9,0) wurden Eisen- und Stahlbleche behandelt. Bei guter Reinigungswirkung wurde bei 15 °C keine störende Schaumentwicklung beobachtet.Iron and steel sheets were treated with an aqueous solution of this cleaner (pH 9.0). With a good cleaning effect, no disruptive foaming was observed at 15 ° C.

Vergleichsbeispiel 2Comparative Example 2

Figure imgb0004
Figure imgb0004

Im Vergleich zu Beispiel 3 wurde ein Polyethylenglykolether (Ia) gemäß DE-A-33 15 951 getestet. Bei einer Temperatur von 15 °C war die Lösung nicht spritzfähig. Anwendungstechnisch spritzfähig war dieses System erst bei Temperaturen > 30 °C.In comparison to Example 3, a polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. The solution was not sprayable at a temperature of 15 ° C. In terms of application technology, this system was only sprayable at temperatures> 30 ° C.

Beispiel 4Example 4

Figure imgb0005
Figure imgb0005

Mit einer wäßrigen Lösung dieses Reinigers (pH 9,0) wurden Eisen- und Stahlbleche bei 15 °C behandelt. Bei guter Reinigungswirkung trat keine störende Schaumentwicklung auf.Iron and steel sheets were treated at 15 ° C. with an aqueous solution of this cleaner (pH 9.0). With a good cleaning effect, no disruptive foam development occurred.

Vergleichsbeispiel 3Comparative Example 3

Figure imgb0006
Figure imgb0006

Im Vergleich zu Beispiel 4 wurde ein längerkettiger Polyethylenglykolether (Ia) gemäß DE-A-33 15 951 getestet. Anwendungstechnisch spritzfähig war dieses System erst bei Temperaturen > 40 °C.In comparison to Example 4, a longer-chain polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. In terms of application technology, this system was only sprayable at temperatures> 40 ° C.

Beispiel 5 (saurer Reiniger) Example 5 (acidic cleaner)

Figure imgb0007
Figure imgb0007

Mit einer wäßrigen Lösung dieses Reinigers (pH 3,5) wurden Eisenbleche bei 15 °C behandelt. Bei guter Reinigungswirkung wurde keine störende Schaumentwicklung beobachtet.Iron sheets were treated at 15 ° C. with an aqueous solution of this cleaner (pH 3.5). With a good cleaning effect, no disruptive foaming was observed.

Vergleichsbeispiel 4Comparative Example 4

Figure imgb0008
Figure imgb0008

Im Vergleich zu Beispiel 5 wurde ein längerkettiger Polyethylenglykolether (Ia) gemäß DE-A-33 15 951 getestet. Bei einer Temperatur von 15 °C schäumte die Anlage über; anwendungstechnisch spritzfähig war dieses System erst bei Temperaturen > 30 °C.In comparison to Example 5, a longer-chain polyethylene glycol ether (Ia) according to DE-A-33 15 951 was tested. The system over-foamed at a temperature of 15 ° C; In terms of application technology, this system was only sprayable at temperatures> 30 ° C.

Claims (2)

  1. The use of polyethylene glycol ethers corresponding to the following formula



            R¹-O-(CH₂CH₂O)n-R²   (I)



    in which
    R¹ is octyl and/or decyl, R² is n-butyl and n = 3 or 4, as foam-inhibiting additives for low-foam detergents.
  2. The use of polyethylene glycol ethers as claimed in claim 1, characterized in that the terminated polyethylene glycol ethers are used in such quantities that their concentration in the in-use solutions is between 10 and 2500 ppm and preferably between 50 and 500 ppm.
EP88112874A 1987-08-17 1988-08-08 Foam depressing additives in cleaning agents producing little foam Expired - Lifetime EP0303928B1 (en)

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AT88112874T ATE68820T1 (en) 1987-08-17 1988-08-08 FOAM SUPPRESSING ADDITIVES IN LOW FOAM CLEANERS.

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DE19873727378 DE3727378A1 (en) 1987-08-17 1987-08-17 FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS
DE3727378 1987-08-17

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EP0303928B1 true EP0303928B1 (en) 1991-10-23

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DE19920559A1 (en) * 1999-05-05 2000-11-16 Cognis Deutschland Gmbh Process for the preparation of alkyl-terminated alkyl and / or alkenyl ethers
WO2011071492A1 (en) 2009-12-09 2011-06-16 Dow Global Technologies Llc Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof

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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
DE3823454A1 (en) * 1988-07-11 1990-01-25 Henkel Kgaa MERCERIZING AND / OR LYING AGENT
DE3928604A1 (en) * 1989-08-30 1991-03-07 Henkel Kgaa USE OF SELECTED MIXTURES OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM DETERGENTS
DE3928603A1 (en) * 1989-08-30 1991-03-07 Henkel Kgaa ANTI-FOAM AGENTS FOR COMMERCIAL CLEANING, ESPECIALLY FOR BOTTLE AND CIP CLEANING
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
EP0420802B1 (en) * 1989-09-26 1995-08-09 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
DE3935374A1 (en) * 1989-10-24 1991-04-25 Henkel Kgaa ALKYLPOLYETHYLENGLYKOLETHER AS FOAM-PRESSING ADDITIVES FOR CLEANERS
GB2238530A (en) * 1989-10-31 1991-06-05 Grace W R & Co Antifoaming and defoaming compositions
DE4243643C1 (en) * 1992-12-22 1993-08-26 Henkel Kgaa, 4000 Duesseldorf, De
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DE4324396A1 (en) * 1993-07-21 1995-01-26 Henkel Kgaa Detergents with high wettability
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DE4439086C2 (en) * 1994-11-02 1997-11-27 Henkel Kgaa Process for the preparation of end-capped nonionic surfactants
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
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DE19940797A1 (en) 1999-08-27 2001-03-01 Goldschmidt Ag Th Obtained by Akoxylierung block copolymers, styrene oxide-containing polyalkylene oxides and their use
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ATE68519T1 (en) * 1986-07-24 1991-11-15 Henkel Kgaa LOW-FOAMING AND/OR ANTI-FOAMING SURFACTANT MIXTURES AND THEIR USE.
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DE19920559A1 (en) * 1999-05-05 2000-11-16 Cognis Deutschland Gmbh Process for the preparation of alkyl-terminated alkyl and / or alkenyl ethers
WO2011071492A1 (en) 2009-12-09 2011-06-16 Dow Global Technologies Llc Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof

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NO883651D0 (en) 1988-08-16
FI883797A (en) 1989-02-18
DE3727378A1 (en) 1989-03-02
GR3002987T3 (en) 1993-01-25
AU597510B2 (en) 1990-05-31
ES2026610T3 (en) 1992-05-01
ATE68820T1 (en) 1991-11-15
ZA886062B (en) 1989-04-26
AU2106888A (en) 1989-02-23
CA1304271C (en) 1992-06-30
US4973423A (en) 1990-11-27
JPS6469696A (en) 1989-03-15
DK456388D0 (en) 1988-08-15
BR8804128A (en) 1989-03-07
NO172062C (en) 1993-06-02
DK456388A (en) 1989-02-18

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