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EP0303928A1 - 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
EP0303928A1
EP0303928A1 EP88112874A EP88112874A EP0303928A1 EP 0303928 A1 EP0303928 A1 EP 0303928A1 EP 88112874 A EP88112874 A EP 88112874A EP 88112874 A EP88112874 A EP 88112874A EP 0303928 A1 EP0303928 A1 EP 0303928A1
Authority
EP
European Patent Office
Prior art keywords
foam
polyethylene glycol
glycol ethers
cleaning agents
formula
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.)
Granted
Application number
EP88112874A
Other languages
German (de)
French (fr)
Other versions
EP0303928B1 (en
Inventor
Jürgen Dr. Geke
Erich Boebers
Gilbert Dr. Schenker
Robert Dr. Piorr
Karl-Heinz Dr. Schmid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT88112874T priority Critical patent/ATE68820T1/en
Publication of EP0303928A1 publication Critical patent/EP0303928A1/en
Application granted granted Critical
Publication of EP0303928B1 publication Critical patent/EP0303928B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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.
  • DE-OS 33 15 951 describes the use of polyethylene glycol ethers of the general formula (Ia) R1-O- (CH2CH2O) n -R2 (Ia) in the R1 is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 C atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 12 mean as foam-suppressing additives in cleaning agents.
  • these compounds show no anti-foaming action below 20 to 25 ° C. Foam inhibition at low temperatures is, however, desirable.
  • 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.degree.
  • the invention therefore relates to the use of polyethylene glycol ethers of the formula I, R1 - O - (CH2CH2O) n - R2 (I) in the R1 is a straight-chain or branched alkyl radical or alkenyl radical having 6 to 18 carbon atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 2 to 6 mean as foam-suppressing additives for low-foam cleaning agents.
  • polyethylene glycol ethers of the formula I are used in which n is 3 or 4. Particular preference is given to the use of compounds of the formula I in which R2 is n-butyl and R1 is octyl and / or decyl.
  • the fatty alcohols n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n -Heptadecanol, n-octadecanol, n-octadec-9-en-1-ol (oleyl alcohol) 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 with an even number of carbon atoms are preferred.
  • alkyl polyethylene glycol ethers to be used according to the invention, it is more expedient to use as one or more of the above-described fatty alcohols with ethylene oxide in a molar ratio of 1: 2 to 1: 6 um 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 or branched C4-C8 alkyl halides, for example with n-butyl iodide, sec-butyl bromide, tert-butyl chloride, amyl chloride, tert-amyl bromide, n- Hexyl chloride, n-heptyl bromide and n-octyl chloride. It may be expedient here 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. 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.
  • cleaning agents are once the aqueous solutions intended for direct application to the substrates to be cleaned Roger that.
  • cleaning agent also includes the concentrates and solid mixtures intended for the production 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 respective application temperatures 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 according to DE-OS 33 15 951, in which R1 is C8 ⁇ 18-n-alkyl, R2 is a C4-alkyl and n is 10.
  • Table 1 Surfactant Composition (I) E.g. sprayable R1 R2 n A C8 ⁇ 10H17 ⁇ 21 C4H9 4th 1,3,5 ⁇ 15 ° C B C8 ⁇ 10H17 ⁇ 21 C4H9 3rd 2.4 ⁇ 15 ° C C. C12 ⁇ 18H25 ⁇ 37 C4H9 10th See 1,3,4 > 35-40 ° C D C8H17 C4H9 10th See 2 > 30 ° C
  • 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-OS 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) was tested in accordance with DE-OS 33 15 951. 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 a longer-chain polyethylene glycol ether (Ia) was tested in accordance with DE-OS 33 15 951.
  • 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 & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (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)
  • Cosmetics (AREA)
  • Degasification And Air Bubble Elimination (AREA)

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-OS 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-OS 33 15 951 describes the use of polyethylene glycol ethers of the general formula (Ia)

R¹-O- (CH₂CH₂O) n -R² (Ia)

in the
R¹ is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 C atoms,
R² is an alkyl radical with 4 to 8 carbon atoms and
n is 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-OS 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 polyethylene glycol ethers of DE-OS 33 15 951, shorter-chain polyethylene glycol ethers have an excellent antifoam action even at temperatures of less than 20 to 25.degree.

Die Erfindung betrifft daher die Verwendung von Poly­ethylenglykolethern der Formel I,

R¹ - O - (CH₂CH₂O)n - R²      (I)

in der
R¹ einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 6 bis 18 Kohlenstoffatomen,
R² einen Alkylrest mit 4 bis 8 Kohlenstoffatomen und
n eine Zahl von 2 bis 6
bedeuten, als schaumdrückende Zusätze für schaumarme Reinigungsmittel.The invention therefore relates to the use of polyethylene glycol ethers of the formula I,

R¹ - O - (CH₂CH₂O) n - R² (I)

in the
R¹ is a straight-chain or branched alkyl radical or alkenyl radical having 6 to 18 carbon atoms,
R² is an alkyl radical with 4 to 8 carbon atoms and
n is a number from 2 to 6
mean as foam-suppressing additives for low-foam cleaning agents.

In einer speziellen Ausführungsform der Erfindung wer­den Polyethylenglykolether der Formel I eingesetzt, in der n gleich 3 oder 4 ist. Besonders bevorzugt ist die Verwendung von Verbindungen der Formel I, in der R² gleich n-Butyl und R¹ gleich Octyl und/oder Decyl ist.In a special embodiment of the invention, polyethylene glycol ethers of the formula I are used in which n is 3 or 4. Particular preference is given to the use of compounds of the formula I in which R² is n-butyl and R¹ is octyl and / or decyl.

Als Ausgangsmaterial für die Herstellung der Polygly­kolether der Formel I können die Fettalkohole n-Oc­tanol, n-Nonanol, n-Decanol, n-Undecanol, n-Dodecanol, n-Tridecanol, n-Tetradecanol, n-Pentadecanol, n-Hexa­decanol, n-Heptadecanol, n-Octadecanol, n-Octadec-9-­en-1-ol (Oleylalkohol) 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 mit einer geraden Zahl von C-Atomen.As the starting material for the preparation of the polyglycol ethers of the formula I, the fatty alcohols n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n -Heptadecanol, n-octadecanol, n-octadec-9-en-1-ol (oleyl alcohol) 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 with an even number of carbon atoms are preferred.

Zur Herstellung der erfindungsgemäß zu verwendenden Alkylpolyethylenglykolether setzt man zweckmäßiger­ weise 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 oder verzweigten C₄-C₈-Alkylhalogeniden durchgeführt, beispielsweise mit n-Butyliodid, sec.-Butylbromid, tert.-Butylchlo­rid, Amylchlorid, tert.-Amylbromid, n-Hexylchlorid, n-Heptylbromid und n-Octylchlorid. Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkaliverbindung im stöchiometrischen Überschuß, beispielsweise von 100 bis 200 %, über die zu verethernden Hydroxylgruppen einzusetzen.To produce the alkyl polyethylene glycol ethers to be used according to the invention, it is more expedient to use as one or more of the above-described fatty alcohols with ethylene oxide in a molar ratio of 1: 2 to 1: 6 um 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 or branched C₄-C₈ alkyl halides, for example with n-butyl iodide, sec-butyl bromide, tert-butyl chloride, amyl chloride, tert-amyl bromide, n- Hexyl chloride, n-heptyl bromide and n-octyl chloride. It may be expedient here 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. 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, cleaning agents are once the aqueous solutions intended for direct application to the substrates to be cleaned Roger that. In addition, the term cleaning agent also includes the concentrates and solid mixtures intended for the production 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 respective application temperatures 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-OS 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 according to DE-OS 33 15 951, in which R¹ is C₈₋₁₈-n-alkyl, R² is a C₄-alkyl and n is 10.

Die im einzelnen eingesetzten Verbindungen sind der nachfolgenden Tabelle I zu entnehmen. Tabelle 1 Tensid Zusammensetzung (I) Bsp. spritzfähig R¹ R² n A C₈₋₁₀H₁₇₋₂₁ C₄H₉ 4 1,3,5 ≧ 15 °C B C₈₋₁₀H₁₇₋₂₁ C₄H₉ 3 2,4 ≧ 15 °C C C₁₂₋₁₈H₂₅₋₃₇ C₄H₉ 10 Vgl.1,3,4 >35-40 °C D C₈H₁₇ C₄H₉ 10 Vgl.2 > 30 °C The compounds used in detail can be found in Table I below. Table 1 Surfactant Composition (I) E.g. sprayable R¹ R² n A C₈₋₁₀H₁₇₋₂₁ C₄H₉ 4th 1,3,5 ≧ 15 ° C B C₈₋₁₀H₁₇₋₂₁ C₄H₉ 3rd 2.4 ≧ 15 ° C C. C₁₂₋₁₈H₂₅₋₃₇ C₄H₉ 10th See 1,3,4 > 35-40 ° C D C₈H₁₇ C₄H₉ 10th See 2 > 30 ° C

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-OS 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-OS 33 15 951 was tested. In terms of application technology, this surfactant solution was only sprayable at temperatures> 35 ° C.

Beispiel 3Example 3

Figure imgb0001
Figure imgb0001

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 imgb0002
Figure imgb0002

Im Vergleich zu Beispiel 3 wurde ein Polyethylengly­kolether (Ia) gemäß DE-OS 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-OS 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 imgb0003
Figure imgb0003

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 imgb0004
Figure imgb0004

Im Vergleich zu Beispiel 4 wurde ein längerkettiger Polyethylenglykolether (Ia) gemäß DE-OS 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) was tested in accordance with DE-OS 33 15 951. In terms of application technology, this system was only sprayable at temperatures> 40 ° C.

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

Figure imgb0005
Figure imgb0005

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 imgb0006
Figure imgb0006

Im Vergleich zu Beispiel 5 wurde ein längerkettiger Polyethylenglykolether (Ia) gemäß DE-OS 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) was tested in accordance with DE-OS 33 15 951. 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 (4)

1. Verwendung von Polyethylenglykolethern der Formel I

R¹ - O - (CH₂CH₂O)n - R²      (I)

in der
R¹ einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 6 bis 18 Kohlenstoffatomen,
R² einen Alkylrest mit 4 bis 8 Kohlenstoffatomen und
n eine Zahl von 2 bis 6 bedeuten,
als schaumdrückende Zusätze für schaumarme Reinigungs­mittel.1. Use of polyethylene glycol ethers of the formula I

R¹ - O - (CH₂CH₂O) n - R² (I)

in the
R¹ is a straight-chain or branched alkyl radical or alkenyl radical having 6 to 18 carbon atoms,
R² is an alkyl radical with 4 to 8 carbon atoms and
n is a number from 2 to 6,
as foam-suppressing additives for low-foam cleaning agents. 2. Verwendung von Polyethylenglykolethern nach An­spruch 1, dadurch gekennzeichnet, daß in der Formel I n gleich 3 oder 4 ist.2. Use of polyethylene glycol ethers according to claim 1, characterized in that in the formula I n is 3 or 4. 3. Verwendung von Polyethylenglykolethern nach An­spruch 1, dadurch gekennzeichnet, daß in der Formel I R² gleich n-Butyl und R¹ gleich Octyl und/oder Decyl ist.3. Use of polyethylene glycol ethers according to claim 1, characterized in that in the formula I R² is n-butyl and R¹ is octyl and / or decyl. 4. Verwendung von Polyethylenglykolethern nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die endgruppenverschlossenen Polyethylenglykolether in solchen Mengen eingesetzt werden, daß ihre Konzentra­tion in den gebrauchsfertigen Lösungen 10 bis 2500 ppm, vorzugsweise 50 bis 500 ppm ausmacht.4. Use of polyethylene glycol ethers according to claims 1 to 3, characterized in that the end group-capped polyethylene glycol ethers are used in such amounts that their concentration in the ready-to-use solutions makes up 10 to 2500 ppm, preferably 50 to 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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DE19873727378 DE3727378A1 (en) 1987-08-17 1987-08-17 FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS

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WO1991003537A1 (en) * 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Use of polyglycol ether mixtures as anti-foaming agents
WO1991003539A1 (en) * 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Anti-foaming agent for commercial cleaning applications
EP0420802A2 (en) * 1989-09-26 1991-04-03 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
US5013327A (en) * 1988-07-11 1991-05-07 Henkel Kommanditgesellschaft Auf Aktien Mercerizing and/or causticizing wetting agent: 2-ethyl-hexyl-sulfate and mixture of alkyl end-blocked polyethers
WO1991006620A1 (en) * 1989-10-24 1991-05-16 Henkel Kommanditgesellschaft Auf Aktien Alkyl polyethyleneglycol ethers as foam-inhibiting additives in cleaning agents
DE4439086A1 (en) * 1994-11-02 1996-05-09 Henkel Kgaa Process for the preparation of end-capped nonionic surfactants
DE19500842A1 (en) * 1995-01-13 1996-07-18 Henkel Kgaa Process for the preparation of end-capped nonionic surfactants
US5677273A (en) * 1992-12-22 1997-10-14 Schmid; Karl-Heinz Wetting agents for the pretreatment of textiles
US5707956A (en) * 1993-12-10 1998-01-13 Henkel Kommanditgesellschaft Auf Aktien Nonionic detergent mixtures based on specific mixed ethers
US5811594A (en) * 1994-09-01 1998-09-22 Henkel Kommanditgesellschaft Auf Aktien Methyl-end-capped alkyl and/or alkenyl polyglycol ethers
US5935920A (en) * 1993-07-21 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Cleaner with high wetting power
US6552091B1 (en) 1999-08-27 2003-04-22 Goldschmidt Ag Block-copolymeric polyalkylene oxides containing styrene oxide, obtained by alkoxylation, and their use

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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
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
GB2238530A (en) * 1989-10-31 1991-06-05 Grace W R & Co Antifoaming and defoaming compositions
DE4323252C2 (en) * 1993-07-12 1995-09-14 Henkel Kgaa Rinse aid for machine cleaning hard surfaces
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
DE19920559A1 (en) * 1999-05-05 2000-11-16 Cognis Deutschland Gmbh Process for the preparation of alkyl-terminated alkyl and / or alkenyl ethers
US7097715B1 (en) * 2000-10-11 2006-08-29 R. R. Street Co. Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
US6558432B2 (en) 1999-10-15 2003-05-06 R. R. Street & Co., Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
US6755871B2 (en) 1999-10-15 2004-06-29 R.R. Street & Co. Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
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US20050233915A1 (en) * 2004-04-15 2005-10-20 Ecolab Inc. Foaming soap, and methods
US20100317824A1 (en) * 2009-06-15 2010-12-16 Dow Global Technologies Inc. Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof
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Cited By (17)

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Publication number Priority date Publication date Assignee Title
US5013327A (en) * 1988-07-11 1991-05-07 Henkel Kommanditgesellschaft Auf Aktien Mercerizing and/or causticizing wetting agent: 2-ethyl-hexyl-sulfate and mixture of alkyl end-blocked polyethers
WO1991003537A1 (en) * 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Use of polyglycol ether mixtures as anti-foaming agents
WO1991003539A1 (en) * 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Anti-foaming agent for commercial cleaning applications
US5921910A (en) * 1989-08-30 1999-07-13 Henkel Kommanditgesellschaft Auf Aktien Polyglycol ether mixtures as foam inhibitors
EP0420802A2 (en) * 1989-09-26 1991-04-03 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
EP0420802A3 (en) * 1989-09-26 1991-05-15 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
WO1991006620A1 (en) * 1989-10-24 1991-05-16 Henkel Kommanditgesellschaft Auf Aktien Alkyl polyethyleneglycol ethers as foam-inhibiting additives in cleaning agents
TR25066A (en) * 1989-10-24 1992-11-01 Henkel Kgaa ALKILPOLIETILENGLIKOETER AS FOAM REMOVER ADDITIVES FOR CLEANING AGENTS.
US5677273A (en) * 1992-12-22 1997-10-14 Schmid; Karl-Heinz Wetting agents for the pretreatment of textiles
US5935920A (en) * 1993-07-21 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Cleaner with high wetting power
US5707956A (en) * 1993-12-10 1998-01-13 Henkel Kommanditgesellschaft Auf Aktien Nonionic detergent mixtures based on specific mixed ethers
US5811594A (en) * 1994-09-01 1998-09-22 Henkel Kommanditgesellschaft Auf Aktien Methyl-end-capped alkyl and/or alkenyl polyglycol ethers
US5847229A (en) * 1994-11-02 1998-12-08 Henkel Kommanditgesellschaft Auf Aktien Process for the production of end-capped nonionic surfactants
DE4439086A1 (en) * 1994-11-02 1996-05-09 Henkel Kgaa Process for the preparation of end-capped nonionic surfactants
DE19500842A1 (en) * 1995-01-13 1996-07-18 Henkel Kgaa Process for the preparation of end-capped nonionic surfactants
US6028229A (en) * 1995-01-13 2000-02-22 Henkel Kommanditgesellschaft Auf Aktien Process for producing end-group-locked non-ionic tensides
US6552091B1 (en) 1999-08-27 2003-04-22 Goldschmidt Ag Block-copolymeric polyalkylene oxides containing styrene oxide, obtained by alkoxylation, and their use

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