EP0126967A1 - Use of polyglycol ethers as foam depressing additives in low-foaming cleansing agents - Google Patents

Use of polyglycol ethers as foam depressing additives in low-foaming cleansing agents Download PDF

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Publication number
EP0126967A1
EP0126967A1 EP84104557A EP84104557A EP0126967A1 EP 0126967 A1 EP0126967 A1 EP 0126967A1 EP 84104557 A EP84104557 A EP 84104557A EP 84104557 A EP84104557 A EP 84104557A EP 0126967 A1 EP0126967 A1 EP 0126967A1
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EP
European Patent Office
Prior art keywords
foam
weight
cleaning
low
polyglycol ethers
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP84104557A
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German (de)
French (fr)
Inventor
Karl Dr. Schmid
Horst Dr. Baumann
Jürgen Dr. Geke
Hans-Günther Dr. Germscheid
Werner Lüdecke
Robert Dr. Piorr
Christian Rossmann
Rolf Scharf
Hans-Joachim Dr. Schlüssler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0126967A1 publication Critical patent/EP0126967A1/en
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    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • 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

Definitions

  • the invention relates to the use of end-capped polyglycerol 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, as a rule 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.
  • these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents.
  • the compounds of this class are not sufficiently biodegradable to meet the applicable legal regulations (RVO on the Detergent Act).
  • the present invention was therefore based on the object of finding foam-suppressing substances whose application properties are at least equivalent to those of the known prior art and which moreover have improved biodegradability.
  • the solution to this problem is based on the knowledge that certain end group-capped addition products of ethylene oxide with polyglycerols, which are defined below, are able to meet the requirements, both with regard to the usability in terms of application technology and with regard to the improved biodegradability .
  • the invention relates to the use of polyethylene glycol ethers as can be obtained by adding 4 to 20 parts by weight of ethylene oxide to 1 part by weight of polyglycerol with a hydroxyl number in the range from 900 to 1200 and subsequent etherification of the free hydroxyl groups with straight-chain or branched alkyl halides with 4 to 8 carbon atoms , as a foam-suppressing additive for low-foam cleaning agents.
  • the polyglycerols to be used as starting material for the production of the polyglycol ethers to be used according to the invention are obtained as distillation residues in the industrial production of the glycerol. These are mixtures of higher molecular weight condensation products of glycerol, preferably those with 2 to 10 glycerol residues in the molecule. This P olyglycerine are characterized by their hydroxyl number, which is usually between 900 and 1200.
  • Corresponding polyglycerols can of course also be obtained synthetically, for example by heating glycerol to 220 to 240 ° C. in the presence of caustic alkali, preferably in a protective gas atmosphere, and distilling off the water formed during the condensation.
  • the polyglycerols described above are advantageously reacted with ethylene oxide in a weight ratio of 1: 4 to 1:20 and the etherification of the hydroxyl groups present in the reaction product obtained is then etherified.
  • 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 preferred under the known conditions Williamson's ether synthesis is carried out with straight-chain or branched C 4 -C 8 -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 can be expedient to use alkyl halide and alkali in a stoichiometric excess, for example from 100 to 200%, over the hydroxyl groups to be etherified. However, the etherification of the free hydroxyl groups can also be carried out in analogy to DE-PS 868 147 by reaction with isoolefins, for example isobutylene, in the presence of an acidic catalyst.
  • the end group-capped polyglycol ethers to be used according to the invention are notable for their alkali and acid stability. Their foam-preventing effect in alkaline to weakly acidic cleaning flottan is at least as good as that of comparable known foam inhibitors.
  • the cleaning agents in which the end groups of closed polyglycol ethers are used according to the invention can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and, if appropriate, also antimicrobial active substances 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 alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acid sulfonic acids and alkylbenzenesulfonic acid and alkylbenzenesulfonic acids
  • 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 alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acid sulfonic acids and alkylbenzen
  • the cleaning agents can, in particular, alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates as well as citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane acids, amine-1,1-diphosphonic acids methylenephosphonic acid) and ethylenediaminetetra- (methylenephosphonic acid), phosphonoalkane polycarboxylic acids such as Contain phosphonobutane tricarboxylic acid and alkali metal salts of these acids.
  • Ilochalkalic 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 alkylolamines.
  • cleaning agents are once understood to mean the aqueous solutions intended for direct application to the substrates to be cleaned.
  • 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 polyglycol ethers to be used according to the invention are added to the cleaning agents in such amounts that their concentration in the ready-to-use solutions is 10 to 2500 ppm, preferably 50 to 500 ppm.
  • test solutions which contained 1% by weight sodium hydroxide and 0.03% by weight (300 ppm) defoamer.
  • test solutions which contained 1% by weight sodium hydroxide and 0.03% by weight (300 ppm) defoamer.
  • increasing amounts of triethanolamine tetrapropylene benzene sulfonate were added to these solutions as test foams in increments of 100 ppm each.
  • Substances A to H were used as defoamers and as reference substances
  • a stable, stable mixture of active substances of the following composition was obtained by mechanical mixing of the components:
  • Beer bottles were cleaned at 85 ° C in a bottle cleaning system with three lye zones and an hourly output of 80,000 bottles.
  • the beer bottles were labeled with paper labels using casein glue, which would otherwise cause excessive foaming in the immersion baths. If 1.5% by weight sodium hydroxide solution containing 0.15% by weight of the active ingredient mixture described above was used as the cleaning solution, the system could be operated without disruptive foaming.
  • the inserted bottles were cleaned perfectly.
  • a stable detergent concentrate of the following composition was produced by dissolving the components in phosphoric acid:
  • a mechanical degreasing agent for metallic materials with the following composition was produced by mechanical mixing of the components: The foam formation and foam disintegration of a 4 percent by weight solution of this immersion degreasing agent was tested according to DIN 53 902 at 60 ° C. in comparison to an agent without the addition of product G, but otherwise with the same composition. The results are shown in Table III.
  • a mechanical degreasing agent for metallic materials was produced by mechanical mixing of the components, which had the following composition:
  • a storage-stable concentrate for cleaning metal surfaces with the following composition was prepared by dissolving the components in water:

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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)
  • Detergent Compositions (AREA)

Abstract

Polyethylenglykolether, wie sie durch Anlagerung von 4 bis 20 Gewichtsteilen Ethylenoxid an 1 Gewichtsteil Polyglycerin mit einer Hydroxylzahl im Bereich von 900 bis 1200 und anschließende Veretherung der freien Hydroxylgruppen mit geradkettigen oder verzweigten Alkylhalogeniden mit 4 bis 8 Kohlenstoffatomen erhältlich sind, werden als schaumdrückende Zusatze für schaumarme Reinigungsmittel eingesetzt.Polyethylene glycol ethers, as can be obtained by adding 4 to 20 parts by weight of ethylene oxide to 1 part by weight of polyglycerol with a hydroxyl number in the range from 900 to 1200 and subsequent etherification of the free hydroxyl groups with straight-chain or branched alkyl halides with 4 to 8 carbon atoms, are used as low-foaming additives for low-foaming agents Detergent used.

Description

Die Erfindung betrifft die Verwendung von endgruppenverschlossenen Polyglycerinpolyethylenglykolethern als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln.The invention relates to the use of end-capped polyglycerol 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 aufgrund 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 nichtionische Tenside.Aqueous cleaning agents intended for use in trade and industry, in particular those for cleaning metal, glass, ceramic and plastic surfaces, as a rule 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.

Als schaumdrückende Zusätze werden seit langem Anlagerungsprodukte von Alkylenoxiden an organische Verbindungen, die - vorzugsweise mehrere - reaktive Wasserstoffatome im Molekül besitzen, mit gutem Erfolg eingesetzt. Hier haben sich insbesondere Anlagerungsprodukte von Propylenoxid an aliphatische Polyalkohole (siehe DE-PS 1 280 455 und DE-PS 1 621 592) und an aliphatische Polyamine (siehe DE-PS 1 289 597 und DE-PS 1 621 593) sowie Anlagerungsprodukte von Ethylenoxid und Propylenoxid an aliphatische Polyamine, insbesondere Ethylendiamin (siehe DE-PS 1 944 569), in der Praxis bewährt. Diese Alkylenoxidanlagerungsprodukte besitzen neben einer guten schaumdrückenden Wirkung auch die für die Anwendung in gewerblichen und industriellen Reinigungsmitteln zumeist erforderliche Alkalistabilität. Die Verbindungen dieser Klasse sind jedoch nicht hinreichend biologisch abbaubar, um den geltenden gesetzlichen Vorschriften (RVO zum Waschmittelgesetz) zu genügen.Additions of alkylene oxides to organic compounds which have — preferably several — reactive hydrogen atoms in the molecule have long been used successfully as foam-suppressing additives. In particular, adducts of propylene oxide with aliphatic polyalcohols (see DE-PS 1 280 455 and DE-PS 1 621 592) and with aliphatic polyamines (see DE-PS 1 289 597 and DE-PS 1 621 593) as well as adducts of ethylene oxide and propylene oxide on aliphatic polyamines, especially ethylenediamine (see DE-PS 1 944 569), proven in practice. In addition to a good foam-suppressing effect, these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents. However, the compounds of this class are not sufficiently biodegradable to meet the applicable legal regulations (RVO on the Detergent Act).

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, schaumdrückende Substanzen aufzufinden, deren anwendungstechnische Eigenschaften denen der Mittel des bekannten Standes der Technik zumindest gleichkommen und die darüber hinaus eine verbesserte biologische Abbaubarkeit besitzen. Die Lösung dieser Aufgabe geht von der Erkenntnis aus, daß bestimmte, im Folgenden definierte, endgruppenverschlossene Anlagerungsprodukte des Ethylenoxids an Polyglycerine in der Lage sind, die gestellten Anforderungen, sowohl im Hinblick auf die anwendungstechnische Brauchbarkeit als auch im Hinblick auf die verbesserte biologische Abbaubarkeit zu erfüllen.The present invention was therefore based on the object of finding foam-suppressing substances whose application properties are at least equivalent to those of the known prior art and which moreover have improved biodegradability. The solution to this problem is based on the knowledge that certain end group-capped addition products of ethylene oxide with polyglycerols, which are defined below, are able to meet the requirements, both with regard to the usability in terms of application technology and with regard to the improved biodegradability .

Gegenstand der Erfindung ist die Verwendung von Polyethylenglykolethern, wie sie durch Anlagerung von 4 bis 20 Gewichtsteilen Ethylenoxid an 1 Gewichtsteil Polyglycerin mit einer Hydroxylzahl im Bereich von 900 bis 1200 und anschließende Veretherung der freien Hydroxylgruppen mit geradkettigen oder verzweigten Alkylhalogeniden mit 4 bis 8 Kohlenstoffatomen erhältlich sind, als schaumdrückende Zusätze für schaumarme Reinigungsmittel.The invention relates to the use of polyethylene glycol ethers as can be obtained by adding 4 to 20 parts by weight of ethylene oxide to 1 part by weight of polyglycerol with a hydroxyl number in the range from 900 to 1200 and subsequent etherification of the free hydroxyl groups with straight-chain or branched alkyl halides with 4 to 8 carbon atoms , as a foam-suppressing additive for low-foam cleaning agents.

Die als Ausgangsmaterial für die Herstellung der erfindungsgemäß zu verwendenden Polyglykolether einzusetzenden Polyglycerine fallen bei der großtechnischen Herstellung des Glycerins als Destillationsrückstände an. Es handelt sich dabei um Gemische aus höhermolekularen Kondensationsprodukten des Glycerins, bevorzugt aus solchen mit 2 bis 10 Glycerinresten im Molekül. Diese Polyglycerine sind durch ihre Hydroxylzahl charakterisiert, die in der Regel zwischen 900 und 1200 liegt. Entsprechende Polyglycerine können natürlich auch auf synthetischem Weg erhalten werden, beispielsweise durch längeres Erhitzen von Glycerin auf 220 bis 240 °C in Gegenwart von Ätzalkali, vorzugsweise in Schutzgasatmosphäre, und Abdestillieren des bei der Kondensation gebildeten Wassers.The polyglycerols to be used as starting material for the production of the polyglycol ethers to be used according to the invention are obtained as distillation residues in the industrial production of the glycerol. These are mixtures of higher molecular weight condensation products of glycerol, preferably those with 2 to 10 glycerol residues in the molecule. This P olyglycerine are characterized by their hydroxyl number, which is usually between 900 and 1200. Corresponding polyglycerols can of course also be obtained synthetically, for example by heating glycerol to 220 to 240 ° C. in the presence of caustic alkali, preferably in a protective gas atmosphere, and distilling off the water formed during the condensation.

Zur Herstellung der erfindungsgemäß zu verwendenen Polyglycerinpolyglykolether setzt man zweckmäßigerweise die vorstehend beschriebenen Polyglycerine mit Ethylenoxid im Gewichtsverhältnis von 1 : 4 bis 1 : 20 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 Alkali im stöchiometrischen Überschuß, beispielsweise von 100 bis 200 %, über die zu verethernden Hydroxylgruppen einzusetzen. Die Veretherung der freien Hydroxylgruppen kann aber auch in Analogie zur DE-PS 868 147 durch Umsetzung mit Isoolefinen, beispielsweise Isobutylen, in Gegenwart eines sauren Katalysators erfolgen.To prepare the polyglycerol polyglycol ethers to be used according to the invention, the polyglycerols described above are advantageously reacted with ethylene oxide in a weight ratio of 1: 4 to 1:20 and the etherification of the hydroxyl groups present in the reaction product obtained is then etherified. 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 preferred under the known conditions Williamson's ether synthesis is carried out with straight-chain or branched C 4 -C 8 -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 can be expedient to use alkyl halide and alkali in a stoichiometric excess, for example from 100 to 200%, over the hydroxyl groups to be etherified. However, the etherification of the free hydroxyl groups can also be carried out in analogy to DE-PS 868 147 by reaction with isoolefins, for example isobutylene, in the presence of an acidic catalyst.

Die erfindungsgemäß zu verwendenden endgruppenverschlossenen Polyglykolether zeichnen sich durch ihre Alkali- und Säurestabilität aus. Ihre schaumverhindernde Wirkung in alkalischen bis schwach sauren Reinigungsflottan ist zumindest ebenso gut wie die von vergleichbaren bekannten Schauminhibitoren.The end group-capped polyglycol ethers to be used according to the invention are notable for their alkali and acid stability. Their foam-preventing effect in alkaline to weakly acidic cleaning flottan is at least as good as that of comparable known foam inhibitors.

Die Reinigungsmittel, in denen die Endgruppen verschlossenen Polyglykolether erfindungsgemäß zur Anwendung kommen, können die in solchen Mitteln üblichen Bestandteile, wie Netzmittel, Gerüstsubstanzen und Komplexbildner, Alkalien oder Säuren, Korrosionsinhibitoren und gegebenenfalls auch antimikrobielle Wirkstoffen und/oder organische Lösungsmittel enthalten. Als Netzmittel kommen nichtionogene oberflächenaktive Substanzen, wie Polyglykolether, die durch Anlagerung von Ethylenoxid an Alkohole, insbesondere Fettalkohole, Alkylphenole, Fettamine und Carbonsäureamide erhalten werden, und anionenaktivc Netzmittel, wie Alkalimetall-, Amin- und Alkylolaminsalze von Fettsäuren, Alkylschwefelsäuren, Alkylsulfonsäurfen und AlkylbenzolsulfonsäurenThe cleaning agents in which the end groups of closed polyglycol ethers are used according to the invention can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and, if appropriate, also antimicrobial active substances 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 alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acid sulfonic acids and alkylbenzenesulfonic acid and alkylbenzenesulfonic acids

in Betracht. An Gerüstsubstanzen und Komplexbildnern können die Reinigungsmittel vor allem Alkalimetallorthophosphate, -polymerphosphate, -silikate, -borate, -carbonate, -polyacrylate und -glukonate sowie Zitronensäure, Nitriloessigsäure, Ethylendiamintetraessigsäure, 1-Hydro- xyalkan-1,1-diphosphonsäuren, Aminotri-(methylenphosphon- säure)und Ethylendiamintetra-(methylenphosphonsäure), Phosphonoalkanpolycarbonsäuren wie z.B. Phosphonobutantricarbonsäure und Alkalimetallsalze dieser Säuren enthalten. ilochalkalische 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 Alkylolamine enthalten.into consideration. On builders and complexing agents, the cleaning agents can, in particular, alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates as well as citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane acids, amine-1,1-diphosphonic acids methylenephosphonic acid) and ethylenediaminetetra- (methylenephosphonic acid), phosphonoalkane polycarboxylic acids such as Contain phosphonobutane tricarboxylic acid and alkali metal salts of these acids. Ilochalkalic 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 alkylolamines.

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 understood to mean the aqueous solutions intended for direct application to the substrates to be cleaned. 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 Polyglykolether werden den Reinigungsmitteln in solchen Mengen zugesetzt, daß ihre Konzentration in den gebrauchsfertigen Lösungen 10 bis 2500 ppm, vorzugsweise 50 bis 500 ppm ausmacht.The end group-capped polyglycol ethers to be used according to the invention are added to the cleaning agents in such amounts that their concentration in the ready-to-use solutions is 10 to 2500 ppm, preferably 50 to 500 ppm.

BeispieleExamples Herstellung der endgruppenverschlossenen PolyglycerinpolyethylenglykoletherProduction of the end-capped polyglycerol polyethylene glycol ether

In einem Hubrührautoklaven wurden 137 g Polyglycerin (Hydroxylzahl 961) in Gegenwart von 3 g Natriummethylat mit 1176 g Ethylenoxid (Gewichtsverhältnis 1 : 8,6) bei 180 °C und 10 bar umgesetzt. Es wurden 1313 g Polyglycerinethylenglykolether mit einer Hydroxylzahl von 113 erhalten.137 g of polyglycerol (hydroxyl number 961) in the presence of 3 g of sodium methylate were reacted with 1176 g of ethylene oxide (weight ratio 1: 8.6) at 180 ° C. and 10 bar in a stirred autoclave. 1313 g of polyglycerol ethylene glycol ether with a hydroxyl number of 113 were obtained.

350 g des erhaltenen Produkts, 171 g n-Hexylchlorid und 228 g 75 gewichtsprozentige Natriumhydroxidlösung wurden 4 Stunden lang bei 120 C gerührt. Aus dem abgekühlten Reaktionsgemisch wurde die wässrige Phase abgetrennt. Die organische Phase wurde so lange mit Wasser von 50 °C gewaschen, bis die Waschflüssigkeit neutral reagierte. Nicht umgesetztes Hexylchlorid und Wasser wurden aus dem Reaktionsgemisch durch Erhitzen auf 150 °C im Wasserstrahlvakuum entfernt. Es wurden 281,5 g Polyglycerinpolyethylenglykolhexylether (1 GT Polyglycerin + 8,6 GT EO + Butyl) erhalten. Die Hydroxylzahl des Produktes betrug 3,5.350 g of the product obtained, 171 g of n-hexyl chloride and 228 g of 75% by weight sodium hydroxide solution were stirred at 120 ° C. for 4 hours. The aqueous phase was separated off from the cooled reaction mixture. The organic phase was washed with water at 50 ° C. until the washing liquid reacted neutral. Unreacted hexyl chloride and water were removed from the reaction mixture by heating to 150 ° C. in a water jet vacuum. 281.5 g of polyglycerol polyethylene glycol hexyl ether (1 pbw of polyglycerol + 8.6 pbw of EO + butyl) were obtained. The hydroxyl number of the product was 3.5.

In analoger Weise wurden weitere endgruppenverschlossene Polyglycerinpolyethylenglykolether hergestellt. Diese Substanzen und das vorstehend beschriebene Produkt sind in der Tabelle I zusammen mit ihren Trübungspunkten in Wasser oder 1 gewichtsprozentiger NaOH-Lösung wiederge- geben.

Figure imgb0001
In an analogous manner, further end group-capped polyglycerol polyethylene glycol ethers were produced. These substances and the product is described above along with their cloud points in water or 1 weight percent in Table I NaOH solution wiederge - enter.
Figure imgb0001

Beispiel 1example 1

Die Prüfung der Antischaumwirkung erfolgte mit Testlösungen, die 1 Gewichtsprozent Natriumhydroxid und 0,03 Gewichtsprozent (300 ppm) Entschäumer enthielten. Diesen Lösungen wurden im Verlauf der Tests in Sprüngen von jeweils 100 ppm steigende Mengen von Triethanolamintetrapropylenbenzolsulfonat als Testschäumer zugesetzt. Als Entschäumer wurden die Substanzen A bis H und als VergleichssubstanzThe antifoam effect was tested using test solutions which contained 1% by weight sodium hydroxide and 0.03% by weight (300 ppm) defoamer. In the course of the tests, increasing amounts of triethanolamine tetrapropylene benzene sulfonate were added to these solutions as test foams in increments of 100 ppm each. Substances A to H were used as defoamers and as reference substances

I) Ethylendiamin + 30 EO + 60 POI) ethylenediamine + 30 EO + 60 PO

(PO = Propylenoxid) geprüft.(PO = propylene oxide) tested.

Jeweils 200 ml der Testlösungen wurden bei 65 °C in der Schaumschlagapparatur nach DIN 53 902 geprüft. Das Schaumvolumen in ml wurde jeweils 5 Sekunden nach einer Serie von 100 Schlägen in 100 Sekunden abgelesen. Für jede Testschäumerkonzentration wurde ein Durchschnittswert aus 5 Einzelmessungen ermittelt. Aus den erhaltenen Ergebnissen ist in der zweiten Spalte der nachstehenden Tabelle II jeweils das Schaumvolumen angegeben, das bei einer Testschäumerkonzentration von 1200 ppm beobachtet wurde. Als zweiter repräsentativer Meßwert ist in der dritten Spalte der Tabelle II die Testschäumerkonzentration angegeben, bei der zum ersten Mal ein Schaumvolumen über 200 ml gemssen wurde.200 ml portions of the test solutions were tested at 65 ° C in the foam whipping apparatus according to DIN 53 902. The foam volume in ml was read 5 seconds after a series of 100 beats in 100 seconds. An average value of 5 individual measurements was determined for each test foam concentration. From the results obtained in the second column of Table II below is indicated in each case the volume of foam which was observed in a Testschäumerkonzentration ppm of 12 00th As the second representative measurement value in the third column of the table indicates the T estschäumerkonzentration II, a foam volume was about 200 ml gemssen in for the first time.

Figure imgb0002
Figure imgb0002

Beispiel 2Example 2

Durch mechanisches Vermischen der Komponenten wurde ein lagerbeständiges festes Flaschenreinigungsmittel folgender Zusammensetzung (GT = Gewichtsteile) hergestellt:

Figure imgb0003
A storage-stable, solid bottle cleaning agent of the following composition (GT = parts by weight) was produced by mechanical mixing of the components:
Figure imgb0003

Mit einer 1 gewichtsprozentigen Lösung dieses Reinigungsmittels wurden Milchflaschen bei 30 °C in einer handels-üblichen Flaschenreinigungsanlage mit zwei Laugenzonen und einer Stundenleistung von 18000 Flaschen gereinigt. Bei guter Reinigungswirkung wurde keine störende Schaumentwicklung beobachtet.With a 1 weight percent solution of this detergent M were ilchflaschen at 30 ° C in a commercially-available bottle cleaning system with two liquor zones and an hourly capacity of 18,000 bottles cleaned. With a good cleaning effect, no disruptive foaming was observed.

Beispiel 3Example 3

Durch mechanisches Vermischen der Komponenten wurde ein lagerbeständiges festes Wirkstoffgemisch folgender Zusammensetzung erhalten:

Figure imgb0004
A stable, stable mixture of active substances of the following composition was obtained by mechanical mixing of the components:
Figure imgb0004

In einer Flaschenreinigungsanlage mit drei Laugenzonen und einer Stundenleistung von 80 000 Flaschen wurden bei 85 °C Bierflaschen gereinigt. Die Bierflaschen waren mit Papieretiketten unter Verwendung eines Kaseinleims etikettiert, der sonst zu starkem Schäumen in den Tauchbädern führt. Wurde als Reinigungslösung 1,5 gewichtsprozentige Natronlauge eingesetzt, die 0,15 Gewichtsprozent des oben beschriebenen Wirkstoffgemisches enthielt, so konnte die Anlage ohne störende Schaumentwicklung betrieben werden.Beer bottles were cleaned at 85 ° C in a bottle cleaning system with three lye zones and an hourly output of 80,000 bottles. The beer bottles were labeled with paper labels using casein glue, which would otherwise cause excessive foaming in the immersion baths. If 1.5% by weight sodium hydroxide solution containing 0.15% by weight of the active ingredient mixture described above was used as the cleaning solution, the system could be operated without disruptive foaming.

Beispiel 4Example 4

Durch mechanisches Vermischen der Komponenten wurde ein lagerbeständiges Wirkstoffgemisch folgender Zusammensetzung erhalten:

Figure imgb0005
Mechanical storage of the active ingredient mixture of the following composition was obtained by mechanical mixing of the components:
Figure imgb0005

In einer handelsüblichen Flaschenreinigungsanlage mit zwei Laugenzonen und einer Stundenleistung von 24 000 Flaschen wurden Weinflaschen bei 65 C gereinigt. Als Reinigungslösung wurde 1,5 gewichtsprozentige Natronlauge verwendet, der 0,5 Gewichtsprozent des oben beschriebenen Wirkstoffgemischs zugesetzt worden waren. Die Reinigung verlief ohne störende Schaumentwicklung.Wine bottles were cleaned at 65 C in a commercially available bottle cleaning system with two lye zones and an hourly output of 24,000 bottles. 1.5% by weight sodium hydroxide solution, to which 0.5% by weight of the active substance mixture described above had been added, was used as the cleaning solution. The cleaning was done without disturbing foam development.

Die durchgesetzten Flaschen waren einwandfrei gereinigt.The inserted bottles were cleaned perfectly.

Beispiel 5Example 5

Durch Auflösen der Komponenten in Phosphorsäure wurde ein stabiles Reinigungsmittelkonzentrat der folgenden Zusammensetzung hergestellt:

Figure imgb0006
A stable detergent concentrate of the following composition was produced by dissolving the components in phosphoric acid:
Figure imgb0006

In einer Flaschenreinigungsanlage mit drei Laugebädern und einer Stundenleistung von 120 000 Flaschen wurden Mineralwasserflaschen bei 80 °C gereinigt. Als Reinigungslösung diente eine 2 gewichtsprozentige Natronlauge, der 1 Gewichtsprozent des oben beschriebenen Konzentrats zugesetzt worden war. Die Reinigung verlief ohne störende Schaumentwicklung. Die durchgesetzten Flaschen waren einwandfrei gereinigt.In a bottle cleaning installation with three liquor baths and an hourly capacity of 120 M 000 bottles were ineralwasserflaschen cleaned at 80 ° C. A 2% by weight sodium hydroxide solution, to which 1% by weight of the concentrate described above had been added, served as the cleaning solution. The cleaning was done without disturbing foam development. The inserted bottles were cleaned perfectly.

Beispiel 6Example 6

Durch mechanisches Vermischen der Komponenten wurde ein Tauchentfettungsmittel für metallische Werkstoffe folgender Zusammensetzung hergestellt:

Figure imgb0007
Die Schaumbildung und der Schaumzerfall einer 4 gewichtsprozentigen Lösung dieses Tauchentfettungsmittels wurde nach DIN 53 902 bei 60 °C im Vergleich zu einem Mittel ohne Zusatz von Produkt G jedoch sonst gleicher Zusammensetzung geprüft. Die Ergebnisse sind in der Tabelle III wiedergegeben.
Figure imgb0008
 A mechanical degreasing agent for metallic materials with the following composition was produced by mechanical mixing of the components:
Figure imgb0007
 The foam formation and foam disintegration of a 4 percent by weight solution of this immersion degreasing agent was tested according to DIN 53 902 at 60 ° C. in comparison to an agent without the addition of product G, but otherwise with the same composition. The results are shown in Table III.
Figure imgb0008

Beispiel 7Example 7

Durch mechanisches Vermischen der Komponenten wurde ein Tauchentfettungsmittel für metallische Werkstoffe hergestellt, das folgende Zusammensetzung hatte:

Figure imgb0009
A mechanical degreasing agent for metallic materials was produced by mechanical mixing of the components, which had the following composition:
Figure imgb0009

Mit einer 4 gewichtsprozentigen Lösung dieses Reinigungs- mittels wurden fettverschmutzte Formteile aus Stahl bei 60 °C im Tauchverfahren gereinigt. Die Entfettungswirkung war sehr gut; es wurde keine störende Schaumentwicklung beobachtet.With a 4 weight percent solution of this R unification means of fat soiled molded parts made of steel at 60 ° C have been cleaned in an immersion process. The degreasing effect was very good; no disruptive foaming was observed.

Beispiel 8Example 8

Durch Auflösen der Komponenten in Wasser wurde ein lagerstabiles Konzentrat für die Reinigung von Metalloberflächen mit folgender Zusammensetzung hergestellt:

Figure imgb0010
A storage-stable concentrate for cleaning metal surfaces with the following composition was prepared by dissolving the components in water:
Figure imgb0010

Mit einer 1,5 gewichtsprozentigen Lösung des Reinigungsmittels (pH-Wert 8,5) wurden Stahloberflächen bei 20 - 40 °C im Spritzverfahren gereinigt. Bei guter Reinigungswirkung trat keine störende Schaumentwicklung auf.With a 1.5 percent by weight solution of the cleaning agent (pH 8.5) steel surfaces were cleaned at 2 0 - 4 0 ° C by spraying. With a good cleaning effect, no disruptive foam development occurred.

Beispiel 9Example 9

Durch Auflösen der Komponenten in Wasser wurde ein lagerstabiles Konzentrat für die Reinigung von Metalloberflächen mit folgender Zusammensetzung erhalten:

Figure imgb0011
By dissolving the components in water, a storage-stable concentrate for cleaning metal surfaces with the following composition was obtained:
Figure imgb0011

Eine 1 gewichtsprozentige Lösung dieses Reinigungsmittels wurde bei 50 - 55 °C zur Spritzreinigung von Graugußteilen eingesetzt. Bei guter Reinigungswirkung wurde keine störende Schaumentwicklung beobachtet.A 1% by weight solution of this cleaning agent was used at 50 - 55 ° C for spray cleaning gray cast iron parts. With a good cleaning effect, no disruptive foaming was observed.

Claims (2)

1. Verwendung von Polyethylenglykolethern, wie sie durch Anlagerung von 4 bis 20 Gewichtsteilen Ethylenoxid an 1 Gewichtsteil Polyglycerin mit einer Hydroxylzahl im Bereich von 900 bis 1200 und anschließende Veretherung der freien Hydroxylgruppen mit geradkettigen oder verzweigten Alkylhalogeniden mit 4 bis 8 Kohlenstoffatomen erhältlich sind, als schaumdrückende Zusätze für schaumarme Reinigungsmittel.1. Use of polyethylene glycol ethers, such as those obtainable by adding 4 to 20 parts by weight of ethylene oxide to 1 part by weight of polyglycerol with a hydroxyl number in the range from 900 to 1200 and subsequent etherification of the free hydroxyl groups with straight-chain or branched alkyl halides with 4 to 8 carbon atoms, as foam-suppressing agents Additives for low-foaming cleaning agents. 2. Verwendung von Polyethylenglykolethern nach Anspruch 1, dadurch gekennzeichnet, daß die endgruppenverschlossenen Polyglykolether in solchen Mengen eingesetzt werden, daß ihre Konzentration in den gebrauchsfertigen Lösungen 10 bis 2500 ppm, vorzugsweise 50 bis 500 ppm ausmacht.2. Use of polyethylene glycol ethers according to claim 1, characterized in that the end-capped polyglycol ethers are used in such amounts that their concentration in the ready-to-use solutions is 10 to 2500 ppm, preferably 50 to 500 ppm.
EP84104557A 1983-05-02 1984-04-21 Use of polyglycol ethers as foam depressing additives in low-foaming cleansing agents Withdrawn EP0126967A1 (en)

Applications Claiming Priority (2)

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DE19833315952 DE3315952A1 (en) 1983-05-02 1983-05-02 USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS

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EP0264826A3 (en) * 1986-10-23 1989-03-15 Henkel Kommanditgesellschaft Auf Aktien Fatty acid esters of polyglycerinpolyglycol ethers, their production and their use

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US4522740A (en) 1985-06-11
BR8402024A (en) 1984-12-11
DK94684A (en) 1984-11-03
ZA843243B (en) 1984-12-24
ES8505715A1 (en) 1985-06-01
JPS59207996A (en) 1984-11-26

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