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EP0254208A2 - Low foaming and/or foam inhibiting mixtures of tensides and their use - Google Patents

Low foaming and/or foam inhibiting mixtures of tensides and their use Download PDF

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Publication number
EP0254208A2
EP0254208A2 EP87110283A EP87110283A EP0254208A2 EP 0254208 A2 EP0254208 A2 EP 0254208A2 EP 87110283 A EP87110283 A EP 87110283A EP 87110283 A EP87110283 A EP 87110283A EP 0254208 A2 EP0254208 A2 EP 0254208A2
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EP
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Prior art keywords
weight
iii
foam
general formula
chain
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
EP87110283A
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German (de)
French (fr)
Other versions
EP0254208B1 (en
EP0254208A3 (en
Inventor
Karl-Heinz Dr. Schmid
Adolf Asbeck
Detlev Stanislowski
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BASF Personal Care and Nutrition GmbH
Original Assignee
Henkel AG and Co KGaA
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Priority to AT87110283T priority Critical patent/ATE68519T1/en
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Publication of EP0254208A3 publication Critical patent/EP0254208A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • Aqueous cleaning agents for use in commerce and industry in particular those for cleaning metal, glass, ceramic and plastic surfaces, generally contain active ingredients which are able to counteract undesirable foam development.
  • the use of low-foam or foam-suppressing surfactant auxiliaries in particular is due in most cases to the fact that the contaminants detached from the substrates to be cleaned and accumulating in the cleaning baths act as foaming agents. This has a particular effect on high-speed cleaning machines, for example in machine bottle cleaning systems, or in applications in which the cleaning liquor is sprayed onto the surfaces to be cleaned under high pressure, for example in spray cleaning.
  • addition products of alkylene oxides to organic compounds which have — preferably several — reactive hydrogen atoms in the molecule have long been used as low-foaming or foam-suppressing additives with a surfactant effect.
  • addition products of propylene oxide onto aliphatic polyalcohols see DE-PS 12 80 45 5 and DE-PS 16 21 592
  • aliphatic polyamines see DE-PS 12 89 597 and DE-PS 16 21 -593
  • addition products of ethylene oxide and propylene oxide on aliphatic polyamines, especially ethylenediamine see DE-PS 19 44 569) proven in practice.
  • these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents.
  • the compounds in this class are not sufficiently biodegradable to meet the applicable legal regulations (RVO on the Detergent Act).
  • the present invention is based on the task of finding foam-suppressing or foam-suppressing auxiliaries with surfactant character, the application properties of which are at least equal to those of the prior art, but which also have the required biodegradability.
  • the invention intends to provide means of the type mentioned which can also be used effectively in the low temperature range below approximately 50 ° C., which has hitherto been difficult to master even with the best relevant auxiliaries.
  • DE-OS 33 15 951 describes end group-capped polyethylene glycol ethers which can be used with advantage in the fields of application described and which are also biodegradable. In practical use, however, it has been shown that these compounds from the cited published patent develop their best activity at temperatures of about 50 ° C., while improvements in the foam behavior in the temperature range below appear particularly desirable when cleaning processes are used which are derived from the Mechanics of the process measures used particularly favor foam formation.
  • surfactant mixtures described below are already effective in the temperature range from +10 ° C., but at the same time open up the possibility of safely mastering any foam problems that may arise.
  • Wetting agent mixtures of the type according to the invention and described below can thus, for example, overcome difficulties which arise when cold starting bottle cleaning systems.
  • the surfactant mixtures according to the invention can also advantageously be used as low-foaming wetting agents for high-pressure spray cleaners which can be cold sprayed.
  • the R 1 radical in the compounds of the general formula I denotes a straight-chain or branched alkyl radical or alkenyl radical having 12 to 18 C atoms
  • the preferred R 2 radical in these compounds of the general formula I denotes the butyl radical
  • the preferred meaning for the radical R 3 is a straight-chain or branched alkyl radical having 12 to 14 carbon atoms
  • the preferred chain length for the radical R 4 in the compounds of the general formula III is 16 to 18 carbon atoms lies.
  • the residues R 1 , R 3 and R 4 are residues of corresponding longer-chain alcohols, it being a further preferred embodiment of the invention that alcohol cuts, as are obtained in practice in the synthesis of such alcohols, are particularly suitable, at least then the predominant one Proportion of the individual components actually present in these alcohol cuts correspond to the specified C number ranges.
  • Corresponding synthetic alcohols, but in particular corresponding fatty alcohols or fatty alcohol mixtures are suitable, as are obtained in a known manner from the conversion of natural fats and / or oils.
  • a particularly suitable alcohol cut for the radical R 1 in the compounds of the general formula I can be so-called "LT coconut alcohol", which shows the following carbon chain length distribution - with consistently saturated hydrocarbon radicals
  • Alcohol cuts particularly suitable for the radical R 3 in the compounds of the general formula II are characterized by the so-called “LS coconut alcohol” with the following carbon chain length distribution - likewise consistently saturated hydrocarbon radicals:
  • n is a number from 3 to 7 means.
  • Corresponding fatty alcohols and / or oxo alcohols of the stated carbon number can be used individually or as a mixture as starting material for the preparation of these polyglycol ethers of the formula I. These alcohols are reacted with ethylene oxide in a molar ratio of from 1: 3 to 1: 7, and the hydroxyl groups present in the reaction product obtained are then etherified.
  • the reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline ones 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 C 4 to 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.
  • preference is given here to the corresponding C 4 -alkyl halides. 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.
  • the compounds of the general formulas 11 and III are likewise prepared in a manner known per se by reacting the starting alcohols or alcohol mixtures with ethylene oxide and propylene oxide (compounds of the general formula II) or with propylene oxide (compounds of the general formula III) under the known alkoxylation conditions .
  • the biodegradability of the surfactant mixtures according to the invention is over 80% BiAS decrease with BOD / COD values of greater than 60%.
  • the invention relates to the use of the low-foam or foam-suppressing surfactant mixtures described at the outset in the context of detergents which are to be used in particular for the aqueous-surfactant cleaning of hard surfaces.
  • the area of such cleaning processes is particularly affected here, in which increased foam loading is to be expected due to the mechanics used and / or the impurity to be removed, in particular here mechanical cleaning processes, such as spray cleaning or other washing or rinsing processes cleaning with high-pressure application, are suitable.
  • the wetting agent mixtures according to the invention are used in cleaning agents which are also intended for use at washing temperatures below 50 ° C., in particular in the range from approximately 10 to 50 ° C.
  • cleaning agent comprises on the one hand the ready-to-use aqueous solutions of the corresponding active ingredient components, but on the other hand also the concentrates and / or solid active ingredient mixtures intended for the preparation of the application solutions.
  • the general details of the prior art apply here in detail.
  • the ready-to-use solutions can be slightly acidic to strongly alkaline.
  • the surfactant mixtures 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.
  • the substance mixtures according to the invention are compared with the substance mixtures from the comparative examples. It shows that the substance mixtures according to the invention are almost always better Antifoam behavior show than the materials from the comparative examples.
  • a product can only be used in practice if it also has a satisfactory emulsifying power.
  • the surfactants or surfactant mixtures to be determined are emulsified in 1% by weight aqueous sodium hydroxide solution at room temperature in each case in an amount of 0.1 to 1% by weight of surfactant. Only products that do not frame here are suitable for practical use.
  • test foam A 1% by weight aqueous solution of the trlethanolamine salt of tetrapropylene benzosulfonate is used as the test foam. This is metered in at intervals of one minute in amounts of 1 ml each of the liquor in circulation. The resulting total volume of foam and liquid is determined. The longer the time it takes to reach the 2,000 ml mark in the measuring cylinder due to the total volume of the liquid and foam phases, the better the foam-inhibiting effect of the surfactant material used. In Examples 1 to 6 below, the respective corresponding numerical values for this point in time are given in minutes or in ml of test foamers. At the same time, the emulsifying power is assessed as previously described. In the evaluation, a distinction is made between the 3 evaluations: good, still satisfactory, inadequate.
  • a mechanical degreasing agent for metallic materials with the following composition was produced by mechanical mixing of the components:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • 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)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Low-foam or foam-depressing surfactant mixtures based on water-soluble and/or water-emulsifiable polyalkylene glycol ethers of relatively long-chain alcohols containing components I, II and, if desired, III in the quantities indicated: (I) from 20 to 80% by weight of polyethylene glycol ethers corresponding to the following general formula R1-O-(CH2CH2O)n-R2 (I) in which R1 is a straight-chain or branched C8-C18 alkyl or alkenyl radical, R2 is a C4-C8 alkyl radical and n is a number of from 3 to 7, (II) from 10 to 40% by weight of alkyl polyalkylene glycol mixed ethers corresponding to the following general formula <IMAGE> (II) in which R3 is a straight-chain or branched C8-C18 alkyl radical, x is a number of from 1 to 3 and y is a number of from 3 to 6, and (III) from 0 to 40% by weight of alkyl (poly)propylene glycol ethers corresponding to the following general formula <IMAGE> (III) in which R4 is a straight-chain or branched C16-C22 alkyl or alkenyl radical and z is a number of from 1 to 3.

Description

Wäßrige Reinigungsmittel für die Verwendung in Gewerbe und Industrie, insbesondere solche für die Reinigung von Metall-, Glas-, Keramik- und Kunststoffoberflächen, enthalten in der Regel Wirkstoffe, die in der Lage sind, einer unerwünschten Schaumentwicklung entgegenzusteuern. Der Einsatz insbesondere von schaumarmen bzw. schaumdämpfenden tensidischen Hilfsstoffen ist in den meisten Fällen dadurch bedingt, daß die von den zu reinigenden Substraten abgelösten und in den Reinigungsbädern sich ansammelnden Verunreinigungen als Schaumbildner wirken. Besonders wirkt sich das bei schnell laufenden Reinigungsmaschinen, zum Beispiel bei maschinellen Flaschenreinigungsanlagen, aus oder bei Anwendungen, bei denen die Reinigungsflotte unter hohem Druck auf die zu reinigenden Oberflächen aufgesprüht wird, beispielsweise beim Spritzreinigen.Aqueous cleaning agents for use in commerce and industry, in particular those for cleaning metal, glass, ceramic and plastic surfaces, generally contain active ingredients which are able to counteract undesirable foam development. The use of low-foam or foam-suppressing surfactant auxiliaries in particular is due in most cases to the fact that the contaminants detached from the substrates to be cleaned and accumulating in the cleaning baths act as foaming agents. This has a particular effect on high-speed cleaning machines, for example in machine bottle cleaning systems, or in applications in which the cleaning liquor is sprayed onto the surfaces to be cleaned under high pressure, for example in spray cleaning.

Mit gutem Erfolg werden seit langem als schaumarme bzw. schaumdrückende Zusätze mit Tensidwirkung Anlagerungsprodukte von Alkylenoxiden an organische Verbindungen eingesetzt, die - vorzugsweise mehrere - reaktive Wasserstoffatome im Molekül besitzen. Hier haben sich insbesondere Anlagerungsprodukte von Propylenoxid an aliphatische Polyalkohole (siehe DE-PS 12 80 455 und DE-PS 16 21 592) und an aliphatische Polyamine (siehe DE-PS 12 89 597 und DE-PS 16 21 -593) sowie Anlagerungsprodukte von Ethylenoxid und Propylenoxid an aliphatische Polyamine, insbesondere Ethylendiamin (siehe DE-PS 19 44 569) in der Praxis bewährt. Diese Alkylenoxidanlagerungsprodukte besitzen neben einer guten schaumdrückenden bzw. -dämpfenden Wirkung auch die für die Anwendung in gewerblichen und industriellen Reinigungsmitteln zumeist erforderliche Alkalistabilität. Die Verbindungen dieser Klasse sind jedoch nicht ausreichend biologisch abbaubar, um den geltenden gesetzlichen Vorschriften (RVO zum Waschmittelgesetz) zu genügen.With good success, addition products of alkylene oxides to organic compounds which have — preferably several — reactive hydrogen atoms in the molecule have long been used as low-foaming or foam-suppressing additives with a surfactant effect. Here, in particular, addition products of propylene oxide onto aliphatic polyalcohols (see DE-PS 12 80 45 5 and DE-PS 16 21 592) and aliphatic polyamines (see DE-PS 12 89 597 and DE-PS 16 21 -593) and addition products of ethylene oxide and propylene oxide on aliphatic polyamines, especially ethylenediamine (see DE-PS 19 44 569) proven in practice. In addition to a good foam-suppressing or -damping 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 in this class are not sufficiently biodegradable to meet the applicable legal regulations (RVO on the Detergent Act).

Die vorliegende Erfindung geht von der Aufgabe aus, schaumdrückende bzw. schaumdämpfende Hilfsstoffe mit Tensidcharakter aufzufinden, deren anwendungstechnische Eigenschaften denen der Mittel des Standes der Technik zumindest gleich kommen, die darüber hinaus aber auch noch die geforderte biologische Abbaubarkeit besitzen. Die Erfindung will insbesondere Mittel der genannten Art zur Verfügung stellen, die wirkungsvoll auch in dem niedrigen Temperaturbereich unterhalb etwa 50 °C eingesetzt werden können, der bisher selbst mit den besten einschlägigen Hilfsstoffen nur schwer zu bewältigen ist.The present invention is based on the task of finding foam-suppressing or foam-suppressing auxiliaries with surfactant character, the application properties of which are at least equal to those of the prior art, but which also have the required biodegradability. In particular, the invention intends to provide means of the type mentioned which can also be used effectively in the low temperature range below approximately 50 ° C., which has hitherto been difficult to master even with the best relevant auxiliaries.

In der DE-OS 33 15 951 sind endgruppenverschlossene Polyethylenglykolether beschrieben, die in den beschriebenen Anwendungsgebieten mit Vorteil eingesetzt werden können und zudem biologisch abbaubar sind. 1n dem praktischen Einsatz hat sich jedoch gezeigt, daß diese Verbindungen aus der zitierten Offenlegungsschrift ihre beste Wirksamkeit bei Temperaturen von etwa 50 °C ab entfalten, während im darunter liegenden Temperaturbereich Verbesserungen des Schaumverhaltens insbesondere dann wünschenswert erscheinen, wenn Reinigungsverfahren eingesetzt werden, die aus der Mechanik der eingesetzten Verfahrensmaßnahmen die Schaumbildung besonders begünstigen.DE-OS 33 15 951 describes end group-capped polyethylene glycol ethers which can be used with advantage in the fields of application described and which are also biodegradable. In practical use, however, it has been shown that these compounds from the cited published patent develop their best activity at temperatures of about 50 ° C., while improvements in the foam behavior in the temperature range below appear particularly desirable when cleaning processes are used which are derived from the Mechanics of the process measures used particularly favor foam formation.

Es wurde nun überraschend gefunden, daß die im folgenden beschriebenen Tensidmischungen bereits im Temperaturbereich ab +10 °C gut wirksam sind, gleichzeitig aber die Möglichkeit eröffnen, eventuell auftretende Schaumprobleme sicher zu beherrschen. Netzmittelgemische der erfindungsgemäßen und im nachfolgenden beschriebenen Art können also beispielsweise Schwierigkeiten bewältigen, die beim sogenannten Kaltanfahren von Flaschenreinigungsanlagen auftreten. Vorteilhaft lassen sich die erfindungsgemäßen Tensidmischungen auch als schaumarme Netzmittel für Hochdruckspritzreiniger verwenden, die kaltspritzbar sind.It has now surprisingly been found that the surfactant mixtures described below are already effective in the temperature range from +10 ° C., but at the same time open up the possibility of safely mastering any foam problems that may arise. Wetting agent mixtures of the type according to the invention and described below can thus, for example, overcome difficulties which arise when cold starting bottle cleaning systems. The surfactant mixtures according to the invention can also advantageously be used as low-foaming wetting agents for high-pressure spray cleaners which can be cold sprayed.

Gegenstand der Erfindung sind dementsprechend in einer ersten Ausführungsform schaumarme bzw. schaumdämpfende Tensidgemische auf Basis von wasserlöslichen und/oder wasseremulgierbaren Polyalkylenglykolethern längerkettiger Alkohole, wobei das Kennzeichen der Erfindung darin liegt, daß diese Tensidgemische die nachfolgend angegebenen Komponenten I, II und gewünschtenfalls III in den nachfolgend ebenfalls ausgewiesenen Mengenverhältnissen enthalten - die Mengenverhältnisse in Gew.-% beziehen sich dabei jeweils auf das Gesamtgewicht der Mischung der Komponenten von 1 bis III:

  • I) 20 bis 80 Gew. % an Polyethylenglykolethern der allgemeinen Formel I
    Figure imgb0001
    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 3 bis 7 bedeuten,
  • II) 10 bis 40 Gew.-% Alkylpolyalkylenglykol-Mischether der allgemeinen Formel II
    Figure imgb0002
    in der R3 einen geradkettigen oder verzweigten Alkylrest mit 8 bis 18 C-Atomen, x eine Zahl von 1 bis 3 und y eine Zahl von 3 bis 6 bedeuten sowie
  • III) 0 bis 40 Gew.-% Alkyl-(poly)-propylenglykolether der allgemeinen Formel 111
    Figure imgb0003
    in der R4 einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 16 bis 22 C-Atomen und z eine Zahl von 1 bis 3 bedeuten.
Accordingly, the invention in a first embodiment provides low-foam or foam-suppressing surfactant mixtures based on water-soluble and / or water-emulsifiable polyalkylene glycol ethers of longer-chain alcohols, the characteristic of the invention being that these surfactant mixtures contain the components I, II and, if desired, III in the following also contain specified proportions - the proportions in% by weight relate to the total weight of the mixture of components from 1 to III:
  • I) 20 to 80% by weight of polyethylene glycol ethers of the general formula I
    Figure imgb0001
     in which R 1 is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 C atoms R 2 is an alkyl radical with 4 to 8 C atoms and n is a number from 3 to 7,
  • II) 10 to 40 wt .-% alkyl polyalkylene glycol mixed ether of the general formula II
    Figure imgb0002
     in which R 3 is a straight-chain or branched alkyl radical having 8 to 18 carbon atoms, x is a number from 1 to 3 and y is a number from 3 to 6 and
  • III) 0 to 40% by weight of alkyl (poly) propylene glycol ether of the general formula III
    Figure imgb0003
     in which R 4 is a straight-chain or branched alkyl or alkenyl radical having 16 to 22 carbon atoms and z is a number from 1 to 3.

Bevorzugt liegen die Gewichtsanteile der Komponenten 1 bis 111 innerhalb der folgenden Mengenbereiche:

  • Verbindungen der allgemeinen Formel 1 50 bis 80 Gew.-%
  • Verbindungen der allgemeinen Formel II 10 bis 25 Gew.-%
  • Verbindungen der allgemeinen Formel 111 0 bis 20 Gew.-%.
The proportions by weight of components 1 to 111 are preferably within the following quantitative ranges:
  • Compounds of the general formula 1 50 to 80% by weight
  • Compounds of the general formula II 10 to 25% by weight
  • Compounds of general formula 111 0 to 20 wt .-%.

Der Rest R1 in den Verbindungen der allgemeinen Formel I bedeutet in der bevorzugten Ausführungsform einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 12 bis 18 C-Atomen, während der bevorzugte Rest R2 in diesen Verbindungen der allgemeinen Formel I den Butylrest bedeutet. In den Verbindungen der allgemeinen Formel II ist die bevorzugte Bedeutung für den Rest R3 ein geradkettiger oder verzweigter Alkylrest mit 12 bis 14 C-Atomen, während die bevorzugte Kettenlänge für den Rest R4 in den Verbindungen der allgemeinen Formel III bei 16 bis 18 Kohlenstoffatomen liegt.In the preferred embodiment, the R 1 radical in the compounds of the general formula I denotes a straight-chain or branched alkyl radical or alkenyl radical having 12 to 18 C atoms, while the preferred R 2 radical in these compounds of the general formula I denotes the butyl radical. In the compounds of the general formula II, the preferred meaning for the radical R 3 is a straight-chain or branched alkyl radical having 12 to 14 carbon atoms, while the preferred chain length for the radical R 4 in the compounds of the general formula III is 16 to 18 carbon atoms lies.

Die Reste R1, R3 und R4 sind Reste entsprechender längerkettiger Alkohole, wobei in einer weiterhin bevorzugten Ausführungsform der Erfindung gilt, daß Alkoholschnitte, wie sie bei der Synthese solcher Alkohole in der Praxis anfallen, besonders geeignet sind, wobei dann wenigstens der überwiegende Anteil der konkret in diesen Alkoholschnitten vorliegenden individuellen Komponenten den angegebenen C-Zahlbereichen entsprechen. Es sind entsprechende Synthesealkohole, insbesondere aber entsprechende Fettalkohole bzw. Fettalkoholgemische geeignet, wie sie in bekannter Weise aus der Umwandlung natürlicher Fette und/oder Öle anfallen.The residues R 1 , R 3 and R 4 are residues of corresponding longer-chain alcohols, it being a further preferred embodiment of the invention that alcohol cuts, as are obtained in practice in the synthesis of such alcohols, are particularly suitable, at least then the predominant one Proportion of the individual components actually present in these alcohol cuts correspond to the specified C number ranges. Corresponding synthetic alcohols, but in particular corresponding fatty alcohols or fatty alcohol mixtures are suitable, as are obtained in a known manner from the conversion of natural fats and / or oils.

Ein besonders geeigneter Alkoholschnitt für den Rest R1 in den Verbindungen der allgemeinen Formel I kann sogenannter "LT-Kokosalkohol" sein, der die folgende Kohlenstoffkettenlängenverteilung - bei durchweg gesättigten Kohlenwasserstoffresten - zeigt

Figure imgb0004
Für den Rest R3 in den Verbindungen der allgemeinen Formel II besonders geeignete Alkoholschnitte sind durch den sogenannten "LS-Kokosalkohol" mit der folgenden Kohlenstoffkettenlängenverteilung gekennzeichnet - ebenfalls durchweg gesättigte Kohlenwasserstoffreste:
Figure imgb0005
 A particularly suitable alcohol cut for the radical R 1 in the compounds of the general formula I can be so-called "LT coconut alcohol", which shows the following carbon chain length distribution - with consistently saturated hydrocarbon radicals
Figure imgb0004
 Alcohol cuts particularly suitable for the radical R 3 in the compounds of the general formula II are characterized by the so-called "LS coconut alcohol" with the following carbon chain length distribution - likewise consistently saturated hydrocarbon radicals:
Figure imgb0005

Als Rest R4 in den Verbindungen der allgemeinen Formel III ist insbesondere ein Oleylalkoholschnitt mit der folgenden Kohlenstoffkettenlängenverteilung und einer Jodzahl im Bereich von 40 bis 110 geeignet:

Figure imgb0006
An oleyl alcohol cut with the following carbon chain length distribution and an iodine number in the range from 40 to 110 is particularly suitable as the radical R 4 in the compounds of the general formula III:
Figure imgb0006

Die Herstellung von Verbindungen der allgemeinen Formel I kann analog zu den in der DE-OS 33 15 951 enthaltenen Angaben erfolgen, jedoch mit der Abweichung, daß dort der Ethoxilierungsgrad n dem Zahlenwert von 7 bis 12 entspricht, während erfindungsgemäß n eine Zahl von 3 bis 7 bedeutet. Als Ausgangsmaterial für die Herstellung dieser Polyglykolether der Formel I können also entsprechende Fettalkohole und/oder Oxoalkohole der genannten Kohlenstoffzahl einzeln oder im Gemisch eingesetzt werden. Man setzt diese Alkohole mit Ethylenoxid im Molverhältnis von 1 : 3 bis 1 : 7 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxilierungsbedingungen, 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- bis C8-Alkylhalogeniden durchgeführt, beispielsweise mit n-Butyljodid, sec.-Butylbromid, tert.-Butylchlorid, Amylchlorid, tert.-Amylbromid, n-Hexylchlorid, n-Heptylbromid und n-Octylchlorid. Bevorzugt sind hier - wie angegeben - die entsprechenden C4-Alkyihalogenide. Dabei kann es zweckmäßig sein, Alkylhalogenid und Akali im stöchiometrischen Überschuß, beispielsweise von 100 bis 200 %, über die zu verethernden Hydroxylgruppen einzusetzen.Compounds of the general formula I can be prepared analogously to the information contained in DE-OS 33 15 951, but with the difference that the degree of ethoxylation n there corresponds to the numerical value from 7 to 12, while according to the invention n is a number from 3 to 7 means. Corresponding fatty alcohols and / or oxo alcohols of the stated carbon number can be used individually or as a mixture as starting material for the preparation of these polyglycol ethers of the formula I. These alcohols are reacted with ethylene oxide in a molar ratio of from 1: 3 to 1: 7, and the hydroxyl groups present in the reaction product obtained are then etherified. The reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline ones 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 C 4 to 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. As indicated, preference is given here to the corresponding C 4 -alkyl halides. 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.

Die Herstellung der Verbindungen der allgemeinen Formeln 11 und III erfolgt ebenfalls in an sich bekannter Weise durch Umsetzung der Ausgangsalkohole bzw. Alkoholgemische mit Ethylenoxid und Propylenoxid (Verbindungen der allgemeinen Formel II) bzw. mit Propylenoxid (Verbindungen der allgemeinen Formel III) unter den bekannten Alkoxilierungsbedingungen.The compounds of the general formulas 11 and III are likewise prepared in a manner known per se by reacting the starting alcohols or alcohol mixtures with ethylene oxide and propylene oxide (compounds of the general formula II) or with propylene oxide (compounds of the general formula III) under the known alkoxylation conditions .

Die biologische Abbaubarkeit der erfindungsgemäßen Tensidmischungen liegt nach den gesetzlichen Bestimmungsmethoden (OECD-Screeningtest, OECD, Paris 1976 (26181)) über 80 % BiAS-Abnahme bei BSB/CSB-Werten von größer 60 %.According to the legal determination methods (OECD screening test, OECD, Paris 1976 (26181)), the biodegradability of the surfactant mixtures according to the invention is over 80% BiAS decrease with BOD / COD values of greater than 60%.

Die Erfindung betrifft in einer weiteren Ausführungsform den Einsatz der eingangs beschriebenen schaumarmen bzw. schaumdämpfenden Tensidmischungen im Rahmen von Reinigungsmitteln., die insbesondere für die wäßrig-tensidische Reinigung von harten Oberflächen zum Einsatz kommen sollen. Besonders betroffen ist hier das Gebiet solcher Reinigungsvorgänge, bei denen aufgrund der eingesetzten Mechanik und/oder der abzulösenden Verunreingung mit erhöhter Schaumbelastung zu rechnen ist, wobei hier insbesondere mechanische Reinigungsverfahren, wie die Spritzreinigung oder andere mit Hochdruckanwendung reinigende Wasch- bzw. Spülverfahren in Betracht kommen. In einer besonders wichtigen Ausführungsform finden dabei die erfindungsgemäßen Netzmittelmischungen in solchen Reinigungsmitteln Einsatz, die auch für die Anwendung bei Waschtemperaturen unterhalb 50 °C, insbesondere im Bereich von etwa 10 bis 50 °C, Verwendung finden sollen.In a further embodiment, the invention relates to the use of the low-foam or foam-suppressing surfactant mixtures described at the outset in the context of detergents which are to be used in particular for the aqueous-surfactant cleaning of hard surfaces. The area of such cleaning processes is particularly affected here, in which increased foam loading is to be expected due to the mechanics used and / or the impurity to be removed, in particular here mechanical cleaning processes, such as spray cleaning or other washing or rinsing processes cleaning with high-pressure application, are suitable. In a particularly important embodiment, the wetting agent mixtures according to the invention are used in cleaning agents which are also intended for use at washing temperatures below 50 ° C., in particular in the range from approximately 10 to 50 ° C.

Der erfindungemäße Begriff "Reinigungsmittel" umfaßt dabei einerseits die gebrauchsfertigen wäßrigen Lösungen der entsprechenden Wirkstoffbestandteile, andererseits aber auch die zur Herstellung der Anwendungslösungen bestimmten Konzentrate und/oder festen Wirkstoffmischungen. Im einzelnen gelten hier die allgemeinen Angaben des Standes der Technik.The term “cleaning agent” according to the invention comprises on the one hand the ready-to-use aqueous solutions of the corresponding active ingredient components, but on the other hand also the concentrates and / or solid active ingredient mixtures intended for the preparation of the application solutions. The general details of the prior art apply here in detail.

So enthalten beispielsweise Reinigungsmittel für den Bereich der maschinellen Flaschenreinigung oder allgemein für die Spritz- bzw. Hochdruckreinigung neben Netzmitteln weitere übliche Bestandteile, nämlich Gerüstsubstanzen und Komplexbildner, Alkalien oder Säuren, Korrosionsinhibitoren und ggf. auch antimikrobielle Wirkstoffe und/oder organische Lösungsmittel. Als mögliche Netzmittel kommen - zusätzlich zu den erfindungsgemäß beschriebenen Netzmittelgemischen nichtionogene oberflächenaktive Substanzen, wie Polyglykolether., die durch Anlagerung von Ethylenoxid an Alkohole, insbesondere Fettalkohole, Alkylphenole, Fettamine und Carbonsäureamide erhalten werden, und anionenaktive Netzmittel, wie Alkalimetall-, Amin- und Alkylolaminsalze von Fettsäuren, Alkylschwefelsäuren, Alkylsulfonsäuren und Alkylbenzolsulfonsäuren in Betracht. An Gerüstsubstanzen und Komplexbildnern können die Reinigungsmittel vor allem Alkalimetallorthophosphate, -polymerphosphate, -silikate, -borate, -carbonate, -polyacrylate und -glukonate sowie Zitronensäure, Nitrilotriessigsäure,

  • Ethylendiamintetraessigsäure,
  • 1-Hydroxyalkan-1 ,1-diphosphonsäure,
  • Aminotri(methylenphosphonsäure) und Ethylendiamintetra- methylenphosphonsäure) , Phosphonoalkanpolycarbonsäuren wie z. B. Phosphonobutantricarbonsäure und Alkalimetallsalze 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 Alkylolamine enthalten.
For example, cleaning agents for machine bottle cleaning or generally for spray or high-pressure cleaning contain, in addition to wetting agents, other common components, namely builders and complexing agents, alkalis or acids, corrosion inhibitors and possibly also antimicrobial agents and / or organic solvents. Possible wetting agents are, in addition to the wetting agent mixtures described according to the invention, 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 acids and alkylbenzenesulfonic acids. The builders can contain alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates as well as citric acid, nitrilotriacetic acid,
  • Ethylenediaminetetraacetic acid,
  • 1-hydroxyalkane-1, 1-diphosphonic acid,
  • Aminotri (methylenephosphonic acid) and ethylenediaminetetra methylenephosphonic acid), phosphonoalkane polycarboxylic acids such as. B. phosphonobutane tricarboxylic acid and alkali metal 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 alkylolamines.

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 Tensidmischungen werden den Reinigungsmitteln in solchen Mengen zugesetzt, daß ihre Konzentration in den gebrauchsfertigen Lösungen 10 bis 2.500 ppm, vorzugsweise 50 bis 500 ppm, ausmacht.The surfactant mixtures 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.

In den nachfolgenden Beispielen sind zunächst 6 schaumarme bzw. schaumdämpfende Tensidgemische im Sinne der erfindungsgemäßen Lehre (Beispiele 1 bis 6) aufgezählt und gegenübergestellt einer Reihe von konstitutionell ähnlichen, jedoch nicht der erfindungsgemäßen Definition entsprechenden Stoffen bzw. Stoffgemischen (Vergleichsbeispiele 1 bis 6).In the following examples, 6 low-foam or foam-suppressing surfactant mixtures in the sense of the teaching according to the invention (examples 1 to 6) are initially enumerated and compared with a series of constitutionally similar substances or substance mixtures which do not correspond to the definition according to the invention (comparative examples 1 to 6).

In dem im nachfolgenden beschriebenen Standardtest zur Prüfung der entschäumenden bzw. schaumdämpfenden Wirkung werden die Stoffgemische gemäß der Erfindung mit den Stoffgemischen aus den Vergleichsbeispielen verglichen. Dabei zeigt sich, daß fast durchweg die erfindungsgemäßen Stoffgemische ein besseres Antischaumverhalten zeigen als die Materialien aus den Vergleichsbeispielen.In the standard test described below for testing the defoaming or foam-suppressing effect, the substance mixtures according to the invention are compared with the substance mixtures from the comparative examples. It shows that the substance mixtures according to the invention are almost always better Antifoam behavior show than the materials from the comparative examples.

Neben der Schaumbewertung ist allerdings für die Praxis ein Produkt nur dann einsetzbar, wenn es gleichzeitig ein befriedigendes Emulgiervermögen aufweist. Zur Beurteilung dieses Parameters werden die zu bestimmenden Tenside bzw. Tensidgemische in 1 Gew.-%iger wäßriger Natronlauge bei Raumtemperatur jeweils in einer Tensidmenge von 0,1 bis 1 Gew.-% emulgiert. Nur solche Produkte, die hier nicht aufrahmen, sind für den praktischen Einsatz geeignet.In addition to the foam evaluation, a product can only be used in practice if it also has a satisfactory emulsifying power. To assess this parameter, the surfactants or surfactant mixtures to be determined are emulsified in 1% by weight aqueous sodium hydroxide solution at room temperature in each case in an amount of 0.1 to 1% by weight of surfactant. Only products that do not frame here are suitable for practical use.

Die Berücksichtigung dieses zusätzlichen Parameters zeigt die Überlegenheit der erfindungsgemäßen Stoffgemische gemäß Beispielen 1 bis 6 über diejenigen der Vergleichsbeispiele 1 bis 6.The consideration of this additional parameter shows the superiority of the substance mixtures according to the invention according to Examples 1 to 6 over those of Comparative Examples 1 to 6.

Die Prüfung der Entschäumungswirkung wird unter den folgenden Bedingungen vorgenommen:

  • In einem doppelwandigen 2-I-Meßzylinder werden 300 ml einer 1 Gew.-%igen wäßrigen Natronlauge auf 20 °C temperiert. Diese Lösung wird mit 0,1 ml des zu bestimmenden Tensides bzw. Tensidgemisches mit entschäumender und/oder schaumdämpfender Wirkung versetzt. Mit Hilfe einer Schlauchpumpe wird die Flüssigkeit mit einer Umwälzgeschwindigkeit von 4 l/min umgepumpt. Dabei wird die Prüfflotte ca. 5 mm über dem Boden des Meßzylinders mittels eines 55 cm langen Glasrohres (Innendurchmesser 8,5 mm, Außendurchmesser 11 mm), das mit der Pumpe über einen 1,6 m langen Siliconschlauch (Innendurchmesser 8 mm, Außendurchmesser 12 mm) verbunden ist, angesaugt und über ein zweites Glasrohr (Länge 20 cm), das an der 2.000 ml-Marke des Meßzylinders angebracht ist, in freiem Fall zurückgeführt.
The defoaming effect is tested under the following conditions:
  • 300 ml of a 1% strength by weight aqueous sodium hydroxide solution are heated to 20 ° C. in a double-walled 2 liter measuring cylinder. This solution is mixed with 0.1 ml of the surfactant or surfactant mixture to be determined with a defoaming and / or foam-suppressing effect. With the help of a peristaltic pump, the liquid is pumped at a circulation rate of 4 l / min. The test liquor is approx. 5 mm above the bottom of the measuring cylinder using a 55 cm long glass tube (inner diameter 8.5 mm, outer diameter 11 mm), which is connected to the pump via a 1.6 m long silicone hose (inner diameter 8 mm, outer diameter 12 mm) is sucked in and returned in free fall via a second glass tube (length 20 cm) attached to the 2,000 ml mark on the measuring cylinder.

Als Testschäumer dient eine 1 Gew.-%ige wäßrige Lösung des Trlethanolamlnsalzes von Tetrapropylenbenzosulfonat. Diese wird In Abständen von jeweils einer Minute in Mengen von jeweils 1 ml der In Umwälzung befindlichen Flotte zudosiert. Das entstehende Gesamtvolumen von Schaum und Flüssigkeit wird bestimmt. Die schauminhibierende Wirkung des jeweils eingesetzten tensidischen Materials ist um so besser, je länger der Zeitraum ist, der zum Erreichen der 2.000 ml Markierung im Meßzylinder durch das Gesamtvolumen von Flüssig- und Schaumphase benötigt wird. In den nachfolgenden Beispielen 1 bis 6 sind die jeweiligen entsprechenden Zahlenwerte für diesen Zeitpunkt in Minuten bzw. in ml Testschäumer angegeben. Gleichzeitig wird das Emulgiervermögen wie vorher beschrieben beurteilt. In der Bewertung wird dabei unterschieden zwischen den 3 Beurteilungen: gut, noch befriedigend, unzureichend.A 1% by weight aqueous solution of the trlethanolamine salt of tetrapropylene benzosulfonate is used as the test foam. This is metered in at intervals of one minute in amounts of 1 ml each of the liquor in circulation. The resulting total volume of foam and liquid is determined. The longer the time it takes to reach the 2,000 ml mark in the measuring cylinder due to the total volume of the liquid and foam phases, the better the foam-inhibiting effect of the surfactant material used. In Examples 1 to 6 below, the respective corresponding numerical values for this point in time are given in minutes or in ml of test foamers. At the same time, the emulsifying power is assessed as previously described. In the evaluation, a distinction is made between the 3 evaluations: good, still satisfactory, inadequate.

Die in den erfindungsgemäßen Beispielen und den Vergleichsbeispielen angeführten Symbole "LT-", "LS-" und "OCENOL-" beziehen sich dabei auf die Reste R1 (Verbindungen der allgemeinen Formel I), R3 (Verbindungen der allgemeinen Formel II) und R4 (Verbindungen der allgemeinen Formel III) und entsprechen den im Rahmen der Erfindungsbeschreibung angegebenen Definition zum "LT-Kokosalkohol", "LS-Kokosalkohol" bzw. zum Oleylalkoholschnitt mit der Jodzahl im Bereich von 40 bis 110.The symbols "LT-", "LS-" and "OCENOL-" cited in the examples according to the invention and the comparative examples relate to the radicals R 1 (compounds of the general formula I), R 3 (compounds of the general formula II) and R 4 (compounds of the general formula III) and correspond to the definition given in the context of the description of the invention for “LT coconut alcohol”, “LS coconut alcohol” or for oleyl alcohol cut with the iodine number in the range from 40 to 110.

BeispieleExamples Beispiel 1example 1

Figure imgb0007
Standzeit im Entschäumungstest: 20 Emulgiervermögen: gut
Figure imgb0007
 Service life in the defoaming test: 20 emulsifying power: good

Beispiel 2Example 2

Figure imgb0008
Standzeit im Entschäumungstest: 23 Emulgiervermögen: gut
Figure imgb0008
 Service life in the defoaming test: 23 Emulsifying power: good

Beispiel 3Example 3

Figure imgb0009
Standzeit im Entschäumungstest: 19 Emulgiervermögen: noch befriedigend
Figure imgb0009
 Service life in the defoaming test: 19 emulsifying power: still satisfactory

Beispiel 4Example 4

Figure imgb0010
Standzeit im Entschäumungstest: 17 Emulgiervermögen: gut
Figure imgb0010
 Service life in the defoaming test: 17 Emulsifying power: good

Beispiel 5Example 5

Figure imgb0011
Standzeit im Entschäumungstest: 18 Emulgiervermögen: gut
Figure imgb0011
 Service life in the defoaming test: 18 Emulsifying power: good

Beispiel 6Example 6

Figure imgb0012
Standzeit im Entschäumungstest: 21 Emulgiervermögen: gut
Figure imgb0012
 Service life in the defoaming test: 21 Emulsifying power: good

Vergleichsbeispiel 1Comparative Example 1

100 % Ocenol-2 PO Standzeit im Entschäumungstest: 18 Emulgiervermögen: ungenügend100% Ocenol-2 PO Service life in the defoaming test: 18 Emulsifying power: insufficient

Vergleichsbeispiel 2Comparative Example 2

100 % Ethylendiamin + 30 EO + 70 PO Standzeit im Entschäumungstest: 5 Emulgiervermögen: gut100% ethylenediamine + 30 EO + 70 PO service life in defoaming test: 5 emulsifying power: good

Vergleichsbeispiel 3Comparative Example 3

100 % LT-10 EO-n-Butylether der Formel I Standzeit im Entschäumungstest: 9 Emulgiervermögen: gut100% LT-10 EO-n-butyl ether of the formula I Service life in the defoaming test: 9 Emulsifying power: good

Vergleichsbeispiel 4Comparative Example 4

100 % LS-2 EO-4 PO der Formel II Standzeit im Entschäumungstest: 13 Emulgiervermögen: ungenügend100% LS-2 EO-4 PO of the formula II Service life in the defoaming test: 13 Emulsifying power: insufficient

Vergleichsbeispiel 5Comparative Example 5

100 % LT-7 EO-n-Butylether der Formel I Standzeit im Entschäumungstest: 10 Emulgiervermögen: gut100% LT-7 EO-n-butyl ether of the formula I Service life in the defoaming test: 10 Emulsifying power: good

Vergleichsbeispiel 6Comparative Example 6

100 % LS-3 EO-6 PO der Formel II Standzeit im Entschäumungstest: 10 Emulgiervermögen: noch befriedigend100% LS-3 EO-6 PO of the formula II Service life in the defoaming test: 10 Emulsifying power: still satisfactory

Im nachfolgenden sind eine Reihe -von Rezepturbeispielen - erfindungsgemäße Beispiele 7 bis 13 - für den Einsatz der neuen schaumarmen bzw. schaumdämpfenden Wirkstoffgemische im Sinne der Erfindung angegeben.A number of recipe examples - examples 7 to 13 according to the invention - for the use of the new low-foam or foam-suppressing active substance mixtures according to the invention are given below.

Beispiel 7Example 7 FlaschenreinigerBottle cleaner

Figure imgb0013
Figure imgb0013

Beispiel 8Example 8

Figure imgb0014
Figure imgb0014

Beispiel 9Example 9

Figure imgb0015
Figure imgb0015

Beispiel 10Example 10 Reiniger für die MilchwirtschaftDairy cleaner

Figure imgb0016
Figure imgb0016
Figure imgb0017
Figure imgb0017

Beispiel 11Example 11

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

Figure imgb0018
A mechanical degreasing agent for metallic materials with the following composition was produced by mechanical mixing of the components:
Figure imgb0018

Mit einer 4-gewichtsprozentigen Lösung dieses Reinigungsmittels wurden fettverschmutzte Formteile aus Stahl bei 40 °C im Tauchverfahren gereinigt. Die Entfettungswirkung war sehr gut; es wurde keine störende Schaumentwicklung beobachtet.A 4% by weight solution of this cleaning agent was used to clean grease-contaminated steel moldings at 40 ° C in an immersion process. The degreasing effect was very good; no disruptive foaming was observed.

Beispiel 12Example 12

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

Figure imgb0019
Figure imgb0020
Mit einer 1,5-gewichtsprozentigen Lösung des Reinigungsmittels (pH-Wert 8,5) wurden Eisenoberflächen bei 30 - 40 °C im Spritzverfahren gereinigt. Bei guter Reinigungswirkung trat keine störende Schaumentwicklung auf.By dissolving the components in water, a storage-stable concentrate for cleaning metal surfaces with the following composition was produced:
Figure imgb0019
Figure imgb0020
 Iron surfaces were cleaned at 30 - 40 ° C with a 1.5% by weight solution of the cleaning agent (pH 8.5). With a good cleaning effect, no disruptive foam development occurred.

Beispiel 13Example 13

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

Figure imgb0021
By dissolving the components in water, a Iaget-siabil concentrate for cleaning metal surfaces with the following composition was obtained:
Figure imgb0021

Eine 1-gewichtsprozentige Lösung dieses Reinigungsmittels wurde bei 30 - 40 °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 30 - 40 ° C for spray cleaning gray cast iron parts. With a good cleaning effect, no disruptive foaming was observed.

Claims (3)

1. Schaumarme bzw. schaumdämpfende Tensidgemische auf Basis von wasserlöslichen und/oder wasseremulgierbaren Polyalkylenglykolethern längerkettiger Alkohole, dadurch gekennzeichnet, daß sie in Abmischung die nachfolgenden Komponenten I, II und gewünschtenfalls III in den angegebenen Mengenverhältnissen - Gew.-% bezogen auf das Gewicht der Mischung von I bis III - enthalten. I) 20 bis 80 Gew. % an Polyethylenglykolethern der allgemeinen Formel I
Figure imgb0022
in der R 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 3 bis 7 bedeuten, II) 10 bis 40 Gew.-% Alkylpolyalkylenglykol-Mischether der allgemeinen Formel II
Figure imgb0023
in der R3 einen geradkettigen oder verzweigten Alkylrest mit 8 bis 18 C-Atomen, x eine Zahl von 1 bis 3 und y eine Zahl von 3 bis 6 bedeuten sowie III) 0 bis 40 Gew.-% Alkyl-(poly)-propylenglykolether der allgemeinen Formel III
Figure imgb0024
in der R4 einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 16 bis 22 C-Atomen und z eine Zahl von 1 bis 3 bedeuten. 1. Low-foam or foam-suppressing surfactant mixtures based on water-soluble and / or water-emulsifiable polyalkylene glycol ethers of longer-chain alcohols, characterized in that, in a mixture, they contain the following components I, II and, if desired, III in the proportions stated -% by weight based on the weight of the mixture from I to III - included. I) 20 to 80% by weight of polyethylene glycol ethers of the general formula I
Figure imgb0022
 in which R is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 C atoms, R 2 is an alkyl radical with 4 to 8 C atoms and n is a number from 3 to 7, II) 10 to 40 wt .-% alkyl polyalkylene glycol mixed ether of the general formula II
Figure imgb0023
 in which R 3 is a straight-chain or branched alkyl radical having 8 to 18 carbon atoms, x is a number from 1 to 3 and y is a number from 3 to 6 such as III) 0 to 40% by weight of alkyl (poly) propylene glycol ether of the general formula III
Figure imgb0024
 in which R 4 is a straight-chain or branched alkyl or alkenyl radical having 16 to 22 carbon atoms and z is a number from 1 to 3. 2. Tensidgemische nach Anspruch 1 dadurch gekennzeichnet, daß die Komponenten bis III in den folgenden Mischungsverhältnissen vorliegen: I 50 - 80 Gew.-% II 10-25 Gew.-% III 0 - 20 Gew.-% 2. Surfactant mixtures according to claim 1, characterized in that the components to III are present in the following mixing ratios: I 50 - 80% by weight II 10-25% by weight III 0-20% by weight 3. Verwendung der Tensidgemische nach den Ansprüchen 1 und 2 in wäßrigen Reinigungsmitteln, die insbesondere auch für den Einsatz im Bereich der maschinellen Spritz- bzw. Hochdruckreinigung bei Temperaturen unterhalb 50 °C geeignet sind.3. Use of the surfactant mixtures according to claims 1 and 2 in aqueous cleaning agents, which are particularly suitable for use in the field of machine spray or high pressure cleaning at temperatures below 50 ° C.
EP87110283A 1986-07-24 1987-07-16 Low foaming and/or foam inhibiting mixtures of tensides and their use Expired - Lifetime EP0254208B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2614898A1 (en) * 1987-05-06 1988-11-10 Sandoz Sa BIODEGRADABLE LIQUID DETERGENT COMPOSITIONS
WO1991003540A1 (en) 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Anti-foaming agents for machine-washing of crockery and bottles
WO1991009925A2 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of non-ionic surface-active agents
WO1991014760A1 (en) * 1990-03-24 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Weakly foaming, nonionic tenside mixture
WO1991017233A1 (en) * 1990-05-09 1991-11-14 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of ionic and non-ionic tensides
WO1992014808A1 (en) * 1991-02-22 1992-09-03 Basf Aktiengesellschaft Mixture of at least two alkoxylated alcohols and its use as antifoam tenside additive in cleaning products for mechanical washing processes
WO1995002668A1 (en) * 1993-07-12 1995-01-26 Henkel Kommanditgesellschaft Auf Aktien Hard surface cleaning agent
DE4416303A1 (en) * 1994-05-09 1995-11-16 Bayer Ag Low-foaming wetting agent and its use
WO1998032527A1 (en) * 1997-01-29 1998-07-30 Henkel Kommanditgesellschaft Auf Aktien Low-foam emulgator system and emulsion concentrate containing the same
EP0916717A1 (en) * 1997-11-14 1999-05-19 HENKEL-ECOLAB GmbH & CO. OHG Hard surface cleaning agent
WO2000046327A1 (en) * 1999-02-02 2000-08-10 Henkel-Ecolab Gmbh & Co. Ohg Agent for cleaning hard surfaces
WO2000050551A1 (en) * 1999-02-22 2000-08-31 The Procter & Gamble Company Automatic dishwashing compositions comprising selected nonionic surfactants
US6530383B1 (en) 1997-11-22 2003-03-11 Ecolab Gmbh & Co. Ohg Agent for cleaning hard surfaces
US6596674B2 (en) 2000-02-29 2003-07-22 Henkel Corporation Metal working lubricants and their use
US7012052B1 (en) 1999-02-22 2006-03-14 The Procter & Gamble Company Automatic dishwashing compositions comprising selected nonionic surfactants
WO2008071582A1 (en) * 2006-12-14 2008-06-19 Basf Se Nonionic emulsifiers for emulsion concentrates for spontaneous emulsification
DE102010048948A1 (en) 2010-10-19 2011-12-29 Clariant International Ltd. Aqueous defoamer emulsion, useful e.g. as protective colloids, comprises oil phase, emulsifiers, and water-soluble or -swellable, crosslinked copolymers containing e.g. acrylamidoalkylsulfonic acid- and cyclic N-vinylcarboxamide-compounds
WO2012045364A3 (en) * 2010-10-08 2013-03-28 Ecolab Inc. Laundry detergent composition for low temperature washing and disinfection
CN113754371A (en) * 2021-08-30 2021-12-07 广东盛瑞科技股份有限公司 Foamed light soil with high stone powder content and preparation method thereof

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3639322A1 (en) * 1986-11-17 1988-05-26 Henkel Kgaa METHOD FOR CLEANING AND DISINFECTING ENDOSCOPES AND MEANS FOR IMPLEMENTING THE METHOD
US5223166A (en) * 1986-11-17 1993-06-29 Henkel Kommanditgesellschaft Auf Aktien Preparations and processes for cleaning and disinfecting endoscopes
US5584943A (en) * 1987-06-01 1996-12-17 Henkel Corporation Cleaning and surface conditioning of formed metal surfaces
DE3727378A1 (en) * 1987-08-17 1989-03-02 Henkel Kgaa FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS
DE3800493A1 (en) * 1988-01-11 1989-07-20 Henkel Kgaa USE OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS, IN PARTICULAR ALSO SUITABLE FOR COLD CLEANING
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
US4988462A (en) * 1988-04-29 1991-01-29 Lever Brothers Company, Division Of Conopco, Inc. Non-aqueous cleaning compositions containing bleach and capped nonionic surfactant
GB8906820D0 (en) * 1989-03-23 1989-05-10 Ici Plc Novel chemical compounds and their use as low foam surfactants and antifoamingagents
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
DE59009494D1 (en) * 1989-09-26 1995-09-14 Ciba Geigy Ag Aqueous, storage stable, low foaming wetting agent.
EP0462059B1 (en) * 1990-06-11 1997-07-02 Ciba SC Holding AG Low-foaming, silicone-free, aqueous textile auxiliaries, their preparation and their use
US5152933A (en) * 1990-08-20 1992-10-06 Basf Corporation Ethylene oxide/propylene oxide copolymers as co-surfactants with detergency boosting properties in compositions also containing alkyl benzene sulfonate and ethoxylated alcohol
DE4342214C1 (en) * 1993-12-10 1995-05-18 Henkel Kgaa Nonionic detergent mixtures
DE4426889A1 (en) * 1994-07-29 1996-02-01 Hoechst Ag Mixtures of alkoxylates as foam suppressants and their use
DE19515086A1 (en) * 1995-04-25 1996-10-31 Hoechst Ag Process for removing contaminating coatings from metal surfaces
WO1998036042A1 (en) * 1997-02-14 1998-08-20 The Procter & Gamble Company Liquid hard-surface cleaning compositions based on specific dicapped polyalkylene glycols
US6460548B1 (en) * 1997-02-14 2002-10-08 The Procter & Gamble Company Liquid hard-surface cleaning compositions based on specific dicapped polyalkylene glycols
DE19738866A1 (en) * 1997-09-05 1999-03-11 Henkel Kgaa Low-foaming surfactant mixtures with hydroxy mixed ethers
WO2000050549A2 (en) * 1999-02-22 2000-08-31 The Procter & Gamble Company Cleaning compositions containing selected nonionic surfactants
DE10020145A1 (en) * 2000-04-20 2001-10-31 Henkel Ecolab Gmbh & Co Ogh Microbicidal surfactants
US7001634B2 (en) * 2002-11-07 2006-02-21 Bayer Materialscience Llc Process for suppressing the foaming of an aqueous system
US6878682B1 (en) 2003-05-23 2005-04-12 Colonial Chemical Inc. Capped nonionic surfactants
JP4947266B2 (en) * 2006-02-17 2012-06-06 日産化学工業株式会社 Detergent composition for food production line
JP6035447B1 (en) * 2016-05-30 2016-11-30 株式会社ニイタカ Cleaning composition for automatic cleaning machine
AU2022323258A1 (en) * 2021-08-05 2023-12-07 Stepan Company Surfactant compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3684723A (en) * 1964-04-21 1972-08-15 Lever Brothers Ltd Detergent composition
GB1445716A (en) * 1973-04-24 1976-08-11 Diversey Ltd Cleaning compositions
US4405490A (en) * 1980-04-11 1983-09-20 Bayer Aktiengesellschaft Anti-foam formulation containing an organopolysiloxane
EP0124815A2 (en) * 1983-05-02 1984-11-14 Henkel Kommanditgesellschaft auf Aktien Use of polyglycol ethers as foam-depressing additives in cleaning agents producing little foam
EP0180664A1 (en) * 1984-09-24 1986-05-14 Henkel Kommanditgesellschaft auf Aktien Defoamer for yeast fermentation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL285082A (en) * 1962-02-28
DE1280455B (en) * 1964-10-24 1968-10-17 Henkel & Cie Gmbh Highly alkaline, storage-stable and low-foaming bottle cleaning agents
ZA672169B (en) * 1966-04-16
DE1617119A1 (en) * 1966-11-18 1971-02-18 Henkel & Cie Gmbh Low-foaming stain treatment agent for textiles
BE755617A (en) * 1969-09-03 1971-03-02 Henkel & Cie Gmbh DETERGENTS CONTAINING FOAM INHIBITOR ADDITIVES
DE2918047A1 (en) * 1979-05-04 1980-12-11 Huels Chemische Werke Ag BIODEGRADABLE AND LOW-FOAMING SURFACES, METHOD FOR THEIR PRODUCTION AND THEIR USE IN CLEANING AGENTS
US4272394A (en) * 1979-11-19 1981-06-09 Basf Wyandotte Corporation Machine dishwashing detergents containing low-foaming nonionic surfactants

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3684723A (en) * 1964-04-21 1972-08-15 Lever Brothers Ltd Detergent composition
GB1445716A (en) * 1973-04-24 1976-08-11 Diversey Ltd Cleaning compositions
US4405490A (en) * 1980-04-11 1983-09-20 Bayer Aktiengesellschaft Anti-foam formulation containing an organopolysiloxane
EP0124815A2 (en) * 1983-05-02 1984-11-14 Henkel Kommanditgesellschaft auf Aktien Use of polyglycol ethers as foam-depressing additives in cleaning agents producing little foam
EP0180664A1 (en) * 1984-09-24 1986-05-14 Henkel Kommanditgesellschaft auf Aktien Defoamer for yeast fermentation

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2614898A1 (en) * 1987-05-06 1988-11-10 Sandoz Sa BIODEGRADABLE LIQUID DETERGENT COMPOSITIONS
WO1991003540A1 (en) 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Anti-foaming agents for machine-washing of crockery and bottles
TR25486A (en) * 1989-12-22 1993-05-01 Henkel Kgaa USING A COMBINATION WITH NON-IONIC TENSIDS
WO1991009925A2 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of non-ionic surface-active agents
WO1991009925A3 (en) * 1989-12-22 1992-01-09 Henkel Kgaa Use of a combination of non-ionic surface-active agents
WO1991014760A1 (en) * 1990-03-24 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Weakly foaming, nonionic tenside mixture
WO1991017233A1 (en) * 1990-05-09 1991-11-14 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of ionic and non-ionic tensides
WO1992014808A1 (en) * 1991-02-22 1992-09-03 Basf Aktiengesellschaft Mixture of at least two alkoxylated alcohols and its use as antifoam tenside additive in cleaning products for mechanical washing processes
WO1995002668A1 (en) * 1993-07-12 1995-01-26 Henkel Kommanditgesellschaft Auf Aktien Hard surface cleaning agent
US5759987A (en) * 1993-07-12 1998-06-02 Haerer; Juergen Mixtures of nonionic ethers for use as rinse aids and/or cleaning hard surfaces
DE4416303A1 (en) * 1994-05-09 1995-11-16 Bayer Ag Low-foaming wetting agent and its use
WO1998032527A1 (en) * 1997-01-29 1998-07-30 Henkel Kommanditgesellschaft Auf Aktien Low-foam emulgator system and emulsion concentrate containing the same
US6420323B2 (en) 1997-01-29 2002-07-16 Henkel Kommanditgesellschaft Auf Aktien Low-foam emulgator system and emulsion concentrate containing the same
EP0916717A1 (en) * 1997-11-14 1999-05-19 HENKEL-ECOLAB GmbH & CO. OHG Hard surface cleaning agent
US6530383B1 (en) 1997-11-22 2003-03-11 Ecolab Gmbh & Co. Ohg Agent for cleaning hard surfaces
WO2000046327A1 (en) * 1999-02-02 2000-08-10 Henkel-Ecolab Gmbh & Co. Ohg Agent for cleaning hard surfaces
WO2000050551A1 (en) * 1999-02-22 2000-08-31 The Procter & Gamble Company Automatic dishwashing compositions comprising selected nonionic surfactants
US7012052B1 (en) 1999-02-22 2006-03-14 The Procter & Gamble Company Automatic dishwashing compositions comprising selected nonionic surfactants
US6596674B2 (en) 2000-02-29 2003-07-22 Henkel Corporation Metal working lubricants and their use
WO2008071582A1 (en) * 2006-12-14 2008-06-19 Basf Se Nonionic emulsifiers for emulsion concentrates for spontaneous emulsification
WO2012045364A3 (en) * 2010-10-08 2013-03-28 Ecolab Inc. Laundry detergent composition for low temperature washing and disinfection
EP3284808A1 (en) * 2010-10-08 2018-02-21 Ecolab USA Inc. Method for low temperature washing and disinfection of laundry
DE102010048948A1 (en) 2010-10-19 2011-12-29 Clariant International Ltd. Aqueous defoamer emulsion, useful e.g. as protective colloids, comprises oil phase, emulsifiers, and water-soluble or -swellable, crosslinked copolymers containing e.g. acrylamidoalkylsulfonic acid- and cyclic N-vinylcarboxamide-compounds
CN113754371A (en) * 2021-08-30 2021-12-07 广东盛瑞科技股份有限公司 Foamed light soil with high stone powder content and preparation method thereof
CN113754371B (en) * 2021-08-30 2022-10-21 广东盛瑞科技股份有限公司 Foamed light soil with high stone powder content and preparation method thereof

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JPS6335697A (en) 1988-02-16
EP0254208B1 (en) 1991-10-16
US4780237A (en) 1988-10-25
ATE68519T1 (en) 1991-11-15
JP2533555B2 (en) 1996-09-11
CA1305640C (en) 1992-07-28
DE3773781D1 (en) 1991-11-21
ES2026494T3 (en) 1992-05-01
EP0254208A3 (en) 1989-07-05

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