EP0527824B1 - Use of a combination of ionic and non-ionic tensides - Google Patents

Use of a combination of ionic and non-ionic tensides Download PDF

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Publication number
EP0527824B1
EP0527824B1 EP91908642A EP91908642A EP0527824B1 EP 0527824 B1 EP0527824 B1 EP 0527824B1 EP 91908642 A EP91908642 A EP 91908642A EP 91908642 A EP91908642 A EP 91908642A EP 0527824 B1 EP0527824 B1 EP 0527824B1
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carbon atoms
component
general formula
alkyl group
parts
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EP91908642A
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German (de)
French (fr)
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EP0527824A1 (en
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Jürgen Geke
Bernd Stedry
Raina Hirthe
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to the use of a combination of ionic and nonionic surfactants - optionally with customary additives - for cleaning hard surfaces. So-called “industrial cleaners” are usually used for such tasks.
  • Industrial cleaners of this type are mainly used in the automotive industry and their supplier industries for cleaning and passivation, primarily in spray cleaning systems. They are suitable for intermediate and final cleaning without cutting as well as machined parts in unit and assembly plants. Practically all relevant materials, such as iron and steel, aluminum, silumin, copper, brass, zinc and plastics, can be treated and the majority of all contaminations on an organic or inorganic basis, such as cooling lubricants, rust protection oils, processing oils, drawing aids, pigments and light metal abrasion, can be removed. Such cleaning agents can also be used in customary immersion processes, but their use in the spraying process is usually preferred.
  • anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves contain constituents which, under the given working conditions - i.e. especially in spraying processes - give rise to undesirable foaming, for example anionic surfactants or nonionic surfactants foaming at the respective working temperature.
  • DE-A-36 20 011 describes cationic surfactants based on quaternary ammonium compounds and their use in cleaning agents.
  • the cationic surfactants are used in the alkaline pH range in addition to other detergent components.
  • EP-A-0 116 151 describes a process for the regeneration or recycling of aqueous degreasing and cleaning solutions by adding cationic surfactants or cationically modified polymers or mixtures thereof.
  • EP-A-0 054 894 describes a surfactant-containing mixture for the mechanical cleaning of hard surfaces in the alkaline liquor range, which contains nonionic surfactants of the alkyl ethoxylate or propoxylate type (component A), quaternary ammonium compounds (component B) and fluorinated alcohols ( Component C) contains.
  • the nonionic surfactants of this type mentioned in the examples contain only tertiary butyl groups as C1 ⁇ 4-alkyl radical.
  • the quaternary ammonium compounds only have short to medium carbon chains - up to a maximum of 12 carbon atoms. It is also necessary to add fluorinated alcohols as an anti-foaming agent.
  • EP-A-0 054 895 also describes a surfactant mixture for cleaning hard surfaces in the alkaline liquor range, which contains nonionic surfactants (component A) and selected quaternary ammonium compounds as cationic surfactants (component B).
  • Suitable nonionic surfactants here are alkyl-polyethylene glycol mixed ethers of the type C6 ⁇ 18-alkyl - 6 to 12 EO - C1 ⁇ 4-alkyl, in turn the compounds of this type mentioned in the examples as C1 ⁇ 4-alkyl radical being exclusively tertiary butyl groups contain.
  • the quaternary ammonium compounds only have short to medium carbon chains - up to a maximum of 8 carbon atoms.
  • DE-A-25 56 499 relates to low-foaming disinfectant cleaners which, as nonionic surfactants, include alkyl-polyethylene glycol mixed ethers of the type C6 ⁇ 2 2-alkyl - 5 to 50 EO - tert. Contain butyl.
  • formulations of this type can contain, among other things, quaternary ammonium compounds, which also have long-chain alkyl radicals with 8 to 18 carbon atoms, as a disinfectant component.
  • EP-A-0 254 208 relates to low-foam and / or foam-suppressing surfactant mixtures which are also suitable for use in the field of machine spray or high-pressure cleaning at temperatures below 50 ° C.
  • the object of the present invention was to provide surfactant combinations for cleaning hard surfaces which have low-foaming properties in the entire temperature range relevant to the application, namely in the range from 15 to 80 ° C., and are therefore suitable for use in spraying processes.
  • these surfactant combinations should have a high cleaning ability and excellent wetting properties compared to the substrates treated with them;
  • these surfactant combinations should be easy to assemble with additives customary in industrial cleaners, allow the cleaning agent solutions to run off the treated substrate surfaces without stains and have demulsifying properties with regard to non-self-emulsifying oils and fats.
  • advantageous electrostatic effects are to be achieved.
  • R8 is a linear or branched alkyl radical or alkenyl radical having 6 to 18 carbon atoms.
  • R8 the following radicals in question: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl and the branched chain isomers of the alkyl radicals mentioned.
  • R8 can also mean the unsaturated alkyl radicals (alkenyl radicals) with a number of carbon atoms in the above range, which can also be linear or branched. Furthermore, R8 can also be a cyclic alkyl radical having 5 to 6 carbon atoms, i.e. Cyclopentyl or cyclohexyl. The number of ethoxy residues in the molecule - index m - is in the range from 2 to 12.
  • component (c) those compounds of the general formula (III) are preferably used as component (c) in which R8 is a linear alkyl radical or alkenyl radical having 6 to 18 carbon atoms and m is a number in the range from 2 to 10.
  • R linear represents a linear or branched alkyl radical or alkenyl radical with 6 to 18 carbon atoms or a cyclic alkyl radical with 5 to 6 carbon atoms.
  • Suitable substituents R9 are all those radicals which have already been explained above in connection with the substituent R8 of the general formula (III).
  • the number of ethoxy radicals in the molecule - index p - is in the range from 2 to 10.
  • the substituent A in the general formula (IV) stands for propoxy radicals, the number of propoxy radicals - index (q + r) - in the range from 2 to 8 lies.
  • those compounds of the general formula (IV) are preferably used as component (d) in which R9 is a linear alkyl radical having 8 to 18 carbon atoms, p is a number in the range from 2 to 5 and A is propoxy radicals, and the sum (q + r) is a number in the range 4 to 6.
  • the reaction product of technical lauryl alcohol - which has alkyl radicals with 12 to 18 carbon atoms (thereof approx.
  • 80% with 12 to 14 carbon atoms) - is used as the surfactant component (d) with 2 up to 4 moles of ethylene oxide and 4 to 6 moles of propylene oxide or the reaction product of n-octanol with 2 to 6 moles of ethylene oxide and 2 to 5 moles of propylene oxide.
  • surfactant combinations of cationic surfactant (a) and nonionic surfactant (b) to be used according to the invention are further characterized by a specific weight ratio of components (a): (b), which is preferably in the range from 20: 1 to 1:20 is in the range from 2: 1 to 1:10.
  • the mixture also contains the nonionic surfactants (c) and / or (d)
  • these ratios also apply to (a): [(b) + (c)], (a): [ (b) + (d)] and (a): [(b) + (c) + (d)].
  • the total of the mixed ethers in (b) and any ethoxylated and / or propoxylated fatty alcohols [(c) and / or (d)] are to be understood as nonionic surfactants.
  • the ratio of mixed ether (b) to ethoxylated and / or propoxylated fatty alcohols [(c) and / or (d)] is between 10: 1 and 1:10.
  • the surfactant combinations to be used according to the invention are notable for high cleaning and demulsifying properties at temperatures in the range from 15 to 80.degree. In the temperature range mentioned, they can also be used without any problems in the spraying process, since they do not cause any undesirable foaming. Further advantages are: very good wetting properties, enabling the cleaning liquids to drain off the items to be cleaned without stains, very good demulsifying properties with regard to Non-self-emulsifying oils and greases, achieving antistatic effects, easy to assemble with additives commonly used in industrial cleaners and a low foam height in the Götte foam whipping apparatus (DIN 53902).
  • additives which are preferably used in addition to the surfactant combinations to be used according to the invention are: builder substances and / or complexing agents, corrosion inhibitors and bases or acids.
  • stabilizers, solubilizers or antimicrobial agents can also be used as additives.
  • alkali metal orthophosphates for example, alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates can be used, as well as phosphonic acids or phosphonoalkane carboxylic acids or their water-soluble alkali metal salts, for example 1-hydroxyethane-1,1-diphosphate or 2-phosphonobutane-1,2,4-tricarboxylic acid.
  • Straight-chain or branched aliphatic carboxylic acids or their salts are suitable as effective corrosion inhibitors.
  • alkanolamine salts of straight-chain or branched monocarboxylic acids with 8 to 11 carbon atoms are used as corrosion inhibitors.
  • the aqueous solutions of the surfactant combinations to be used according to the invention can be acidic or also alkaline; accordingly, they contain excess acid or bases, for example sodium hydroxide and / or potassium hydroxide.
  • the surfactant combinations to be used according to the invention are produced by simply mixing the individual components.
  • Corresponding powdery or liquid cleaning agents are also produced in the same way by mixing the Surfactant combinations to be used according to the invention with the other additives and optionally water.
  • cleaning agents of this type contain 1 to 70% by weight, preferably 2 to 20% by weight, of the surfactant combinations to be used according to the invention.
  • the surfactant combinations to be used according to the invention are preferably used in the form of application solutions diluted with water.
  • Such application solutions preferably contain the surfactant combinations to be used according to the invention in concentrations of 0.0001 to 1.5% by weight, in particular 0.0005 to 0.5% by weight.
  • Ready-to-use application solutions of this type which are used in the sense of the invention for cleaning hard surfaces in the spray process have a pH of ⁇ 7. The preparation of such application solutions is carried out by simply mixing the surfactant combinations with water.
  • Demineralized water was used in all experiments.
  • Mixtures 1 to 4 are designed so that the mixed ethers (b) have gradations in both the fatty alcohol and the EO content.
  • the mixed ether in mixtures 1 and 2 is outside the invention.
  • the quaternary ammonium compounds (a), however, are all within the scope of the present invention.
  • Foam test in the foam whipping apparatus according to DIN 53902 (foam height in ml) 100 blows / 25 ° C t / s mixture 1* 2 * 3rd 4th 0 800 260 20th 350 30th 700 30th 10th 40 60 680 30th 5 10th 100 blows / 30 ° C t / s mixture 1* 2 * 3rd 4th 0 800 50 10th 350 30th 780 15 5 20th 60 750 ⁇ 10 ⁇ 5 ⁇ 5 100 blows / 45 ° C t / s mixture 1* 2 * 3rd 4th 0 750 40 10th 200 30th 700 10th ⁇ 5 ⁇ 5 60 600 10th ⁇ 5 0

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Abstract

PCT No. PCT/EP91/00823 Sec. 371 Date Nov. 9, 1992 Sec. 102(e) Date Nov. 9, 1992 PCT Filed Apr. 30, 1991 PCT Pub. No. WO91/17233 PCT Pub. Date Nov. 14, 1991.The present invention relates to the use for cleaning hard surfaces of a combination of ionic and nonionic surfactants containing (a) at least one quaternary ammonium compound having the general formula (I) R1(-CHOH-CHR2)n-N+R3R4R5X-(I) (b) at least one alk(en)yl polyethylene glycol mixed ether having the general formula (II): R6-O-(CH2CH2-O)2-R7(II).

Description

Die vorliegende Erfindung betrifft die Verwendung einer Kombination ionischer und nichtionischer Tenside - gegebenenfalls mit üblichen Zusatzstoffen - zur Reinigung harter Oberflächen. Für solche Aufgaben werden üblicherweise sogenannte "Industriereiniger" eingesetzt.The present invention relates to the use of a combination of ionic and nonionic surfactants - optionally with customary additives - for cleaning hard surfaces. So-called "industrial cleaners" are usually used for such tasks.

Derartige Industriereiniger werden hauptsächlich in der Automobilindustrie sowie deren Zulieferindustrien zur Reinigung und Passivierung vorwiegend in Spritzreinigungsanlagen verwendet. Sie eignen sich zur Zwischen- und Endreinigung spanlos sowie spangebend bearbeiteter Teile in Aggregate- und Montagewerken. Praktisch alle relevanten Materialien, wie Eisen und Stahl, Aluminium, Silumin, Kupfer, Messing, Zink und Kunststoffe, können behandelt werden und die Mehrzahl aller Kontaminationen auf organischer oder anorganischer Basis, wie Kühlschmierstoffe, Rostschutzöle, Bearbeitungsöle, Ziehhilfsmittel, Pigmente und leichter Metallabrieb, können entfernt werden. Derartige Reinigungsmittel können auch in üblichen Tauchverfahren Anwendung finden, jedoch ist deren Anwendung im Spritzverfahren üblicherweise bevorzugt.Industrial cleaners of this type are mainly used in the automotive industry and their supplier industries for cleaning and passivation, primarily in spray cleaning systems. They are suitable for intermediate and final cleaning without cutting as well as machined parts in unit and assembly plants. Practically all relevant materials, such as iron and steel, aluminum, silumin, copper, brass, zinc and plastics, can be treated and the majority of all contaminations on an organic or inorganic basis, such as cooling lubricants, rust protection oils, processing oils, drawing aids, pigments and light metal abrasion, can be removed. Such cleaning agents can also be used in customary immersion processes, but their use in the spraying process is usually preferred.

Die chemischen Basiskomponenten derartiger Industriereiniger sind üblicherweise Tenside und organische Korrosionsinhibitoren. Die letzteren gewährleisten einen temporären Korrosionsschutz während und nach der Behandlung. Zusätzlich enthalten derartige Reinigungsmittel in der Regel Substanzen, die in der Lage sind, einer unerwünschten Schaumentwicklung entgegenzuwirken. Der Einsatz solcher schauminhibierender Zusätze ist in den meisten Fällen dadurch bedingt, daß die von den Substraten abgelösten und in den Reinigungsbädern sich ansammelnden Verunreinigungen als Schaumbildner wirken.The chemical basic components of such industrial cleaners are usually surfactants and organic corrosion inhibitors. The latter ensure temporary protection against corrosion during and after treatment. In addition, cleaning agents of this type generally contain substances which are able to counteract undesirable foam development. The use of such foam-inhibiting additives is in most cases due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents.

Daneben kann die Verwendung von sogenannten Antischaummitteln auch aufgrund der Tatsache erforderlich sein, daß die Reinigungsmittel selbst Bestandteile enthalten, die unter den vorgegebenen Arbeitsbedingungen - d.h. insbesondere bei Spritzverfahren - zu unerwünschter Schaumbildung Anlaß geben, beispielsweise anionische Tenside oder bei der jeweiligen Arbeitstemperatur schäumende nichtionische Tenside.In addition, the use of so-called anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves contain constituents which, under the given working conditions - i.e. especially in spraying processes - give rise to undesirable foaming, for example anionic surfactants or nonionic surfactants foaming at the respective working temperature.

Aus "Ullmanns Encyklopädie der technischen Chemie", 4. Auflage, Band 22 (1982), Seiten 489 bis 493, ist die Verwendung von Fettalkohol-polyethylenglykolethern - auch Fettalkohol-ethoxylate genannt - als Tensidkomponente in Wasch- und Reinigungsmitteln bekannt. Jedoch sind derartige Anlagerungprodukte von Ethylenoxid an Fettalkohole nicht für den Einsatz in Spritzverfahren geeignet, da sie bei Anwendungstemperaturen im Bereich von 15 bis 80 °C stark schäumen. Es ist ferner bekannt, Fettalkohol-ethoxylatpropoxylate als schwach schäumende Waschrohstoffe einzusetzen; vgl. beispielsweise den vorstehend zitierten Ullmann-Band, Seite 494.From "Ullmann's Encyclopedia of Industrial Chemistry", 4th edition, volume 22 (1982), pages 489 to 493, the use of fatty alcohol polyethylene glycol ethers - also known as fatty alcohol ethoxylates - is known as a surfactant component in detergents and cleaning agents. However, such addition products of ethylene oxide with fatty alcohols are not suitable for use in spray processes, since they foam strongly at application temperatures in the range from 15 to 80.degree. It is also known to use fatty alcohol ethoxylate propoxylates as low-foaming wash raw materials; see. for example the Ullmann volume cited above, page 494.

DE-A-36 20 011 beschreibt Kationtenside auf der Basis von quartären Ammoniumverbindungen und ihre Verwendung in Reinigungsmitteln. Die Kationtenside werden im alkalischen pH-Wert-Bereich neben weiteren Reinigerbestandteilen verwendet.DE-A-36 20 011 describes cationic surfactants based on quaternary ammonium compounds and their use in cleaning agents. The cationic surfactants are used in the alkaline pH range in addition to other detergent components.

EP-A-0 116 151 beschreibt ein Verfahren zur Regenerierung bzw. zum Recycling von wäßrigen Entfettungs- und Reinigungslösungen durch Zusatz von kationischen Tensiden oder kationisch modifizerten Polymeren oder Gemischen daraus.EP-A-0 116 151 describes a process for the regeneration or recycling of aqueous degreasing and cleaning solutions by adding cationic surfactants or cationically modified polymers or mixtures thereof.

In der EP-A-0 054 894 wird ein tensidhaltiges Gemisch zur maschinellen Reinigung harter Oberflächen im alkalischen Flottenbereich beschrieben, welches nichtionische Tenside vom Typ der Alkyl-ethoxylate oder -propoxylate (Komponente A), quartäre Ammoniumverbindungen (Komponente B) und fluorierte Alkohole (Komponente C) enthält. Als nichtionische Tenside kommen unter anderem Alkyl-polyethylenglykol-Mischether des Typs C₆₋₂₂-Alkyl - 5 bis 20 EO - C₁₋₄-Alkyl (EO = Ethylenoxideinheiten) in Frage. Die in den Beispielen genannten nichtionischen Tenside dieses Typs enthalten als C₁₋₄-Alkylrest ausschließlich tertiäre Butylgruppen. Die quartären Ammoniumverbindungen weisen ausschließlich kurze bis mittlere C-Ketten - bis zu maximal 12 C-Atomen - auf. Zudem ist hierbei ein Zusatz an fluorierten Alkoholen als Antischaummittel erforderlich.EP-A-0 054 894 describes a surfactant-containing mixture for the mechanical cleaning of hard surfaces in the alkaline liquor range, which contains nonionic surfactants of the alkyl ethoxylate or propoxylate type (component A), quaternary ammonium compounds (component B) and fluorinated alcohols ( Component C) contains. Suitable nonionic surfactants include alkyl-polyethylene glycol mixed ethers of the type C₆₋₂₂-alkyl - 5 to 20 EO - C₁₋₄-alkyl (EO = ethylene oxide units). The nonionic surfactants of this type mentioned in the examples contain only tertiary butyl groups as C₁₋₄-alkyl radical. The quaternary ammonium compounds only have short to medium carbon chains - up to a maximum of 12 carbon atoms. It is also necessary to add fluorinated alcohols as an anti-foaming agent.

Die EP-A-0 054 895 beschreibt gleichfalls ein Tensidgemisch zur Reinigung harter Oberflächen im alkalischen Flottenbereich, welches nichtionische Tenside (Komponente A) und ausgewählte quartäre Ammoniumverbindungen als kationische Tenside (Komponente B) enthält. Als nichtionische Tenside kommen hierbei Alkyl-polyethylenglykol-Mischether des Typs C₆₋₁₈-Alkyl - 6 bis 12 EO - C₁₋₄-Alkyl in Frage, wobei wiederum die in den Beispielen genannten Verbindungen dieses Typs als C₁₋₄-Alkylrest ausschließlich tertiäre Butylgruppen enthalten. Die quartären Ammoniumverbindungen weisen hierbei ausschließlich kurze bis mittlere C-Ketten - bis zu maximal 8 C-Atomen - auf.EP-A-0 054 895 also describes a surfactant mixture for cleaning hard surfaces in the alkaline liquor range, which contains nonionic surfactants (component A) and selected quaternary ammonium compounds as cationic surfactants (component B). Suitable nonionic surfactants here are alkyl-polyethylene glycol mixed ethers of the type C₆₋₁₈-alkyl - 6 to 12 EO - C₁₋₄-alkyl, in turn the compounds of this type mentioned in the examples as C₁₋₄-alkyl radical being exclusively tertiary butyl groups contain. The quaternary ammonium compounds only have short to medium carbon chains - up to a maximum of 8 carbon atoms.

Die DE-A-25 56 499 betrifft schaumarme Desinfektionsreiniger, die als nichtionische Tenside unter anderem Alkyl-polyethylenglykol-Mischether des Typs C₆₋₂₂-Alkyl - 5 bis 50 EO - tert. Butyl enthalten. Zusätzlich können derartige Formulierungen als desinfizierend wirkende Komponente unter anderem quartäre Ammoniumverbindungen, die auch langkettige Alkylreste mit 8 bis 18 C-Atomen aufweisen, enthalten.DE-A-25 56 499 relates to low-foaming disinfectant cleaners which, as nonionic surfactants, include alkyl-polyethylene glycol mixed ethers of the type C₆ ₋₂ ₂-alkyl - 5 to 50 EO - tert. Contain butyl. In addition, formulations of this type can contain, among other things, quaternary ammonium compounds, which also have long-chain alkyl radicals with 8 to 18 carbon atoms, as a disinfectant component.

Gegenstand der EP-A-0 254 208 sind schaumarme und/oder schaumdämpfende Tensidgemische, die auch für den Einsatz im Bereich der maschinellen Spritz- bzw. Hochdruckreinigung bei Temperaturen unterhalb 50 °C geeignet sind. Diese Gemische enthalten die folgenden nichtionischen Tenside: Endgruppenverschlossene Polyethylenglykolether des Typs C₈₋₁₈-Alkyl - 3 bis 7 EO - C₄₋₈-Alkyl (Komponente I), Alkylpolyalkylenglykol-Mischether des Typs C₈₋₁₈-Alkyl - 1 bis 3 EO - 3 bis 6 PO -H (Komponente II, mit PO = Propylenoxideinheiten) sowie gegebenenfalls Alkyl-(poly)-propylenglykolether des Typs C₁₆₋₂₂-Alkyl - 1 bis 3 PO-H (Komponente III).EP-A-0 254 208 relates to low-foam and / or foam-suppressing surfactant mixtures which are also suitable for use in the field of machine spray or high-pressure cleaning at temperatures below 50 ° C. These mixtures contain the following nonionic surfactants: end-capped polyethylene glycol ethers of the type C₈ ₋ ₁₈-alkyl - 3 to 7 EO - C₄ ₋ ₈-alkyl (component I), alkylpolyalkylene glycol-mixed ethers of the type C₈ ₋ ₁₈-alkyl - 1 to 3 EO - 3 to 6 PO -H (component II, with PO = propylene oxide units) and optionally alkyl (poly) propylene glycol ether of the type C₁₆ ₋ ₂₂-alkyl - 1 to 3 PO-H (component III).

Der vorliegenden Erfindung lag demgegenüber die Aufgabe zugrunde, Tensid-Kombinationen zur Reinigung harter Oberflächen bereitzustellen, welche im gesamten anwendungstechnisch relevanten Temperaturbereich, nämlich im Bereich von 15 bis 80 °C, schaumarme Eigenschaften zeigen und somit für den Einsatz in Spritzverfahren geeignet sind. Darüber hinaus sollen diese Tensid-Kombinationen ein hohes Reinigungsvermögen und ausgezeichnete Benetzungseigenschaften gegenüber den damit behandelten Substraten aufweisen; ferner sollen sich diese Tensid-Kombinationen mit in Industriereinigern üblichen Zusätzen gut konfektionieren lassen, ein gutes, fleckenfreies Ablaufen der Reinigungsmittellösungen von den behandelten Substratoberflächen ermöglichen und demulgierende Eigenschaften bezüglich nicht-selbstemulgierender Öle und Fette aufweisen. Des weiteren sollen vorteilhafte elektrostatische Effekte erzielt werden.In contrast, the object of the present invention was to provide surfactant combinations for cleaning hard surfaces which have low-foaming properties in the entire temperature range relevant to the application, namely in the range from 15 to 80 ° C., and are therefore suitable for use in spraying processes. In addition, these surfactant combinations should have a high cleaning ability and excellent wetting properties compared to the substrates treated with them; Furthermore, these surfactant combinations should be easy to assemble with additives customary in industrial cleaners, allow the cleaning agent solutions to run off the treated substrate surfaces without stains and have demulsifying properties with regard to non-self-emulsifying oils and fats. Furthermore, advantageous electrostatic effects are to be achieved.

Überraschenderweise hat sich gezeigt, daß Mischungen von speziellen ionischen und nichtionischen Tensiden über einen weiten Mischungsbereich die in der vorstehenden Aufgabenstellung beschriebenen Forderungen voll erfüllen.Surprisingly, it has been found that mixtures of special ionic and nonionic surfactants over a wide range of mixtures fully meet the requirements described in the above task.

Die vorliegende Erfindung betrifft somit die Verwendung einer Kombination ionischer und nichtionischer Tenside, enthaltend:

  • (a) mindestens eine quartäre Ammoniumverbindung der allgemeinen Formel (I)



            R¹(-CHOH-CHR²)n-N⁺R³R⁴R⁵ X⁻   (I)



    in der
    R¹
    ein linearer oder verzweigter Alkylrest mit 1 bis 22 C-Atomen,
    R²
    Wasserstoff oder ein linearer oder verzweigter Alkylrest mit 1 bis 21 C-Atomen sein kann,
    wobei die Gesamtzahl der C-Atome der Substituenten R¹ und R² im Bereich von 10 bis 22 liegt,
    n
    = 0 oder 1 ist,
    R³ und R⁴
    für Methyl, Ethyl, 2-Hydroxyethyl oder Hydroxypropyl,
    R⁵
    für Alkylreste mit 4 bis 6 C-Atomen oder Phenalkylreste mit 1 bis 3 C-Atomen im Alkylrest und
    X⁻
    für Halogenid oder das Anion einer organischen Säure mit 4 bis 15 C-Atomen stehen
    und
  • (b) mindestens einen Alk(en)yl-polyethylenglykol-Mischether der allgemeinen Formel (II)



            R⁶-O-(CH₂CH₂-O)s-R⁷   (II)



    in der
    R⁶
    einen linearen Alkylrest mit 8 bis 10 C-Atomen,
    s
    eine Zahl im Bereich von 3,5 bis 4,5 und
    R⁷
    einen linearen Alkylrest mit 4 C-Atomen bedeuten,
    wobei das Gewichtsverhältnis der Komponenten (a) : (b) im Bereich von 20 : 1 bis 1 : 20 liegt, zur Reinigung von harten Oberflächen.
    Besonders bevorzugt ist ein Gewichtsverhältnis der Komponenten (a) : (b) von 2 : 1 bis 1 : 10.
    Als Anion der quartären Ammoniumverbindung X⁻ sind insbesondere bevorzugt Benzoat, oder mit CH₃, NH₂, NO₂, COOH, OH oder SO₃H monosubstituiertes Benzoat oder Isononanoat als Anionen von organischen Säuren. Als Halogenid findet insbesondere Chlorid oder Bromid Verwendung.
    Als quartäre Ammoniumverbindung eignen sich insbesondere Lauryldimethylbenzylammoniumchlorid, N-Benzyl-N-2-hydroxydodecyl-N,N-dimethylammoniumisononanoat oder N-Benzyl-N-2-hydroxydodecyl-N,N-dimethylammoniumbenzoat.
    In der allgemeinen Formel (II) der Tensidkomponente (b) steht R⁶ mithin für einen linearen Alkylrest mit 8 bis 10 C-Atomen. Als Substituent R⁶ kommen somit die folgenden Reste in Frage: n-Octyl, n-Nonyl, und n-Decyl. Die Anzahl der Ethoxyreste im Molekül - Index s - liegt hier im Bereich von 3,5 bis 4,5. Der Substituent R⁷ in der allgemeinen Formel (II) steht für einen linearen Alkylrest mit 4 C-Atomen, somit für n-Butyl. Derartige Alk(en)yl-ethoxylat-Mischether, die auch als endgruppenverschlossene Fettalkohol-polyethylenglykolether bezeichnet werden, werden in den DE-A-33 15 951, 37 27 378 und 38 00 490 näher beschrieben. In diesen DE-A wird auch die Herstellung dieser nichtionischen Tenside im einzelnen offenbart.
    Die erfindungsgemäße Tensid-Kombination erfüllt voll die Anforderungen der vorstehend aufgezeigten Aufgabenstellung. Die erfindungsgemäße Kombination der speziellen Komponenten (a) und (b) bedingt neben einem hohen Reinigungsvermögen insbesondere eine wirkungsvolle Demulgierung anionischer Tenside bzw. Emulgatoren, wobei - selbst beim Einsatz im Spritzverfahren - keine störende Schaumentwicklung auftritt.
    Der Tensidkombination, bestehend aus den Komponenten (a) und (b), können gegebenenfalls noch weitere Komponenten zugegeben werden. Es handelt sich dabei um
  • (c) mindestens ein Alk(en)yl-ethoxylat der allgemeinen Formel (III)



            R⁸-O(CH₂CH₂-O)m-H   (III)



    in der
    R⁸
    einen linearen oder verzweigten Alkylrest oder Alkenylrest mit 6 bis 18 C-Atomen oder einen cyclischen Alkylrest mit 5 bis 6 C-Atomen und
    m
    eine Zahl im Bereich von 2 bis 12
       bedeuten und/oder
  • (d) mindestens ein Alk(en)yl-ethoxylatpropoxylat der allgemeinen Formel (IV)



            R⁹-O(CH₂CH₂O)p-A-H   (IV)



    in der
    R⁹
    einen linearen oder verzweigten Alkylrest oder Alkenylrest mit 6 bis 18 C-Atomen oder einen cyclischen Alkylrest mit 5 bis 6 C-Atomen,
    p
    eine Zahl im Bereich von 2 bis 10 und
    A
    Reste vom Typ -(CH₂-CH(CH₃)-O)q und -(CH(CH₃)-CH₂-O)r- bedeuten, wobei die Summe (q + r) eine Zahl im Bereich von 2 bis 8 ist.
The present invention thus relates to the use of a combination of ionic and nonionic surfactants, comprising:
  • (a) at least one quaternary ammonium compound of the general formula (I)



    R¹ (-CHOH-CHR²) n -N⁺R³R⁴R⁵ X⁻ (I)



    in the
    R¹
    a linear or branched alkyl radical with 1 to 22 C atoms,
    R²
    Can be hydrogen or a linear or branched alkyl radical having 1 to 21 carbon atoms,
    the total number of carbon atoms of the substituents R 1 and R 2 is in the range from 10 to 22,
    n
    = 0 or 1,
    R³ and R⁴
    for methyl, ethyl, 2-hydroxyethyl or hydroxypropyl,
    R⁵
    for alkyl radicals with 4 to 6 carbon atoms or phenalkyl radicals with 1 to 3 carbon atoms in the alkyl radical and
    X⁻
    stand for halide or the anion of an organic acid with 4 to 15 carbon atoms
    and
  • (b) at least one alk (en) yl-polyethylene glycol mixed ether of the general formula (II)



    R⁶-O- (CH₂CH₂-O) s -R⁷ (II)



    in the
    R⁶
    a linear alkyl radical with 8 to 10 carbon atoms,
    s
    a number in the range from 3.5 to 4.5 and
    R⁷
    represent a linear alkyl radical with 4 carbon atoms,
    wherein the weight ratio of components (a): (b) is in the range from 20: 1 to 1:20, for cleaning hard surfaces.
    A weight ratio of components (a): (b) of 2: 1 to 1:10 is particularly preferred.
    As an anion of the quaternary ammonium compound X⁻ are particularly preferred benzoate, or with CH₃, NH₂, NO₂, COOH, OH or SO₃H mono-substituted benzoate or isononanoate as anions of organic acids. In particular, chloride or bromide is used as the halide.
    Particularly suitable quaternary ammonium compounds are lauryldimethylbenzylammonium chloride, N-benzyl-N-2-hydroxydodecyl-N, N-dimethylammoniumisononanoate or N-benzyl-N-2-hydroxydodecyl-N, N-dimethylammoniumbenzoate.
    In the general formula (II) of the surfactant component (b), R⁶ therefore represents a linear alkyl radical having 8 to 10 carbon atoms. The following radicals are thus suitable as substituent R⁶: n-octyl, n-nonyl, and n-decyl. The number of ethoxy residues in the molecule - index s - is in the range from 3.5 to 4.5. The substituent R⁷ in the general formula (II) stands for a linear alkyl radical with 4 carbon atoms, thus for n-butyl. Such alk (en) yl ethoxylate mixed ethers, which are also referred to as end-capped fatty alcohol polyethylene glycol ethers, are described in more detail in DE-A-33 15 951, 37 27 378 and 38 00 490. These DE-A also disclose the production of these nonionic surfactants in detail.
    The surfactant combination according to the invention fully meets the requirements of the task outlined above. The combination of the special components (a) and (b) according to the invention requires, in addition to a high cleaning capacity, in particular an effective demulsification of anionic surfactants or emulsifiers, wherein - even when used in the spraying process - no disruptive foaming occurs.
    The surfactant combination consisting of components (a) and (b) can, if appropriate, be added to further components. It is about
  • (c) at least one alk (en) yl ethoxylate of the general formula (III)



    R⁸-O (CH₂CH₂-O) m -H (III)



    in the
    R⁸
    a linear or branched alkyl radical or alkenyl radical with 6 to 18 carbon atoms or a cyclic alkyl radical with 5 to 6 carbon atoms and
    m
    a number in the range from 2 to 12
    mean and / or
  • (d) at least one alk (en) yl ethoxylate propoxylate of the general formula (IV)



    R⁹-O (CH₂CH₂O) p -AH (IV)



    in the
    R⁹
    a linear or branched alkyl radical or alkenyl radical with 6 to 18 C atoms or a cyclic alkyl radical with 5 to 6 C atoms,
    p
    a number in the range from 2 to 10 and
    A
    Residues of the type - (CH₂-CH (CH₃) -O) q and - (CH (CH₃) -CH₂-O) r - mean, the sum (q + r) being a number in the range from 2 to 8.

Bezüglich der gegebenenfalls verwendbaren Tensidkomponenten (c) und (d) gilt im einzelnen das Folgende:With regard to the surfactant components (c) and (d) which may be used, the following applies in detail:

In der vorstehend genannten allgemeinen Formel (III) der Komponenten (c) steht R⁸ für einen linearen oder verzweigten Alkylrest oder Alkenylrest mit 6 bis 18 C-Atomen. Als Substituent R⁸ kommen somit die folgenden Reste in Frage: n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl und n-Octadecyl sowie die verzweigtkettigen Isomere der genannten Alkylreste.In the above general formula (III) of components (c) R⁸ is a linear or branched alkyl radical or alkenyl radical having 6 to 18 carbon atoms. Thus come as a substituent R⁸ the following radicals in question: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl and the branched chain isomers of the alkyl radicals mentioned.

Anstelle der gesättigten Alkylreste kann R⁸ auch die ungesättigten Alkylreste (Alkenylreste) mit einer Anzahl von C-Atomen im oben genannten Bereich bedeuten, die gleichfalls linear oder verzweigt sein können. Ferner kann R⁸ auch für einen cyclischen Alkylrest mit 5 bis 6 C-Atomen, d.h. Cyclopentyl oder Cyclohexyl, stehen. Die Anzahl der Ethoxyreste im Molekül - Index m - liegt im Bereich von 2 bis 12.Instead of the saturated alkyl radicals, R⁸ can also mean the unsaturated alkyl radicals (alkenyl radicals) with a number of carbon atoms in the above range, which can also be linear or branched. Furthermore, R⁸ can also be a cyclic alkyl radical having 5 to 6 carbon atoms, i.e. Cyclopentyl or cyclohexyl. The number of ethoxy residues in the molecule - index m - is in the range from 2 to 12.

Im Sinne der Erfindung werden bevorzugt solche Verbindungen der allgemeinen Formel (III) als Komponente (c) eingesetzt, in denen R⁸ einen linearen Alkylrest oder Alkenylrest mit 6 bis 18 C-Atomen und m eine Zahl im Bereich von 2 bis 10 bedeuten. Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung verwendet man als Tensidkomponente (c) das Umsetzungsprodukt von Octanol (R⁸ = linearer Alkylrest mit 8 C-Atomen) mit 4 Molen Ethylenoxid.For the purposes of the invention, those compounds of the general formula (III) are preferably used as component (c) in which R⁸ is a linear alkyl radical or alkenyl radical having 6 to 18 carbon atoms and m is a number in the range from 2 to 10. According to a particularly preferred embodiment of the present invention the surfactant component (c) is the reaction product of octanol (R⁸ = linear alkyl radical with 8 carbon atoms) with 4 moles of ethylene oxide.

Zur Herstellung von Verbindungen der allgemeinen Formel (III) sei beispielsweise auf die vorstehend zitierte Ullmann-Monographie verwiesen. Derartige Produkte sind auch im Handel erhältlich, beispielsweise unter der Markenbezeichnung DehydolR (Henkel KGaA, Düsseldorf).For the preparation of compounds of the general formula (III), reference is made, for example, to the Ullmann monograph cited above. Such products are also commercially available, for example under the brand name Dehydol R (Henkel KGaA, Düsseldorf).

In der vorstehend genannten allgemeinen Formel (IV) der Tensidkomponenten (d) steht R⁹ für eine linearen oder verzweigten Alkylrest oder Alkenylrest mit 6 bis 18 C-Atomen oder einen cyclischen Alkylrest mit 5 bis 6 C-Atomen. Als Substituent R⁹ kommen somit alle diejenigen Reste in Frage, die vorstehend bereits im Zusammenhang mit dem Substituenten R⁸ der allgemeinen Formel (III) erläutert worden sind. Die Anzahl der Ethoxyreste im Molekül - Index p - liegt im Bereich von 2 bis 10. Der Substituent A in der allgemeinen Formel (IV) steht für Propoxyreste, wobei die Anzahl der Propoxyreste - Index (q + r) - im Bereich von 2 bis 8 liegt.In the above-mentioned general formula (IV) of the surfactant components (d), R linear represents a linear or branched alkyl radical or alkenyl radical with 6 to 18 carbon atoms or a cyclic alkyl radical with 5 to 6 carbon atoms. Suitable substituents R⁹ are all those radicals which have already been explained above in connection with the substituent R⁸ of the general formula (III). The number of ethoxy radicals in the molecule - index p - is in the range from 2 to 10. The substituent A in the general formula (IV) stands for propoxy radicals, the number of propoxy radicals - index (q + r) - in the range from 2 to 8 lies.

Im Sinne der Erfindung werden als Komponente (d) bevorzugt solche Verbindungen der allgemeinen Formel (IV) eingesetzt, in denen R⁹ einen linearen Alkylrest mit 8 bis 18 C-Atomen, p eine Zahl im Bereich von 2 bis 5 und A Propoxyreste bedeuten, und die Summe (q + r) eine Zahl im Bereich von 4 bis 6 ist. Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung verwendet man als Tensid-Komponenten (d) das Umsetzungsprodukt von technischem Laurylalkohol - der Alkylreste mit 12 bis 18 C-Atomen aufweist (davon ca. 80 % mit 12 bis 14 C-Atomen) - mit 2 bis 4 Molen Ethylenoxid und 4 bis 6 Molen Propylenoxid oder das Umsetzungsprodukt von n-Octanol mit 2 bis 6 Molen Ethylenoxid und 2 bis 5 Molen Propylenoxid.For the purposes of the invention, those compounds of the general formula (IV) are preferably used as component (d) in which R⁹ is a linear alkyl radical having 8 to 18 carbon atoms, p is a number in the range from 2 to 5 and A is propoxy radicals, and the sum (q + r) is a number in the range 4 to 6. According to a particularly preferred embodiment of the present invention, the reaction product of technical lauryl alcohol - which has alkyl radicals with 12 to 18 carbon atoms (thereof approx. 80% with 12 to 14 carbon atoms) - is used as the surfactant component (d) with 2 up to 4 moles of ethylene oxide and 4 to 6 moles of propylene oxide or the reaction product of n-octanol with 2 to 6 moles of ethylene oxide and 2 to 5 moles of propylene oxide.

Zur Herstellung von Verbindungen der allgemeinen Formel (IV) sei beispielsweise gleichfalls auf die vorstehend zitierte Ullmann-Monographie verwiesen. Auch derartige Produkte sind im Handel erhältlich, beispielsweise unter der Markenbezeichnung DEHYPONR-LS bzw. -LT (Henkel KGaA, Düsseldorf).For the preparation of compounds of the general formula (IV), reference is also made, for example, to the Ullmann monograph cited above. Products of this type are also commercially available, for example under the brand name DEHYPON R -LS or -LT (Henkel KGaA, Düsseldorf).

Die erfindungsgemäß zu verwendenden Tensid-Kombinationen aus kationischem Tensid (a) und nichtionischem Tensid (b) zeichnen sich ferner durch ein bestimmtes Gewichtsverhältnis der Komponenten (a) : (b) aus, welches im Bereich von 20 : 1 bis 1 : 20, vorzugsweise im Bereich von 2 : 1 bis 1 : 10, liegt.The surfactant combinations of cationic surfactant (a) and nonionic surfactant (b) to be used according to the invention are further characterized by a specific weight ratio of components (a): (b), which is preferably in the range from 20: 1 to 1:20 is in the range from 2: 1 to 1:10.

Sind neben dem nichtionischen Tensid (b) außerdem die nichtionischen Tenside (c) und/oder (d) im Gemisch enthalten, so gelten diese Verhältnisse auch für (a) : [(b) + (c)], (a) : [(b) + (d)] und (a) : [(b) + (c) + (d)].If, in addition to the nonionic surfactant (b), the mixture also contains the nonionic surfactants (c) and / or (d), these ratios also apply to (a): [(b) + (c)], (a): [ (b) + (d)] and (a): [(b) + (c) + (d)].

Die Mischether in (b) und die gegebenenfalls enthaltenen ethoxylierten und/oder propoxylierten Fettalkohole [(c) und/oder (d)] sind in ihrer Summe als nichtionische Tenside zu verstehen. Das Verhältnis von Mischether (b) zu ethoxylierten und/oder propoxylierten Fettalkoholen [(c) und/oder (d)] beträgt zwischen 10 : 1 und 1 : 10.The total of the mixed ethers in (b) and any ethoxylated and / or propoxylated fatty alcohols [(c) and / or (d)] are to be understood as nonionic surfactants. The ratio of mixed ether (b) to ethoxylated and / or propoxylated fatty alcohols [(c) and / or (d)] is between 10: 1 and 1:10.

Die erfindungsgemäß zu verwendenden Tensid-Kombinationen zeichnen sich durch ein hohes Reinigungs- und Demulgiervermögen bei Temperaturen im Bereich von 15 bis 80 °C aus. In dem genannten Temperaturbereich sind sie darüberhinaus auch im Spritzverfahren problemlos verwendbar, da sie keine unerwünschte Schaumentwicklung bedingen. Weitere Vorteile sind: sehr gute Benetzungseigenschaften, Ermöglichung von fleckenfreiem Ablaufen der Reinigungsflüssigkeiten vom Reinigungsgut, sehr gute demulgierende Eigenschaften bezüglich nicht-selbstemulgierender Öle und Fette, Erzielung antistatischer Effekte, eine gute Konfektionierbarkeit mit in Industriereinigern üblicherweise verwendeten Zusatzstoffen sowie eine geringe Schaumhöhe in der Schaumschlagapparatur nach Götte (DIN 53902).The surfactant combinations to be used according to the invention are notable for high cleaning and demulsifying properties at temperatures in the range from 15 to 80.degree. In the temperature range mentioned, they can also be used without any problems in the spraying process, since they do not cause any undesirable foaming. Further advantages are: very good wetting properties, enabling the cleaning liquids to drain off the items to be cleaned without stains, very good demulsifying properties with regard to Non-self-emulsifying oils and greases, achieving antistatic effects, easy to assemble with additives commonly used in industrial cleaners and a low foam height in the Götte foam whipping apparatus (DIN 53902).

Als Zusatzstoffe, die im Sinne der Erfindung vorzugsweise zusätzlich zu den erfindungsgemäß zu verwendenden Tensid-Kombinationen eingesetzt werden, kommen in Frage: Gerüstsubstanzen und/oder Komplexbildner, Korrosionsinhibitoren sowie Basen oder Säuren. Gegebenenfalls können auch noch Stabilisatoren, Lösungsvermittler oder antimikrobielle Wirkstoffe als Zusätze Verwendung finden.Possible additives which are preferably used in addition to the surfactant combinations to be used according to the invention are: builder substances and / or complexing agents, corrosion inhibitors and bases or acids. Optionally, stabilizers, solubilizers or antimicrobial agents can also be used as additives.

Als Gerüstsubstanzen und/oder Komplexbildner können beispielsweise Alkalimetallorthophosphate, -polyphosphate, -silikate, -borate, -carbonate, -polyacrylate und -gluconate eingesetzt werden, sowie Phosphonsäuren oder Phosphonoalkancarbonsäuren bzw. deren wasserlösliche Alkalimetallsalze, beispielsweise 1-Hydroxyethan-1,1-diphosphonsäure oder 2-Phosphonobutan-1,2,4-tricarbonsäure. Geradkettige oder verzweigte aliphatische Carbonsäuren bzw. deren Salze sind als wirkungsvolle Korrosionsinhibitoren geeignet. Insbesondere werden hierbei Alkanolaminsalze von geradkettigen oder verzweigten Monocarbonsäuren mit 8 bis 11 C-Atomen als Korrosionsinhibitoren verwendet. Je nach Anwendungszweck können die wäßrigen Lösungen der erfindungsgemäß zu verwendenden Tensid-Kombinationen sauer oder auch alkalisch sein; dementsprechend enthalten sie überschüssige Säure oder aber Basen, beispielsweise Natriumhydroxid und/oder Kaliumhydroxid.As builders and / or complexing agents, for example, alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates can be used, as well as phosphonic acids or phosphonoalkane carboxylic acids or their water-soluble alkali metal salts, for example 1-hydroxyethane-1,1-diphosphate or 2-phosphonobutane-1,2,4-tricarboxylic acid. Straight-chain or branched aliphatic carboxylic acids or their salts are suitable as effective corrosion inhibitors. In particular, alkanolamine salts of straight-chain or branched monocarboxylic acids with 8 to 11 carbon atoms are used as corrosion inhibitors. Depending on the intended use, the aqueous solutions of the surfactant combinations to be used according to the invention can be acidic or also alkaline; accordingly, they contain excess acid or bases, for example sodium hydroxide and / or potassium hydroxide.

Die Herstellung der erfindungsgemäß zu verwendenden Tensid-Kombinationen erfolgt durch einfaches Vermischen der einzelnen Komponenten. In gleicher Weise erfolgt auch die Herstellung entsprechender pulverförmiger oder flüssiger Reinigungmittel durch Vermischen der erfindungsgemäß zu verwendenden Tensid-Kombinationen mit den anderen Zusatzstoffen und gegebenenfalls Wasser. Im Sinne der Erfindung enthalten derartige Reinigungsmittel 1 bis 70 Gew.-%, vorzugsweise 2 bis 20 Gew.-% der erfindungsgemäß zu verwendenden Tensid-Kombinationen.The surfactant combinations to be used according to the invention are produced by simply mixing the individual components. Corresponding powdery or liquid cleaning agents are also produced in the same way by mixing the Surfactant combinations to be used according to the invention with the other additives and optionally water. For the purposes of the invention, cleaning agents of this type contain 1 to 70% by weight, preferably 2 to 20% by weight, of the surfactant combinations to be used according to the invention.

Im Sinne der Erfindung werden die erfindungsgemäß zu verwendenden Tensid-Kombinationen vorzugsweise in Form von mit Wasser verdünnten Anwendungslösungen eingesetzt. Vorzugsweise enthalten derartige Anwendungslösungen die erfindungsgemäß zu verwendenden Tensid-Kombinationen in Konzentrationen von 0,0001 bis 1,5 Gew.-%, insbesondere von 0,0005 bis 0,5 Gew.-%. Solche gebrauchsfertigen Anwendungslösungen, die im Sinne der Erfindung zur Reinigung harter Oberflächen im Spritzverfahren eingesetzt werden, besitzen einen pH von ≧ 7. Die Herstellung solcher Anwendungslösungen erfolgt durch einfaches Vermischen der Tensid-Kombinationen mit Wasser.For the purposes of the invention, the surfactant combinations to be used according to the invention are preferably used in the form of application solutions diluted with water. Such application solutions preferably contain the surfactant combinations to be used according to the invention in concentrations of 0.0001 to 1.5% by weight, in particular 0.0005 to 0.5% by weight. Ready-to-use application solutions of this type which are used in the sense of the invention for cleaning hard surfaces in the spray process have a pH of ≧ 7. The preparation of such application solutions is carried out by simply mixing the surfactant combinations with water.

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

Beispiel 1example 1 Erfindungsgemäße Tensid-Kombinationen und Vergleichs-Formulierungen (*)Surfactant combinations according to the invention and comparative formulations (*)

Die nachstehend verwendeten Abkürzungen haben die folgende Bedeutung: EO = Ethylenoxid, PO = Propylenoxid.

A*
20 Teile Octanol + 4 EO (c)
20 Teile Octanol/Decanol + 3 EO-butylether (b)
7 Teile Lauryldimethylbenzylammoniumchlorid (a)
30 Teile Fettalkohol C₁₂₋₁₈ + 2 EO + 4 PO (d)
B*
4 Teile Decanol + 2,9 EO (c)
36 Teile Decanol + 2 EO-butylether (b)
7 Teile Lauryldimethylbenzylammoniumchlorid (a)
C
2 Teile Octanol/Hexadecanol + 4 EO (c)
4 Teile Octanol/Decanol + 4 EO-butylether (b)
5 Teile N-Benzyl-N-2-hydroxydodecyl-N,N-dimethylammoniumisononanoat (a)
D*
6 Teile Octadecenol + 2 EO (c)
2 Teile Fettalkohol C₁₂₋₁₄ + 10 EO-butylether (b)
13 Teile N-Benzyl-N-2-hydroxydodecyl-N,N-dimethylammoniumisononanoat (a)
E
15 Teile Octanol + 4 EO-butylether (b)
3 Teile N-Benzyl-N-2-hydroxydodecyl-N,N-dimethylammoniumbenzoat (a)
2 Teile Fettalkohol C₁₂₋₁₈ - 2 EO - 4 PO (d)
F
15 Teile Octanol/Decanol + 4 EO-butylether (b)
1 Teil Lauryldimethylbenzylammoniumchlorid (a)
G
2 Teile Octanol + 10 EO (c)
4 Teile Octanol/Decanol + 4 EO-butylether (b)
5 Teile N-Benzyl-N-2-hydroxydodecyl-N,N-dimethylammoniumisononanoat (a)
5 Teile Fettalkohol C₁₂₋₁₈ + 3 EO + 6 PO (d)
The abbreviations used below have the following meanings: EO = ethylene oxide, PO = propylene oxide.
A *
20 parts octanol + 4 EO (c)
20 parts octanol / decanol + 3 EO-butyl ether (b)
7 parts lauryldimethylbenzylammonium chloride (a)
30 parts of fatty alcohol C₁₂₋₁₈ + 2 EO + 4 PO (d)
B *
4 parts decanol + 2.9 EO (c)
36 parts decanol + 2 EO-butyl ether (b)
7 parts lauryldimethylbenzylammonium chloride (a)
C.
2 parts octanol / hexadecanol + 4 EO (c)
4 parts octanol / decanol + 4 EO-butyl ether (b)
5 parts of N-benzyl-N-2-hydroxydodecyl-N, N-dimethylammonium isononanoate (a)
D *
6 parts octadecenol + 2 EO (c)
2 parts of fatty alcohol C₁₂₋₁₄ + 10 EO-butyl ether (b)
13 parts of N-benzyl-N-2-hydroxydodecyl-N, N-dimethylammonium isononanoate (a)
E
15 parts octanol + 4 EO-butyl ether (b)
3 parts of N-benzyl-N-2-hydroxydodecyl-N, N-dimethylammonium benzoate (a)
2 parts of fatty alcohol C₁₂₋₁₈ - 2 EO - 4 PO (d)
F
15 parts octanol / decanol + 4 EO-butyl ether (b)
1 part lauryldimethylbenzylammonium chloride (a)
G
2 parts octanol + 10 EO (c)
4 parts octanol / decanol + 4 EO-butyl ether (b)
5 parts of N-benzyl-N-2-hydroxydodecyl-N, N-dimethylammonium isononanoate (a)
5 parts of fatty alcohol C₁₂₋₁₈ + 3 EO + 6 PO (d)

Beispiel 2Example 2 Reinigungsmittel-Grundlagen, als Zusätze zu den erfindungsgemäßen Tensid-Kombinationen und den Vergleichs-FormulierungenDetergent basics, as additives to the surfactant combinations according to the invention and the comparison formulations Grundlage 1:Basis 1:

55,3 Teile Wasser
7,0 Teile Ethanolamin
10,0 Teile Triethanolamin
8,0 Teile Diethanolamin
15,0 Teile verzweigte Carbonsäure mit 9 C-Atomen
1,0 Teile 2-Phosphonobutan-1,2,4-tricarbonsäure
0,2 Teile Tolyltriazol
3,5 Teile Pentakaliumtriphosphat55.3 parts water
7.0 parts of ethanolamine
10.0 parts triethanolamine
8.0 parts diethanolamine
15.0 parts of branched carboxylic acid with 9 carbon atoms
1.0 part of 2-phosphonobutane-1,2,4-tricarboxylic acid
0.2 parts tolyltriazole
3.5 parts of pentapotassium triphosphate

Grundlage 2:Basis 2:

59,2 Teile Wasser
10,0 Teile Ethanolamin
10,0 Teile Triethanolamin
5,0 Teile Diisopropanolamin
5,0 Teile n-Octansäure
2,0 Teile verzweigte Carbonsäure mit 9 C-Atomen
5,0 Teile verzweigte Carbonsäure mit 8 C-Atomen
3,0 Teile Borsäure
0,8 Teile Polyacrylat (MG ca. 1500)59.2 parts water
10.0 parts ethanolamine
10.0 parts triethanolamine
5.0 parts diisopropanolamine
5.0 parts of n-octanoic acid
2.0 parts of branched carboxylic acid with 9 carbon atoms
5.0 parts of branched carboxylic acid with 8 carbon atoms
3.0 parts boric acid
0.8 parts polyacrylate (MW approx. 1500)

Grundlage 3:Basis 3:

54,0 Teile Wasser
20,0 Teile Triethanolamin
5,0 Teile Diisopropanolamin
5,0 Teile Triisopropanolamin
10,0 Teile Gemisch verzweigter Carbonsäuren mit 9 bis 11 C-Atomen
2,5 Teile Natriumgluconat
3,5 Teile Hexahydrotriazinderivat54.0 parts water
20.0 parts triethanolamine
5.0 parts diisopropanolamine
5.0 parts of triisopropanolamine
10.0 parts mixture of branched carboxylic acids with 9 to 11 carbon atoms
2.5 parts sodium gluconate
3.5 parts of hexahydrotriazine derivative

Grundlage 4:Basis 4:

72,3 Teile Wasser
9,0 Teile Kaliumhydroxid
2,5 Teile Natriumhydroxid
5,0 Teile Pentakaliumtriphosphat
5,0 Teile Kaliumglukonat
5,0 Teile Gemisch verzweigter Carbonsäuren mit 9 bis 11 C-Atomen
1,2 Teile 1-Hydroxyethan-1,1-diphosphonsäure72.3 parts water
9.0 parts of potassium hydroxide
2.5 parts sodium hydroxide
5.0 parts of pentapotassium triphosphate
5.0 parts of potassium gluconate
5.0 parts mixture of branched carboxylic acids with 9 to 11 carbon atoms
1.2 parts of 1-hydroxyethane-1,1-diphosphonic acid

Grundlage 5:Basis 5:

30,3 Teile Pentanatriumtriphosphat
30,3 Teile Tetranatriumdiphosphat
30,3 Teile Trinatriumphosphat * 12 H₂O30.3 parts of pentasodium triphosphate
30.3 parts of tetrasodium diphosphate
30.3 parts of trisodium phosphate * 12 H₂O

Beispiel 3Example 3

Die anwendungstechnischen Eigenschaften der erfindungsgemäß zu verwendenden Tensid-Kombinationen sowie der Vergleichs-Formulierungen gemäß Beispiel 1 wurden in Reinigungsmittel-Grundlagen gemäß Beispiel 2 in einer Labor-Spritzanlage geprüft. Bei dieser Prüfung wurden Stahlbleche (Qualität St 37), die mit Korrosionsschutzöl behaftet waren, mit wäßrigen Anwendungslösungen, die in der nachstehenden Tabelle 1 näher charakterisiert sind, im Spritzverfahren (Spritzdruck 2,5 bis 5 bar) behandelt. Es wurden die Reinigungswirkung, das Schaumverhalten sowie die Benetzung der Blechoberflächen und das Ablaufverhalten der Anwendungslösungen von den Blechoberflächen visuell beurteilt.The application properties of the surfactant combinations to be used according to the invention and of the comparative formulations according to Example 1 were tested in the detergent basics according to Example 2 in a laboratory spraying system. In this test, steel sheets (quality St 37), which were contaminated with corrosion protection oil, were treated with aqueous application solutions, which are characterized in more detail in Table 1 below, in a spraying process (spray pressure 2.5 to 5 bar). It the cleaning effect, the foaming behavior as well as the wetting of the sheet metal surfaces and the drainage behavior of the application solutions from the sheet metal surfaces were assessed visually.

In allen Fällen der in Tabelle 1 zusammengefaßten Einzelbeispiele zeigte sich eine gute Reinigungswirkung der getesteten Anwendungslösungen. Ferner ergab sich, daß die eingesetzten Anwendungslösungen bei den in Tabelle 1 angegebenen Temperaturen gut spritzbar waren und keine störenden Schaumentwicklungen zeigten. Die erhaltenen Resultate bezüglich "Benetzung" und "Ablaufverhalten" sind jeweils in Tabelle 1 in der Spalte "Bemerkungen" wiedergegeben.In all cases of the individual examples summarized in Table 1, the tested application solutions showed a good cleaning effect. Furthermore, it was found that the application solutions used were readily sprayable at the temperatures given in Table 1 and showed no disruptive foam developments. The results obtained with regard to "wetting" and "run-off behavior" are each shown in Table 1 in the "Comments" column.

Nachstehend werden die einzelnen Spalten von Tabelle 1 erläutert:

"Grundlage":

Angabe der Nummer der im jeweiligen Beispiel verwendeten Reinigungsmittel-Grundlage gemäß Beispiel 2.
"Tensid-Kombination":

Angabe der Bezeichnung (Nr.) der im jeweiligen Beispiel verwendeten Tensid-Kombination gemäß Beispiel 1;
"Anteil":
bedeutet die jeweilige Konzentration der Tensid-Kombination bezogen auf die Reiniungsmittel-Grundlage in Gew.-%.
"Konzentration":

Konzentration des Reinigungsmittels in der Anwendungslösung in g/l.
"Spritztemperatur":

Temperatur der Anwendungslösung bei deren Anwendung im Spritzverfahren, ohne störende Schaumbildung.
The individual columns in Table 1 are explained below:
"Basis":

Indication of the number of the detergent base used in the respective example according to example 2.
"Surfactant combination":

(No.) Indicating the name of the surfactant combination used in each example ACCORDING ß Example 1;
"Proportion of":
means the respective concentration of the surfactant combination based on the detergent base in% by weight.
"Concentration":

Concentration of the detergent in the application solution in g / l.
"Spray temperature":

Temperature of the application solution when used in the spray process, without annoying foaming.

In allen Versuchen wurde vollentsalztes Wasser verwendet.

Figure imgb0001
Demineralized water was used in all experiments.
Figure imgb0001

Beispiel 4Example 4

Mischung 1*:Mix 1 *: 20 Teile Fettalkohol C₁₂₋₁₄ + 10 EO-butylether20 parts of fatty alcohol C₁₂₋₁₄ + 10 EO-butyl ether (b)(b) 80 Teile Lauryldimethylbenzylammoniumchlorid80 parts of lauryldimethylbenzylammonium chloride (a)(a) Mischung 2*:Mix 2 *: 85 Teile Fettalkohol C₁₂₋₁₈ + 5 EO-butylether85 parts of fatty alcohol C₁₂₋₁₈ + 5 EO-butyl ether (b)(b) 15 Teile Lauryldimethylbenzylammoniumchlorid15 parts of lauryldimethylbenzylammonium chloride (a)(a) Mischung 3 :Mix 3: 85 Teile Octanol/Decanol + 4 EO-butylether85 parts octanol / decanol + 4 EO-butyl ether (b)(b) 15 Teile Lauryldimethylbenzylammoniumchlorid15 parts of lauryldimethylbenzylammonium chloride (a)(a) Mischung 4 :Mix 4: 20 Teile Octanol/Decanol + 4 EO-butylether20 parts octanol / decanol + 4 EO-butyl ether (b)(b) 80 Teile Lauryldimethylbenzylammoniumchlorid80 parts of lauryldimethylbenzylammonium chloride (a)(a) *) = Vergleichsbeispiele*) = Comparative examples

Die Mischungen 1 bis 4 sind so konzipiert, daß die Mischether (b) Abstufungen sowohl im Fettalkohol- als auch im EO-Anteil aufweisen. Hierbei liegt der Mischether in den Mischungen 1 und 2 außerhalb der Erfindung. Die quartären Ammoniumverbindungen (a) hingegen liegen alle im Rahmen der vorliegenden Erfindung.Mixtures 1 to 4 are designed so that the mixed ethers (b) have gradations in both the fatty alcohol and the EO content. Here, the mixed ether in mixtures 1 and 2 is outside the invention. The quaternary ammonium compounds (a), however, are all within the scope of the present invention.

Der nachfolgende Schaumtest zeigt, daß die Mischungen 1 und 2 gemäß Vergeichsbeispiele - im Vergleich zu den erfindungsgemäßen Mischungen 3 und 4 - stärker schäumen.The following foam test shows that mixtures 1 and 2 according to comparative examples - compared to mixtures 3 and 4 according to the invention - foam more strongly.

Schaumtest nach DIN 53902Foam test according to DIN 53902

Schaumtest in der Schaumschlagapparatur nach DIN 53902 (Schaumhöhe in ml) 100 Schläge / 25 °C t/s Mischung 1* 2* 3 4 0 800 260 20 350 30 700 30 10 40 60 680 30 5 10 100 Schläge / 30 °C t/s Mischung 1* 2* 3 4 0 800 50 10 350 30 780 15 5 20 60 750 <10 <5 <5 100 Schläge / 45 °C t/s Mischung 1* 2* 3 4 0 750 40 10 200 30 700 10 <5 <5 60 600 10 <5 0 Foam test in the foam whipping apparatus according to DIN 53902 (foam height in ml) 100 blows / 25 ° C t / s mixture 1* 2 * 3rd 4th 0 800 260 20th 350 30th 700 30th 10th 40 60 680 30th 5 10th 100 blows / 30 ° C t / s mixture 1* 2 * 3rd 4th 0 800 50 10th 350 30th 780 15 5 20th 60 750 <10 <5 <5 100 blows / 45 ° C t / s mixture 1* 2 * 3rd 4th 0 750 40 10th 200 30th 700 10th <5 <5 60 600 10th <5 0

Claims (11)

  1. The use of a combination of ionic and nonionic surfactants containing
    (a) at least one quaternary ammonium compound corresponding to general formula (I):



            R¹ (-CHOH-CHR²)n-N⁺R³R⁴R⁵ X⁻   (I)



    in which
    R¹   may be a linear or branched alkyl group containing 1 to 22 carbon atoms,
    R²   may be hydrogen or a linear or branched alkyl group containing 1 to 21 carbon atoms,
    the total number of carbon atoms in the substituents
    R¹ and R²   being from 10 to 22,
    n   = 0 or 1,
    R³ and R⁴   represent methyl, ethyl, 2-hydroxyethyl or hydroxypropyl,
    R⁵   represents alkyl groups containing 4 to 6 carbon atoms or phenalkyl groups containing 1 to 3 carbon atoms in the alkyl component and
    X⁻   is halide or the anion of an organic acid containing 4 to 15 carbon atoms,
    and
    (b) at least one alk(en)yl polyethylene glycol mixed ether corresponding to general formula (II):



            R⁶-O-(CH₂CH₂-O)s-R⁷   (II)



    in which
    R⁶   is a linear alkyl group containing 8 to 10 carbon atoms,
    s   is a number of 3.5 to 4.5 and
    R⁷   is a linear alkyl group containing 4 carbon atoms,
    the ratio by weight of component (a) to (b) being in the range from 20:1 to 1:20, for cleaning hard surfaces.
  2. The use claimed in claim 1, characterized in that the ratio by weight of component (a) to component (b) is in the range from 2:1 to 1:10.
  3. The use claimed in claim 1 or 2, characterized in that the anion of component (a) is chloride, bromide, benzoate or mono-CH₃-, NH₂-, NO₂-, COOH-, OH or SO₃H-substituted benzoate or isononanoate.
  4. The use claimed in claim 1 or 2, characterized in that lauryl dimethyl benzylammonium chloride, N-benzyl-N-2-hydroxydodecyl-N,N-dimethylammonium isononanoate or N-benzyl-N-2-hydroxydodecyl-N,N-dimethylammonium benzoate is used as the quaternary ammonium compound.
  5. The use claimed in one or more of claims 1 to 4, characterized in that the surfactant combination additionally contains at least one alk(en)yl ethoxylate corresponding to general formula (III):



            R⁸-O(CH₂CH₂-O)m-H   (III)



    in which
    R⁸   is a linear or branched alkyl group or alkenyl group containing 6 to 18 carbon atoms or a cyclic alkyl group containing 5 to 6 carbon atoms and
    m   is a number of 2 to 12.
  6. The use claimed in one or more of claims 1 to 4, characterized in that the surfactant combination additionally contains at least one alk(en)yl ethoxylate propoxylate corresponding to general formula (IV):



            R⁹-O(CH₂CH₂O)p-A-H   (IV)



    in which
    R⁹   is a linear or branched alkyl group or alkenyl group containing 6 to 18 carbon atoms or a cyclic alkyl group containing 5 to 6 carbon atoms,
    p   is a number of 2 to 10 and
    A   represents groups of the -(CH₂-CH(CH₃)-O)q- and -(CH(CH₃)-CH₂-O)r type where the sum (q + r) is a number of 2 to 8.
  7. The use claimed in one or more of claims 1 to 4, characterized in that the surfactant combination additionally contains an alk(en)yl ethoxylate corresponding to general formula (III) in claim 5 and an alk(en)yl ethoxylate propoxylate corresponding to general formula (IV) in claim 6.
  8. The use claimed in one or more of claims 1 to 7, characterized in that the ratio by weight of component (a) to components (b) + (c), of component (a) to components (b) + (d) or of component (a) to components (b) + (c) + (d) is 20:1 to 1:20 and preferably 2:1 to 1:10.
  9. The use claimed in one or more of claims 1 to 8, characterized in that the ratio by weight of component (b) to component(s) (c) and/or (d) is 10:1 to 1:10.
  10. The use claimed in one or more of claims 1 to 9, characterized in that the surfactant combination additionally contains builders and/or complexing agents, corrosion inhibitors and also bases or acids.
  11. The use claimed in one or more of claims 1 to 10, characterized in that the surfactant combination is used in concentrations of 0.0001 to 1.5% by weight and preferably in concentrations of 0.0005 to 0.5% by weight in in-use solutions diluted with water.
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AU7769091A (en) 1991-11-27
PT97594A (en) 1992-02-28
CA2082517A1 (en) 1991-11-10
WO1991017233A1 (en) 1991-11-14
PT97594B (en) 1998-08-31
DK0527824T3 (en) 1995-06-19
ATE116681T1 (en) 1995-01-15
ES2066441T3 (en) 1995-03-01
US5308401A (en) 1994-05-03
DE59104163D1 (en) 1995-02-16
JPH05506689A (en) 1993-09-30
EP0527824A1 (en) 1993-02-24

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