EP0511253B1 - Anti-froth cleaning agents and use thereof - Google Patents

Anti-froth cleaning agents and use thereof Download PDF

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Publication number
EP0511253B1
EP0511253B1 EP91902214A EP91902214A EP0511253B1 EP 0511253 B1 EP0511253 B1 EP 0511253B1 EP 91902214 A EP91902214 A EP 91902214A EP 91902214 A EP91902214 A EP 91902214A EP 0511253 B1 EP0511253 B1 EP 0511253B1
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EP
European Patent Office
Prior art keywords
weight
cleaning
water
contain
general formula
Prior art date
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Expired - Lifetime
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EP91902214A
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German (de)
French (fr)
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EP0511253A1 (en
Inventor
Jürgen Dr. Geke
Friedbert Zetzsche
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/02—Anionic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic 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

Definitions

  • the present invention relates to demulsifying, powdered or liquid cleaning agents with which painted and unpainted surfaces of vehicles, engines, floors in workshops or other work surfaces can be cleaned and degreased, the contaminants removed thereby being demulsified.
  • the invention further relates to the use of these cleaning agents.
  • US-A-3,663,445 describes liquid storage-stable concentrates and cleaning and degreasing preparations, in particular for metallic surfaces, which are obtained from said concentrates by dilution with water and which consist of 6 to 45% by weight of a nonionic surfactant, for example a fatty alcohol ethoxylate, 4 up to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight of an ethanolamine and 0 to 50% by weight of water.
  • a nonionic surfactant for example a fatty alcohol ethoxylate, 4 up to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight of an ethanolamine and 0 to 50% by weight of water.
  • AT-A-308,936 relates to liquid storage-stable concentrates and from these cleaning and degreasing agents which can be prepared by dilution with water and which comprise at least 5% by weight of a nonionic surfactant, for example a fatty alcohol ethoxylate, at least 3% by weight of a saturated or unsaturated fatty acid with 8 to 22 carbon atoms in the molecule, at least 4.5 wt .-% of one or more alkanolamines and conventional additives such as complexing agents, and water.
  • a nonionic surfactant for example a fatty alcohol ethoxylate
  • a saturated or unsaturated fatty acid with 8 to 22 carbon atoms in the molecule at least 4.5 wt .-% of one or more alkanolamines and conventional additives such as complexing agents, and water.
  • GB-A-1,321,513 relates to a cleaning process for metallic surfaces with two cleaning baths to be used in succession, the pre-cleaning bath and the degreasing bath.
  • the pre-cleaning bath consists of at least 5% by weight of a nonionic surfactant containing 3 to 5 moles of ethylene oxide, at least 3% by weight of a fatty acid and / or an alkyl polyethylene oxide carboxylic acid, at least 1.5% by weight of an alkanolamine and / or oxazine and as Rest of water.
  • the degreasing bath consists of an inorganic or organic alkaline substance, for example potassium hydroxide, potassium carbonate, potassium orthophosphate, potassium pyrophosphate, potassium borate, alkanolamine, preferably mono-, di- or triethanolamine, morpholine, and a complexing agent, a low-foaming surfactant, for example a condensation product of fatty acids with 3 to 5 moles of ethylene oxide and other additives and the rest water.
  • an inorganic or organic alkaline substance for example potassium hydroxide, potassium carbonate, potassium orthophosphate, potassium pyrophosphate, potassium borate, alkanolamine, preferably mono-, di- or triethanolamine, morpholine, and a complexing agent, a low-foaming surfactant, for example a condensation product of fatty acids with 3 to 5 moles of ethylene oxide and other additives and the rest water.
  • AT-A-299,421 relates to an aqueous liquid composition for mechanical dishwashing, which contains 2 to 6% by weight of a nonionic surfactant, 15 to 25% by weight of an organic sequestering agent, 7 to 15% by weight of a hydrotropic substance, Contains 3 to 15 wt .-% of an ethanolamine and 0.1 to 0.6% of a corrosion inhibitor.
  • DE-A-25 05 252 relates to a process for the industrial cleaning and degreasing of objects, in particular metals, by treating the objects with a solvent-free, aqueous solution which contains an organic sequestering agent and a hydrotropic substance, which is characterized in that an aqueous solution is used which contains 0.1 to 20% by weight of an organic, hydrotropic electrolyte in the form of benzenesulfonates, lower alkylbenzenesulfonates, di (lower alkyl) benzenesulfonates or mixtures thereof and from 0.1 to 25% by weight.
  • sequestering agent in the form of aminopolycarboxylic acids or aminopolyphosphonic acids or their salts or mixtures thereof, the weight ratio of the electrolyte to the sequestering agent being from 2: 1 to 1: 3 and the pH of the solution being from 9 to 13.
  • US-A-4,321,166 relates to liquid cleaners which contain 20 to 70% by weight of a surfactant, for example a fatty alcohol ethoxylate, 0.85 to 2% by weight of a corrosion inhibitor system which essentially consists of a mixture of an oligomeric olefinic fatty acid and an aromatic Triazole consists, as well as 1 to 75 wt .-% water.
  • a surfactant for example a fatty alcohol ethoxylate
  • a corrosion inhibitor system which essentially consists of a mixture of an oligomeric olefinic fatty acid and an aromatic Triazole consists, as well as 1 to 75 wt .-% water.
  • DE-A-35 30 623 relates to demulsifying cleaning agents with surface moisturizing effect, containing builders / complexing agents in an amount of 0.5 to 10% by weight, one or more alkanolamine (s) in an amount of 20 to 60% by weight. , one or more nonionic surfactant (s) in an amount of 1 to 15% by weight and the balance water.
  • These cleaning agents and corresponding cleaning agent preparations are suitable for cleaning and degreasing painted and unpainted vehicle surfaces, engines, floors and walls of workshops etc. already at room temperature with demulsification of the removed oily or greasy impurities.
  • EP-A-0 335 471 describes liquid detergent formulations which consist of a liquid base component and a solid abrasive component.
  • the liquid base component contains an anionic surfactant, a nonionic surfactant, a non-polar, water-insoluble solvent, builder substances, water and optionally perfumes and dyes.
  • Various inorganic or organic substances of certain hardness and particle size can be considered as the abrasive component.
  • EP-A-0 292 910 also relates to liquid, aqueous cleaning formulations for hard surfaces which contain a solid abrasive component.
  • Such cleaners consist of a fatty acid or a fatty acid soap, a further anionic surfactant, a nonionic surfactant, builder substances, water and organic polymers of certain hardness and particle size as an abrasive component.
  • These cleaners preferably contain a hydrocarbon solvent.
  • FR-A-1 537 265 describes so-called cold cleaners for cleaning solid surfaces.
  • These cold cleaners consist of solutions of nonionic surfactants and aliphatic straight-chain or branched or cycloaliphatic C4 ⁇ 14 ⁇ monocarboxylic acids or their alkali or amine salts in water-insoluble solvents.
  • the preferred monocarboxylic acid is ⁇ -ethylhexanoic acid;
  • Suitable organic solvents are hydrocarbons or chlorinated hydrocarbons.
  • the object of the present invention to provide such demulsifying cleaning agents for cleaning oil-contaminated hard surfaces which have a better demulsifying activity and furthermore a better cleaning action than the known cleaning agents of the prior art.
  • the demulsifying effect of the cleaning agents should result in improved oil separation and thus lower residual oil values in the wastewater.
  • the demulsifying cleaning agents according to the invention have an excellent cleaning potential. Due to the good demulsifying effectiveness of these cleaning agents, the removed oil-containing contaminants separate themselves when the aqueous application solution is diluted. Fats and oils washed off the substrate surfaces in this way can be easily and easily removed from aqueous media, for example using simple oil separators. In this way, wastewater suitable for receiving water always results.
  • R 1 represents a linear alkyl radical with 8 carbon atoms.
  • the following radical can therefore be used as substituent R1: n-octyl.
  • the number of ethoxy radicals in the molecule - n - is in the range from 4 to 6.
  • corresponding addition products of ethylene oxide with fatty alcohols are used in particular as component (a).
  • Such fatty alcohol ethoxylates can be used either individually or in combination.
  • component (a) is in particular the adduct of 4 moles of ethylene oxide with n-octanol.
  • R2 is a branched alkyl radical having 8 to 9 carbon atoms.
  • These monocarboxylic acids of component (b) can also be used both alone and in combination.
  • Suitable water-soluble salts of such monocarboxylic acids are, in particular, the alkali metal salts, preferably their sodium salts.
  • 2-ethylhexanoic acid is preferably used as component (b).
  • At least one anionic surfactant which is selected from the group of the alkyl sulfates of the general formula (III), the alkyl polyglycol ether sulfates of the general formula (IV) and the alkylarylsulfonates of the general formula (V), is used as component (c) in the demulsifying cleaning agents according to the invention.
  • the substituents R3 and R4 independently of one another each represent linear or branched alkyl radicals having 10 to 18 carbon atoms.
  • radicals R3 and R4 are suitable as substituents R3 and R4: n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl and also branched chain isomers of the alkyl radicals mentioned.
  • the number of ethylene oxide units - m - in the alkylpolyglycol ether sulfates of the general formula (IV) is in the range from 1 to 6.
  • the radical R5 in the alkylarylsulfonates of the general formula (V) represents alkylbenzene residues with 7 to 9 carbon atoms, selected from the Group toluene, xylene, mesithylene and cumene.
  • R5 in the alkylarylsulfonates of the general formula (V) represents alkylbenzene residues with 7 to 9 carbon atoms, selected from the Group toluene, xylene, mesithylene and cumene.
  • Me each represents an alkali metal atom, preferably sodium.
  • the content of components (a), (b) and (c) defined above in the cleaning agents according to the invention is 2.5 to 12.5% by weight in total. It is also important in the context of the invention that the weight ratio of component (a) to component (b) is in the range from 3: 1 to 1: 6 and also the weight ratio of the sum of components (a) and (b) to component (c) in the range from 3: 1 to 1: 3.
  • component C is a C12 C14 fatty alcohol sulfate sodium salt and / or a C12 ⁇ 14 fatty alcohol ether sulfate sodium salt with 3 to 5 moles of ethylene oxide and / or the cumene sulfonate sodium salt.
  • the demulsifying cleaning agents contain at least one organic or inorganic builder.
  • organic or inorganic builder examples include oligo- or polycarboxylic acids and their water-soluble salts, for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or n- (2-hydroxyethyl) ethylenediaminetriacetic acid, preferably in the form of their alkali metal salts, especially the sodium salts.
  • Further suitable builder substances within the meaning of the invention are alkali metal phosphates, polyphosphates, silicates, borates, carbonates and / or hydroxides, preferably also in the form of the corresponding sodium salts.
  • the sodium salts of ethylenediaminetetraacetic acid and / or nitrilotriacetic acid are preferably used as builder substances.
  • the demulsifying cleaning agents according to the invention also contain powdery or liquid auxiliaries and / or adjusting agents which add up to 100% by weight of the components (a), (b), (c) and (d) contained in the cleaning agents. They are used in particular for the packaging of either powdered or liquid formulations of the cleaning agents according to the invention. If liquid formulations are desired, water is used in particular as an adjusting agent. Suitable powdered adjusting agents which then lead to powdered formulations are alkali metal sulfates or carbonates, especially in the form of sodium salts, or urea. Furthermore, the cleaning agents according to the invention can also contain small amounts of oleic acid or its sodium salt and of diethanolamine and / or triethanolamine as auxiliaries.
  • the cleaning agents according to the invention are produced by mixing the abovementioned components in the respective amounts by methods known per se.
  • the cleaning agents are generally stored or shipped in the form of an aqueous or powdery concentrate containing the combination of the specified components, to which the stated amounts (in% by weight) also relate.
  • the demulsifying cleaning agents according to the invention depending on the type of application and degree of contamination of the surfaces to be cleaned - are used in any dilution with water.
  • the cleaning agents are used in water-diluted application solutions for cleaning and degreasing hard surfaces, the concentration of components (a), (b) and (c) in these application solutions being 0.01 in total up to 3% by weight, in particular 0.025 to 1% by weight.
  • the pH of these aqueous application solutions is in the range from 7.5 to 13, in particular in the range from 9.5 to 11.5.
  • a liquid detergent is made by mixing 1.8% by weight of a condensation product of n-octanol with 4 mol of EO, 1.8% by weight of 2-ethylhexanoic acid, 0.3% by weight of C12-C14 fatty alcohol ether sulfate with 3 mol of EO sodium salt, 2.6% by weight sodium cumene sulfonate, 28.0% by weight of sodium ethylenediaminetetraacetic acid, 0.8% by weight of triethanolamine, 0.4% by weight oleic acid 64.3 wt% water manufactured.
  • a powder detergent is made by mixing 3.0% by weight of a condensation product of n-octanol with 4 mol of EO 2.0% by weight of 2-ethylhexanoic acid, 1.0% by weight of C12-C14 fatty alcohol sulfate sodium salt, 3.0% by weight sodium cumene sulfonate, 36.8% by weight of nitrilotriacetic acid sodium salt 1.0% by weight of oleic acid, 38.6% by weight sodium carbonate 14.6% by weight urea manufactured.
  • a comparative cleaner was made by mixing 5.0% by weight of a condensation product of n-octanol with 4 mol of EO, 1.6% by weight sodium cumene sulfonate, 2.4% by weight of ethylenediaminetetraacetic acid sodium salt 42.0% by weight of a mixture of diethanolamine and triethanolamine in a ratio of 2: 1, and 49.0 wt% water manufactured.
  • the separation time or rest time for phase separation was only 5 minutes in Examples 1 and 2, compared to a time of 30 minutes that was required for the comparative cleaner.
  • cleaning agent solutions as test solutions were prepared from the cleaning agents according to Examples 1, 2 and the comparative example by dilution with water (16 ° d).
  • the cleaning action and the relative cleaning action RW rel were determined in such a way that the number of wipings with the comparative cleaner was divided by the number of wipings with the cleaner according to the invention to be tested.
  • the quotient gave the relative cleaning effect RW rel , based on the comparative cleaner.

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  • Engineering & Computer Science (AREA)
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Abstract

PCT No. PCT/EP91/00039 Sec. 371 Date Jul. 20, 1992 Sec. 102(e) Date Jul. 20, 1992 PCT Filed Jan. 12, 1991 PCT Pub. No. WO91/10718 PCT Pub. Date Jul. 25, 1991.The invention is a demulsifying cleaning preparation comprising a mixture of nonionic surfactants, anionic surfactants, monocarboxylic acids having 8 to 9 carbon atoms, builders and auxiliaries. The particular proportions of surfactants permits demulsification and rapid separation of oily materials from the detergent mixture.

Description

Die vorliegende Erfindung betrifft demulgierende, pulverförmige oder flüssige Reinigungsmittel, mit denen lackierte und nicht lackierte Oberflächen von Fahrzeugen, Motoren, Fußböden in Werkstätten oder anderen Arbeitsflächen gereinigt und entfettet werden können, wobei die hierbei entfernten Verunreinigungen demulgiert werden. Die Erfindung betrifft weiterhin die Verwendung dieser Reinigungsmittel.The present invention relates to demulsifying, powdered or liquid cleaning agents with which painted and unpainted surfaces of vehicles, engines, floors in workshops or other work surfaces can be cleaned and degreased, the contaminants removed thereby being demulsified. The invention further relates to the use of these cleaning agents.

Die US-A-3,663,445 beschreibt flüssige lagerstabile Konzentrate sowie reinigende und entfettende Zubereitungen, insbesondere für metallische Oberflächen, welche aus besagten Konzentraten durch Verdünnen mit Wasser erhalten werden, welche aus 6 bis 45 Gew.-% eines nichtionischen Tensids, beispielsweise eines Fettalkoholethoxylats, 4 bis 33 Gew.-% eines Ethanolaminsalzes einer Fettsäure, 2 bis 90 Gew.-% eines Ethanolamins und 0 bis 50 Gew.-% Wasser bestehen.US-A-3,663,445 describes liquid storage-stable concentrates and cleaning and degreasing preparations, in particular for metallic surfaces, which are obtained from said concentrates by dilution with water and which consist of 6 to 45% by weight of a nonionic surfactant, for example a fatty alcohol ethoxylate, 4 up to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight of an ethanolamine and 0 to 50% by weight of water.

Die AT-A-308,936 betrifft flüssige lagerbeständige Konzentrate und aus diesen durch Verdünnen mit Wasser herstellbare Reinigungs- und Entfettungsmittel, die aus mindestens 5 Gew.-% eines nichtionischen Tensids, beispielsweise eines Fettalkoholethoxylats, mindestens 3 Gew.-% einer gesättigten oder ungesättigten Fettsäure mit 8 bis 22 Kohlenstoffatomen im Molekül, mindestens 4,5 Gew.-% eines oder mehrerer Alkanolamine sowie üblichen Zusatzstoffen, wie Komplexierungsmitteln, und Wasser bestehen.AT-A-308,936 relates to liquid storage-stable concentrates and from these cleaning and degreasing agents which can be prepared by dilution with water and which comprise at least 5% by weight of a nonionic surfactant, for example a fatty alcohol ethoxylate, at least 3% by weight of a saturated or unsaturated fatty acid with 8 to 22 carbon atoms in the molecule, at least 4.5 wt .-% of one or more alkanolamines and conventional additives such as complexing agents, and water.

Die GB-A-1,321,513 betrifft ein Reinigungsverfahren für metallische Oberflächen mit zwei zeitlich nacheinander anzuwendenden Reinigungsbädern, dem Vorreinigungsbad und dem Entfettungsbad. Das Vorreinigungsbad besteht aus wenigstens 5 Gew.-% eines 3 bis 5 Mol Ethylenoxid enthaltenden nichtionischen Tensids, mindestens 3 Gew.-% einer Fettsäure und/oder einer Alkylpolyethylenoxidcarbonsäure, mindestens 1,5 Gew.-% eines Alkanolamins und/oder Oxazins und als Rest Wasser. Das Entfettungsbad besteht aus einer anorganischen oder organischen alkalischen Substanz, beispielsweise Kaliumhydroxid, Kaliumcarbonat, Kaliumorthophosphat, Kaliumpyrophosphat, Kaliumborat, Alkanolamin, vorzugsweise Mono-, Di- oder Triethanolamin, Morpholin, und einem Komplexierungsmittel, einem wenig schäumenden Tensid, beispielsweise einem Kondensationsprodukt von Fettsäuren mit 3 bis 5 Mol Ethylenoxid, sowie sonstigen Zusatzstoffen und als Rest Wasser.GB-A-1,321,513 relates to a cleaning process for metallic surfaces with two cleaning baths to be used in succession, the pre-cleaning bath and the degreasing bath. The pre-cleaning bath consists of at least 5% by weight of a nonionic surfactant containing 3 to 5 moles of ethylene oxide, at least 3% by weight of a fatty acid and / or an alkyl polyethylene oxide carboxylic acid, at least 1.5% by weight of an alkanolamine and / or oxazine and as Rest of water. The degreasing bath consists of an inorganic or organic alkaline substance, for example potassium hydroxide, potassium carbonate, potassium orthophosphate, potassium pyrophosphate, potassium borate, alkanolamine, preferably mono-, di- or triethanolamine, morpholine, and a complexing agent, a low-foaming surfactant, for example a condensation product of fatty acids with 3 to 5 moles of ethylene oxide and other additives and the rest water.

Die AT-A-299,421 betrifft eine wäßrige flüssige Zusammensetzung für das mechanische Geschirrspülen, welche 2 bis 6 Gew.-% eines nichtionischen Tensids, 15 bis 25 Gew.-% eines organischen Sequestriermittels, 7 bis 15 Gew.-% einer hydrotropen Substanz, 3 bis 15 Gew.-% eines Ethanolamins und 0,1 bis 0,6 % eines Korrosionsinhibitors enthält.AT-A-299,421 relates to an aqueous liquid composition for mechanical dishwashing, which contains 2 to 6% by weight of a nonionic surfactant, 15 to 25% by weight of an organic sequestering agent, 7 to 15% by weight of a hydrotropic substance, Contains 3 to 15 wt .-% of an ethanolamine and 0.1 to 0.6% of a corrosion inhibitor.

Die DE-A-25 05 252 betrifft ein Verfahren zum industriellen Reinigen und Entfetten von Gegenständen, insbesondere von Metallen, durch Behandeln der Gegenstände mit einer lösungsmittelfreien, wäßrigen Lösung, welche ein organisches Sequestriermittel und eine hydrotrope Substanz enthält, das dadurch gekennzeichnet ist, daß eine wäßrige Lösung verwendet wird, welche 0,1 bis 20 Gew.-% eines organischen, hydrotropen Elektrolyten in Form von Benzolsulfonaten, niederen Alkylbenzolsulfonaten, Di-(niedrig-Alkyl)-benzolsulfonaten oder Mischungen hiervon und von 0,1 bis 25 Gew.-% eines organischen Sequestriermittels in Form von Aminopolycarbonsäuren oder Aminopolyphosphonsäuren beziehungsweise deren Salzen oder Mischungen hiervon enthält, wobei das Gewichtsverhältnis des Elektrolyten zum Sequestriermittel von 2 : 1 bis 1 : 3 und der pH-Wert der Lösung von 9 bis 13 betragen.DE-A-25 05 252 relates to a process for the industrial cleaning and degreasing of objects, in particular metals, by treating the objects with a solvent-free, aqueous solution which contains an organic sequestering agent and a hydrotropic substance, which is characterized in that an aqueous solution is used which contains 0.1 to 20% by weight of an organic, hydrotropic electrolyte in the form of benzenesulfonates, lower alkylbenzenesulfonates, di (lower alkyl) benzenesulfonates or mixtures thereof and from 0.1 to 25% by weight. -% of an organic Contains sequestering agent in the form of aminopolycarboxylic acids or aminopolyphosphonic acids or their salts or mixtures thereof, the weight ratio of the electrolyte to the sequestering agent being from 2: 1 to 1: 3 and the pH of the solution being from 9 to 13.

Die US-A-4,321,166 betrifft flüssige Reiniger, die 20 bis 70 Gew.-% eines Tensids, beispielsweise eines Fettalkoholethoxylats, 0,85 bis 2 Gew.-% eines Korrosionsinhibitorsystems, welches im wesentlichen aus einer Mischung einer oligomeren olefinischen Fettsäure und einem aromatischen Triazol besteht, sowie 1 bis 75 Gew.-% Wasser, enthalten.US-A-4,321,166 relates to liquid cleaners which contain 20 to 70% by weight of a surfactant, for example a fatty alcohol ethoxylate, 0.85 to 2% by weight of a corrosion inhibitor system which essentially consists of a mixture of an oligomeric olefinic fatty acid and an aromatic Triazole consists, as well as 1 to 75 wt .-% water.

Die DE-A-35 30 623 betrifft demulgierende Reinigungsmittel mit Flächenfeuchthalteeffekt, enthaltend Builder/Komplexbildner in einer Menge von 0,5 bis 10 Gew.-%, ein oder mehrere Alkanolamin(e) in einer Menge von 20 bis 60 Gew.-%, ein oder mehrere nichtionische(s) Tensid(e) in einer Menge von 1 bis 15 Gew.-% sowie als Rest Wasser. Diese Reinigungsmittel und entsprechende Reinigungsmittelzubereitungen eignen sich zur Reinigung und Entfettung lackierter und unlackierter Fahrzeugoberflächen, Motoren, Fußböden und Wände von Werkstätten etc. bereits bei Raumtemperatur unter Demulgierung der entfernten öligen bzw. fetthaltigen Verunreinigungen.DE-A-35 30 623 relates to demulsifying cleaning agents with surface moisturizing effect, containing builders / complexing agents in an amount of 0.5 to 10% by weight, one or more alkanolamine (s) in an amount of 20 to 60% by weight. , one or more nonionic surfactant (s) in an amount of 1 to 15% by weight and the balance water. These cleaning agents and corresponding cleaning agent preparations are suitable for cleaning and degreasing painted and unpainted vehicle surfaces, engines, floors and walls of workshops etc. already at room temperature with demulsification of the removed oily or greasy impurities.

Die demulgierende Wirkung dieser aus dem Stand der Technik bekannten Reinigungsmittel ist jedoch im Hinblick auf die heutigen Anforderungen nicht zufriedenstellend. Dies bedeutet, daß die hiermit erzielte Demulgierung der entfernten, ölhaltigen Verunreinigungen beziehungsweise die daraus resultierende, anschließende Ölabscheidung nicht ausreicht, um die Restölwerte im Abwasser auf die heutzutage geforderten, niedrigen Werte abzusenken.However, the demulsifying effect of these cleaning agents known from the prior art is unsatisfactory with regard to today's requirements. This means that the demulsification of the removed, oil-containing impurities or the subsequent oil separation resulting therefrom is not sufficient to reduce the residual oil values in the waste water to the low values required today.

Ferner werden in der EP-A-0 335 471 flüssige Reinigungsmittel-Formulierungen beschrieben, welche aus einer flüssigen Basiskomponente und einer festen Abrasiv-Komponente bestehen. Die flüssige Basiskomponente enthält ein anionisches Tensid, ein nichtionisches Tensid, ein nicht-polares, wasserunlösliches Lösungsmittel, Buildersubstanzen, Wasser sowie gegebenenfalls Parfüm- und Farbstoffe. Als Abrasiv-Komponente kommen verschieden anorganische oder organische Stoffe bestimmter Härte und Teilchengröße in Frage.Furthermore, EP-A-0 335 471 describes liquid detergent formulations which consist of a liquid base component and a solid abrasive component. The liquid base component contains an anionic surfactant, a nonionic surfactant, a non-polar, water-insoluble solvent, builder substances, water and optionally perfumes and dyes. Various inorganic or organic substances of certain hardness and particle size can be considered as the abrasive component.

Die EP-A-0 292 910 betrifft gleichfalls flüssige, wäßrige Reinigungs-Formulierungen für harte Oberflächen, die eine feste Abrasiv-Komponente enthalten. Derartige Reiniger bestehen aus einer Fettsäure oder einer Fettsäureseife, einem weiteren anionischen Tensid, einem nichtionischen Tensid, Buildersubstanzen, Wasser und organischen Polymeren bestimmter Härte und Teilchengröße als Abrasiv-Komponente. Vorzugsweise enthalten diese Reinger ein Kohlenwasserstoff-Lösungsmittel.EP-A-0 292 910 also relates to liquid, aqueous cleaning formulations for hard surfaces which contain a solid abrasive component. Such cleaners consist of a fatty acid or a fatty acid soap, a further anionic surfactant, a nonionic surfactant, builder substances, water and organic polymers of certain hardness and particle size as an abrasive component. These cleaners preferably contain a hydrocarbon solvent.

In der FR-A-1 537 265 werden sogenannte Kaltreiniger für die Reinigung fester Oberflächen beschrieben. Diese Kaltreiniger bestehen aus Lösungen nichtionischer Tenside und aliphatischer geradkettiger oder verzweigter oder cycloaliphatischer C₄₋₁₀-Monocarbonsäuren oder deren Alkali- oder Aminsalzen in wasserunlöslichen Lösungsmitteln. Als Monocarbonsäure kommt bevorzugt die α-Ethylhexansäure in Betracht; geeignete organische Lösungsmittel sind Kohlenwasserstoffe oder Chlorkohlenwasserstoffe.FR-A-1 537 265 describes so-called cold cleaners for cleaning solid surfaces. These cold cleaners consist of solutions of nonionic surfactants and aliphatic straight-chain or branched or cycloaliphatic C₄₋₁₄₋ monocarboxylic acids or their alkali or amine salts in water-insoluble solvents. The preferred monocarboxylic acid is α-ethylhexanoic acid; Suitable organic solvents are hydrocarbons or chlorinated hydrocarbons.

Demgegenüber ist es die Aufgabe der vorliegenden Erfindung, solche demulgierenden Reinigungsmittel für die Reinigung von mit Öl verunreinigten harten Oberflächen bereitzustellen, die eine bessere demulgierende Wirksamkeit und ferner eine bessere Reinigungswirkung als die bekannten Reinigungsmittel des Standes der Technik aufweisen. Darüber hinaus sollte die Demulgierwirkung der Reinigungsmittel eine verbesserte Ölabscheidung und somit geringere Restölwerte im Abwasser bedingen.In contrast, it is the object of the present invention to provide such demulsifying cleaning agents for cleaning oil-contaminated hard surfaces which have a better demulsifying activity and furthermore a better cleaning action than the known cleaning agents of the prior art. In addition, the demulsifying effect of the cleaning agents should result in improved oil separation and thus lower residual oil values in the wastewater.

Überraschenderweise wurde gefunden, daß eine spezielle Kombination von Alkyl-ethoxylaten, Monocarbonsäuren und anionischen Tensiden, die noch Buildersubstanzen enthält, die gestellten Anforderungen erfüllt.Surprisingly, it was found that a special combination of alkyl ethoxylates, monocarboxylic acids and anionic surfactants, which still contains builder substances, meets the requirements.

Die, Erfindung betrifft somit demulgierende, pulverförmige oder flüssige Reinigungsmittel auf Basis von nichtionischen Tensiden, anionischen Tensiden und Buildersubstanzen und frei von wasserunlöslichen organischen Lösungsmitteln, dadurch gekennzeichnet, daß sie eine Kombination der folgenden Bestandteile enthalten:

  • a) mindestens ein Alkyl-ethoxylat der allgemeinen Formel (I):



            R¹-O-(CH₂CH₂O)n-H   (I)



    worin R¹ einen linearen Alkylrest mit 8 C-Atomen und n eine Zahl im Bereich von 4 bis 6 bedeuten,
  • b) mindestens eine Monocarbonsäure oder deren wasserlösliche Salze der allgemeinen Formel (II):



            R²-COOH   (II)



    worin R² einen verzweigten Alkylrest mit 8 bis 9 C-Atomen bedeutet,
  • c) mindestens ein anionisches Tensid, ausgewählt aus der Gruppe der
    • c1) Alkylsulfate der allgemeinen Formel (III):



              R³-O-SO₃Me   (III)



    • c2) Alkyl-polyglykolether-sulfate der allgemeinen Formel (IV):



              R⁴-O-(CH₂CH₂O)m-SO₃Me   (IV)



    • c3) Alkylarylsulfonate der allgemeinen Formel (V):



              R⁵-SO₃-Me   (V)



      worin R³ und R⁴ unabhängig voneinander jeweils lineare oder verzweigte Alkylreste mit 10 bis 18 C-Atomen, m eine Zahl im Bereich von 1 bis 6, R⁵ Alkylbenzolreste mit 7 bis 9 C-Atomen und Me jeweils ein Alkalimetallatom bedeuten,
wobei der Gehalt der Reinigungsmittel an den vorstehenden Komponenten a, b und c insgesamt 2,5 bis 12,5 Gew.-% beträgt und das Gewichtsverhältnis von a zu b im Bereich von 3:1 bis 1:6 und das Gewichtsverhältnis von (a+b):c im Bereich von 3:1 bis 1:3 liegt,
  • d) 5 bis 97,5 Gew.-% mindestens eines organischen oder anorganischen Builderstoffes, ausgewählt aus der Gruppe der Oligo- und Polycarbonsäuren oder deren wasserlöslichen Salzen sowie der Alkalimetall-phosphate, -silikate, -borate, -carbonate und -hydroxide,
  • e) bis 100 Gew.-% an pulverförmigen oder flüssigen Hilfsstoffen oder Stellmitteln.
The invention thus relates to demulsifying, powdered or liquid cleaning agents based on nonionic surfactants, anionic surfactants and builder substances and free of water-insoluble organic solvents, characterized in that they contain a combination of the following constituents:
  • a) at least one alkyl ethoxylate of the general formula (I):



    R¹-O- (CH₂CH₂O) n -H (I)



    in which R 1 is a linear alkyl radical having 8 carbon atoms and n is a number in the range from 4 to 6,
  • b) at least one monocarboxylic acid or its water-soluble salts of the general formula (II):



    R²-COOH (II)



    wherein R² is a branched alkyl radical having 8 to 9 carbon atoms,
  • c) at least one anionic surfactant selected from the group of
    • c1) alkyl sulfates of the general formula (III):



      R³-O-SO₃Me (III)



    • c2) alkyl polyglycol ether sulfates of the general formula (IV):



      R⁴-O- (CH₂CH₂O) m -SO₃Me (IV)



    • c3) alkylarylsulfonates of the general formula (V):



      R⁵-SO₃-Me (V)



      in which R³ and R⁴ independently of one another each represent linear or branched alkyl radicals with 10 to 18 C atoms, m is a number in the range from 1 to 6, R⁵ alkylbenzene radicals with 7 to 9 C atoms and Me each represent an alkali metal atom,
wherein the detergent content of the above components a, b and c is 2.5 to 12.5% by weight in total and the weight ratio of a to b is in the range from 3: 1 to 1: 6 and the weight ratio of (a + b): c is in the range from 3: 1 to 1: 3,
  • d) 5 to 97.5% by weight of at least one organic or inorganic builder, selected from the group of the oligo- and polycarboxylic acids or their water-soluble salts and the alkali metal phosphates, silicates, borates, carbonates and hydroxides,
  • e) up to 100% by weight of powdered or liquid auxiliaries or adjusting agents.

Die erfindungsgemäßen demulgierenden Reinigungsmittel besitzen ein hervorragendes Reinigungspotential. Aufgrund der guten demulgierenden Wirksamkeit dieser Reinigungsmittel scheiden sich die entfernten ölhaltigen Kontaminationen bei Verdünnung der wäßrigen Anwendungslösung von selbst ab. Auf diese Art und Weise von den Substratoberflächen abgewaschene Fette und Öle lassen sich so leicht und problemlos aus wäßrigen Medien entfernen, beispielsweise über simple Ölabscheider. Auf diese Art und Weise resultieren stets Vorfluter-geeignete Abwässer.The demulsifying cleaning agents according to the invention have an excellent cleaning potential. Due to the good demulsifying effectiveness of these cleaning agents, the removed oil-containing contaminants separate themselves when the aqueous application solution is diluted. Fats and oils washed off the substrate surfaces in this way can be easily and easily removed from aqueous media, for example using simple oil separators. In this way, wastewater suitable for receiving water always results.

In der vorstehend genannten allgemeinen Formel (I) der Komponente (a) (Alkyl-ethoxylate) steht R¹ für einen linearen Alkylrest mit 8 C-Atomen. Als Substituent R¹ kommt somit folgender Rest in Frage:
n-Octyl. Die Anzahl der Ethoxyreste im Molekül - n - liegt im Bereich von 4 bis 6. Im Sinne der Erfindung werden insbesondere als Komponente (a) entsprechende Anlagerungsprodukte von Ethylenoxid an Fettalkohole verwendet. Derartige Fettalkoholethoxylate können sowohl einzeln oder in Kombination Verwendung finden.In the above-mentioned general formula (I) of component (a) (alkyl ethoxylates), R 1 represents a linear alkyl radical with 8 carbon atoms. The following radical can therefore be used as substituent R¹:
n-octyl. The number of ethoxy radicals in the molecule - n - is in the range from 4 to 6. For the purposes of the invention, corresponding addition products of ethylene oxide with fatty alcohols are used in particular as component (a). Such fatty alcohol ethoxylates can be used either individually or in combination.

Nach einer bevorzugten Ausführungsform der vorliegenden Erfindung verwendet man als Komponente (a) insbesondere das Anlagerungsprodukt von 4 Mol Ethylenoxid an n-Octanol.According to a preferred embodiment of the present invention, component (a) is in particular the adduct of 4 moles of ethylene oxide with n-octanol.

In der vorstehend genannten allgemeinen Formel (II) der Komponente (b) steht R² für einen verzweigten Alkylrest mit 8 bis 9 C-Atomen. Auch diese Monocarbonsäuren der Komponente (b) können sowohl alleine als auch in-Kombination Verwendung finden. Als wasserlösliche Salze derartiger Monocarbonsäuren kommen insbesondere die Alkalimetallsalze, vorzugsweise deren Natriumsalze, in Frage.In the general formula (II) of component (b) mentioned above, R² is a branched alkyl radical having 8 to 9 carbon atoms. These monocarboxylic acids of component (b) can also be used both alone and in combination. Suitable water-soluble salts of such monocarboxylic acids are, in particular, the alkali metal salts, preferably their sodium salts.

Nach einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung wird als Komponente (b) vorzugsweise die 2-Ethylhexansäure eingesetzt.According to a further preferred embodiment of the present invention, 2-ethylhexanoic acid is preferably used as component (b).

Als Komponente (c) wird in den erfindungsgemäßen demulgierenden Reinigungsmitteln mindestens ein anionisches Tensid eingesetzt, welches ausgewählt ist aus der Gruppe der Alkylsulfate der allgemeinen Formel (III), der Alkylpolyglykolethersulfate der allgemeinen Formel (IV) sowie der Alkylarylsulfonate der allgemeinen Formel (V). In den vorstehend definierten allgemeinen Formeln (III) und (IV) bedeuten die Substituenten R³ und R⁴ unabhängig voneinander jeweils lineare oder verzweigte Alkylreste mit 10 bis 18 C-Atomen. Somit kommen als Substituenten R³ und R⁴ die folgenden Reste in Frage: 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. Die Anzahl der Ethylenoxideinheiten - m - in den Alkylpolyglykolethersulfaten der allgemeinen Formel (IV) liegt im Bereich von 1 bis 6. Der Rest R⁵ in den Alkylarylsulfonaten der allgemeinen Formel (V) steht für Alkylbenzolreste mit 7 bis 9 C-Atomen, ausgewählt aus der Gruppe Toluol, Xylol, Mesithylen und Cumol. In den allgemeinen Formeln (III), (IV) und (V) bedeutet Me jeweils ein Alkalimetallatom, vorzugsweise Natrium.At least one anionic surfactant, which is selected from the group of the alkyl sulfates of the general formula (III), the alkyl polyglycol ether sulfates of the general formula (IV) and the alkylarylsulfonates of the general formula (V), is used as component (c) in the demulsifying cleaning agents according to the invention. In the general formulas (III) and (IV) defined above, the substituents R³ and R⁴ independently of one another each represent linear or branched alkyl radicals having 10 to 18 carbon atoms. Thus, the following radicals are suitable as substituents R³ and R⁴: n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl and also branched chain isomers of the alkyl radicals mentioned. The number of ethylene oxide units - m - in the alkylpolyglycol ether sulfates of the general formula (IV) is in the range from 1 to 6. The radical R⁵ in the alkylarylsulfonates of the general formula (V) represents alkylbenzene residues with 7 to 9 carbon atoms, selected from the Group toluene, xylene, mesithylene and cumene. In the general formulas (III), (IV) and (V) Me each represents an alkali metal atom, preferably sodium.

Der Gehalt der erfindungsgemäßen Reinigungsmittel an den vorstehend definierten Komponenten (a), (b) und (c) beträgt insgesam 2,5 bis 12,5 Gew.-%. Ferner ist es im Sinne der Erfindung von Bedeutung, daß das Gewichtsverhältnis der Komponente (a) zu der Komponente (b) im Bereich von 3 : 1 bis 1 : 6 liegt und ferner das Gewichtsverhältnis der Summe der Komponenten (a) und (b) zu der Komponenten (c) im Bereich von 3 : 1 bis 1 : 3.The content of components (a), (b) and (c) defined above in the cleaning agents according to the invention is 2.5 to 12.5% by weight in total. It is also important in the context of the invention that the weight ratio of component (a) to component (b) is in the range from 3: 1 to 1: 6 and also the weight ratio of the sum of components (a) and (b) to component (c) in the range from 3: 1 to 1: 3.

Nach einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung setzt man als Komponente (c) ein C₁₂₋₁₄-Fettalkoholsulfat-Natriumsalz und/oder ein C₁₂₋₁₄-Fettalkoholethersulfat-Natriumsalz mit 3 bis 5 Mol Ethylenoxid und/oder das Cumolsulfonat-Natriumsalz ein.According to a further preferred embodiment of the present invention, component C is a C₁₂ C₁₄ fatty alcohol sulfate sodium salt and / or a C₁₂₋₁₄ fatty alcohol ether sulfate sodium salt with 3 to 5 moles of ethylene oxide and / or the cumene sulfonate sodium salt.

Zur Unterstützung der Wirksamkeit der erfindungsgemäßen demulgierenden Reinigungsmittel enthalten diese mindestens einen organischen oder anorganischen Builderstoff. Als solche kommen beispielsweise Oligo- oder Polycarbonsäuren sowie deren wasserlösliche Salze in Frage, beispielsweise Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Diethylentriaminpentaessigsäure oder n-(2-Hydroxyethyl)-ethylendiamintriessigsäure, vorzugsweise in Form ihrer Alkalimetallsalze, insbesondere der Natriumsalze. Weitere geeignete Buildersubstanzen im Sinne der Erfindung sind Alkalimetall-Phosphate, -Polyphosphate, -Silikate, -Borate, -Carbonate und/oder -Hydroxide, vorzugsweise gleichfalls in Form der entsprechenden Natriumsalze.To support the effectiveness of the demulsifying cleaning agents according to the invention, they contain at least one organic or inorganic builder. Examples include oligo- or polycarboxylic acids and their water-soluble salts, for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or n- (2-hydroxyethyl) ethylenediaminetriacetic acid, preferably in the form of their alkali metal salts, especially the sodium salts. Further suitable builder substances within the meaning of the invention are alkali metal phosphates, polyphosphates, silicates, borates, carbonates and / or hydroxides, preferably also in the form of the corresponding sodium salts.

Im Sinne der Erfindung werden als Builderstoffe vorzugsweise die Natriumsalze der Ethylendiamintetraessigsäure und/oder der Nitrilotriessigsäure verwendet.For the purposes of the invention, the sodium salts of ethylenediaminetetraacetic acid and / or nitrilotriacetic acid are preferably used as builder substances.

Die erfindungsgemäßen demulgierenden Reinigungsmittel enthalten ferner pulverförmige oder flüssige Hilfsstoffe und/oder Stellmittel, welche die Anteile der in den Reinigungsmitteln enthaltenen Komponenten (a), (b), (c) und (d) auf 100 Gew.-% ergänzen. Sie dienen insbesondere zur Konfektionierung von entweder pulverförmigen oder aber flüssigen Formulierungen der erfindungsgemäßen Reinigungsmittel. Sind flüssige Formulierungen erwünscht, so wird insbesondere Wasser als Stellmittel verwendet. Geeignete pulverförmige Stellmittel, die dann zu pulverförmigen Formulierungen führen, sind Alkalimetall-Sulfate oder -Carbonate, insbesondere in Form der Natriumsalze, oder Harnstoff. Weiterhin können die erfindungsgemäßen Reinigungsmittel als Hilfsstoffe auch geringe Mengen von Ölsäure oder deren Natriumsalz sowie von Diethanolamin und/oder Triethanolamin enthalten.The demulsifying cleaning agents according to the invention also contain powdery or liquid auxiliaries and / or adjusting agents which add up to 100% by weight of the components (a), (b), (c) and (d) contained in the cleaning agents. They are used in particular for the packaging of either powdered or liquid formulations of the cleaning agents according to the invention. If liquid formulations are desired, water is used in particular as an adjusting agent. Suitable powdered adjusting agents which then lead to powdered formulations are alkali metal sulfates or carbonates, especially in the form of sodium salts, or urea. Furthermore, the cleaning agents according to the invention can also contain small amounts of oleic acid or its sodium salt and of diethanolamine and / or triethanolamine as auxiliaries.

Die Herstellung der erfindungsgemäßen Reinigungsmittel erfolgt durch Vermischen der vorstehend genannten Komponenten in den jeweiligen Mengen nach an sich bekannten Methoden. Die Lagerung bzw. der Versand der Reinigungsmittel erfolgt in der Regel in Form eines die Kombination der angegebenen Komponenten enthaltenen wäßrigen oder pulverförmigen Konzentrates, auf welche sich auch die angegebenen Mengen (in Gew.-%) beziehen. Zur Reinigung und Entfettung von lackierten und unlackierten Oberflächen von Fahrzeugen, Motoren, Fußböden und Wänden etc. werden die erfindungsgemäßen demulgierenden Reinigungsmittel - je nach Applikationsart und Verschmutzungsgrad der zu reinigenden Flächen - in beliebiger Verdünnung mit Wasser eingesetzt. Im Sinne der Erfindung ist es hierbei bevorzugt, daß man die Reinigungsmittel in mit Wasser verdünnten Anwendungslösungen zum Reinigen und Entfetten von harten Oberflächen verwendet, wobei die Konzentration der Komponenten (a), (b) und (c) in diesen Anwendungslösungen insgesamt 0,01 bis 3 Gew.-%, insbesondere 0,025 bis 1 Gew.-%, beträgt.The cleaning agents according to the invention are produced by mixing the abovementioned components in the respective amounts by methods known per se. The cleaning agents are generally stored or shipped in the form of an aqueous or powdery concentrate containing the combination of the specified components, to which the stated amounts (in% by weight) also relate. For the cleaning and degreasing of painted and unpainted surfaces of vehicles, engines, floors and walls etc., the demulsifying cleaning agents according to the invention - depending on the type of application and degree of contamination of the surfaces to be cleaned - are used in any dilution with water. For the purposes of the invention, it is preferred that the cleaning agents are used in water-diluted application solutions for cleaning and degreasing hard surfaces, the concentration of components (a), (b) and (c) in these application solutions being 0.01 in total up to 3% by weight, in particular 0.025 to 1% by weight.

Der pH-Wert dieser wäßrigen Anwendungslösungen liegt im Bereich von 7,5 bis 13, insbesondere im Bereich von 9,5 bis 11,5.The pH of these aqueous application solutions is in the range from 7.5 to 13, in particular in the range from 9.5 to 11.5.

Die Erfindung wird im Folgenden durch Ausführungsbeispiele weiter erläutert (die Abkürzung EO steht für Ethylenoxid):The invention is further explained below by means of exemplary embodiments (the abbreviation EO stands for ethylene oxide):

Beispiel 1example 1

Ein flüssiges Reinigungsmittel wird durch Mischen von
1,8 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol EO,
1,8 Gew.-% 2-Ethylhexansäure,
0,3 Gew.-% C₁₂-C₁₄-Fettalkoholethersulfat mit 3 Mol EO-Natriumsalz,
2,6 Gew.-% Natriumcumolsulfonat,
28,0 Gew.-% Ethylendiamintetraessigsäure-Natriumsalz,
0,8 Gew.-% Triethanolamin,
0,4 Gew.-% Ölsäure
64,3 Gew.-% Wasser
hergestellt.A liquid detergent is made by mixing
1.8% by weight of a condensation product of n-octanol with 4 mol of EO,
1.8% by weight of 2-ethylhexanoic acid,
0.3% by weight of C₁₂-C₁₄ fatty alcohol ether sulfate with 3 mol of EO sodium salt,
2.6% by weight sodium cumene sulfonate,
28.0% by weight of sodium ethylenediaminetetraacetic acid,
0.8% by weight of triethanolamine,
0.4% by weight oleic acid
64.3 wt% water
manufactured.

Beispiel 2Example 2

Ein pulverförmiges Reinigungsmittel wird durch Mischen von
3,0 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol EO
2,0 Gew.-% 2-Ethylhexansäure,
1,0 Gew.-% C₁₂-C₁₄-Fettalkoholsulfat-Natriumsalz,
3,0 Gew.-% Natriumcumolsulfonat,
36,8 Gew.-% Nitrilotriessigsäure-Natriumsalz
1,0 Gew.-% Ölsäure,
38,6 Gew.-% Natriumcarbonat
14,6 Gew.-% Harnstoff
hergestellt.A powder detergent is made by mixing
3.0% by weight of a condensation product of n-octanol with 4 mol of EO
2.0% by weight of 2-ethylhexanoic acid,
1.0% by weight of C₁₂-C₁₄ fatty alcohol sulfate sodium salt,
3.0% by weight sodium cumene sulfonate,
36.8% by weight of nitrilotriacetic acid sodium salt
1.0% by weight of oleic acid,
38.6% by weight sodium carbonate
14.6% by weight urea
manufactured.

Vergleichsbeispiel (Handelsprodukt gemäß DE-A-35 30 623)Comparative example (commercial product according to DE-A-35 30 623)

Ein Vergleichsreiniger wurde durch Mischen von
5,0 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol EO,
1,6 Gew.-% Natriumcumolsulfonat,
2,4 Gew.-% Ethylendiamintetraessigsäure-Natriumsalz
42,0 Gew.-% einer Mischung von Diethanolamin und Triethanolamin im Verhältnis 2 : 1, und
49,0 Gew.-% Wasser
hergestellt.A comparative cleaner was made by mixing
5.0% by weight of a condensation product of n-octanol with 4 mol of EO,
1.6% by weight sodium cumene sulfonate,
2.4% by weight of ethylenediaminetetraacetic acid sodium salt
42.0% by weight of a mixture of diethanolamine and triethanolamine in a ratio of 2: 1, and
49.0 wt% water
manufactured.

Anwendungsbeispiel 1: Ölwerte im AbwasserApplication example 1: Oil values in wastewater

Mit den vorstehenden Reinigungsmitteln gemäß Beispielen 1 und 2 sowie dem Vergleichsbeispiel wurden gemäß der Technischen Liefervorschrift der Deutschen Bundesbahn TL 918 81, Blatt 6, ölhaltige Abwässer hergestellt. Die Konzentration der Reinigungsmittel in den wäßrigen Losungen betrug 1,2 Gew.-%; die Ölbelastung - erzeugt mit Squalan als Mineralöl - 1000 ppm. Nach Abtrennung der Ölphase von der wäßrigen Phase wurden die Restölwerte in der letzteren gemäß der zitierten Technischen Liefervorschrift bestimmt. Hierbei resultierten die folgenden Restölwerte im Abwasser: Beispiel 1: 12 ppm Beispiel 2: 31 ppm Vergleichsbeispiel: 78 ppm With the above cleaning agents according to Examples 1 and 2 and the comparative example, oil-containing waste water was produced in accordance with the technical delivery specification of the German Federal Railroad TL 918 81, sheet 6. The concentration of the cleaning agents in the aqueous solutions was 1.2% by weight; the oil pollution - produced with squalane as mineral oil - 1000 ppm. After the oil phase had been separated from the aqueous phase, the residual oil values in the latter were determined in accordance with the technical delivery specification cited. The following residual oil values resulted in the wastewater: Example 1: 12 ppm Example 2: 31 ppm Comparative example: 78 ppm

Die Abtrennzeit beziehungsweise Ruhezeit zur Phasenseparation betrug bei den Beispielen 1 und 2 nur 5 Minuten, im Vergleich zu einer Zeit von 30 Minuten, die beim Vergleichsreiniger erforderlich war.The separation time or rest time for phase separation was only 5 minutes in Examples 1 and 2, compared to a time of 30 minutes that was required for the comparative cleaner.

Anwendungsbeispiel 2: ReinigungswirkungExample of use 2: cleaning effect

Prüfung der Reinigungswirkung und relativen Reinigung wirkung WRrel (wiederum im Vergleich zu dem Reiniger gemäß der DE-A-35 30 623).Testing the cleaning effect and relative cleaning effect WR rel (again in comparison to the cleaner according to DE-A-35 30 623).

Eine lackierte, stark verschmutzte Innenseite einer PKW-Motorhaube wurde senkrecht aufgestellt. Aus den Reinigungsmitteln gemäß Beispielen 1, 2 und dem Vergleichsbeispiel wurden jeweils durch Verdünnen mit Wasser (16 °d) 2,5 Gew.-%ige Reinigungsmittellösungen als Prüflösungen hergestellt.A painted, heavily soiled inside of a car bonnet was placed vertically. 2.5% by weight cleaning agent solutions as test solutions were prepared from the cleaning agents according to Examples 1, 2 and the comparative example by dilution with water (16 ° d).

In diese Prüflösungen wurden jeweils Viskoseschwämme mit den Abmessungen 90 x 50 x 40 mm gegeben, satt getränkt und jeweils einzeln zum Aus laufen der überschüssigen Lösung 3 min hochkant aufgestellt.In each of these test solutions, viscose sponges with the dimensions 90 x 50 x 40 mm were placed, saturated and each placed upright for 3 minutes to drain off the excess solution.

Diese so präparierten Schwämme wurden einer neben dem anderen in einem Winkel von 45 ° mit der Kante je einmal pro Sekunde mit geringem Druck über die verschmutzte Fläche gewischt, bis die Fläche sauber war. Das Tränken, Hochkantaufstellen und Wischen wurde zehnmal vorgenommen und die erhaltenen Werte gemittelt.These prepared sponges were wiped one after the other at an angle of 45 ° with the edge once per second with light pressure over the soiled area until the area was clean. The impregnation, upright erection and wiping were carried out ten times and the values obtained were averaged.

Die Ermittlung der Reinigungswirkung und der relativen Reinigungswirkung RWrel erfolgte in der Weise, daß die Zahl der Wischungen mit dem Vergleichsreiniger durch die Zahl der Wischungen mit dem zu prüfenden erfindungsgemäßen Reiniger geteilt wurde. Der Quotient ergab die relative Reinigungswirkung RWrel, bezogen auf den Vergleichsreiniger. Es ergaben sich für die Reinigungsmittelzusammensetzungen folgende Werte: Reinigungsmittelzusammensetzung gemäß Beispiel 1: 2,4 Reinigungsmittelzusammensetzung gemäß Beispiel 2: 2,6 Reinigungsmittelzusammensetzung gemäß Vergleichsbeispiel (Standard): 1,0 The cleaning action and the relative cleaning action RW rel were determined in such a way that the number of wipings with the comparative cleaner was divided by the number of wipings with the cleaner according to the invention to be tested. The quotient gave the relative cleaning effect RW rel , based on the comparative cleaner. The following values resulted for the detergent compositions: Detergent composition according to Example 1: 2.4 Detergent composition according to Example 2: 2.6 Detergent composition according to comparative example (standard): 1.0

Claims (7)

  1. Demulsifying, powder-form or liquid cleaning preparations based on nonionic surfactants, anionic surfactants and builders and free from water-insoluble organic solvents, characterized in that they contain a combination of the following constituents:
    a) at least one alkyl ethoxylate corresponding to general formula (I):



            R¹-O-(CH₂CH₂O)n-H   (I)



    in which R¹ is a linear alkyl radical containing 8 carbon atoms and n is a number of 4 to 6,
    b) at least one monocarboxylic acid corresponding to general formula (II):



            R²-COOH   (II)



    in which R² is a branched alkyl radical containing 8 to 9 carbon atoms, or water-soluble salts thereof,
    c) at least one anionic surfactant selected from the group consisting of
    c1) alkyl sulfates corresponding to general formula (III):



            R³-O-SO₃Me   (III)



    c2) alkyl polyglycol ether sulfates corresponding to general formula (IV):



            R⁴-O-(CH₂CH₂O)m-SO₃Me   (IV)



    c3) alkylaryl sulfonates corresponding to general formula (V):



            R⁵-SO₃-Me   (V)



    in which R³ and R⁴ independently of one another represent linear or branched alkyl radicals containing 10 to 18 carbon atoms, m is a number of 1 to 6, R⁵ represents alkylbenzene groups containing 7 to 9 carbon atoms and Me is an alkali metal atom,
    the total content of components a), b) and c) in the cleaning preparation being from 2.5 to 12.5% by weight, the ratio by weight of a) to b) being from 3:1 to 1:6 and the ratio by weight of (a+b) to c being from 3:1 to 1:3,
    d) 5 to 97.5% by weight of at least one organic or inorganic builder selected from the group consisting of oligo- and polycarboxylic acids or water-soluble salts thereof and the alkali metal phosphates, silicates, borates, carbonates and hydroxides,
    e) up to 100% by weight of powder-form or liquid auxiliaries or diluents.
  2. Cleaning preparations as claimed in claim 1, characterized in that they contain an adduct of 4 moles of ethylene oxide with n-octanol as component (a).
  3. Cleaning preparations as claimed in claim 1, characterized in that they contain 2-hexyl hexanoic acid as component (b).
  4. Cleaning preparations as claimed in claim 1, characterized in that they contain a C₁₂₋₁₄ fatty alcohol sulfate sodium salt and/or a C₁₂₋₁₄ fatty alcohol ether sulfate sodium salt containing 3 to 5 moles of ethylene oxide and/or the sodium salt of cumenesulfonate as component (c).
  5. Cleaning preparations as claimed in any of claims 1 to 4, characterized in that they contain the sodium salt of ethylenediamine tetraacetic acid and/or nitrilotriacetic acid as builder.
  6. Cleaning preparations as claimed in any of claims 1 to 5, characterized in that they contain oleic acid, sodium carbonate, urea and/or water as auxiliaries and/or diluents.
  7. The use of the cleaning preparations claimed in any of claims 1 to 6 for cleaning and degreasing hard surfaces, characterized in that the concentration of components (a), (b) and (c) together in the water-diluted in-use solutions is from 0.01 to 3% by weight and, more particularly, from 0.025 to 1% by weight.
EP91902214A 1990-01-20 1991-01-12 Anti-froth cleaning agents and use thereof Expired - Lifetime EP0511253B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4001595A DE4001595A1 (en) 1990-01-20 1990-01-20 DEMULGATING, POWDERFUL, OR LIQUID CLEANSING AGENTS AND THEIR USE
DE4001595 1990-01-20
PCT/EP1991/000039 WO1991010718A1 (en) 1990-01-20 1991-01-12 Anti-froth cleaning agents and use thereof

Publications (2)

Publication Number Publication Date
EP0511253A1 EP0511253A1 (en) 1992-11-04
EP0511253B1 true EP0511253B1 (en) 1995-02-22

Family

ID=6398453

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Country Status (9)

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US (1) US5286402A (en)
EP (1) EP0511253B1 (en)
JP (1) JPH05504155A (en)
AT (1) ATE118809T1 (en)
DE (2) DE4001595A1 (en)
DK (1) DK0511253T3 (en)
ES (1) ES2068568T3 (en)
NO (1) NO180202C (en)
WO (1) WO1991010718A1 (en)

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US8309050B2 (en) 2005-05-26 2012-11-13 Smith International, Inc. Polycrystalline diamond materials having improved abrasion resistance, thermal stability and impact resistance
US8852304B2 (en) 2004-05-06 2014-10-07 Smith International, Inc. Thermally stable diamond bonded materials and compacts
US8881851B2 (en) 2003-12-05 2014-11-11 Smith International, Inc. Thermally-stable polycrystalline diamond materials and compacts

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US8881851B2 (en) 2003-12-05 2014-11-11 Smith International, Inc. Thermally-stable polycrystalline diamond materials and compacts
US8852304B2 (en) 2004-05-06 2014-10-07 Smith International, Inc. Thermally stable diamond bonded materials and compacts
US8309050B2 (en) 2005-05-26 2012-11-13 Smith International, Inc. Polycrystalline diamond materials having improved abrasion resistance, thermal stability and impact resistance

Also Published As

Publication number Publication date
NO922692L (en) 1992-07-08
DK0511253T3 (en) 1995-07-10
ATE118809T1 (en) 1995-03-15
US5286402A (en) 1994-02-15
EP0511253A1 (en) 1992-11-04
ES2068568T3 (en) 1995-04-16
NO922692D0 (en) 1992-07-08
DE4001595A1 (en) 1991-07-25
NO180202B (en) 1996-11-25
WO1991010718A1 (en) 1991-07-25
DE59104713D1 (en) 1995-03-30
NO180202C (en) 1997-03-05
JPH05504155A (en) 1993-07-01

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