EP0511253A1 - Anti-froth cleaning agents and use thereof. - Google Patents

Anti-froth cleaning agents and use thereof.

Info

Publication number
EP0511253A1
EP0511253A1 EP91902214A EP91902214A EP0511253A1 EP 0511253 A1 EP0511253 A1 EP 0511253A1 EP 91902214 A EP91902214 A EP 91902214A EP 91902214 A EP91902214 A EP 91902214A EP 0511253 A1 EP0511253 A1 EP 0511253A1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
contain
cleaning
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91902214A
Other languages
German (de)
French (fr)
Other versions
EP0511253B1 (en
Inventor
Juergen Geke
Friedbert Zetzsche
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0511253A1 publication Critical patent/EP0511253A1/en
Application granted granted Critical
Publication of EP0511253B1 publication Critical patent/EP0511253B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 de-emulsifying, 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 Pat. No. 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 to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight of an ethanol ins and 0 to 50% by weight of water.
  • a nonionic surfactant for example a fatty alcohol ethoxylate, 4 to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight of an ethanol ins and 0 to 50% by weight of water.
  • Austrian patent specification 308,936 relates to liquid storage-stable concentrates and to cleaning and degreasing agents which can be prepared by dilution with water and which contain 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 up 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.
  • British Patent 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 alkanol and / or Oxazine and the rest 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, as well as 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, as well as other additives and the rest water.
  • Austrian patent specification 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, 3 to Contains 15% by weight of an ethanolamine and 0.1 to 0.6% of a corrosion inhibitor.
  • DE-OS 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 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.
  • US Pat. No. 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 exists, 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 exists, as well as 1 to 75 wt .-% water.
  • DE-OS 35 30 623 relates to demulsifying cleaning agents with a 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., even at room temperature, while removing the oily or greasy contaminants removed.
  • 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 lower the residual oil values in the wastewater to the low values required today.
  • the demulsifying action of the cleaning agents should result in improved oil separation and thus lower residual oil values in the waste water.
  • the invention thus relates to demulsifying, powdered or liquid cleaning agents based on nonionic surfactants, carboxylic acids, anionic surfactants and optionally builder substances, characterized in that they contain a combination of the following constituents:
  • R- is a linear or branched alkyl radical having 6 to 9 carbon atoms and n is a number in the range from 3 to 10,
  • R and R 4 are each, independently of one another, linear or branched alkyl radicals having 10 to 18 carbon atoms, m is a number in the range from 1 to 6, R alkylbenzene radicals having 7 to 9 carbon atoms and Me are each an alkali metal atom,
  • the content of the cleaning agents in the above components a, b and c is a total of 1.5 to 15% by weight 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) 0 to 98.5% by weight of at least one organic or inorganic builder substance, 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 ,
  • 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.
  • the demulsifying cleaning agents contain 2.5 to 12.5% by weight of a combination of those defined above
  • R - stands for a linear or branched alkyl radical with 6 to 9 carbon atoms.
  • the following radicals are therefore suitable as substituent R *: n-hexyl, n-heptyl, n-octyl and n-nonyl and the branched chain isomers of the alkyl radicals mentioned.
  • the number of ethoxy radicals in the molecule - n - is in the range from 3 to 10.
  • 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.
  • an adduct of 4 to 6 moles of ethylene oxide with n-octanol in particular the adduct of 4 moles of ethylene oxide with n-octanol, is used as component (a).
  • R 2 represents a linear or branched alkyl radical having 5 to 11 carbon atoms.
  • Monocarboxylic acids in the sense of this general formula are therefore the following linear fatty acids: hexanoic acid (caproic acid), heptanoic acid (onanthic acid), octanoic acid (capyrylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid and dodecanoic acid (lauric acid).
  • the corresponding branched-chain monocarboxylic acids are also suitable as component (b).
  • 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.
  • branched-chain monocarboxylic acids having a total of 8 to 9 carbon atoms are 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.
  • substituents R 3 and R 4 each independently represent linear or branched alkyl radicals having 10 to 18 carbon atoms.
  • the following radicals are therefore suitable as substituents R 3 and R 4 : 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.
  • 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 R - in the alkylarylsulfonates of the general formula (V) is selected from alkylbenzene radicals having 7 to 9 carbon atoms the group of 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 1.5 to 15% 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 Ci2-i4-fatty alcohol sulfate sodium salt and / or a Ci2-i4-fatty alcohol ether sulfate.
  • these may optionally contain at least one organic or inorganic builder.
  • organic or inorganic builder such as, for example, oligo- or polycarboxylic acids and their water-soluble salts, for example ethylene-diamine-tetraacetic acid, nitrilotriacetic acid, diethylenetriamine-pentaacetic acid or n- (2-hydroxyethyl) -ethylenediamine-triacetic 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 likewise 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 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 optionally (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.
  • EO ethylene oxide
  • a liquid detergent is made by mixing
  • a powder detergent is mixed by Misc: -n of 3.0 wt .-% of a condensation product of n-octanol with 4 mol E0
  • Ci2-Ci4-fatty alcohol sulfate sodium salt 1.0% by weight of Ci2-Ci4-fatty alcohol sulfate sodium salt
  • a comparative cleaner was made by mixing
  • Ratio 2 1, and 49.0 wt .-% water.
  • 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.
  • the residual oil values in the latter were determined in accordance with the technical delivery specification cited.
  • the following residual oil values in the wastewater resulted:
  • Example 1 12 ppm
  • Example 2 31 ppm Comparative example: 78 ppm
  • a painted, heavily soiled inside of a car bonnet was placed vertically. 2.5% by weight of 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).
  • viscose sponges with the dimensions 90 ⁇ 50 ⁇ 40 mm were placed, saturated soaked, and placed individually upright for 3 minutes to allow the excess solution to run out.
  • the cleaning agent compositions had the following values: 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

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

Demulqierende. pulverförmige oder flüssige Reinigungsmittel und deren VerwendungDemulking. powdery or liquid detergents and their use
Die vorliegende Erfindung betrifft de ulgierende, 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 de-emulsifying, 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.
Das US-Patent 3,663,445 beschreibt flüssige lagerstabile Konzen¬ trate 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 Fettalkohol- ethoxylats, 4 bis 33 Gew.-% eines Ethanolaminsalzes einer Fettsäu¬ re, 2 bis 90 Gew.-% eines Ethanola ins und 0 bis 50 Gew.-% Wasser bestehen.US Pat. No. 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 to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight of an ethanol ins and 0 to 50% by weight of water.
Die österreichische Patentschrift 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. Die britische Patentschrift 1,321,513 betrifft ein Reinigungsver¬ fahren für metallische Oberflächen mit zwei zeitlich nacheinander anzuwendenden Reinigungsbädern, dem Vorreinigungsbad und dem Ent¬ fettungsbad. Das Vorreinigungsbad besteht aus wenigstens 5 Gew.-% eines 3 bis 5 Mol Ethylenoxid enthaltenden nichtionischen Tensids, mindestens 3 Gew.-% einer Fettsäure und/oder einer Alkylpolyethylen- oxidcarbonsäure, mindestens 1,5 Gew.-% eines Alkanola ins und/oder Oxazins und als Rest Wasser. Das Entfettungsbad besteht aus einer anorganischen oder organischen alkalischen Substanz, beispielsweise Kaliumhydroxid, Kaliumcarbonat, Kaliumorthophosphat, Kaliumpyro- phosphat, 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.Austrian patent specification 308,936 relates to liquid storage-stable concentrates and to cleaning and degreasing agents which can be prepared by dilution with water and which contain 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 up 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. British Patent 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 alkanol and / or Oxazine and the rest 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, as well as other additives and the rest water.
Die österreichische Patentschrift 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 % ei¬ nes Korrosionsinhibitors enthält.Austrian patent specification 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, 3 to Contains 15% by weight of an ethanolamine and 0.1 to 0.6% of a corrosion inhibitor.
Die DE-OS 25 05 252 betrifft ein Verfahren zum industriellen Rei¬ nigen 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 A inopolycarbonsäuren oder Aminopoly- phosphonsäuren 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-OS 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 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.
Das US-Patent 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 Pat. No. 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 exists, as well as 1 to 75 wt .-% water.
Die DE-OS 35 30 623 betrifft demulgierende Reinigungsmittel mit Flächenfeuchthalteeffekt, enthaltend Builder/Komplexbildner in ei¬ ner 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 Reinigungsmittelzuberei¬ tungen eignen sich zur Reinigung und Entfettung lackierter und unlackierter Fahrzeugoberflächen, Motoren, Fußböden und Wände von Werkstätten etc. bereits bei Raumtemperatur unter De ulgierung der entfernten öligen bzw. fetthaltigen Verunreinigungen.DE-OS 35 30 623 relates to demulsifying cleaning agents with a 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., even at room temperature, while removing the oily or greasy contaminants removed.
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 hier¬ mit erzielte Demulgierung der entfernten, ölhaltigen Verunreini¬ gungen beziehungsweise die daraus resultierende, anschließende Olabscheidung nicht ausreicht, um die Restölwerte im Abwasser auf die heutzutage geforderten, niedrigen Werte abzusenken. Demgegenüber ist es die Aufgabe der vorliegenden Erfindung, solche demulgierenden Reinigungsmittel für die Reinigung von mit Öl ver¬ unreinigten harten Oberflächen bereitzustellen, die eine bessere demulgierende Wirksamkeit und ferner eine bessere Reinigungswirkung als die bekannten Reinigungsmittel des Standes der Technik auf¬ weisen. Darüber hinaus sollte die Demulgierwirkung der Reini¬ gungsmittel eine verbesserte Olabscheidung und somit geringere Restölwerte im Abwasser bedingen.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 lower the residual oil values in the wastewater to the low values required today. In contrast, it is the object of the present invention to provide such demulsifying cleaning agents for cleaning hard 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 action of the cleaning agents should result in improved oil separation and thus lower residual oil values in the waste water.
Überraschenderweise wurde gefunden, daß eine spezielle Kombination von Alkyl-ethoxylaten, Monocarbonsäureπ und anionischen Tensiden, die gegebenenfalls noch Buildersubstanzen enthält, die gestellten Anforderungen erfüllt.Surprisingly, it was found that a special combination of alkyl ethoxylates, monocarboxylic acids and anionic surfactants, which may also contain builder substances, meets the requirements.
Die Erfindung betrifft somit demulgierende, pulverförmige oder flüssige Reinigungsmittel auf Basis von nichtionischen Tensiden, Carbonsäuren, anionischen Tensiden und gegebenenfalls Builder¬ substanzen, dadurch gekennzeichnet, daß sie eine Kombination der folgenden Bestandteile enthalten:The invention thus relates to demulsifying, powdered or liquid cleaning agents based on nonionic surfactants, carboxylic acids, anionic surfactants and optionally builder substances, characterized in that they contain a combination of the following constituents:
a) mindestens ein Alkyl-ethoxylat der allgemeinen Formel (I):a) at least one alkyl ethoxylate of the general formula (I):
worin R- einen linearen oder verzweigten Alkylrest mit 6 bis 9 C-Atomen und n eine Zahl im Bereich von 3 bis 10 bedeuten,in which R- is a linear or branched alkyl radical having 6 to 9 carbon atoms and n is a number in the range from 3 to 10,
b) mindestens eine Monocarbonsäure oder deren wasserlösliche Salze der allgemeinen Formel (II):b) at least one monocarboxylic acid or its water-soluble salts of the general formula (II):
R2-C00H (II) worin R- einen linearen oder verzweigten Alkylrest mit 5 bis 11 C-Atomen bedeutet,R 2 -C00H (II) in which R- is a linear or branched alkyl radical having 5 to 11 carbon atoms,
c) mindestens ein anionisches Tensid, ausgewählt aus der Gruppe derc) at least one anionic surfactant selected from the group of
cl) Alkylsulfate der allgemeinen Formel (III):cl) alkyl sulfates of the general formula (III):
R3-0-S03Me (III)R 3 -0-S03Me (III)
c2) Alkyl-polyglykolether-sulfate der allgemeinen Formel (IV):c2) alkyl polyglycol ether sulfates of the general formula (IV):
R4-0-(CH2CH20)m-S03Me (IV)R 4 -0- (CH2CH 2 0) m -S03Me (IV)
c3) Alkylarylsulfonate der allgemeinen Formel (V):c3) alkylarylsulfonates of the general formula (V):
worin R- und R4 unabhängig voneinander jeweils lineare oder verzweigte Alkylreste mit 10 bis 18 C-Atomen, m eine Zahl im Bereich von 1 bis 6, R- Alkylbenzolreste mit 7 bis 9 C-Atomen und Me jeweils ein Alkalimetallatom bedeuten,in which R and R 4 are each, independently of one another, linear or branched alkyl radicals having 10 to 18 carbon atoms, m is a number in the range from 1 to 6, R alkylbenzene radicals having 7 to 9 carbon atoms and Me are each an alkali metal atom,
wobei der Gehalt der Reinigungsmittel an den vorstehenden Kompo¬ nenten a, b und c insgesamt 1,5 bis 15 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) 0 bis 98,5 Gew.-% mindestens eines organischen oder anor¬ ganischen Builderstoffes, ausgewählt aus der Gruppe der Oligo- und Polycarbonsäuren oder deren wasserlöslichen Salzen sowie der Alkalimetall-phosphate, -silikate, -borate, -carbonate und -hydroxide,wherein the content of the cleaning agents in the above components a, b and c is a total of 1.5 to 15% by weight 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) 0 to 98.5% by weight of at least one organic or inorganic builder substance, 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) bis 100 Gew.-% an pulverförmigen oder flüssigen Hilfsstoffen oder Stellmitteln.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 demul- gierenden 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.
Nach einer bevorzugten Ausführungsform der vorliegenden Erfindung enthalten die demulgierenden Reinigungsmittel 2,5 bis 12,5 Gew.-% einer Kombination der vorstehend definiertenAccording to a preferred embodiment of the present invention, the demulsifying cleaning agents contain 2.5 to 12.5% by weight of a combination of those defined above
Komponenten a), b) und c), 5 bis 97,5 Gew.-% eines Builderstoffes und bis 100 Gew.-% Hilfsstoffe und/oder Stellmittel.Components a), b) and c), 5 to 97.5% by weight of a builder and up to 100% by weight of auxiliaries and / or adjusting agents.
In der vorstehend genannten allgemeinen Formel (I) der Komponente (a) (Alkyl-ethoxylate) steht R- für einen linearen oder verzweigten Alkylrest mit 6 bis 9 C-Atomen. Als Substituent R* kommen somit die folgenden Reste in Frage: n-Hexyl, n-Heptyl, n-Octyl und n-Nonyl sowie die verzweigtkettigen Isomere der genannten Alkylreste. Die Anzahl der Ethoxyreste im Molekül - n - liegt im Bereich von 3 bis 10. Im Sinne der Erfindung werden insbesondere als Komponente (a) entsprechende Anlagerungs¬ produkte 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 - stands for a linear or branched alkyl radical with 6 to 9 carbon atoms. The following radicals are therefore suitable as substituent R *: n-hexyl, n-heptyl, n-octyl and n-nonyl and the branched chain isomers of the alkyl radicals mentioned. The number of ethoxy radicals in the molecule - n - is in the range from 3 to 10. 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) ein Anlagerungsprodukt von 4 bis 6 Mol Ethylenoxid an n-Octanol, insbesondere das Anlagerungsprodukt von 4 Mol Ethylenoxid an n-Octanol.According to a preferred embodiment of the present invention, an adduct of 4 to 6 moles of ethylene oxide with n-octanol, in particular the adduct of 4 moles of ethylene oxide with n-octanol, is used as component (a).
In der vorstehend genannten allgemeinen Formel (II) der Komponente (b) steht R2 für einen linearen oder verzweigten Alkylrest mit 5 bis 11 C-Atomen. Als Monocarbonsäuren im Sinne dieser allgemeinen Formel kommen somit die folgenden linearen Fettsäuren in Frage: Hexansäure (Capronsäure), Heptansäure (Onanthsäure), Octansäure (Capyrylsäure), Nonansäure (Pelargonsäure) , Decansäure (Caprin- säure), Undecansäure und Dodecansäure (Laurinsäure). Als Komponente (b) kommen ferner die entsprechenden verzweigtkettigen Monocarbon¬ säuren in Frage. Auch diese Monocarbonsäuren der Komponente (b) können sowohl alleine als auch in Kombination Verwendung finden. Als wasserlösliche Salze derartiger Monocarbonsäuren kommen ins¬ besondere die Alkali etallsalze, vorzugsweise deren Natriumsalze, in Frage.In the general formula (II) of component (b) mentioned above, R 2 represents a linear or branched alkyl radical having 5 to 11 carbon atoms. Monocarboxylic acids in the sense of this general formula are therefore the following linear fatty acids: hexanoic acid (caproic acid), heptanoic acid (onanthic acid), octanoic acid (capyrylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid and dodecanoic acid (lauric acid). The corresponding branched-chain monocarboxylic acids are also suitable as component (b). 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 werden als Komponente (b) verzweigtkettige Monocarbon¬ säuren mit insgesamt 8 bis 9 C-Atomen, vorzugsweise die 2-Ethyl- hexansäure, eingesetzt. 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 der vorstehend definierten allgemeinen Formel (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 R- 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.According to a further preferred embodiment of the present invention, branched-chain monocarboxylic acids having a total of 8 to 9 carbon atoms, preferably 2-ethylhexanoic acid, are 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. In the general formulas (III) and (IV) defined above, the substituents R 3 and R 4 each independently represent linear or branched alkyl radicals having 10 to 18 carbon atoms. The following radicals are therefore suitable as substituents R 3 and R 4 : 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. 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 R - in the alkylarylsulfonates of the general formula (V) is selected from alkylbenzene radicals having 7 to 9 carbon atoms the group of 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 insgesamt 1,5 bis 15 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 1.5 to 15% 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 Ci2-i4-Fettalkohol- sulfat-Natriumsalz und/oder ein Ci2-i4-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 Ci2-i4-fatty alcohol sulfate sodium salt and / or a Ci2-i4-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 erfiπdungsgemäßen demul- gierenden Reinigungsmittel können diese gegebenenfalls mindestens einen organischen oder anorganischen Builderstoff enthalten. Als solche kommen beispielsweise Oligo- oder Polycarbonsäuren sowie deren wasserlösliche Salze in Frage, beispielsweise Ethylen- diamintetraessigsäure, Nitrilotriessigsäure, Diethylentriamin- pentaessigsäure oder n-(2-Hydroxyethyl)-ethylendiamintriessigsäure, vorzugsweise in Form ihrer Alkalimetallsalze, insbesondere der Natriumsalze. Weitere geeignete Buildersubstanzen im Sinne der Erfindung sind Alkali etall-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, these may optionally contain at least one organic or inorganic builder. Such as, for example, oligo- or polycarboxylic acids and their water-soluble salts, for example ethylene-diamine-tetraacetic acid, nitrilotriacetic acid, diethylenetriamine-pentaacetic acid or n- (2-hydroxyethyl) -ethylenediamine-triacetic 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 likewise 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 de ulgierenden Reinigungsmittel enthalten ferner pulverförmige oder flüssige Hilfsstoffe und/oder Stell¬ mittel, welche die Anteile der in den Reinigungsmitteln enthaltenen Komponenten (a), (b), (c) und gegebenenfalls (d) auf 100 Gew.-% ergänzen. Sie dienen insbesondere zur Konfektionierung von entweder pulverförmigen oder aber flüssigen Formulierungen der erfindungs¬ gemäßen Reinigungsmittel. Sind flüssige Formulierungen erwünscht, so wird insbesondere Wasser als Stellmittel verwendet. Geeignete pulverförmige Stellmittel, die dann zu pulverförmigen Formu¬ lierungen 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 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 optionally (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 jewe ligen 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 Konzentrate, 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. Die Erfindung wird im Folgenden durch Ausführungsbeispiele weiter erläutert (die Abkürzung EO steht für Ethylenoxid):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. 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 vonA liquid detergent is made by mixing
1,8 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol EO,1.8% by weight of a condensation product of n-octanol with 4 mol of EO,
1,8 Gew.-% 2-Ethylhexansäure,1.8% by weight of 2-ethylhexanoic acid,
0,3 Gew.-% Ci2-Ci4-Fettalkoholethersulfat mit 3 Mol EO-Natrium- salz,0.3% by weight of Ci2-Ci4 fatty alcohol ether sulfate with 3 mol of EO sodium salt,
2,6 Gew.-% Natriumcumolsulfonat, 28,0 Gew.-% Ethylendiamintetraessigsäure-Natriu salz,2.6% by weight sodium cumene sulfonate, 28.0% by weight ethylenediaminetetraacetic acid sodium salt,
0,8 Gew.-% Triethanolamin,0.8% by weight of triethanolamine,
0,4 Gew.-% Ölsäure 64,3 Gew.-% Wasser hergestellt.0.4 wt .-% oleic acid 64.3 wt .-% water.
Beispiel 2Example 2
Ein pulverförmiges Reinigungsmittel wird durch Misc:-n von 3,0 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol E0A powder detergent is mixed by Misc: -n of 3.0 wt .-% of a condensation product of n-octanol with 4 mol E0
2,0 Gew.-% 2-Ethylhexansäure,2.0% by weight of 2-ethylhexanoic acid,
1,0 Gew.-% Ci2-Ci4-Fettalkoholsulfat-Natriumsalz,1.0% by weight of Ci2-Ci4-fatty alcohol sulfate sodium salt,
3,0 Gew.-% Natriumcumolsulfonat, 36,8 Gew.-% Nitrilotriessigsäure-Natriumsalz3.0% by weight sodium cumene sulfonate, 36.8% by weight nitrilotriacetic acid sodium salt
1,0 Gew.-% Ölsäure, 38,6 Gew.-% Natriu carbonat 14,6 Gew.-% Harnstoff hergestellt. Verqleichsbeispiel (Handelsprodukt gemäß DE-OS 35 30 623)1.0% by weight of oleic acid, 38.6% by weight of sodium carbonate and 14.6% by weight of urea. Comparative example (commercial product according to DE-OS 35 30 623)
Ein Vergleichsreiniger wurde durch Mischen vonA comparative cleaner was made by mixing
5,0 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol EO,5.0% by weight of a condensation product of n-octanol with 4 mol of EO,
1,6 Gew.-% Natriumcumolsulfonat,1.6% by weight sodium cumene sulfonate,
2,4 Gew.-% Ethylendiamintetraessigsäure-Natriumsalz 42,0 Gew.-% einer Mischung von Diethanolamin und Triethanolamin im2.4% by weight of ethylenediaminetetraacetic acid sodium salt 42.0% by weight of a mixture of diethanolamine and triethanolamine in
Verhältnis 2 : 1, und 49,0 Gew.-% Wasser hergestellt.Ratio 2: 1, and 49.0 wt .-% water.
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 Liefer¬ vorschrift der Deutschen Bundesbahn TL 918 81, Blatt 6, ölhaltige Abwässer hergestellt. Die Konzentration der Reinigungsmittel in den wäßrigen Lösungen 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 resul¬ tierten die folgenden Restölwerte im Abwasser: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 in the wastewater resulted:
Beispiel 1: 12 ppm Beispiel 2: 31 ppm Vergleichsbeispiel: 78 ppmExample 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. Anwendungsbeispiel 2: ReinigungswirkungThe 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. Example of use 2: cleaning effect
Prüfung der Reinigungswirkung und relativen Reinigungswirkung WRreι (wiederum im Vergleich zu dem Reiniger gemäß der DE-OS 35 30623).Testing the cleaning effect and relative cleaning effect WR re ι (again in comparison to the cleaner according to DE-OS 35 30623).
Eine lackierte, stark verschmutzte Innenseite einer PKW-Motorhaube wurde senkrecht aufgestellt. Aus den Reinigungsmitteln gemäß Bei¬ spielen 1, 2 und dem Vergleichsbeispiel wurden jeweils durch Ver¬ dünnen 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 of 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 Ab¬ messungen 90 x 50 x 40 mm gegeben, satt getränkt und jeweils ein¬ zeln zum Auslaufen der überschüssigen Lösung 3 min hochkant aufge¬ stellt.In each of these test solutions, viscose sponges with the dimensions 90 × 50 × 40 mm were placed, saturated soaked, and placed individually upright for 3 minutes to allow the excess solution to run out.
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 Flä¬ che sauber war. Das Tränken, Hochkantaufstellen und Wischen wurde zehnmal vorgenommen und die erhaltenen Werte gemittelt.These sponges prepared in this way were wiped one after the other at an angle of 45 ° with the edge once per second with slight pressure over the soiled surface until the surface 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 Reinigungs¬ wirkung RWre-| 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 RWre , bezogen auf den Vergleichsreiniger. Es ergaben sich für die Reinigungsmittel- Zusammensetzungen folgende Werte: Reinigungsmittelzusammensetzung gemäß Beispiel 1: 2,4 Reinigungsmittelzusammensetzung gemäß Beispiel 2: 2,6 Reinigungsmittelzusammensetzung gemäß Vergleichs¬ beispiel (Standard): 1,0 The determination of the cleaning effect and the relative cleaning effect RW re - | was carried out in such a manner that the number of wipes with the comparison cleaning by the number of wipes has been shared with the to 'test the inventive cleaner. The quotient gave the relative cleaning effect RW re , based on the comparative cleaner. The cleaning agent compositions had the following values: 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

P a t e n t a n s p r ü c h e Patent claims
1. Demulgierende, pulverförmige oder flüssige Reinigungsmittel auf Basis von nichtionischen Tensiden, Carbonsäuren, anionischen Tensiden und gegebenenfalls Buildersubstanzen, dadurch gekenn¬ zeichnet, daß sie eine Kombination der folgenden Bestandteile enthalten:1. Demulsifying, powdered or liquid cleaning agents based on nonionic surfactants, carboxylic acids, anionic surfactants and optionally builder substances, characterized in that they contain a combination of the following constituents:
a) mindestens ein Alkyl-ethoxylat der allgemeinen Formel (I):a) at least one alkyl ethoxylate of the general formula (I):
R1-0-(CH CH2θ)n-H (I)R 1 -0- (CH CH2θ) n -H (I)
worin R- einen linearen oder verzweigten Alkylrest mit 6 bis 9 C-Atomen und n eine Zahl im Bereich von 3 bis 10 bedeuten,in which R- is a linear or branched alkyl radical having 6 to 9 carbon atoms and n is a number in the range from 3 to 10,
b) mindestens eine Monocarbonsäure oder deren wasserlösliche Salze der allgemeinen Formel (II):b) at least one monocarboxylic acid or its water-soluble salts of the general formula (II):
R2-C00H (II)R 2 -C00H (II)
worin R- einen linearen oder verzweigten Alkylrest mit 5 bis 11 C-Atomen bedeutet,in which R- is a linear or branched alkyl radical having 5 to 11 carbon atoms,
c) mindestens ein anionisches Tensid, ausgewählt aus der Gruppe der cl) Alkylsulfate der al lgemeinen Formel (III) :c) at least one anionic surfactant selected from the group of c1) alkyl sulfates of the general formula (III):
R -0-S03Me ( III ) c2) Alkyl-polyglykolether-sulfate der al lgemeinen Formel (IV) :R -0-S03Me (III) c2) alkyl polyglycol ether sulfates of the general formula (IV):
R4-0-(CH2CH2θ)m-S03Me ( IV)R 4 -0- (CH2CH2θ) m -S0 3 Me (IV)
c3) Alkylarylsulfonate der allgemeinen Formel (V):c3) alkylarylsulfonates of the general formula (V):
R5-S03-Me (V)R 5 -S03-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, R- Alkylbenzolreste mit 7 bis 9 C-Atomen und Me jeweils ein Alkalimetallatom bedeuten,in which R 3 and R 4 independently of one another each represent linear or branched alkyl radicals having 10 to 18 carbon atoms, m is a number in the range from 1 to 6, R alkylbenzene radicals having 7 to 9 carbon atoms and Me each represent an alkali metal atom,
wobei der Gehalt der Reinigungsmittel an den vorstehenden Kompo¬ nenten a, b und c insgesamt 1,5 bis 15 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,wherein the detergent content of the above components a, b and c is a total of 1.5 to 15% by weight 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) 0 bis 98,5 Gew.-% mindestens eines organischen oder anorganischen Builderstoffes, ausgewählt aus der Gruppe der Oligo- und Polycarbonsäuren oder deren wasserlöslichen Salzen sowie der Alkali etall-phosphate, -silikate, -borate, -carbonate und -hydroxide,d) 0 to 98.5% 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) bis 100 Gew.-% an pulverförmigen oder flüssigen Hilfsstoffen oder Stellmitteln. 2. Reinigungsmittel nach Anspruch lt dadurch gekennzeichnet, daß siee) up to 100% by weight of powdered or liquid auxiliaries or adjusting agents. 2. Detergent according to claim l t, characterized in that it
2,5 bis 12,5 Gew.-% einer Kombination der Komponenten a), b) und c) ,2.5 to 12.5% by weight of a combination of components a), b) and c),
5 bis 97,5 Gew.-% eines Builderstoffes und bis 100 Gew.-% Hilfsstoffe oder Stellmittel5 to 97.5% by weight of a builder and up to 100% by weight of auxiliaries or agents
enthalten.contain.
3. Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß sie als Komponente (a) ein Anlagerungsprodukt von 4 bis 6 Mol Ethylenoxid an n-Octanol, vorzugsweise das Anlagerungs¬ produkt von 4 Mol Ethylenoxid an n-Octanol, enthalten.3. Cleaning agent according to claim 1 or 2, characterized gekenn¬ characterized in that they contain as component (a) an adduct of 4 to 6 moles of ethylene oxide with n-octanol, preferably the Anlagungs¬ product of 4 moles of ethylene oxide with n-octanol.
4. Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß sie als Komponente (b) eine verzweigtkettige Mono¬ carbonsäure mit 8 bis 9 C-Atomen, vorzugsweise 2-Ethylhexansäure, enthalten.4. Cleaning agent according to claim 1 or 2, characterized gekenn¬ characterized in that they contain as component (b) a branched chain monocarboxylic acid having 8 to 9 carbon atoms, preferably 2-ethylhexanoic acid.
5. Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß sie als Komponente (c) ein Ci2-i4-Fettalkohol- sulfat-Natriumsalz und/oder ein sulfat-Natriumsalz mit 3 bis 5 Mol Ethylenoxid und/oder Cumolsulfonat-Natriumsalz enthalten.5. Cleaning agent according to claim 1 or 2, characterized gekenn¬ characterized in that it as component (c) a Ci2-i4-fatty alcohol sulfate sodium salt and / or a contain sulfate sodium salt with 3 to 5 moles of ethylene oxide and / or cumene sulfonate sodium salt.
6. Reinigungsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie als Builderstoff das Natriumsalz der6. Cleaning agent according to one of claims 1 to 5, characterized in that it is the sodium salt of the builder
Ethylendiamintetraessigsäure und/oder der Nitrilotriessigsäure enthalten. Contain ethylenediaminetetraacetic acid and / or nitrilotriacetic acid.
7. Reinigungsmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß sie als Hilfsstoffe und/oder Stellmittel Ölsäure, Natriumcarbonat, Harnstoff und/oder Wasser enthalten.7. Cleaning agent according to one of claims 1 to 6, characterized in that it contains oleic acid, sodium carbonate, urea and / or water as auxiliaries and / or adjusting agents.
8. Verwendung der Reinigungsmittel nach einem der Ansprüche 1 bis 7 zum Reinigen und Entfetten von harten Oberflächen, dadurch gekennzeichnet, daß die Konzentration der Komponenten (a), (b) und (c) in den mit Wasser verdünnten Anwendungslösungen insgesamt 0,01 bis 3 Gew.-%, insbesondere 0,025 bis 1 Gew.-%, beträgt. 8. Use of the cleaning agent according to one of claims 1 to 7 for cleaning and degreasing hard surfaces, characterized in that the concentration of components (a), (b) and (c) in the application solutions diluted with water in total from 0.01 to 3% by weight, in particular 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
DE4001595 1990-01-20
DE4001595A DE4001595A1 (en) 1990-01-20 1990-01-20 DEMULGATING, POWDERFUL, OR LIQUID CLEANSING AGENTS AND THEIR USE
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 true EP0511253A1 (en) 1992-11-04
EP0511253B1 EP0511253B1 (en) 1995-02-22

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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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8852546B2 (en) 2005-05-26 2014-10-07 Smith International, Inc. Polycrystalline diamond materials having improved abrasion resistance, thermal stability and impact resistance

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4208066A1 (en) * 1992-02-13 1992-09-24 Martin Wilke Environmentally acceptable cleaning system for milking equipment - has closed system to remove grease and recycle cleaning agent
DE4227863A1 (en) * 1992-08-22 1994-02-24 Henkel Kgaa Pourable liquid aqueous detergent concentrates
US5749977A (en) * 1992-10-28 1998-05-12 Elf Atochem S.A. Process and composition for degreasing the surface of an object
FR2697265B1 (en) * 1992-10-28 1994-12-09 Atochem Elf Sa Use of an alkylene glycol etheroxide ester for degreasing the surface of an object and process and composition for this use.
DE69325589T2 (en) * 1992-11-03 2000-01-27 The Procter & Gamble Co., Cincinnati CLEAN WITH SHORT-CHAIN SURFACES
DE4321023C1 (en) * 1993-06-24 1994-02-10 Henkel Kgaa Recovery of fats and oils with improved purity from emulsions or dispersion - comprises adding alkyl sulphate and then separating by known methods
US5501816A (en) * 1994-07-12 1996-03-26 Basf Corporation Aqueous based solvent free degreaser composition
US5770549A (en) * 1996-03-18 1998-06-23 Henkel Corporation Surfactant blend for non-solvent hard surface cleaning
DE19719606C2 (en) * 1997-05-09 1999-02-18 Henkel Kgaa Solid preparations
US6492317B1 (en) 2000-05-19 2002-12-10 Basf Corporation High forming hard surface cleaning formulations
DE10144051A1 (en) * 2001-09-07 2002-12-05 Sasol Germany Gmbh Surfactant composition, e.g. useful as hard surface cleaner or textile auxiliary, comprises branched carboxylic acid salt and optionally alkoxylated and/or sulfated primary alcohol
US6583103B1 (en) 2002-08-09 2003-06-24 S.C. Johnson & Son, Inc. Two part cleaning formula resulting in an effervescent liquid
GB2400375A (en) * 2003-04-09 2004-10-13 Hassan Scott Lisa Non-emulsifying aqueous cleaner-degreaser
CA2489187C (en) 2003-12-05 2012-08-28 Smith International, Inc. Thermally-stable polycrystalline diamond materials and compacts
US7647993B2 (en) 2004-05-06 2010-01-19 Smith International, Inc. Thermally stable diamond bonded materials and compacts
DE102006018216B4 (en) * 2006-04-18 2008-09-25 Chemetall Gmbh Process for the demulsifying cleaning of metallic surfaces
US20100311633A1 (en) * 2007-02-15 2010-12-09 Ecolab Usa Inc. Detergent composition for removing fish soil
US8093200B2 (en) 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent
FR2917094B1 (en) * 2007-06-08 2011-05-06 Dalta COMPOSITION FOR IMPREGNATION IN WIPES FOR CLEANING AND / OR CONTAMINATED SURFACE LUSTERING

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1537265A (en) * 1966-09-10 1968-08-23 Basf Ag Cold cleaning products for solid surfaces
US3663445A (en) * 1969-08-22 1972-05-16 Lever Brothers Ltd Surface cleaning and defatting composition
DE2710355C2 (en) * 1977-03-10 1979-04-05 Basf Ag, 6700 Ludwigshafen Use of melamine derivatives as foam suppressors
US4368146A (en) * 1979-01-12 1983-01-11 Lever Brothers Company Light duty hand dishwashing liquid detergent composition
DE3501775A1 (en) * 1985-01-21 1986-07-24 Henkel KGaA, 4000 Düsseldorf NEW QUARTAINE AMMONIUM COMPOUNDS AND THEIR USE IN CLEANING AGENTS
DE3530623A1 (en) * 1985-08-28 1987-03-12 Henkel Kgaa Demulsifying detergent with surface moisturizing effect
DE3852571T2 (en) * 1987-05-28 1995-08-17 Colgate Palmolive Co Detergent composition for hard surfaces.
KR960002629B1 (en) * 1987-06-25 1996-02-24 가오 가부시끼가이샤 Additive for alkaline detergent and the composition containing the same
US4869842A (en) * 1988-03-31 1989-09-26 Colgate-Palmolive Co. Liquid abrasive cleansing composition containing grease-removal solvent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9110718A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8852546B2 (en) 2005-05-26 2014-10-07 Smith International, Inc. Polycrystalline diamond materials having improved abrasion resistance, thermal stability and impact resistance

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ES2068568T3 (en) 1995-04-16
US5286402A (en) 1994-02-15
NO922692D0 (en) 1992-07-08
EP0511253B1 (en) 1995-02-22
DE4001595A1 (en) 1991-07-25
WO1991010718A1 (en) 1991-07-25
NO922692L (en) 1992-07-08
NO180202B (en) 1996-11-25
JPH05504155A (en) 1993-07-01
NO180202C (en) 1997-03-05
DK0511253T3 (en) 1995-07-10
ATE118809T1 (en) 1995-03-15
DE59104713D1 (en) 1995-03-30

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