EP0213554B1 - Demulsifying cleaning agent retaining superficial humidity - Google Patents
Demulsifying cleaning agent retaining superficial humidity Download PDFInfo
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- EP0213554B1 EP0213554B1 EP86111550A EP86111550A EP0213554B1 EP 0213554 B1 EP0213554 B1 EP 0213554B1 EP 86111550 A EP86111550 A EP 86111550A EP 86111550 A EP86111550 A EP 86111550A EP 0213554 B1 EP0213554 B1 EP 0213554B1
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- European Patent Office
- Prior art keywords
- weight
- cleaning
- acid
- octanol
- cleaning preparations
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
Definitions
- the invention relates to new cleaning agents with which painted or unpainted surfaces of vehicles, engines, floors in workshops or other work surfaces can be cleaned and degreased, the corresponding contaminants removed being demulsified.
- the wastewater is not only contaminated with the fats, oils etc. detached from the treated surfaces, but also with organic solvents, especially with chlorinated hydrocarbons, so that it is absolutely necessary to separate the environmentally harmful components from the corresponding wastewater, because is required by law.
- cold cleaners containing organic solvents have the further disadvantage that flammable, unpleasant odors or even harmful vapors are produced during the cleaning operation, so that the corresponding cleaning operations can only be carried out under extreme precautionary and health protection measures.
- the first-mentioned detergents containing components with an emulsifying effect have the major disadvantage that fats or grease-like contaminations can be removed from the surfaces to be cleaned, but these contaminations are emulsified in water. It is accepted that either larger amounts of oils, fats or other contaminants get into the wastewater, which is undesirable because of the associated environmental pollution, or additional means for breaking the emulsions formed must be added to separate the organic contaminants To enable oil separators. Apart from economic aspects, however, the subsequent addition of demulsifying agents is associated with further pollution of the water, so that this solution too cannot be satisfactory.
- DE-A 2 529 096 discloses agents for the cold cleaning of solid surfaces contaminated with fats or grease-like impurities, which essentially consist of aqueous emulsions of ethoxylated phenols having 8 to 20 carbon atoms in the alkyl chain and ethoxylated aliphatic alcohols having 9 to 18 There are carbon atoms in the alkyl chain.
- the proposed cold cleaners are neutral to weakly alkaline and can be handled safely with good fat dissolving power due to their low or lack of alkalinity.
- DE-A 2 901 927 proposes cleaning agents for removing oily contaminants which contain fatty alcohol ethoxylates in combination with phenol or lower alkylphenol ethoxylates. During the cleaning operation, the greasy or oily contaminants are removed from the surface to be cleaned in the form of an emulsion. The emulsions formed are relatively short-lived, but it takes hours to break them.
- the said cleaning agents have such a consistency that they run off directly on vertical surfaces, for example on walls or on the vertical outer surfaces of vehicles, and a longer one Exposure time can only be achieved by adding an agent to increase the viscosity or by treating the surface several times with the cleaner. The surface is therefore not kept in contact with the cleaner for a sufficiently long time, so that repeated application is usually necessary.
- Such cleaning agents are used to clean various surfaces, for example equipment and containers made of glass or metal, and wall walls, floors or street surfaces which are contaminated with dyes, pigments, fats, proteins, starch derivatives, oils or tar.
- a cleaning agent formulation is given the following composition: 730 parts of demineralized water, 40 parts of ethylenediaminetetraacetic acid in the form of the sodium salt, 110 parts of nonylphenol polyglycol ether with 10 to ethylene oxide units in 35% strength aqueous solution, 100 parts of mono ethanolamine and 20 parts PLURONIC L 61 (ethylene oxide-propylene oxide block copolymer).
- AT-A 308 936 describes liquid, storage-stable concentrates and cleaning and degreasing agents which can be prepared from them by dilution with water and are based on a combination of nonionic / fatty acid / alkanolamine in accordance with AT-A 262 474.
- the new cleaning and degreasing agents are distinguished by the fact that 0 to 100% of the fatty acids in the concentrates are replaced by alkylol polyethylene oxide carboxylic acids, 0 to 100% of the alkanolamines by oxazines, and the nonionic surface-active addition products are present in at least 5% by weight.
- Such agents ensure good removability of grease and pigment dirt, in particular polishing paste dirt, from metal surfaces.
- a cleaning agent formulation of the following composition is given: 10% oleic acid, 10% lauryl alcohol-4 EO methane carboxylic acid, 5% aliphatic, primary, straight-chain Ce 20 alcohols + 8 EO, 50% triethanolamine, 2% Ethylenediaminetetraacetic acid, 23% water.
- US Pat. No. 3,663,445 also relates to liquid, storage-stable concentrates and cleaning and degreasing agents which can be prepared from them by dilution with water and based on a combination of nonionic surface-active substances, alkanolamine salts of fatty acids, alkanolamines and optionally water.
- These agents preferably contain 3.5 to 15% by weight of fatty acids, 20 to 45% by weight of nonionic surface-active substances and alkanolamines in a molar ratio of fatty acid to alkanolamine equal to 1: 6 to 1:20.
- Water can contain up to 50% by weight of the concentrates. Furthermore, the agents can contain up to 50% of the total amount of organic solvents.
- Addition products of 3 to 15 moles of ethylene oxide onto organic compounds with active hydrogen atoms are suitable as nonionic surface-active substances.
- Agents of this type are used for degreasing and cleaning, in particular, metal surfaces which are contaminated, for example, with oils and pigments.
- a cleaning agent formulation is given the following composition: 5% oleic acid, 30% nonylphenol + 6 EO, 50% triethanolamine, 1.1% ethylenediaminetetraacetic acid sodium salt, water up to 100%.
- the object of the present invention was to provide, as an alternative to the agents known from the prior art, those cleaners which can be used without polluting the environment.
- emulsion formation should be avoided and the use of organic solvents, for example chlorinated hydrocarbons, esters and fractions from mineral oil distillation (petrol, hydrocarbons), should be avoided entirely.
- organic solvents for example chlorinated hydrocarbons, esters and fractions from mineral oil distillation (petrol, hydrocarbons)
- the application of the new cleaners should be possible in every way and lead to a lasting wetting of the treated surface.
- a cleaning effect should also be given at room temperature.
- increased demands were placed on the biodegradability beyond the legally prescribed level (detergent law, chemical law).
- cleaners with a good cleaning action and demulsifying properties can be obtained which keep the surface to be cleaned in contact with the cleaning components for a sufficiently long time even without an agent for increasing the viscosity, if aqueous combinations of builders or complexing agents with one or more alkanolamines and one or more nonionic surfactants.
- the demulsifying cleaning agents according to the invention can optionally additionally add solubilizers in an amount of 1 to 10% by weight and / or corrosion inhibitors for light metals in an amount of 0.15 to 0.25% by weight and / or corrosion inhibitors for non-ferrous metals in an amount of Contain 0.2 to 0.4 wt .-% and / or fragrances and / or dyes in an amount of 0 to 12 wt .-%.
- the sodium salts of ethylenediaminetetraacetic acid or nitrilotriacetic acid are also preferably used as builders or complexing agents.
- alkanolamines Another component of the cleaners according to the invention are alkanolamines.
- a compound of this class of substances or several such compounds can be used in any mixing ratio with one another.
- diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine are used as alkanolamines.
- Compounds of this class of substances are preferably used in amounts of 25 to 50% by weight.
- the use of the alkanolamine component in an amount below 20% by weight is critical: amounts below 20% by weight, based on the invention aqueous cleaner concentrate would significantly worsen the desired "dampness effect".
- the demulsifying cleaning agents according to the invention contain nonionic surfactants as a further component.
- nonionic surfactants as a further component.
- a single representative of this group of substances or alternatively a mixture of two or more nonionic surfactants can be used, as long as the amount is in the range from 1 to 15% by weight.
- adducts of 4 mol of ethylene oxide with n- or i-octanol as well as adducts of 2 mol of propylene oxide and 5 to 6 mol of ethylene oxide with the C a -alcohols mentioned are used as nonionic surfactants.
- the preferred amount of the nonionic surfactants used is in the range of 3 to 6% by weight.
- Aromatic sulfonates such as cumene sulfonate or butyl glycol sulfonate, are suitable as solubilizers, which can optionally be additionally added to the demulsifying cleaning agents consisting of the above-mentioned components (a), (b), (c) and (d).
- corrosion inhibitors for light metals for example phosphoric acid
- corrosion inhibitors for non-ferrous metals for example tolyltriazole
- the demulsifying cleaning agents according to the invention can also contain fragrances and / or dyes.
- the cleaners are produced in that the components mentioned are mixed with one another in the respective amounts by methods known per se. Storage or shipping is generally carried out in the form of an aqueous concentrate containing the combination of the specified raw materials, to which the stated amounts (in% by weight) also relate.
- the demulsifying cleaning agents according to the invention with a moisturizing effect are used in any dilution with water.
- 3% or more concentrated aqueous solutions are used.
- the concentrate can even be used.
- the application takes place in the spray, immersion or high pressure spraying process with appropriate devices.
- An excellent cleaning result is achieved even at room temperature.
- the product composition also ensures that the surface to be cleaned is kept moist for approx. 20 to 30 minutes and thus a correspondingly long contact of the cleaning components with the contamination. This is extremely important, for example when cleaning locomotives to achieve a good cleaning result.
- the demulsifying effect is a decisive advantage compared to conventional products. If, for example, an application solution according to the invention is diluted from 10 to 50% concentration with rinsing water to a concentration of less than or equal to 2% at room temperature, additional mineral oil which has been introduced separates practically completely from the solution when it is at rest for 30 minutes. With appropriate waste water collection containers, the oil content of waste water can be reduced to less than 50 mg 1-1 solely by such mechanical oil separation.
- iron (11) sulfate or aluminum sulfate to the wastewater to further reduce the oil content and thereby achieve a flocculation of the contaminants.
- the residual oil content in the waste water can be reduced to a value below 10 mg 1-1.
- the comparative cleaner therefore contained a strongly emulsifying surfactant.
- the product film remaining on the cleaned parts after the treatment also offers - in addition to keeping them moist - the necessary temporary corrosion protection. This is particularly important when cleaning the engine compartment.
- the storage corrosion protection test was carried out according to the so-called "plate climate test”. Steel sheets of quality ST 1405 were cleaned with trichlorethylene and then immersed in 10% solutions of the cleaners according to the invention. After 5 minutes the sheets were removed and dried at room temperature. The sheets were stored in a climate box at 23 ° C and 100% relative humidity. Sheets treated in this way showed no signs of corrosion even after 14 days.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Detergent Compositions (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Printers Or Recording Devices Using Electromagnetic And Radiation Means (AREA)
- Catalysts (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Filters For Electric Vacuum Cleaners (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Table Devices Or Equipment (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Die Erfindung betrifft neue Reinigungsmittel, mit denen lackierte oder nichtlackierte Oberflächen von Fahrzeugen, Motoren, Fußböden in Werkstätten oder andere Arbeitsflächen gereinigt und entfettet werden können, wobei die entsprechenden entfernten Verunreinigungen demulgiert werden.The invention relates to new cleaning agents with which painted or unpainted surfaces of vehicles, engines, floors in workshops or other work surfaces can be cleaned and degreased, the corresponding contaminants removed being demulsified.
Mittel zur Reinigung von festen Oberflächen, die mit Fetten oder fettartigen Verschmutzungen verunreinigt sind, sind insbesondere im technischen Bereich weit verbreitet. Bisher werden für die entsprechenden Reinigungsoperationen entweder Zusammensetzungen verwendet, die Fette oder fettartige Verschmutzungen emulgieren, oder sogenannte "Kaltreiniger" eingesetzt. Letztere sind (nach Römpp's Chemie-Lexikon, Franck'sche Verlagsbuchhandlung Stuttgart, Band 3 (1983), Seite 2033/34) Lösungsmittelgemische, die hohe Anteile chlorierter oder nichtchlorierter Kohlenwasserstoffe (Erdölfraktionen) enthalten und mit oder ohne Emulgatoren und anderen Zusätzen zur Kaltentfernung von Fetten, Ölen, Wachsen, Teer usw. verwendet werden. Bei Verwendung derartiger Kaltreiniger werden die Abwässer nicht nur mit den von den behandelten Oberflächen abgelösten Fetten, Ölen etc. belastet, sondern zusätzlich auch mit organischen Lösungsmitteln, insbesondere mit chlorierten Kohlenwasserstoffen, so daß eine Abtrennung der umweltschädlichen Komponenten von den entsprechenden Abwässern zwingend erforderlich, da gesetzlich vorgeschrieben, ist. Zudem haben organische Lösungsmittel enthaltende Kaltreiniger den weiteren Nachteil, daß bei der Reinigungsoperation feuergefährliche, geruchsbelästigende oder sogar gesundheitsschädliche Dämpfe entstehen, so daß die entsprechenden Reinigungsoperationen nur unter extremen Vorsichts- und Gesundheitsschutzmaßnahmen durchgeführt werden können.Means for cleaning solid surfaces that are contaminated with greases or greasy soiling are particularly widespread in the technical field. So far, either compositions that emulsify fats or greasy soiling, or so-called "cold cleaners" have been used for the corresponding cleaning operations. The latter are (according to Römpp's Chemie-Lexikon, Franck'sche Verlagsbuchhandlung Stuttgart, Volume 3 (1983), page 2033/34) solvent mixtures that contain high proportions of chlorinated or non-chlorinated hydrocarbons (petroleum fractions) and with or without emulsifiers and other additives for the cold removal of Fats, oils, waxes, tar, etc. can be used. When using such cold cleaners, the wastewater is not only contaminated with the fats, oils etc. detached from the treated surfaces, but also with organic solvents, especially with chlorinated hydrocarbons, so that it is absolutely necessary to separate the environmentally harmful components from the corresponding wastewater, because is required by law. In addition, cold cleaners containing organic solvents have the further disadvantage that flammable, unpleasant odors or even harmful vapors are produced during the cleaning operation, so that the corresponding cleaning operations can only be carried out under extreme precautionary and health protection measures.
Die erstgenannten, emulgierend wirkende Komponenten enthaltenden Reinigungsmittel haben den wesentlichen Nachteil, daß zwar Fette oder fettartige Verschmutzungen von den zu reinigenden Oberflächen entfernt werden können, diese Verschmutzungen jedoch im Wasser emulgiert werden. Dabei wird in Kauf genommen, daß entweder größere Mengen von Ölen, Fetten oder anderen Verunreinigungen in das Abwasser gelangen, was wegen der damit verbundenen Umweltverschmutzung unerwünscht ist, oder zusätzliche Mittel zum Brechen der gebildeten Emulsionen zugesetzt werden müssen, um eine Abtrennung der organischen Verunreinigungen in Ölabscheidem zu ermöglichen. Abgesehen von ökonomischen Aspekten ist jedoch der nachträgliche Zusatz demulgierender Agenzien mit einer weiteren Gewässerbelastung verbunden, so daß auch diese Lösung nicht befriedigen kann.The first-mentioned detergents containing components with an emulsifying effect have the major disadvantage that fats or grease-like contaminations can be removed from the surfaces to be cleaned, but these contaminations are emulsified in water. It is accepted that either larger amounts of oils, fats or other contaminants get into the wastewater, which is undesirable because of the associated environmental pollution, or additional means for breaking the emulsions formed must be added to separate the organic contaminants To enable oil separators. Apart from economic aspects, however, the subsequent addition of demulsifying agents is associated with further pollution of the water, so that this solution too cannot be satisfactory.
In der DE-A 2 529 096 werden Mittel zur Kaltreinigung von mit Fetten oder fettartigen Verunreinigungen kontaminierten festen Oberflächen offenbart, die im wesentlichen in wäßrigen Emulsionen aus ethoxylierten Phenolen mit 8 bis 20 C-Atomen in der Alkylkette und ethoxylierten aliphatischen Alkoholen mit 9 bis 18 C-Atomen in der Alkylkette bestehen. Die vorgeschlagenen Kaltreiniger sind neutral bis schwach alkalisch eingestellt und können bei gutem Fettlösevermögen aufgrund ihrer geringen bzw. fehlenden Alkalität gefahrlos gehandhabt werden.DE-A 2 529 096 discloses agents for the cold cleaning of solid surfaces contaminated with fats or grease-like impurities, which essentially consist of aqueous emulsions of ethoxylated phenols having 8 to 20 carbon atoms in the alkyl chain and ethoxylated aliphatic alcohols having 9 to 18 There are carbon atoms in the alkyl chain. The proposed cold cleaners are neutral to weakly alkaline and can be handled safely with good fat dissolving power due to their low or lack of alkalinity.
Ferner werden in der DE-A 2 901 927 Reinigungsmittel zur Entfernung von öligen Verunreinigungen vorgeschlagen, die Fettalkoholethoxylate in Kombination mit Phenol- oder Niederalkylphenolethoxylaten enthalten. Bei der Reinigungsoperation werden die fett- oder ölhaltigen Verunreinigungen in Form einer Emulsion von der zu reinigenden Oberfläche entfernt. Die gebildeten Emulsionen sind zwar relativ kurzlebig, es werden jedoch Stunden bis zum Brechen derselben benötigt.Furthermore, DE-A 2 901 927 proposes cleaning agents for removing oily contaminants which contain fatty alcohol ethoxylates in combination with phenol or lower alkylphenol ethoxylates. During the cleaning operation, the greasy or oily contaminants are removed from the surface to be cleaned in the form of an emulsion. The emulsions formed are relatively short-lived, but it takes hours to break them.
Zusätzlich zu den oben genannten Nachteilen, die den meisten aus dem Stand der Technik bekannten Reinigungsmitteln zueigen sind, haben die genannten Reiniger eine solche Konsistenz, daß sie auf senkrechten Flächen, beispielsweise auf Wänden oder auf den senkrechten Außenflächen von Fahrzeugen, unmittelbar ablaufen und eine längere Einwirkzeit nur dadurch erreicht werden kann, daß ein Mittel zur Viskositätserhöhung zugesetzt oder die Fläche mehrfach mit dem Reiniger behandelt werden muß. Die Fläche wird also nicht für eine genügend lange Zeit mit dem Reiniger in Kontakt gehalten, so daß in der Regel eine wiederholte Applikation erforderlich ist.In addition to the disadvantages mentioned above which are common to most cleaning agents known from the prior art, the said cleaning agents have such a consistency that they run off directly on vertical surfaces, for example on walls or on the vertical outer surfaces of vehicles, and a longer one Exposure time can only be achieved by adding an agent to increase the viscosity or by treating the surface several times with the cleaner. The surface is therefore not kept in contact with the cleaner for a sufficiently long time, so that repeated application is usually necessary.
Die US-A 4 285 849 betrifft eine wäßrige Reinigungsmittel-Lösung, enthaltend die folgenden Komponenten:
- (a) 3 bis 6 Gew.-Teile einer Nitrilocarbonsäure beziehungsweise deren Salze
- (b) 2 bis 11 Gew.-Teile eines Cx-24-Alkyl-phenyl- polyglykolethers mit 5 bis 25 Glykoleinheiten,
- (c) 5 bis 15 Gew.-Teile eines Alkanolamins,
- (d) 1 bis 3 Gew.-Teile eines Propylenoxid-Ethylenoxid-Blockcopolymeres mit einem Molgewicht von 1500 bis 2500 und 5 bis 15 Gew.-% endständigen Ethylenoxideinheiten,
- (e) 0 bis 3 Gew.-Teile eines C"4-Alkohols,
- (f) 0 bis 1 Gew.-Teile eines wasserlöslichen Silikonöls sowie gegebenenfalls eines der folgenden Lösungsmittel:
- (9) 10 bis 40 Gew.-Teile eines aliphatischen oder aromatischen Kohlenwasserstoffes oder einer eines chlorierten Kohlenwasserstoffes,
- (h) 5 bis 20 Gew.-Teile eines Ga-Alkohols oder eines wasserlöslichen Glykols.
- (a) 3 to 6 parts by weight of a nitrilocarboxylic acid or its salts
- (b) 2 to 11 parts by weight of a Cx- 24 -alkylphenyl polyglycol ether with 5 to 25 glycol units,
- (c) 5 to 15 parts by weight of an alkanolamine,
- (d) 1 to 3 parts by weight of a propylene oxide-ethylene oxide block copolymer with a molecular weight of 1500 to 2500 and 5 to 15% by weight of terminal ethylene oxide units,
- (e) 0 to 3 parts by weight of a C "4 alcohol,
- (f) 0 to 1 part by weight of a water-soluble silicone oil and optionally one of the following solvents:
- (9) 10 to 40 parts by weight of an aliphatic or aromatic hydrocarbon or one of a chlorinated hydrocarbon,
- (h) 5 to 20 parts by weight of a Ga alcohol or a water-soluble glycol.
Derartige Reinigungsmittel dienen zur Reinigung verschiedener Oberflächen, beispielsweise Apparaturen und Behältern aus Glas oder Metall sowie Mauerwänden, Fußböden oder Straßenoberflächen, die mit Farbstoffen Pigmenten, Fetten, Proteinen, Stärkederivaten, Ölen oder Teer verunreinigt sind. In einem Beispiel dieser Patentschrift wird eine Reinigungsmittel-Formulierung der folgenden Zusammensetzung angegeben: 730 Teile demineralisiertes Wasser, 40 Teile Ethylendiamintetraessigsäure in Form des Natriumsalzes, 110 Teile Nonylphenolpolyglykolether mit 10 bis Ethylenoxideinheiten in 35%iger wäßriger Lösung, 100 Teile Monoethanolamin und 20 Teile PLURONIC L 61 (Ethylenoxid-Propylenoxid-Blockcopolymer).Such cleaning agents are used to clean various surfaces, for example equipment and containers made of glass or metal, and wall walls, floors or street surfaces which are contaminated with dyes, pigments, fats, proteins, starch derivatives, oils or tar. In one example of this patent, a cleaning agent formulation is given the following composition: 730 parts of demineralized water, 40 parts of ethylenediaminetetraacetic acid in the form of the sodium salt, 110 parts of nonylphenol polyglycol ether with 10 to ethylene oxide units in 35% strength aqueous solution, 100 parts of mono ethanolamine and 20 parts PLURONIC L 61 (ethylene oxide-propylene oxide block copolymer).
In der AT-A 308 936 werden flüssige, lagerbeständige Konzentrate und aus diesen durch Verdünnen mit Wasser herstellbare Reinigungs- und Entfettungsmittel beschrieben, die auf einer Kombination Nonionic/Fettsäure/Alkanolamin gemäß der AT-A 262 474 basieren. Die neuen Reinigungs- und Entfettungsmittel zeichnen sich dadurch aus, daß in den Konzentraten 0 bis 100% der Fettsäuren durch Alkylolpolyethylenoxidcarbonsäuren, 0 bis 100% der Alkanolamine durch Oxazine ersetzt werden und die nichtionogenen oberflächenaktiven Anlagerungsprodukte in mindesens 5 Gew.-% vorliegen. Derartige Mittel gewährleisten eine gute Entfernbarkeit von Fett- und Pigmentschmutz, insbesondere Polierpastenschmutz, von Metalloberflächen. Sie können bis zu etwa 50% der Gesamtmenge organische Lösungsmittel enthalten. Sofern die Konzentrate noch Wasser enthalten, soll dessen Gehalt bis 50% betragen. Die Gebrauchslösungen lassen sich aus den Konzentraten durch Verdünnen mit Wasser herstellen. In einem Beispiel dieser Patentschrift wird eine Reinigungsmittel-Formulierung der folgenden Zusammensetzung angegeben: 10% ÖIsäure, 10% Laurylalkohol-4 EO-methancarbonsäure, 5% aliphatische, primäre, geradkettige Ce-20-Alkohole + 8 EO, 50% Triethanolamin, 2% Ethylendiamintetraessigsäure, 23% Wasser.AT-A 308 936 describes liquid, storage-stable concentrates and cleaning and degreasing agents which can be prepared from them by dilution with water and are based on a combination of nonionic / fatty acid / alkanolamine in accordance with AT-A 262 474. The new cleaning and degreasing agents are distinguished by the fact that 0 to 100% of the fatty acids in the concentrates are replaced by alkylol polyethylene oxide carboxylic acids, 0 to 100% of the alkanolamines by oxazines, and the nonionic surface-active addition products are present in at least 5% by weight. Such agents ensure good removability of grease and pigment dirt, in particular polishing paste dirt, from metal surfaces. They can contain up to about 50% of the total amount of organic solvents. If the concentrate still contains water, its content should be up to 50%. The working solutions can be prepared from the concentrates by dilution with water. In one example of this patent specification, a cleaning agent formulation of the following composition is given: 10% oleic acid, 10% lauryl alcohol-4 EO methane carboxylic acid, 5% aliphatic, primary, straight-chain Ce 20 alcohols + 8 EO, 50% triethanolamine, 2% Ethylenediaminetetraacetic acid, 23% water.
Gegenstand der US-A 3 663 445 sind gleichfalls flüssige, lagerbeständige Konzentrate sowie aus diesen durch Verdünnen mit Wasser herstellbare Reinigungs- und Entfettungsmittel auf der Basis einer Kombination nichtionischer oberflächenaktiver Substanzen, Alkanolaminsalzen von Fettsäuren, Alkanolaminen und gegebenenfalls Wasser. Vorzugsweise enthalten diese Mittel 3,5 bis 15 Gew.-% Fettsäuren, 20 bis 45 Gew.-% nichtionische oberflächenaktive Substanzen und Alkanolamine im Molverhältnis Fettsäure zu Alkanolamin gleich 1:6 bis 1:20. Wasser kann in den Konzentraten bis zu 50 Gew.-% enthalten sein. Ferner können die Mittel bis zu 50% der Gesamtmenge an organischen Lösungsmitteln enthalten. Als nichtionische oberflächenaktive Substanzen kommen Anlagerungsprodukte von 3 bis 15 Mol Ethylenoxid an organische Verbindungen mit aktiven Wasserstoffatomen in Frage. Derartige Mittel dienen zum Entfetten und Reinigen insbesondere von Metalloberflächen, die beispielsweise mit Ölen und Pigmenten verunreinigt sind. In einem Beispiel dieser Patentschrift wird eine Reinigungsmittel-Formulierung der folgenden Zusammensetzung angegeben: 5% Ölsäure, 30% Nonylphenol + 6 EO, 50% Triethanolamin, 1,1% Ethylendiamintetraessigsäure-Natriumsalz, Wasser bis zu 100%.US Pat. No. 3,663,445 also relates to liquid, storage-stable concentrates and cleaning and degreasing agents which can be prepared from them by dilution with water and based on a combination of nonionic surface-active substances, alkanolamine salts of fatty acids, alkanolamines and optionally water. These agents preferably contain 3.5 to 15% by weight of fatty acids, 20 to 45% by weight of nonionic surface-active substances and alkanolamines in a molar ratio of fatty acid to alkanolamine equal to 1: 6 to 1:20. Water can contain up to 50% by weight of the concentrates. Furthermore, the agents can contain up to 50% of the total amount of organic solvents. Addition products of 3 to 15 moles of ethylene oxide onto organic compounds with active hydrogen atoms are suitable as nonionic surface-active substances. Agents of this type are used for degreasing and cleaning, in particular, metal surfaces which are contaminated, for example, with oils and pigments. In one example of this patent, a cleaning agent formulation is given the following composition: 5% oleic acid, 30% nonylphenol + 6 EO, 50% triethanolamine, 1.1% ethylenediaminetetraacetic acid sodium salt, water up to 100%.
Aufgabe der vorliegenden Erfindung war es, altemativ zu den aus dem Stand der Technik bekannten Mitteln solche Reiniger zur Verfügung zu stellen, die ohne Belastung der Umwelt eingesetzt werden können. Insbesondere sollte eine Emulsionsbildung vermieden und auf die Verwendung von organischen Lösungsmitteln, beispielsweise Chlorkohlenwasserstoffen, Estern und Fraktionen der Mineralöldestillation (Benzin, Kohlenwasserstoffe), vollständig verzichtet werden. Die Applikation der neuen Reiniger sollte auf jedem Wege möglich sein und dabei zu einer über längere Zeit anhaltenden Benetzung der behandelten Oberfläche führen. Eine Reinigungswirkung sollte zudem schon bei Raumtemperatur gegeben sein. Außerdem wurden an die biologische Abbaubarkeit über das gesetzlich vorgeschriebene Maß hinaus (Waschmittelgesetz, Chemikaliengesetz) erhöhte Anforderungen gestellt.The object of the present invention was to provide, as an alternative to the agents known from the prior art, those cleaners which can be used without polluting the environment. In particular, emulsion formation should be avoided and the use of organic solvents, for example chlorinated hydrocarbons, esters and fractions from mineral oil distillation (petrol, hydrocarbons), should be avoided entirely. The application of the new cleaners should be possible in every way and lead to a lasting wetting of the treated surface. A cleaning effect should also be given at room temperature. In addition, increased demands were placed on the biodegradability beyond the legally prescribed level (detergent law, chemical law).
Überraschend wurde nun gefunden, daß Reiniger mit guter Reinigungswirkung und demulgierenden Eigenschaften erhalten werden können, die die zu reinigende Fläche auch ohne Mittel zur Viskositätserhöhung ausreichend lange mit den Reinigerkomponenten in Kontakt halten, wenn man wäßrige Kombinationen von Buildem bzw. Komplexbildnern mit einem oder mehreren Alkanolaminen und einem oder mehreren nichtionischen Tensiden verwendet.Surprisingly, it has now been found that cleaners with a good cleaning action and demulsifying properties can be obtained which keep the surface to be cleaned in contact with the cleaning components for a sufficiently long time even without an agent for increasing the viscosity, if aqueous combinations of builders or complexing agents with one or more alkanolamines and one or more nonionic surfactants.
Die Erfindung betrifft somit demulgierende Reinigungsmittel mit Flächenfeuchthalteeffekt auf der Basis von Buildern beziehungsweise Komplexbildnem, Alkanolaminen und nichtionischen Tensiden, welche dadurch gekennzeichnet sind, daß sie die folgenden Komponenten enthalten:
- (a) 0,5 bis 10 Gew.% Builder beziehungsweise Komplexbildner ausgewählt aus der Gruppe Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Diethylentriaminpentaessigsäure, N-(2-Hyroxyethyl)-ethylendiamintriessigsäure und deren wasserlösliche Alkalimetallsalze,
- (b) 20 bis 60 Gew.-% Alkanolamine ausgewählt aus der Gruppe Diethanolamin, Triethanolamin, Diisopropanolamin und Triisopropanolamin,
- (c) 1 bis 15 Gew.-% mindestens eines nichtionischen Tensids ausgewählt aus der Gruppe der Kondensationsprodukte von n-Octanolan 4 Mol Ethylenoxid, i-Octanol an 4 Mol Ethylenoxid, n-Octanol an 2 Mol Propylenoxid und 5 bis 6 Mol Ethylenoxid und i-Octanol an 2 Mol Propylenoxid und 5 bis 6 Mol Ethylenoxid,
- (d) Wasser in einer Menge, die sich mit den Komponenten (a), (b) und (c) zu 100 Gew.-% summiert.
- (a) 0.5 to 10% by weight of builder or complexing agent selected from the group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, N- (2-hydroxyethyl) ethylenediamine triacetic acid and their water-soluble alkali metal salts,
- (b) 20 to 60% by weight of alkanolamines selected from the group consisting of diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine,
- (c) 1 to 15% by weight of at least one nonionic surfactant selected from the group of condensation products of n-octanolane, 4 moles of ethylene oxide, i-octanol with 4 moles of ethylene oxide, n-octanol with 2 moles of propylene oxide and 5 to 6 moles of ethylene oxide and i-octanol on 2 moles of propylene oxide and 5 to 6 moles of ethylene oxide,
- (d) Water in an amount that adds up to 100% by weight with components (a), (b) and (c).
Die erfindungsgemäßen demulgierenden Reinigungsmittel können gegebenenfalls zusätzlich Lösungsvermittler in einer Menge von 1 bis 10 Gew.-% und/oder Korrosionsinhibitoren für Leichtmetalle in einer Menge von 0,15 bis 0,25 Gew.-% und/oder Korrosionsinhibitoren für Buntmetalle in einer Menge von 0,2 bis 0,4 Gew.-% und/oder Duftstoffe und/oder Farbstoffe in einer Menge von 0 bis 12 Gew.-% enthalten.The demulsifying cleaning agents according to the invention can optionally additionally add solubilizers in an amount of 1 to 10% by weight and / or corrosion inhibitors for light metals in an amount of 0.15 to 0.25% by weight and / or corrosion inhibitors for non-ferrous metals in an amount of Contain 0.2 to 0.4 wt .-% and / or fragrances and / or dyes in an amount of 0 to 12 wt .-%.
Als Builder/Komplexbildner werden an sich bekannte, Alkalimetall-, Erdalkalimetall- und/oder Übergangsmetallionen komplexierende Verbindungen eingesetzt: Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Diethylentriaminpentaessigsäure, N-(2-Hydroxyethyi-)ethyiendiamintriessigsäure (Triiono C) und deren wasserlösliche Alkalimetallsalze, bevorzugt deren Natriumsalze. Die genannten Builder/Komplexbildner werden bevorzugt in einer Menge von 2 bis 4 Gew.-% in den erfindungsgemäßen Reinigem eingesetzt.Compounds known per se which complex alkali metal, alkaline earth metal and / or transition metal ions are used as builders / complexing agents: ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, N- (2-hydroxyethyl) ethylenediamine triacetic acid (triiono C) and their sodium-soluble alkali metal salts and their sodium-soluble alkali metal salts. The builders / complexing agents mentioned are preferably used in an amount of 2 to 4% by weight in the cleaners according to the invention.
Im Sinne der Erfindung werden ferner als Builder beziehungsweise Komplexbildner bevorzugt die Natriumsalze der Ethylendiamintetraessigsäure oder der Nitrilotriessigsäure eingesetzt.For the purposes of the invention, the sodium salts of ethylenediaminetetraacetic acid or nitrilotriacetic acid are also preferably used as builders or complexing agents.
Eine weitere Komponente der erfindungsgemäßen Reiniger sind Alkanolamine. Alternativ kann entweder eine Verbindung dieser Stoffklasse oder mehrere derartige Verbindungen in beliebigem Mischungsverhältnis miteinander eingesetzt werden. Erfindungsgemäß werden als Alkanolamine Diethanolamin, Triethanolamin, Diisopropanolamin und Triisopropanolamin eingesetzt. Verbindungen dieser Stoffklasse werden bevorzugt in Mengen von 25 bis 50 Gew.-% eingesetzt.Another component of the cleaners according to the invention are alkanolamines. Alternatively, either a compound of this class of substances or several such compounds can be used in any mixing ratio with one another. According to the invention, diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine are used as alkanolamines. Compounds of this class of substances are preferably used in amounts of 25 to 50% by weight.
Für das Erreichen des erfindungsgemäß angestrebten Effektes der "Feuchthaltung" der behandelten Oberfläche, d.h. das Ermöglichen eines über einen unmittelbaren Ablauf des angewendeten Mittels hinaus andauernden Kontaktes der Reinigerkomponenten mit der behandelten Oberfläche, ist die Verwendung der Alkanolaminkomponente in einer Menge unterhalb von 20 Gew.-% kritisch: Mengen unterhalb von 20 Gew.-%, bezogen auf das erfindungsgemäße wäßrige Reinigerkonzentrat, würden den angestrebten "Feuchthaiteeffekt" deutlich verschlechtern.To achieve the "moisturizing" effect of the treated surface, i.e. In order to allow the detergent components to come into contact with the treated surface beyond the immediate expiry of the agent used, the use of the alkanolamine component in an amount below 20% by weight is critical: amounts below 20% by weight, based on the invention aqueous cleaner concentrate would significantly worsen the desired "dampness effect".
Als weitere Komponente enthalten die erfindungsgemäßen demulgierenden Reinigungsmittel nichtionische Tenside. Auch in diesem Fall kann ein einziger Vertreter dieser Stoffgruppe oder alternativ ein Gemisch zweier oder mehrerer nichtionischer Tenside eingesetzt werden, solange dabei die Menge im Bereich von 1 bis 15 Gew.-% liegt. Erfindungsgemäß werden als nichtionische Tenside Addukte von 4 mol Ethylenoxid an n- oder i-Octanol sowie Addukte von 2 mol Propylenoxid und 5 bis 6 mol Ethylenoxid an die genannten Ca-Alkohole eingesetzt. Die bevorzugte Menge der verwendeten nichtionischen Tenside liegt im Bereich von 3 bis 6 Gew.-%.The demulsifying cleaning agents according to the invention contain nonionic surfactants as a further component. In this case too, a single representative of this group of substances or alternatively a mixture of two or more nonionic surfactants can be used, as long as the amount is in the range from 1 to 15% by weight. According to the invention, adducts of 4 mol of ethylene oxide with n- or i-octanol as well as adducts of 2 mol of propylene oxide and 5 to 6 mol of ethylene oxide with the C a -alcohols mentioned are used as nonionic surfactants. The preferred amount of the nonionic surfactants used is in the range of 3 to 6% by weight.
Als Lösungsvermittler, die den aus den oben genannten Komponenten (a), (b), (c) und (d) bestehenden demulgierenden Reinigungsmitteln gegebenenfalls zusätzlich beigegeben werden können, kommen aromatische Sulfonate, wie Cumolsulfonat oder Butylglykolsulfonat in Frage. Außerdem können gegebenenfalls Korrosionsinhibitoren für Leichtmetalle, beispielsweise Phosphorsäure, und/oder Korrosionsinhibitoren für Buntmetalle, beispielsweise Tolyltriazol, zugesetzt werden. Falls dies erwünscht ist, können die demulgierenden Reinigungsmittel gemäß der Erfindung auch Duftstoffe und/oder Farbstoffe enthalten.Aromatic sulfonates, such as cumene sulfonate or butyl glycol sulfonate, are suitable as solubilizers, which can optionally be additionally added to the demulsifying cleaning agents consisting of the above-mentioned components (a), (b), (c) and (d). In addition, corrosion inhibitors for light metals, for example phosphoric acid, and / or corrosion inhibitors for non-ferrous metals, for example tolyltriazole, can optionally be added. If this is desired, the demulsifying cleaning agents according to the invention can also contain fragrances and / or dyes.
Die Reiniger werden dadurch hergestellt, daß die genannten Komponenten in den jeweiligen Mengen nach an sich bekannten Methoden miteinander vermischt werden. Die Lagerung bzw. der Versand erfolgt in der Regel in Form eines die Kombination der angegebenen Rohstoffe enthaltenden wäßrigen Konzentrates, auf das sich auch die angegebenen Mengen (in Gew.-%) beziehen.The cleaners are produced in that the components mentioned are mixed with one another in the respective amounts by methods known per se. Storage or shipping is generally carried out in the form of an aqueous concentrate containing the combination of the specified raw materials, to which the stated amounts (in% by weight) also relate.
Zur Reinigung und Entfettung von lackierten oder unlackierten Oberflächen von Fahrzeugen, Motoren, Fußböden und Wänden von Werkstätten etc. werden die erfindungsgemäßen demulgierenden Reinigungsmittel mit Feuchthalteeffekt in beliebiger Verdünnung mit Wasser eingesetzt. Je nach Applikationsart und Verschmutzungsgrad der zu reinigenden Flächen werden 3%ige oder höher konzentrierte wäßrige Lösungen eingesetzt. Bei hoher Verschmutzung kann sogar das Konzentrat verwendet werden. Die Applikation erfolgt im Sprüh-, Tauch-oder Hochdruckspritzverfahren mit entsprechenden Geräten. Bereits bei Raumtemperatur wird ein hervorragendes Reinigungsergebnis erzielt. Die Produktzusammensetzung gewährleistet außerdem eine ca. 20- bis 30-minütige Feuchthaltung der zu reinigenden Oberfläche und damit einen entsprechend langen Kontakt der reinigend wirkenden Komponenten mit der Kontamination. Dies ist beispielsweise bei der.Reinigung von Lokomotiven zur Erzielung eines guten Reinigungsergebnisses von außerordentlicher Wichtigkeit.For cleaning and degreasing painted or unpainted surfaces of vehicles, engines, floors and walls of workshops etc., the demulsifying cleaning agents according to the invention with a moisturizing effect are used in any dilution with water. Depending on the type of application and the degree of soiling of the surfaces to be cleaned, 3% or more concentrated aqueous solutions are used. In the case of heavy soiling, the concentrate can even be used. The application takes place in the spray, immersion or high pressure spraying process with appropriate devices. An excellent cleaning result is achieved even at room temperature. The product composition also ensures that the surface to be cleaned is kept moist for approx. 20 to 30 minutes and thus a correspondingly long contact of the cleaning components with the contamination. This is extremely important, for example when cleaning locomotives to achieve a good cleaning result.
Abgesehen von dem oben genannten Feuchthalteeffekt ist gegenüber den herkömmlichen Produkten die demulgierende Wirkung von entscheidendem Vorteil. Wird beispielsweise bei Raumtemperatur Eine erfindungsgemäße Anwendungslösung von 10 bis 50%iger Konzentration mit Spülwässern auf eine Konzentration kleiner/gleich 2% verdünnt, so scheidet sich zusätzlich eingebrachtes Mineralöl von der Lösung selbsttätig praktisch vollständig ab, wenn diese 30 Minuten ruht. Mit entsprechenden Abwasser-Sammelbehältern kann allein durch eine derartige mechanische Ölabscheidung der Ölgehalt von Abwasser auf weniger als 50 mg 1-1 gesenkt werden.Apart from the above-mentioned moisturizing effect, the demulsifying effect is a decisive advantage compared to conventional products. If, for example, an application solution according to the invention is diluted from 10 to 50% concentration with rinsing water to a concentration of less than or equal to 2% at room temperature, additional mineral oil which has been introduced separates practically completely from the solution when it is at rest for 30 minutes. With appropriate waste water collection containers, the oil content of waste water can be reduced to less than 50 mg 1-1 solely by such mechanical oil separation.
Gegebenenfalls ist es möglich, zur weiteren Senkung des Ölgehaltes das Abwasser mit Eisen(11)sulfat oder Aluminiumsulfat zu versetzen und dadurch eine Ausflockung der Verunreinigungen zu erzielen. Durch diesen, aus dem Stand der Technik bekannten, zusätzlichen Reinigungsschritt kann der Restölgehalt im Abwasser auf einen Wert unter 10 mg 1-1 gesenkt werden.If necessary, it is possible to add iron (11) sulfate or aluminum sulfate to the wastewater to further reduce the oil content and thereby achieve a flocculation of the contaminants. By means of this additional cleaning step known from the prior art, the residual oil content in the waste water can be reduced to a value below 10 mg 1-1.
Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.
Entfettete Stahlbleche (50 mm x 100 mm x 1 mm) wurden in eine Mischung von Heißdampfzylinderöl und ASTM III-ÖI im Volumenverhältnis 1:1 eingetaucht, nach 10 min entnommen und 4 h senkrecht aufgehängt. Die so vorbehandelten Testbleche wurden dann in 50%ige Reinigerlösung der nachfolgenden Zusammensetzung getaucht und die Zeit bis zur vollständigen Entfettung (visuelle Beurteilung) wurde gemessen.
- (a) Reiniger gemäß der Erfindung (Konzentrat).
- 7 Gew.-% Nitrilotriacetat-Trinatriumsalz (Triiona A, 38%ig),
- 9,5 Gew.-% Diethanolamin,
- 18,0 Gew.-% Triethanolamin,
- 6,0 Gew.-% eines Kondensationsproduktes von n-Octanol an 4 Mol EO,
- 5,0 Gew.-% Natriumcumolsulfonat, 40%ig und
- 54,5 Gew.-% Wasser.
- (b) Reiniger gemäß der Erfindung (Konzentrat): 4,0 Gew.-% Ethylendiamintetraacetat-Natriumsalz (Trilone B),
- 30,0 Gew.-% Triethanolamin,
- 15,0 Gew.-% Diethanolamin,
- 7,0 Gew.-% eines Kondensationsproduktes von i-Octanol an 2 Mol Propylenoxid und 5 bis 6 Mol Ethylenoxid,
- 3,0 Gew.-% Natriumbutylglykolsulfonat,
- 0,2 Gew.-% Phosphorsäure,
- 0,2 Gew.-% Tolyltriazol und
- 40,6 Gew.-% Wasser. Vergleichsreiniger (Konzentrat):
- 5 Gew.-% eines Kondensationsproduktes von Nonylphenol an 5 Mol EO,
- 2 Gew.-% Natriumcumolsulfonat,
- 5 Gew.-% Ethylenglykolmonobutylether,
- 1 Gew.-% Natronlauge und
- 87 Gew.-% Wasser.
- (a) Cleaner according to the invention (concentrate).
- 7% by weight of nitrilotriacetate trisodium salt (Triiona A, 38%),
- 9.5% by weight diethanolamine,
- 18.0% by weight of triethanolamine,
- 6.0% by weight of a condensation product of n-octanol with 4 mol of EO,
- 5.0% by weight sodium cumene sulfonate, 40% and
- 54.5 wt% water.
- (b) cleaner according to the invention (concentrate): 4.0% by weight of ethylenediaminetetraacetate sodium salt (Trilone B),
- 30.0% by weight of triethanolamine,
- 15.0% by weight of diethanolamine,
- 7.0% by weight of a condensation product of i-octanol with 2 mol of propylene oxide and 5 to 6 mol of ethylene oxide,
- 3.0% by weight sodium butyl glycol sulfonate,
- 0.2% by weight phosphoric acid,
- 0.2% by weight of tolyltriazole and
- 40.6% by weight water. Comparative cleaner (concentrate):
- 5% by weight of a condensation product of nonylphenol with 5 mol of EO,
- 2% by weight sodium cumene sulfonate,
- 5% by weight of ethylene glycol monobutyl ether,
- 1% by weight sodium hydroxide solution and
- 87 wt% water.
Der Vergleichsreiniger enthielt also ein stark emulgierend wirkendes Tensid.The comparative cleaner therefore contained a strongly emulsifying surfactant.
Ergebnis:
- Die Reinigungswirkung der erfindungsgemäßen Mittel lag deutlich höher als die des Vergleichsreinigers. Es wurde ein Zeitfaktor von 0,7 zugunsten der erfindungsgemäßen Mittel erzielt, d.h., daß die erfindungsgemäßen Mittel in einer deutlich kürzeren Zeit, bezogen auf den Vergleichsreiniger, die geforderte vollständige Entfettung bewirkten.
- The cleaning effect of the agents according to the invention was significantly higher than that of the comparative cleaner. A time factor of 0.7 was achieved in favor of the agents according to the invention, ie that the agents according to the invention brought about the required complete degreasing in a significantly shorter time, based on the comparative cleaner.
Feuchthaltung:
- Zur Erzielung eines optimalen Reinigungsergebnisses, insbesondere bei der Außenreinigung von Fahrzeugen, ist eine Feuchthaltung über einen gewissen Zeitraum zwingend erforderlich. Die in Beispiel 1 genannten Reiniger (a) und (b) wurden im Volumenverhältnis 1:10 mit Wasser verdünnt. Ein mit Polyurethanlack beschichtetes Stahlblech (50 mm x 100 mm x 1 mm) wurde in die entsprechende Lösung eingetaucht, nach einigen Minuten entnommen und senkrecht aufgehängt. Nach 25 min war auf den behandelten Lackflächen noch ein mit dem Finger wischbarer Flüssigkeitsfilm vorhanden.
- To achieve an optimal cleaning result, especially when cleaning the exterior of vehicles, it is imperative to keep it moist for a certain period of time. The cleaners (a) and (b) mentioned in Example 1 were diluted 1:10 with water in a volume ratio. A steel sheet coated with polyurethane lacquer (50 mm x 100 mm x 1 mm) was immersed in the corresponding solution, removed after a few minutes and hung upright. After 25 minutes there was still a finger-wipe liquid film on the treated paint surfaces.
Die nachfolgend angegebenen Komponenten wurden in einem 2 I-Becherglas gemischt und 10 min mit einem Flügelrührer (16/15 mm) auf halber Flüssigkeitshöhe mit einer Rührgeschwindigkeit von 800 U . min-1 gerührt:
- 1620 ml Wasser,
- 20 ml Reinigerkonzentrat (vgl. Beispiel 1 (a) (b)) und 2 ml einer Mischung von Heißdampfzylinderöl und ASTM III-ÖI im Volumenverhältnis 1:1.
- 1620 ml water,
- 20 ml cleaner concentrate (see Example 1 (a) (b)) and 2 ml of a mixture of superheated steam cylinder oil and ASTM III oil in a volume ratio of 1: 1.
Ablauf von 10 min wurde der Ansatz in einen 2 I-Scheidetrichter umgefüllt und 30 min ruhen gelassen. Nach 30 min wurde eine Flüssigkeitsprobe von 500 ml aus dem Scheidetrichter abgelassen. Diese Wasserprobe enthielt nur noch geringe Mengen an Restöl (kleiner 50 mg 1-1).After 10 minutes, the mixture was transferred to a 2 l separatory funnel and left to stand for 30 minutes. After 30 minutes a 500 ml liquid sample was drained from the separatory funnel. This water sample contained only small amounts of residual oil (less than 50 mg 1-1).
Zu einer weiteren Probe von 500 ml der aus dem Scheidetrichter abgelassenen Lösung wurden 0,75 g wasserfreies Aluminiumsulfat zugegeben und der pH-Wert mit 1 n-Natronlauge auf 7,3 eingestellt. Danach wurde die Lösung 30 min ruhen gelassen. Der dabei gebildete flockige Niederschlag wurde mit Hilfe eines Filters (NN 651 1/4) abfiltriert. Der Restölgehalt des Filtrates betrug weniger als 10 mg 1-1.0.75 g of anhydrous aluminum sulfate was added to a further sample of 500 ml of the solution drained from the separating funnel, and the pH was adjusted to 7.3 with 1N sodium hydroxide solution. The solution was then left to stand for 30 minutes. The flaky precipitate formed was filtered off using a filter (NN 651 1/4). The residual oil content of the filtrate was less than 10 mg 1-1.
Der auf den gereinigten Teilen nach der Behandlung verbleibende Produktfilm bietet - neben der Feuchthaltung - außerdem einen notwendigen temporären Korrosionsschutz. Dies ist insbesondere bei der Reinigung des Motorenraumes von Bedeutung.The product film remaining on the cleaned parts after the treatment also offers - in addition to keeping them moist - the necessary temporary corrosion protection. This is particularly important when cleaning the engine compartment.
Die Prüfung bezüglich des Lagerungs-Korrosionsschutzes erfolgte gemäß des sogenannten "Platten-Klimatests". Es wurden Stahlbleche der Qualität ST 1405 mit Trichlorethylen gereinigt und anschließend in 10%ige Lösungen der erfindungsgemäßen Reiniger getaucht. Nach 5 min wurden die Bleche entnommen und bei Raumtemperatur getrocknet. Die Lagerung der Bleche erfolgte in einer Klimabox bei 23°C und 100% relativer Luftfeuchtigkeit. Derartig behandelte Bleche zeigten auch nach 14 Tagen noch keine Korrosionserscheinungen.The storage corrosion protection test was carried out according to the so-called "plate climate test". Steel sheets of quality ST 1405 were cleaned with trichlorethylene and then immersed in 10% solutions of the cleaners according to the invention. After 5 minutes the sheets were removed and dried at room temperature. The sheets were stored in a climate box at 23 ° C and 100% relative humidity. Sheets treated in this way showed no signs of corrosion even after 14 days.
Bei Zusatz von 0,15 bis 0,25 Gew.-% Phosphorsäure zum Produktkonzentrat und/oder 0,2 bis 0,4 Gew.-% Tolyltriazol zum Produktkonzentrat wurde auch ein vollständiger Korrosionsschutz von Leichtmetalloberflächen, wie beispielsweise Oberflächen aus Aluminium oder Magnesium, oder von Buntmetalloberflächen erreicht.When 0.15 to 0.25% by weight of phosphoric acid was added to the product concentrate and / or 0.2 to 0.4% by weight of tolyltriazole to the product concentrate, complete corrosion protection of light metal surfaces, such as surfaces made of aluminum or magnesium, was also achieved. or achieved by non-ferrous metal surfaces.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86111550T ATE57955T1 (en) | 1985-08-28 | 1986-08-20 | DEMULSIFYING DETERGENT WITH SURFACE MOISTURIZING EFFECT. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853530623 DE3530623A1 (en) | 1985-08-28 | 1985-08-28 | Demulsifying detergent with surface moisturizing effect |
DE3530623 | 1985-08-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0213554A2 EP0213554A2 (en) | 1987-03-11 |
EP0213554A3 EP0213554A3 (en) | 1988-09-14 |
EP0213554B1 true EP0213554B1 (en) | 1990-10-31 |
Family
ID=6279492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86111550A Expired - Lifetime EP0213554B1 (en) | 1985-08-28 | 1986-08-20 | Demulsifying cleaning agent retaining superficial humidity |
Country Status (15)
Country | Link |
---|---|
US (1) | US4784798A (en) |
EP (1) | EP0213554B1 (en) |
JP (1) | JP2523111B2 (en) |
AT (1) | ATE57955T1 (en) |
AU (1) | AU581779B2 (en) |
CA (1) | CA1282666C (en) |
DE (2) | DE3530623A1 (en) |
DK (1) | DK164707C (en) |
ES (1) | ES2001605A6 (en) |
FI (1) | FI82946C (en) |
GR (1) | GR862167B (en) |
NO (1) | NO166590C (en) |
PT (1) | PT83245B (en) |
TR (1) | TR24410A (en) |
ZA (1) | ZA866512B (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
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DK0420802T3 (en) * | 1989-09-26 | 1995-09-18 | Ciba Geigy Ag | Aqueous, stock-stable, low-foaming wetting agent |
DE4001595A1 (en) * | 1990-01-20 | 1991-07-25 | Henkel Kgaa | DEMULGATING, POWDERFUL, OR LIQUID CLEANSING AGENTS AND THEIR USE |
EP0575355B2 (en) * | 1991-03-12 | 1999-03-17 | Alfred Kärcher GmbH & Co. | Demulsifying cleaning agent |
IT1250656B (en) * | 1991-07-08 | 1995-04-21 | Crinos Ind Farmacobiologia | COMPOSITION FOR CLEANING THE SKIN, HAIR AND HAIR. |
FR2683939B1 (en) * | 1991-11-20 | 1993-12-31 | Gec Alsthom Sa | MEDIUM VOLTAGE SELF-DISCONNECTING CIRCUIT BREAKER AND APPLICATION TO A CELL AND A MEDIUM VOLTAGE STATION. |
TW211595B (en) * | 1991-12-07 | 1993-08-21 | Hoechst Ag | |
JPH05230499A (en) * | 1992-02-19 | 1993-09-07 | Yokohama Yushi Kogyo Kk | Fur detergent for the coated surface of vehicle |
EP0616028A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Cleaning compositions with short chain nonionic surfactants |
EP0616027A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
US5981455A (en) * | 1993-03-19 | 1999-11-09 | The Procter & Gamble Company | Cleaning compositions with short chain nonionic surfactants |
GB9322806D0 (en) * | 1993-11-05 | 1993-12-22 | Dow Europ Sa | Aqueous alkaline composition |
US5770549A (en) * | 1996-03-18 | 1998-06-23 | Henkel Corporation | Surfactant blend for non-solvent hard surface cleaning |
US6350727B1 (en) * | 2000-01-28 | 2002-02-26 | Amway Corporation | Non-streaking no-wipe cleaning compositions with improved cleaning capability |
DE10062267A1 (en) * | 2000-12-14 | 2002-06-20 | Henkel Kgaa | Process and agent for treating the circulating water in paint booths |
US6403546B1 (en) | 2001-01-31 | 2002-06-11 | S. C. Johnson Commercial Markets, Inc. | Floor cleaner and gloss enhancer |
DE102006003034A1 (en) * | 2006-01-20 | 2007-07-26 | Henkel Kgaa | Use of non-ionic surfactants of alkyl alcohol-ethoxylate/propoxylate type, in aqueous cleaning solution vehicles and plastics |
DE102006018216B4 (en) | 2006-04-18 | 2008-09-25 | Chemetall Gmbh | Process for the demulsifying cleaning of metallic surfaces |
JP5346299B2 (en) * | 2007-01-11 | 2013-11-20 | ダウ グローバル テクノロジーズ エルエルシー | Alkoxylate mixture surfactant |
JP5412665B2 (en) * | 2008-05-16 | 2014-02-12 | ライオン株式会社 | Cleaning composition |
EP2310481B1 (en) * | 2008-06-18 | 2014-04-30 | Dow Global Technologies LLC | Cleaning compositions containing mid-range alkoxylates |
EP2346924B1 (en) * | 2008-10-15 | 2022-08-31 | Dow Global Technologies LLC | Method for oil recovery |
BR112012005689B1 (en) * | 2009-09-15 | 2017-05-23 | Union Carbide Chem Plastic | Personal care composition and method for replacing silicone in personal care composition |
CN105385517A (en) * | 2015-12-16 | 2016-03-09 | 重庆嗨馒头网络科技有限公司 | Ecological vehicle washing liquid |
Family Cites Families (13)
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US3663445A (en) * | 1969-08-22 | 1972-05-16 | Lever Brothers Ltd | Surface cleaning and defatting composition |
AT308936B (en) * | 1970-03-31 | 1973-07-25 | Unilever Nv | Liquid, storage-stable concentrates and cleaning and degreasing agents that can be prepared from them by diluting them with water |
AT297442B (en) * | 1970-04-01 | 1972-03-27 | Unilever Nv | Process for cleaning, degreasing, descaling and pickling metals |
US3715324A (en) * | 1971-10-18 | 1973-02-06 | G Krall | Insoluble polymeric diazonium salt chromogen |
AT331610B (en) * | 1974-02-11 | 1976-08-25 | Unilever Nv | USE OF AQUATIC DETERGENT SOLUTIONS FOR INDUSTRIAL CLEANING AND DEGREASING OF OBJECTS, IN PARTICULAR METALS |
US4285840A (en) * | 1977-08-29 | 1981-08-25 | Sandoz Ltd. | Detergent compositions |
US4167488A (en) * | 1977-08-31 | 1979-09-11 | The Drackett Company | Hard surface cleaning compositions |
GB2012804B (en) * | 1978-01-19 | 1982-03-10 | Lankro Chem Ltd | Quick break cleaning composition |
US4321166A (en) * | 1978-12-26 | 1982-03-23 | The Procter & Gamble Company | Liquid detergent compositions containing corrosion inhibiting system |
US4372788A (en) * | 1981-08-17 | 1983-02-08 | Colgate-Palmolive Company | Grill and oven cleaner |
US4477365A (en) * | 1983-01-06 | 1984-10-16 | Miles Laboratories, Inc. | Caustic based aqueous cleaning composition |
DE3338952A1 (en) * | 1983-10-27 | 1985-05-09 | Henkel KGaA, 4000 Düsseldorf | CORROSION INHIBITORS FOR ZINC |
US4627931A (en) * | 1985-01-29 | 1986-12-09 | A. E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
-
1985
- 1985-08-28 DE DE19853530623 patent/DE3530623A1/en not_active Withdrawn
-
1986
- 1986-07-21 CA CA000514258A patent/CA1282666C/en not_active Expired - Fee Related
- 1986-07-28 TR TR86/0414A patent/TR24410A/en unknown
- 1986-08-19 DK DK394386A patent/DK164707C/en not_active IP Right Cessation
- 1986-08-20 GR GR862167A patent/GR862167B/en unknown
- 1986-08-20 DE DE8686111550T patent/DE3675294D1/en not_active Expired - Fee Related
- 1986-08-20 EP EP86111550A patent/EP0213554B1/en not_active Expired - Lifetime
- 1986-08-20 AT AT86111550T patent/ATE57955T1/en not_active IP Right Cessation
- 1986-08-25 PT PT83245A patent/PT83245B/en not_active IP Right Cessation
- 1986-08-27 NO NO863445A patent/NO166590C/en unknown
- 1986-08-27 ZA ZA866512A patent/ZA866512B/en unknown
- 1986-08-27 ES ES8601419A patent/ES2001605A6/en not_active Expired
- 1986-08-27 AU AU61887/86A patent/AU581779B2/en not_active Ceased
- 1986-08-27 FI FI863476A patent/FI82946C/en not_active IP Right Cessation
- 1986-08-28 JP JP61203541A patent/JP2523111B2/en not_active Expired - Lifetime
-
1987
- 1987-12-14 US US07/133,182 patent/US4784798A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US4784798A (en) | 1988-11-15 |
EP0213554A2 (en) | 1987-03-11 |
NO863445L (en) | 1987-03-02 |
ATE57955T1 (en) | 1990-11-15 |
EP0213554A3 (en) | 1988-09-14 |
DK164707C (en) | 1992-12-21 |
FI82946B (en) | 1991-01-31 |
FI863476A (en) | 1987-03-01 |
DE3530623A1 (en) | 1987-03-12 |
CA1282666C (en) | 1991-04-09 |
JP2523111B2 (en) | 1996-08-07 |
DK164707B (en) | 1992-08-03 |
NO166590B (en) | 1991-05-06 |
TR24410A (en) | 1991-10-08 |
ZA866512B (en) | 1987-04-29 |
DK394386A (en) | 1987-03-01 |
AU6188786A (en) | 1987-03-05 |
PT83245A (en) | 1986-09-01 |
FI82946C (en) | 1991-05-10 |
ES2001605A6 (en) | 1988-06-01 |
DE3675294D1 (en) | 1990-12-06 |
AU581779B2 (en) | 1989-03-02 |
PT83245B (en) | 1989-03-30 |
FI863476A0 (en) | 1986-08-27 |
NO863445D0 (en) | 1986-08-27 |
NO166590C (en) | 1991-08-14 |
DK394386D0 (en) | 1986-08-19 |
JPS6253400A (en) | 1987-03-09 |
GR862167B (en) | 1986-12-23 |
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