CLEANING AGENT, PROCEDURE FOR THE PRODUCTION OF THE CLEANING AGENT AS WELL AS ITS USE
The subject of the available invention is containing a cleaning agent, a micro emulsion, those The subject of the available registration is auß erdem a procedure for the production of the cleaning agents as well as the use of the cleaning agents. Substrates must before coating processes, e.g. Lacquer finishes, from contamination to be released. For this cleaning agents of the most different kind are used. The used so-called cold cleaning fluids are various. These cold cleaning fluids are usually solutions of Tensiden or tensidverwandten materials in organic solvents. As solvents hydrocarbons of different boiling ranges are usual. These well-known cleaning agents exhibit however a set of disadvantages. By their high portion of organic solvents they are partly injurious to health and partially also flammable. Auß they remove essentially only impurities oily or greasy art. for erdem. From there also cleaning agents on wäß became; riger basis develops. These cleaning agents exhibit however frequently the disadvantage of an only small cleaning strength, if not mechanical aids, as high-pressure water jet or ultrasonic is supporting used. From the international patent application with the publication number WHERE 93/02169 are wäß rige cleaning agents on the basis of an oil in water micro emulsion admits. These cleaning agents contain Terpene, which due to the strong smell and under toxic criteria is unfavorable as main solvents however. Further 93/11213 are wäß from the international patent application with the publication number WHERE; rige cleaning agents admits, with which the organic phase contains 75 to 95% of an non-aromatic hydrocarbon, 3 to 20% at least one emulsifying agent and 2 to 20% at least one alkyl ester. Preferred as emulsifying agents alkoxilierte Fettalhohole is used, which was manufactured by conversion by 1 mol Fettalkohol with 3 to 7 mol Ethylenoxid. These from the WHERE 93/11213 admitted cleaning agent exhibit however the disadvantage of an insufficient stability in storage and an insufficient thermal stability. Schließ lich sour cleaning agents are well-known, the 0.1 to 15 Gew from the EP-B-340 704. - % at least a high-molecular Polyetherpolyols and 1 to 20 Gew. - % of a nichtionischen Tensids on the basis of alkoxilierten Fettalkoholen contain. The available invention is thus the basis the task to make a cleaning agent available which is suitable for different underground materials (e.g. old lacquer finishes, blank Metallbleche, plastics among other things) and exhibits a good cleaning efficiency both for oily impurities and for bird excrement etc. Auß erdem the cleaning agent should not affect the characteristics of the following coating unfavorably. In particular the cleaning agent should not lead to adhesion problems with the following coating of the substrates. Furthermore the cleaning agent should contain as low a content of easily volatile organic component parts as possible, all to be more pollution free and more simply processable. Schließ lich the cleaning agent a good stability in storage of on behalf at least 12 should months, as high a heat cloud point as possible (prefers exhibiting > 50°C) and a freezing point of at least approx. -5°C. This task is solved surprisingly by a cleaning agent of the kind initially specified, which is characterized by it, daß The subject of the available invention is auß erdem a procedure for the production of the cleaning agents as well as the use of the cleaning agents. It is surprising and was not foreseeable, daß those erfindungsgemäß EN cleaning agent a very good stability in storage of on behalf at least 12 months, a high heat cloud point of prefers > 50°C as well as a relatively low freezing point exhibit (approx. 5°C). Is daß furthermore particularly favourably; the cleaning agents for different undergrounds suitably are and a good cleaning efficiency both for oily and for not-oily contamination, as for example bird excrement, exhibit. Furthermore the cleaning agents draw with ordnungsgemäß it application thereby out, daß it the characteristics of the following coating unfavorably do not affect. Schließ lich the cleaning agents exhibit a low content of easily volatile organic components and are in an environmentally friendly manner and simply processable from there. In the following now first the individual components of the cleaning agent are more near described. It is invention-substantially, daß the cleaning agent a mixture of different organic solvents (component (A)) contains. This mixture consists of less than 5 Gew. - % Terpenen, 20 to 70 Gew. - % aromatic-poor hydrocarbons and at least one solvent, selected from the group of the lower alcohols, the higher alcohols, the Glykolether and the ester, whereby the Gew. - % - Data to the weight of the solvents used as component (A) are related. Preferred the cleaning agent contains a mixture as solvent (A) out As aromatic-poor hydrocarbon (component (A)) the most different, commercial aliphatic and cyclo-aliphatic hydrocarbons are used. In particular aromatic-poor hydrocarbons with a boiling point are used between 170 umd 220°C. Examples of aromatic-poor hydrocarbons suitable as component (A) are in the trade under the following name available products: As component (B) higher alcohols, in particular alcohols with at least 4 C-atoms, with 4 to 8 C-atoms, are preferentially used. For example as component (B) n-butanol, i-butanol, t-butanol, n-Pentanol, i-Pentanole, n-Hexanol, i-Hexanole, n-Heptanol, i-Heptanole, n-Octanol, i-Octanole as well as mixtures of the alcohols mentioned are used. Beside the mono alcohols mentioned also the appropriate high-functional alcohols can be used, whereby however prefers the monofunctional alcohols are used. Preferred as component (B) i-butanol is completely particularly used. As component (C) Glykolether, prefers Glykolether with a middle molecular weight between 100 and 150, begun. As examples of the component (C) Isopropylglykol, Butylglykol, 1-Methoxipropanol, Methyldiglykol, Ethyldiglykol, Butyldiglykol, Hexylglykol, Hexyldiglykol, 1-Butoxiethoxi-2-propanol, Tripropylenglykolmethylether are among other things mentioned. Of course also mixtures of different Glykolether can be used as component (C). Preferred 1-Methoxipropanol and i-Propoxipropanol are used. As component (D) lower alcohols, in particular alcohols with 1 to 3 C-atoms, like methanol, are e.g. used ethanol, n-Propanol and i-Propanol as well as mixtures of different low alcohols, whereby preferentially i-Propanol is used. As component (e) esters, in particular alkyl esters are used of mono carbonic acids. Preferred thereby esters with a middle molecular weight are inserted between 100 and 170. Of course also mixtures of different esters can be used as component (e). Examples of suitable esters are Isobutylformiat, methyl acetate, ethyl acetate, n-Propylacetat, 1-Propylacetat, n-butyl acetate, i-butyl acetate, s-butyl acetate, n-Amylacetat, methyl amyl acetate, Hexylacetat, cyclohexyl acetate, n-Butylbutyrat, i-Butylisobutyrat, Ethyllactat, Butyllactat, Acetessigsäuremethylester, Acetessigsäureethylester, Propylpropionat, 1-Methoxipropylacetat, ethyl glycol acetate, Butylglykolacetat, Methoxibutylacetat, Ethyldiglykolacetat, Butyldiglykolacetat, Ethylenglykoldiacetat among other things natural can also mixtures of the esters mentioned be used. Preferred as component (e) 1-Methoxipropylacetat, Propylpropionat, i-butyl acetate as well as mixtures of the connections mentioned are used. Furthermore it is invention-substantially, daß the cleaning agents as emulsifying agent (component (B)) an accumulation product of Ethylenoxid to a geradkettigen or verzweigtkettigen alcohol with an alkyl chain length of 10 to 18 C-atoms or mixtures of these accumulation products as emulsifying agent contain. These accumulation products exhibit an ethyl oxide content from 45 to 65%, related to the weight of the accumulation product. These as component (B) assigned emulsifying agents are well-known ansich. It manufactured by accumulation of Ethylenoxid to the appropriate alcohols. In particular as component (B) accumulation products are used of 3 to 10 mol Ethylenoxid at 1 mol 10 to 18 C-atoms containing of a Fettalkohols. As alcohols for the production of the emulsifying agents (B) are used in particular Fettalkohole with 11 to 15 C-atoms. Preferred as component (B) the following accumulation products are used: Particularly as component (B) the conversion product of 7 mol Ethylenoxid with 1 mol of a geradkettigen or verzweigtkettigen alcohol with an alkyl chain length of 11 to 15 C-atoms is preferred, prefers 13 C-atoms, begun. Examples of emulsifying agents suitable as component (B) are in the trade under the name the Lutensol® the company BASF AG, Ludwigshafen, and the name Tergitol® the company Union carbide available products, like e.g.: Of course also mixtures of different emulsifying agents can be used as component (B). It is invention-substantially, daß the component (B) in the cleaning agents in a quantity of at least 2 Gew. - one uses %, related to the total weight of the cleaning agent, since is only so ensured, daß a micro emulsion develops, which is warm stable to at least 60°C. When component (C) alkoxilierte Fettalkohole become and/or modified, Fettalkohole and/or alkoxilierte alkyl phenol or mixtures of such connections, excluded alkoxilierte the connections used as component (B), assigned. Likewise the Methylether of the Fettalkoholalkoxilate mentioned is suitable as component (C). The connections used as component (C) are thereby on behalf more hydrophober than than component (B) the assigned connections. The component (C) is used on behalf for the improvement of the cleaning efficiency. For example accumulation products can be used of alkyl oxides with 2 to 4 C-atoms at alkyl phenol, like e.g. the accumulation product from 5 to 7 mol Ethylenoxid at 1 mol Isononylphenol, as component (C). However for ecological reasons as component (C) if alkoxilierte Fettalkohole are preferred and/or modified, Fettalkohole and/or the Methylether of these connections or mixtures of these connections alkoxilierte assigned. In particular as component (C) and from the component (B) the different conversion product of 1 mol of a Fettalkohols, if necessary modified, prefers a Fettalkohols with 11 to 15 C-atoms, preferentially with 13 to 15 C-atoms, with an alkyl oxide with 2 to 4 C-atoms, preferentially with Ethylenoxid and propylene oxide or with Ethylenoxid and Butylenoxid, begun. Likewise to be preferred the Methylether of these connections assigned. This as component (C) prefers assigned connections thereby is in particular manufactured, daß 1 mol one or several Fettalkohole with 11 to 15, prefers with 13 to 15 C-atoms, first with 2 to 6 mol Ethylenoxid and anschließ end in a second stage with 2 to 5 mol propylene oxide one converts. As component (C) are for example in the trade under the name the Plurafac® the company BASF available products suitably, like e.g.: Plurafac® LF 431 of the company BASF AG, Ludwigshafen (Methylether of the C13-Oxoalkohol-Ethylenoxid/Propylenoxid-Adduktes). Of course again mixtures of different emulsifying agents can be used as component (C). By the selection as component (B) and as component (C) assigned connections is controllable the heat cloud point of the cleaning agent. As component (D) in particular Alkanolaminsalze of a nitrogenous organic acid and/or Alkanolaminsalze of a nitrogenous derivative of an organic Di and/or Polycarbonsäure or mixtures of the connections mentioned are used. Particularly preferred the tri ethanol amine salt of the 2-Ethylhexylhalbamids of the maleic acid and/or the tri ethanol amine salt of the n (Phenylsulfonyl) are used - anthranilsäure. In addition, other corrosion inhibitors can be used, if the stability of the cleaning solution is thereby not worsened. Cleaning agents, those are preferential Cleaning agents, those are particularly preferential The cleaning agent exhibits usually a pH value between 7,5 and 9,5, preferentially between 8 and 9. The Teilchengröß e of the micro emulsion is smaller on behalf than the wavelength of the visible light and lies in the colloidal range. The production of the cleaning agents takes place usually via it, daß one at ambient temperature first the individual solvents (component (A)) with the emulsifying agents (components (B) and (C)) and the additives (D) mixes and then under easy agitating the intended quantity of water adds. Special homogenization by means of Homogenisator is not necessary on behalf. Those erfindungsgemäß EN cleaning agents are e.g. suitable for the cleaning of a multiplicity of substrates, like plastics, old lacquer finishes, primings, bright Metallbleche from steel, galvanized steel and aluminum. Those erfindungsgemäß EN cleaning agents are used preferentially in the range of the autorepair lacquer finish. With that erfindungsgemäß EN cleaning agents can be removed the most different impurities, which cannot be oily both oilily and. So can be removed for example Hochdruckfett, polishing agents, waxes, Silikone, tar, preservatives, parting agents, insect secretions, dust or bird excrement. The cleaning takes place thereby according to the usually used methods, for example with the help of a rag or a brush, with the help of a brush, soaked with the cleaning agent, a Scotch Drite or a sponge as well as with the help of the Spritzverfahrens or via the dipping cleaning method. If the cleaned substrates anschließ end with a coating to be provided are, then the substrate is rinsed preferentially after the treatment with the cleaning agent first with water (on behalf 1 rinsing process), to be e.g. removed in order paint-unfriendly arrears, as Tenside, emulsifying agents, surplus corrosion inhibitors etc. One prefers auß erdem anschließ end after-dried, with it arrears (salts) from the rinse water on a Mindestmaß are reduced, because they cause blisters in the structure of lacquer finish in the damp climate by osmose. The drying process can for example by application of a Heiß blower fan or - with small objects - by means of a fuselfreien cloth take place. In the following examples the invention is more near described. All data concerning parts and per cent are declarations of weight, if not expressly something else one indicates. In the examples the 1 to 5 described micro emulsions are clear to opake, translucent liquids with heat cloud points above 60 °C. Furthermore the cleaning agents are characterised by a very good cleaning efficiency in relation to the most different impurities and a good stability in storage. A cleaning agent, contg. (i) a solvent (A); (ii) an emulsifier (B), in an amt. of greater than 2 wt.% (based on total compsn. wt.); and (iii) a corrosion inhibitor as at least part of (D), comprises an organic low-aromatics content solvent (A) comprising a mixt. contg. (based on wt. of (A)) less than 5% terpene, 20-70% low-aromatics content hydrocarbon, and at least a lower or higher alcohol or their glycol ethers or esters; (B) adduct(s) of ethylene oxide (EO) with 10-18 C alcohols, the EO content of the adduct being 45-65%; and opt. (C) an alkoxylated (opt. modified) fatty alcohol, an alkoxylated alkylphenol and/or Me ethers of such cpds. (excluding, cpds. (B)); (D) other additives; and (E) water. The cleaning agent has a heat clouding temp. above 50 degrees C and a freezing pt. of at least -5 degrees C. Cleaner comprising a microemulsion which comprises (A) organic, low-aromatic solvents, (B) an adduct of ethylene oxide and a straight-chain or branched-chain alcohol with an alkyl chain length of 10 to 18 C atoms, where the adduct has an ethylene oxide content of 45 to 65%, based on the weight of the adduct, or mixtures of these adducts, (C) where appropriate an alkoxylated fatty alcohol and/or a modified, alkoxylated fatty alcohol and/or alkoxylated alkylphenols and/or methyl ethers of such compounds or mixtures of such compounds, excepting the compounds employed as component (B), (D) further additives and (E) water, 1.) component (A) is employed in an amount of 10 to 25 parts by weight, based on the total weight of the cleaner, and consists of a mixture of organic solvents which comprises: a) 20 to 70% by weight of at least one low-aromatic hydrocarbon and at least one of the following solvents (b) to (d) b) 0 to 35% by weight of at least one alcohol with at least 4 C atoms, c) 0 to 25% by weight of at least one glycol ether, d) 0 to 20% by weight of at least one alcohol with 1 to 3 C atoms and e) 0 to 20% by weight of at least one organic ester, 2.) component (B) is present in an amount of more than 2 parts by weight to 20 parts by weight of the emulsifier (B), based on the total weight of the cleaner, 3.) the cleaner comprises 2 to 10 parts by weight, based on the total weight of the cleaner, of a corrosion inhibitor (D), 4.) the cleaner comprises 40 to 80 parts by weight of water, based on the total weight of the cleaner, and 5.) the cleaner comprises 0 to 5 parts by weight, based on the total weight of the cleaner, of component (C). Cleaner according to Claim 1, characterized in that it comprises as component (A) a mixture of a) 20 to 70% by weight of at least one low-aromatic hydrocarbon and at least one of the following solvents (b) to (d) b) 15 to 35% by weight of at least one alcohol with 4 to 8 C atoms, c) 5 to 25% by weight of at least one glycol ether, d) 5 to 20% by weight of at least one alcohol with 1 to 3 C atoms and e) 5 to 20% by weight of at least one organic ester. Cleaner according to either of Claims 1 or 2, characterized in that it comprises B) 5 to 20 parts by weight of the emulsifier (B). Cleaner according to any of Claims 1 to 3, characterized in that it comprises A) 15 to 20 parts by weight of organic solvent (A), B) 10 to 20 parts by weight of the emulsifier (B), C) 1 to 5 parts by weight of component (C), D) 3 to 8 parts by weight of the corrosion inhibitor (D), and E) 50 to 70 parts by weight of water. Cleaner according to any of Claims 1 to 4, characterized in that the cleaner comprises as solvent component (a) at least one low-aromatic hydrocarbon with a boiling point between 170 and 220°C and/or as solvent component (c) at least one glycol ether with an average molecular weight between 100 and 150 g/mol and/or as solvent component (e) at lest one ester with an average molecular weight between 100 and 170 g/mol. Cleaner according to any of Claims 1 to 5, characterized in that the cleaner comprises as emulsifier (B) the product of the reaction of 3 to 10 mol of ethylene oxide with 1 mol of a straight-chain or branched-chain alcohol with an alkyl chain length of 10 to 18 C atoms and preferably with an alkyl chain length of 11 to 15 C atoms. Cleaner according to any of Claims 1 to 6, characterized in that the cleaner comprises as emulsifier (B) the product of the reaction of 7 mol of ethylene oxide with 1 mol of a straight-chain or branched-chain alcohol with an alkyl chain length of 11 to 15 C atoms, preferably 13 C atoms. Cleaner according to any of Claims 1 to 7, characterized in that it comprises as component (C) the optionally modified product of the reaction of 1 mol of a fatty alcohol, preferably a fatty alcohol with 11 to 15 C atoms, with an alkylene oxide with 2 to 4 C atoms, preferably with ethylene oxide and propylene oxide or with ethylene oxide and butylene oxide, and/or the methyl ether of these compounds. Cleaner according to any of Claims 1 to 8, characterized in that it comprises as corrosion inhibitor (D) at least one alkanolamine salt of a nitrogen-containing organic acid and/or an alkanolamine salt of a nitrogen-containing derivative of an organic di- and/or polycarboxylic acid, preferably the triethanolamine salt of N-(2-ethylhexyl)maleamic acid and/or the triethanolamine salt of N-(phenylsulphonyl)anthranilic acid. Process for the production of a cleaner, in which organic solvents, emulsifiers, water and, where appropriate, other auxiliaries and additives are processed to the cleaner by stirring and dispersing, characterized in that a cleaner according to any of Claims 1 to 9 is produced. Method for cleaning a substrate, in which 1.) the substrate to be cleaned is brought into contact with a cleaner and 2.) the cleaner is removed together with the contaminants to be removed from the substrate, Method according to Claim 11, characterized in that the cleaner is removed in stage (2) of the method by rinsing with water. Method according to Claim 11 or 12, characterized in that a coating agent is applied after the cleaning of the substrate. Use of the cleaning solution according to any of Claims 1 to 9 in the area of automotive repair painting.
contains.
whereby the sum of the parts by weight of the components (A) to (e) always 100 Gew. - amounts to %.
contained.
contained. Example 1
by agitating at an agitator speed of 750 to 850 revolutions per min to a micro emulsion are converted. The characteristics of this cleaning agent 1 are represented in table 1. Example 2
by agitating at an agitator speed of 750 to 850 revolutions per min to a micro emulsion are converted. The characteristics of this cleaning agent 2 are represented in table 1. Example 3
by agitating at an agitator speed of 750 to 850 revolutions per min to a micro emulsion are converted. The characteristics of this cleaning agent 3 are represented in table 1. Example 4
by agitating at an agitator speed of 750 to 850 revolutions per min to a micro emulsion 4 are converted. The characteristics of this cleaning agent 4 are represented in table 1. Example 5
by agitating at an agitator speed of 750 to 850 revolutions per min to a micro emulsion 5 are converted. The characteristics of this cleaning agent 5 are represented in table 1. Explanations concerning table 1