EP2828370B1 - Produit de nettoyage à base de microémulsion - Google Patents

Produit de nettoyage à base de microémulsion Download PDF

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Publication number
EP2828370B1
EP2828370B1 EP13710857.7A EP13710857A EP2828370B1 EP 2828370 B1 EP2828370 B1 EP 2828370B1 EP 13710857 A EP13710857 A EP 13710857A EP 2828370 B1 EP2828370 B1 EP 2828370B1
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EP
European Patent Office
Prior art keywords
weight
water
microemulsion
salt
ester
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.)
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EP13710857.7A
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German (de)
English (en)
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EP2828370A1 (fr
Inventor
Renate BEISSER
Jürgen Allgaier
Jens HILLERICH
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Bernd Schwegmann & Co KG GmbH
Forschungszentrum Juelich GmbH
Original Assignee
Bernd Schwegmann & Co KG GmbH
Forschungszentrum Juelich GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • C11D3/2079—Monocarboxylic 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
    • 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
    • C11D3/2086—Hydroxy 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/667—Neutral esters, e.g. sorbitan 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention relates to aqueous microemulsions, their use as cleaning agents, in particular for the removal of polymer-like soils, such as, for example, paint residues, as well as a method for cleaning using the aqueous microemulsion.
  • Detergents usually get their effectiveness in that they are specially designed for the soiling to be cleaned.
  • a cleaner for water-soluble contaminants is typically water-based, whereas a cleaner for oily soils is typically oil-based.
  • a cleaner that works against both types of soiling consists of water, an oil and at least one surfactant, so that emulsions can form.
  • Surfactants are washing-active substances (detergents) which are contained in detergents, dishwashing detergents and shampoos. They have a characteristic structure and have at least one hydrophilic and one hydrophobic structural unit. They have an amphiphilic character. If the stabilizing character of water-in-oil mixtures is in the foreground, these amphiphilic substances are used as emulsifiers.
  • Surfactants lower the interfacial tension between immiscible phases, a hydrophilic (water-soluble, lipophobic), mostly aqueous phase, and a hydrophobic (oil-soluble, lipophilic) phase.
  • Such aqueous two-phase mixtures are referred to as emulsions.
  • emulsions may contain hydrophilic and hydrophobic phases in different volumes. They have a continuous and a disperse phase, which is a very small droplet stabilized by surfactant occupancy, in the continuous phase. Depending on the nature of the continuous phase, it is referred to as oil-in-water or water-in-oil emulsions.
  • microemulsions are thermodynamically stable, emulsions separate into two phases due to their instability. At the microscopic level, this difference is reflected in the fact that the emulsified liquids in microemulsions generally have smaller structure sizes than in emulsions, such as in DE 10 2005 049 765 A1 described. Thermodynamically unstable emulsions thus have larger structures.
  • Lamellar mesophases can occur in microemulsions. Lamellar mesophases lead to optical anisotropy and possibly increased viscosity. These properties are e.g. undesirable for cleaners. In addition, phase separation occurs when lamellar phases coexist with microemulsions.
  • Microemulsions consist of at least three components, namely oil, water and a surfactant.
  • the surfactant mediates between these two components and allows a macroscopic-homogeneous mixture. On a microscopic scale, the surfactant forms a film between the oil and water domains. Oil and water are immiscible and therefore form domains on the nanoscale.
  • Microemulsions are macroscopically homogeneous, behave optically isotropically and are thermodynamically stable in contrast to emulsions. There are W / O and O / W droplet microemulsions where water droplets from the oil or oil droplets are enclosed by the water. Approximately equal proportions of oil to water promote the formation of a bicontinuous microemulsion. Characteristic of the efficiency of a surfactant is the minimum amount of surfactant required to obtain a microemulsion.
  • Microemulsions are intensively studied in the field of basic science. The knowledge gained is largely based on the use of pure, defined components: deionized water, chemically pure oils and pure surfactants. In technical microemulsions, the components usually consist of mixtures. As a result, the phase ratio changes considerably and the findings from basic research gained in simplified models can not be readily obtained technical applications are transmitted. Another difficulty lies in the low temperature stability of microemulsions, since in practical formulations the stability must be present over a wide temperature range in order to ensure safe storage, transport and application. Especially systems based on the frequently used fatty alcohol ethoxylates are only stable in a very narrow temperature window of a few degrees Celsius or must have extremely high surfactant concentrations in order to be stable over larger temperature ranges.
  • microemulsions prepared with the aid of sugar surfactants can be stable over larger temperature ranges ( WO 2008/132202 A1 ).
  • mixtures of nonionic and ionic surfactants can be used.
  • the development of microemulsions, which are sensitive to the setting of their parameters, and at the same time stable as well as a high cleaning performance, especially with regard to water-insoluble or only very sparingly soluble substances, is a particular challenge.
  • cleaners which are used in the commercial and private sector, for example as brush cleaners or adhesive removers, consist essentially of low-boiling mixtures of aliphatic and aromatic hydrocarbons or other organic solvents to which surfactants are often added. These cleaners are highly harmful to health and harmful to the environment. In addition, conventional cleaners are often highly alkaline, which can attack the substrates to be cleaned.
  • microemulsions are already known in the prior art. So describes DE 10 2005 049 765 in general a process for cleaning with microemulsions by means of hydrophilic polymeric additives.
  • microemulsions containing sodium salts of sulfosuccinic acid esters, C 2 -C 10 diols and oil.
  • the oil component may be an ester.
  • the microemulsions can contain other solvents and are suitable as a cleaner for degreasing or paint stripping.
  • EP 1 780 259 describes microemulsions for cleaning hard surfaces, which in addition to dibasic esters contain polar solvents as well as anionic surfactants.
  • microemulsions based on ester oils described in the prior art require further solvents for stabilizing the microemulsion or for achieving the cleaning performance and are thus generally not free from labeling according to current German legislation.
  • the object of the present invention was to provide environmentally friendly microemulsions which are stable over a wide temperature range, have a low amount of surfactant and, moreover, have an outstanding cleaning performance, in particular with regard to Farbanschmutzieux, oily and greasy soiling and soiling, the organic components are polymer-based and are particularly preferred no labeling according to current German legislation.
  • the object of the present invention was therefore to remedy the problems identified in the prior art.
  • the cleaning performances of the microemulsions according to the invention are essentially the same as those of the solvent-based cleaners.
  • the microemulsions according to the invention also have a wider range of applications. They are useful, for example, for removing fresh or dried water-based inks. Such colors are usually removed with water, but this can lead to resin residues or residues of dried-on paint. Resin residues can stick eg brush hairs.
  • the microemulsions according to the invention are also suitable for removing water-soluble inks without leaving residual resin. Dried paint is removed, which is not possible with water.
  • Conventional brush cleaners are only suitable for cleaning solvent based paints, they are not suitable for water based paints.
  • the Microemulsions according to the invention are furthermore advantageous if long exposure times are necessary, for example in order to remove dried soiling. Conventional cleaners are not suitable here because the organic solvents evaporate quickly.
  • microemulsions according to the invention are readily dilutable with water while retaining their microemulsion property. This allows you to be used with more easily removable dirt, diluted with water. In addition, detergent residues can be easily removed with water.
  • microemulsions according to the invention in contrast to conventional cleaners after contact with skin and after washing, leave a pleasant feeling on the skin.
  • the microemulsions according to the invention are essentially odorless.
  • the microemulsions according to the invention are also distinguished by the fact that they require only a small amount of surfactant and are stable over a relatively wide temperature range.
  • the microemulsion according to the invention is substantially free of volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • the VOC is a volatile organic compound which has a vapor pressure of 0.01 kPa or more at 293.15 K.
  • VOCs include e.g. Compounds of the substance groups alkanes / alkenes, aromatics, terpenes, halogenated hydrocarbons, ethers, esters, aldehydes and ketones.
  • the microemulsion of the present invention is substantially free of organic solvents, especially VOCs.
  • substantially free in the context of the present invention means that the microemulsion is less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, in particular less than 0.5% by weight, and in particular completely free.
  • the aqueous microemulsion according to the invention comprises as essential components the components a) to e).
  • the aqueous microemulsion according to the invention comprises as component a) one or more liquid carboxylic acid esters, which are also referred to below as "ester oils".
  • the ester oil forms the oil component in the microemulsion.
  • Ester oils have the advantage that they are non-polar and have a lipophilic character, which makes them particularly suitable for oily soiling and, in particular, for soiling whose organic constituents are polymer-based. In addition, they have a high boiling point and are therefore volatile.
  • Suitable liquid carboxylic esters have a melting point which is below 20 ° C, i. the liquid carboxylic esters are liquid at 20 ° C.
  • Suitable carboxylic acid esters have 6 to 40 carbon atoms, preferably 6 to 22 and especially 10 to 22 carbon atoms.
  • the ester oil may contain saturated, unsaturated or aromatic radicals.
  • liquid carboxylic acid esters selected from the group consisting of esters of monohydric alcohol and mono- or dicarboxylic acid and esters of dihydric alcohol and monocarboxylic acid.
  • esters of monohydric alcohols with monocarboxylic acids are particularly preferred.
  • liquid carboxylic acid esters wherein the ester is a C 10 -C 22 monocarboxylic acid and methanol, preferably methyl dodecanoate or rapeseed oil methyl ester.
  • liquid carboxylic acid esters which have a mixture of monocarboxylic acids having 10 to 22 carbon atoms and dicarboxylic acid methyl ester having 6 to 10 carbon atoms.
  • the ester oil comprises one or more components selected from the group consisting of rapeseed oil methyl ester, octyloctanoate, oleic acid ethyl ester, methyl laurate, dimethyl succinate, dimethyl adipate, dimethyl glutarate and isopropyl myristate.
  • the aqueous microemulsions of the present invention comprise the liquid carboxylic acid ester in an amount of 10 to 40% by weight, preferably 20 to 35% by weight, based in each case on the total weight of the microemulsion.
  • the weight ratio of the liquid carboxylic ester (component a)) to the sum of components c), d) and e) to 1.5 to 10 , preferably 2.5 to 8, in particular 3 to 8 or 4 to 8 set.
  • aqueous microemulsions according to the invention have as component b) one or more water-soluble salt (s) with one or more cations, preferably selected from the group consisting of sodium, potassium, calcium, magnesium and ammonium.
  • salts are water-soluble, if at least 1 g of salt per liter of water at 20 ° C can be completely dissolved. Preference is given to the alkali metal or alkaline earth metal or ammonium salts.
  • inorganic and organic anions are suitable.
  • Preferred inorganic anions are selected from the group consisting of sulfate, chloride, hydrogen sulfate, phosphate and hydrogen sulfate.
  • Preferred organic anions are selected from the group consisting of acetate, gluconate, citrate and tartrate.
  • component b) is a water-soluble salt selected from the group consisting of sodium sulfate, sodium chloride, sodium gluconate, sodium citrate, trisodium phosphate, disodium hydrogen phosphate, potassium sulfate, potassium chloride, ammonium sulfate, ammonium chloride, magnesium sulfate, magnesium chloride, calcium chloride, calcium acetate , Magnesium acetate and potassium sodium tartrate.
  • the microemulsions according to the invention comprise calcium acetate and / or magnesium acetate.
  • the salt is typically present in an amount of from 0.1 to 4% by weight, preferably from 0.25 to 3% by weight, based in each case on the total weight of the microemulsion ,
  • the aqueous microemulsion according to the invention additionally contains component c), which is one or more salts of sulfosuccinic acid ester.
  • the salt of the sulfosuccinic acid esters is an alkali metal salt, especially a sodium salt.
  • the salt of sulfosuccinic acid esters acts as an anionic surfactant.
  • sulfosuccinic acid ester salts having C 6 -C 12 -alcohol radicals have been found to be present in the microemulsions according to the invention.
  • the sulfosuccinic ester salt used contributes significantly to the stability of the microemulsion according to the invention.
  • salts of the sulfosuccinic esters selected from the group consisting of diesters of sulfosuccinic acid alkali salt with C 6 -C 10 -alcohols, monoesters of sulfosuccinic acid dialkali salt with C 8 -C 12 -alcohols and monoesters of sulfosuccinic acid dialkali salt with ethoxylated C 10 -C 14 -alcohols.
  • the diester of the sulfosuccinic acid alkali salt is present as a diester having at least one, preferably two, ethoxylated C 10 -C 14 alcohol radicals.
  • the alcohol residues can be linear or branched.
  • the salt of the sulfosuccinic acid esters is the sodium salt of sulfosuccinic acid bis-2-ethylhexyl ester.
  • the salts of the sulfosuccinic acid esters are typically present in an amount of from 1 to 10% by weight, preferably in an amount of from 1.5 to 5% by weight or from 2.0 to 5.0% by weight. %, in each case based on the total weight of the microemulsion.
  • the salt of the sulfosuccinic acid esters is typically present in an amount of from 30 to 75% by weight, preferably in an amount of from 40 to 70% by weight.
  • the microemulsions according to the invention have the component d), which is one or more nonionic surfactant (s) selected from alkoxylated sorbitan ester and alkoxylated vegetable oil.
  • component d is one or more nonionic surfactant (s) selected from alkoxylated sorbitan ester and alkoxylated vegetable oil.
  • the nonionic surfactant is selected from ethoxylated sorbitan ester and / or ethoxylated vegetable oil.
  • Preferred sorbitan esters are the sorbitan monoesters, in particular those sorbitan monoesters which have a saturated or unsaturated, linear or branched fatty acid radical.
  • alkoxylated sorbitan esters which may be, for example, propoxylated and / or ethoxylated.
  • ethoxylated sorbitan esters are particularly preferred, in particular those sorbitan esters which are provided on average with 3 to 30, preferably 4 to 20, ethoxylate groups.
  • the nonionic surfactant is an ethoxylated sorbitan monoester having a saturated or unsaturated C 12 -C 18 fatty acid residue.
  • the nonionic surfactant is an alkoxylated, in particular ethoxylated castor oil.
  • the degree of ethoxylation of the ethoxylated sorbitan ester and / or the ethoxylated vegetable oil is adjusted so that the HLB value is from 11 to 17, more preferably 12 to 16 or 13 to 16.
  • the nonionic surfactant is selected from the group consisting of polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate and polyoxymethylene (20) sorbitan monooleate.
  • the nonionic surfactant is preferably in an amount of 1.0 to 7.0% by weight, more preferably 1.5 to 5.0% by weight or 1.0 to 5.0% by weight, based on the Total weight of the microemulsion before.
  • the nonionic surfactant is present in an amount of from 10 to 70% by weight or from 20 to 60% by weight, preferably in an amount of from 15 to 60% by weight or from 23 to 55% by weight. %, in each case based on the total weight of components c), d) and e).
  • the aqueous microemulsions according to the invention contain one or more boosters.
  • the boosters used serve to increase the surfactant efficiency in the microemulsions according to the invention.
  • the boosters help to increase the temperature range in which the microemulsions are stable.
  • the boosters of the present invention are routinely designed to increase the stability of the microemulsions by stiffening the interface.
  • boosters consist of at least one water-soluble unit which has at least one hydrophobic unit at least at one chain end and / or has a hydrophobic unit as non-terminal substituent.
  • the booster is in the form of a polymer. Throughout the polymer booster the hydrophilic character predominates. Due to the hydrophobic moiety or moieties, the polymers in water preferentially form micelles. Suitable boosters are for example in the DE 198 39 054 and DE 10 2005 049 765 described.
  • the water-soluble unit of the booster is not limited in its design to certain types of structures, but it is according to the invention on the combination of the larger water-soluble unit with the hydrophobic units or on.
  • the water-soluble unit of the polymer is preferably linear, but star-shaped, branched or other types of structures are also possible.
  • Linear means in polymers that the atoms forming the backbone of the chain are a linear unit.
  • the water-soluble unit may be nonionic or ionic, that is, a polyelectrolyte.
  • the electrical charges may be on any part of the water-soluble component of the polymer. Structures are also conceivable which are composed of at least one ionic and one nonionic fraction.
  • the water-soluble units can consist of the following monomers or mixtures thereof of at least two components: ethylene oxide, vinylpyrrolidine, acrylic acid, methacrylic acid and maleic anhydride.
  • the water-soluble portion of the polymeric additive is preferably a polyethylene oxide or polyethylene glycol.
  • Further examples are copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol and its water-soluble derivatives.
  • Also suitable are polyvinylpyrrolidone, polyvinylpyridine, polymaleic anhydride, polymaleic acid, polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid and their water-soluble salts.
  • the water-soluble units are preferably linear.
  • the molecular weight distribution of the water-soluble unit defined by the ratio of the weight-average molecular weight and the number-average molecular weight is preferably ⁇ 1.2.
  • the number-average molecular weight of the water-soluble unit of the polymeric additive is preferably between 500 and 20,000 g / mol, more preferably 1,000 to 7,000 g / mol, or between 1300 and 5000 g / mol.
  • the hydrophobic unit design is not limited to selected types of structures. Rather, here too, only the hydrophobic or water-insoluble properties of this unit are important.
  • Preferred molecular sizes for the hydrophobic moiety are 110-500 g / mol, more preferably 110 to 280 g / mol.
  • the hydrophobic units consist of non-water-soluble residues. These are preferably alkyl radicals which preferably contain between 6 and 50 carbon atoms, more preferably between 8 and 20 carbon atoms.
  • the radicals can also contain aromatic groups or carbon double or triple bonds, they can be linear or branched be.
  • any other hydrophobic organic radicals which contain, for example, oxygen, nitrogen, fluorine or silicon atoms can also be used.
  • the hydrophobic moiety may also be a polymer.
  • the hydrophobic moiety may be a residue of defined structure and molecular weight, such as alkyl groups. Also mixtures of substances, such as occur in technical products, are possible. However, it can also be a polymeric radical, such as polybutylene oxide.
  • the water-soluble moiety of the polymer carries a hydrophobic moiety on at least one chain end.
  • the water-soluble moiety of the polymer may carry a hydrophobic moiety in a non-chain end position.
  • hydrophobic moieties of the polymeric booster may be incorporated at least at one location between the water-soluble moieties such that the water-soluble moieties of the polymer are interrupted by hydrophobic moieties.
  • the ratio of the molecular weights of water-soluble part to hydrophobic part is 7-200, preferably 7-50.
  • the water-soluble unit of the booster is a linear polymer and carries a hydrophobic moiety at one chain end.
  • alkyl ethoxylates obtained by ethoxylation of C 8 -C 20 -alcohols.
  • the booster in water prefers to form micelles.
  • a hydrophobic moiety is located at either end of the water soluble moiety.
  • linear water-soluble polymers which have a hydrophobic unit only at one chain end.
  • alcohol ethoxylates which have a high degree of ethoxylation. These substances can be considered as polyethylene oxide with a hydrophobic alkyl radical or be regarded as long-chain or hydrophilic emulsifiers.
  • hydrophobic components for example, aliphatic alcohols or alkylphenols can be used, which preferably have 8-20 carbon atoms.
  • the alcohol ethoxylates contain from 25 to 500 moles per mole of alcohol, more preferably from 50 to 200 moles of ethylene oxide.
  • An example is the commercially available compound Brij S 100-PA (SG) from Croda.
  • the proportion of water-soluble units which are not linked to hydrophobic units should be as low as possible, that is to say, for example, ⁇ 20% by weight.
  • the booster is in the form of a hydrophilic polymeric additive consisting of a water-soluble unit having at one end of a chain a hydrophobic, water-insoluble group with a Molecular weight of 80 to 500 g / mol and wherein preferably the mass ratio of the water-soluble unit to the hydrophobic, water-insoluble groups is 5 to 200.
  • the booster consists of a linear, water-soluble polymer which carries a hydrophobic, water-insoluble group at one end of the chain.
  • the hydrophobic, water-insoluble group preferably has a molecular weight of 110 to 500 g / mol and particularly preferably a molecular weight of 110 to 280 g / mol.
  • the molecular weight ratio of the water-soluble unit to the hydrophobic water-insoluble groups is preferably 7 to 50.
  • the booster consists of an alcohol ethoxylate of a C 8 -C 20 -alcohol having 25 to 500 ethoxy groups, preferably 50 to 200 ethoxy groups.
  • the booster is present in an amount of 3 to 20% by weight, preferably 5 to 15% by weight, in particular 7 to 15% by weight, in each case based on the total weight of components c), d) and e), before.
  • the aqueous microemulsions according to the invention have the components c) + d) + e) in an amount of 2 to 20% by weight, preferably 3 to 15% by weight, more preferably 3 to 10% by weight and in particular 3 to 8 wt .-% or 4 to 8 wt .-%, each based on the total weight of the microemulsion on.
  • microemulsions according to the invention can be used as cleaning agents in the private as well as in the commercial sector. It is particularly advantageous that the aqueous microemulsions can be used as neutral cleaners and thus replace the known in the prior art aggressive alkaline cleaner for the removal of oily soils, such as paint residues.
  • the microemulsions according to the invention have a pH of from 4 to 11, preferably from 5 to 9.
  • the microemulsions according to the invention may additionally have further additives.
  • Suitable additives are, for example, mono-, di- or triethylene glycol monoalkyl ethers or aryl ethers, such as ethylene glycol propyl ether, ethylene glycol butyl ether (butyl glycol), ethylene glycol hexyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether (butyl diglycol), diethylene glycol hexyl ether, triethylene glycol methyl ether, Triethylene glycol ethyl ether, triethylene glycol butyl ether, ethylene glycol phenyl ether;
  • Mono-di- or tripropylene glycol monoalkyl ethers or aryl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol butyl ether, tripropylene glycol methyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether.
  • Mono-di- or triethylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether
  • N-alkylpyrrolidones having a C 1 -C 12 -alkyl radical for example N-ethylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone.
  • biocides and / or dyes as well as antirust and Antioxdanzstoff can be added.
  • the additives may be present in amounts of 0.01 to 3, preferably 0.1 to 1 wt .-%, based on the total weight of the microemulsion.
  • microemulsions of the invention may be in the form of oil-in-water or water-in-oil microemulsions. Preferably, they are present as a bicontinuous microemulsion. Bicontinuous microemulsions comprise two domains, a hydrophobic and a hydrophilic domain in the form of extended juxtaposed and intertwined domains, at the interface of which stabilizing surface active surfactants are enriched in a monomolecular layer. Microemulsions form very easily because of the very low interfacial tension spontaneously when the individual components water, oil and a suitable surfactant system are mixed.
  • microemulsions Since the domains in at least one dimension only very small extent on the order of nanometers, microemulsions often appear visually transparent and are thermodynamic, ie unlimited in time, stable depending on the surfactant system used in a certain temperature range. If microemulsions have low surfactant contents, they may also be cloudy and yet thermodynamically stable.
  • the microemulsion is particularly stable in the temperature range of 10 to 40 ° C, in particular 5 to 60 ° C.
  • microemulsions according to the invention are stable in a temperature range ⁇ 5 ° C to> 60 ° C.
  • the microemulsion of the present invention may be a water-in-oil or oil-in-water droplet microemulsion wherein water droplets from the oil or oil droplets are enclosed by the water.
  • bicontinuous microemulsions are particularly preferred.
  • the weight fraction of ester oil (component a)) in the ester oil-water mixture is from 12 to 45% by weight, preferably from 23 to 38% by weight, based on the total weight of ester oil and water in the microemulsion.
  • Another object of the present invention is a cleaner, consisting or comprising the microemulsion according to the invention.
  • Another object of the present invention is the use of the microemulsion according to the invention as a cleaning agent, in particular for removing oily soiling or resins and polymer-like soils.
  • the proportion of components c) and d) is less than 15 wt .-%, in particular less than 12 wt .-% or less than 9 wt .-% or less than 7 wt .-%, for example 2.5 to 7 wt .-%, each based on the total weight of the cleaning agent.
  • this very low surfactant content makes it possible to produce products which are not subject to any labeling requirement with respect to their surfactant content.
  • the cleaner according to the invention is particularly suitable as a replacement of organic solvents. This results in a reduction of the amount of organic solvent used up to the abandonment of aromatic solvents result, which is advantageous in terms of occupational safety and environmental protection.
  • both cleaners according to the invention have the microemulsions according to the invention therein increased flash points compared to the organic phases contained therein.
  • the use of the cleaner according to the invention for cleaning colors, especially dried or dry paints, varnishes and tarry compounds and adhesives, as a general purpose cleaner and neutral detergent in the household, in the industry and the commercial sector is possible.
  • a use of the cleaner according to the invention is also recommended when cleaning paints and varnishes on an aqueous and organic basis, in particular for cleaning brushes.
  • the cleaner according to the invention can also be used for cleaning paints, varnishes, oil and / or salt-like residues of metal and / or plastic surfaces.
  • the cleaner according to the invention could thus replace, for example, organic cleaning agents in many areas of application.
  • the microemulsions according to the invention can also be used for cleaning in the printing industry, in particular for removing printing inks and paper dust build-up of printing presses and printing plates. It is suitable, for example, for removing water-based or oil-based printing inks and radiation-curing printing ink.
  • the cleaner finds application in the cleaning of printing cylinders, pressure rollers and surfaces of printing machines, preferably for cleaning printing machines for conventional printing and printing forms, for example, when interrupting the printing process or non-impact printing process.
  • Conventional printing processes in which the cleaner can be used include planographic printing, gravure printing, high-pressure printing, flexographic printing and screen printing, in particular offset and waterless offset printing.
  • the non-impact printing methods without printing form include electrophotography, ionography, magnetography, inkjet and thermography.
  • the microemulsion according to the invention is used for cleaning and / or removing compounds selected from the group consisting of paints, lacquers, greases, oils, resins, bitumen, tar, adhesive residues, sealants, rubber abrasion, cosmetic and make-up remnants and pyrolysis products of organic compounds, in particular for the purification and / or removal of contaminants whose organic constituents are polymer-based, for example, paints, adhesives, sealants, polymer foams, such as polyurethane foams.
  • compounds selected from the group consisting of paints, lacquers, greases, oils, resins, bitumen, tar, adhesive residues, sealants, rubber abrasion, cosmetic and make-up remnants and pyrolysis products of organic compounds, in particular for the purification and / or removal of contaminants whose organic constituents are polymer-based, for example, paints, adhesives, sealants, polymer foams, such as polyurethane foams.
  • microemulsion according to the invention is particularly suitable for the cleaning and / or removal of dried inks and adhesives.
  • the microemulsions according to the invention are used for the purification of dye residue contaminated tools, in particular tools for applying paints, such as brushes, paint rollers or paint sprayers.
  • microemulsions according to the invention show excellent cleaning performance, in particular in the case of polymer-based soiling.
  • the microemulsions according to the invention are suitable for removing organic pyrolysis products.
  • the microemulsions according to the invention are used for cleaning ovens, chimney panes or a grill.
  • Rape methyl ester is an ester oil from Overlack.
  • Octyloctanoate (octanoic acid octyl ester) is an ester oil from Sigma Aldrich.
  • Oleic acid ethyl ester from Sigma Aldrich.
  • Di Basic Ester Mixture of dimethyl succinate (33% by weight), dimethyl adipate (33% by weight), dimethyl glutarate (33% by weight) and methanol (0.2% by weight) from Caldic.
  • Tween 21 is a polyoxyethylene (4) sorbitan monolaurate from Sigma Aldrich, drug content 100%.
  • Tween 40 is a polyoxyethylene (20) sorbitan monopalmitate from Sigma Aldrich, drug content 100%.
  • Tween 80 is a polyoxyethylene (20) sorbitan monooleate from Sigma Aldrich, drug content 100%.
  • Emulan EL is an ethoxylated castor oil from BASF, active ingredient content 100%; HLB: 14.
  • Brij S100-PA- (SG) is a PEG-100 stearyl ether from Croda, drug content 100%.
  • Novel TDA-40 is a PEG-40 isotridecyl ether from Sasol, drug content 100%.
  • Novel 2426-100 is a PEG C 20-28 alkyl ether from Sasol with about 100 EO units, active ingredient content 100%; HLB: 18.3.
  • Emuldac AS-80 is a PEG 80 C 16-18 alkyl ether from Sasol, active ingredient content 100%.
  • Potassium sodium tartrate 4 hydrate trisodium citrate 2 hydrate, disodium hydrogen phosphate 2 hydrate, sodium gluconate (free of water of crystallization), calcium chloride (free of water of crystallization), sodium chloride (free of water of crystallization).
  • the temperature stability of the microemulsions was determined in a thermostated vessel by visual inspection.
  • the temperature phase boundaries of the single-phase microemulsion region were recognized due to the drastically increasing turbidity when the stability window was exceeded or not reached.
  • Lamellar phases were determined by crossed polarizers. In the ranges of stability given for the examples, microemulsions can coexist with lamellar phases.
  • the total surfactant contents relate to the active substance proportions of the surfactant components and of the booster. All percentages are based on the weight of the ingredients.
  • cleaners were tested for the ability to clean other materials. These tests were performed with acrylic sealant, building silicone and adhesive on stainless steel plates.
  • Examples 2 and 5 in WO 2008/132202 were used for comparative experiments.
  • the oil component Hydroseal G232H in Example 2 and Ketrul D85 in Ex. 5
  • the carboxylic acid ester rapeseed methyl ester RME
  • the mass ratio of the two surfactant components was varied around the values given in the examples. This was intended to capture the optimum temperature stability range for the microemulsions.
  • Example 2 from WO 2008/132202 has the following composition (all figures in% by weight): water 46.45 Hydroseal G 232 H 42.38 AG 6210 5.39 Span 20 4.88 Brij 700 0.90
  • the mixture can be characterized from the surfactant side as follows.
  • the surfactant components are AG 6210 (active content 60% by weight, the remainder is water), Span 20 (active content 100% by weight) and Brij 700 (active content 100% by weight). All other details relate to the active contents of the surfactants.
  • the total surfactant content in the above example is 9.0%.
  • the mass fraction of polymeric booster (Brij 700) in the total surfactant mixture is 10.0%.
  • Mass fraction booster m Brij 700 m Active salary AG 6210 + m chip 20 + m Brij 700
  • the stability range of the microemulsion phase is 0 to 52 ° C.
  • Table 1 shows the stability ranges of the microemulsions as a function of the total surfactant content and of delta.
  • the compositions of the individual mixtures are listed in Table 3.
  • Comparative Examples 1 to 15 show that when the hydrocarbon oil is replaced by ester oil, microemulsion phases develop only at total surfactant concentrations above 16%. Apart from the fairly high temperatures at which the microemulsion phases occur, the temperature windows are also quite narrow.
  • Example 5 from WO 2008/132202 has the following composition (all figures in% by weight): water 43.84 Ketrul D85 48.41 AG 6210 3.94 Imwitor 928 3.22 C12E190 0.59
  • the mixture can be characterized from the surfactant side as follows.
  • the surfactant components are AG 6210 (active content 60% by weight, the remainder is water), Imwitor 928 (active content 100% by weight) and C12E190 (active content 100% by weight). All other details relate to the active contents of the surfactants.
  • the total surfactant content in the above example is 6.2%.
  • Mass fraction booster m C 12 e 190 m Active salary AG 6210 + m Imwitor 928 + m C 12 e 190
  • the stability range of the microemulsion phase is 15 to 75 ° C.
  • Example 5 WO 2008/132202 The oil component Ketrul D85 replaced by RME, can not produce a microemulsion phase.
  • the surfactant mixture is not efficient enough to emulsify all water and oil as a microemulsion. Therefore, the total surfactant content in Comparative Examples was increased to about 28%.
  • Table 2 shows the stability ranges of the microemulsions as a function of the total surfactant content and of delta.
  • the compositions of the individual mixtures are listed in Tables 4a-e.
  • Comparative Examples 16 to 38 show that when the hydrocarbon oil is replaced by ester oil, microemulsion phases only form at total surfactant concentrations of about 15%. Apart from the fairly high temperatures at which the microemulsion phases occur, the temperature windows are also quite narrow.
  • composition of microemulsion mixtures in% by mass Composition of microemulsion mixtures in% by mass
  • the information refers to the 60% aqueous solution.
  • the active content is 100%.
  • the mass ratio of water to RME was kept constant for reasons of systematics for the comparative examples 1 to 15 (Tables 3a-c) and 16 to 38 (Tables 4a-e).
  • the water content is composed of the water specified in the tables and the water content of AG 6210. Smaller deviations between the examples are of negligible importance for the phase behavior of the mixtures.
  • Table 3a Comp. 1 Comp. 2 Comp. 3 Comp. 4 Comp. 5 water 31.94 31.54 30.41 30.12 29,69 RME 32.61 32.64 32,70 32.35 32.12 AG 6210 13.39 15.58 17.58 20,06 22.09 Span 20 19.10 17.29 16.36 14.55 13,20 Brij 700 2.96 2.95 2.95 2.92 2.90
  • Table 3b Comp. 6 Comp. 7 Comp. 8th Comp. 9 Comp. 10 water 35,11 34.77 33,60 32,95 32.19 RME 35.13 35.07 35.36 35.25 35.26 AG 6210 11.24 13.12 14.79 17.00 18.83 Span 20 16.04 14.56 13.77 12.33 11.25 Brij 700 2.48 2.48 2.48 2.47 2.47 Table 3c: Comp. 11 Comp.
  • Table 4a Comp. 16 Comp. 17 Comp. 18 Comp. 19 Comp. 20 water 29.94 29.08 28:19 28.06 27.63 RME 36.75 36.84 36.85 36.74 36.77 AG 6210 11,95 13.88 15.96 16.96 17,98 Imwitor 928 18.63 17.49 16.28 15.51 14,92 Brij 700 2.73 2.71 2.74 2.73 2.70
  • Table 4b Comp. 21 Comp. 22 Comp. 23 Comp. 24 Comp. 25 water 27.29 34.03 33.37 32.69 32.75 RME 36.47 39.49 39.91 39.64 39.36 AG 6210 19.72 9.50 10.82 12.60 13.42 Imwitor 928 13.87 14.81 13.72 12.92 12.26 Brij 700 2.65 2.17 2.18 2.15 2.21 Table 4c: Comp.

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Claims (16)

  1. Microémulsion aqueuse, comprenant :
    a) un ou plusieurs esters d'acide carboxylique liquides pour former un composant huileux,
    b) un ou plusieurs sels hydrosolubles avec un ou plusieurs cations, de préférence choisis dans le groupe consistant en sodium, potassium, calcium, magnésium et ammonium,
    c) un ou plusieurs sels d'esters d'acide sulfosuccinique,
    d) un ou plusieurs tensioactifs non ioniques choisis parmi un ester de sorbitan alcoxylé et une huile végétale alcoxylée, et
    e) un ou plusieurs boosters sous forme d'un additif polymérique hydrophile, consistant en une unité hydrosoluble ayant un groupe hydrophobe insoluble dans l'eau ayant un poids moléculaire de 80 à 500 g/mol en au moins une extrémité de chaîne, et le rapport des masses molaires entre l'unité hydrosoluble et les groupes hydrophobes insolubles dans l'eau est de 7 à 200, ou
    ledit booster est un éthoxylate d'alcool provenant d'un alcool en C8 à C20 avec 25 à 500 groupes éthoxy.
  2. Microémulsion aqueuse selon la revendication 1, caractérisée en ce que l'ester d'acide carboxylique liquide présente de 6 à 22, de préférence de 10 à 22, atomes de carbone.
  3. Microémulsion aqueuse selon la revendication 1 ou 2, caractérisée en ce que l'ester d'acide carboxylique liquide est choisi dans le groupe consistant en esters d'alcool monohydrique et d'acide mono- ou dicarboxylique, et esters d'alcool dihydrique et d'acide monocarboxylique, de préférence encore des esters d'alcools monohydriques avec des acides monocarboxyliques, et notamment ledit ester d'acide carboxylique liquide est un ester d'un acide monocarboxylique en C10 à C22 et méthanol, de préférence l'ester méthylique d'acide dodécanoïque, ou l'ester méthylique d'huile de colza.
  4. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que l'ester d'acide carboxylique liquide est présent dans une quantité de 10 à 40 % en poids, de préférence de 20 à 35 % en poids, respectivement par rapport au poids total de la microémulsion.
  5. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que le rapport pondéral de l'ester d'acide carboxylique liquide (composant a)) à la somme des composants (c), (d) et (e) est de 1,5 à 10, de préférence de 2,5 à 8, notamment de 3 à 8, ou de 4 à 8.
  6. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit sel d'esters d'acide sulfosuccinique est choisi dans le groupe consistant en diesters d'un sel alcalin de l'acide sulfosuccinique avec des alcools en C6 à C10, monoesters d'un sel dialcalin de l'acide sulfosuccinique avec des alcools en C8 à C12, et monoesters d'un sel dialcalin de l'acide sulfosuccinique avec des alcools C10 à C14 éthoxylés, et notamment ledit sel d'esters d'acide sulfosuccinique est le sel de sodium du sulfosuccinate de di-2-éthylhexyle.
  7. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit sel d'esters d'acide sulfosuccinique est présent dans une quantité de 1 à 10 % en poids, de préférence dans une quantité de 2 à 5 % en poids, respectivement par rapport au poids total de la microémulsion.
  8. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit sel d'esters d'acide sulfosuccinique est présent dans une quantité de 30 à 75 % en poids, de préférence dans une quantité de 40 à 70 % en poids, respectivement par rapport à la somme des composants (c), (d) et (e).
  9. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit tensioactif non ionique est choisi parmi un ester de sorbitan éthoxylé et/ou une huile végétale éthoxylée, de préférence ledit tensioactif non ionique est un monoester de sorbitan éthoxylé avec un résidu d'acide gras en C12 à C18 saturé ou non saturé, ou de l'huile de ricin éthoxylée, et notamment ledit tensioactif non ionique est un ester de sorbitan éthoxylé et/ou une huile végétale éthoxylée ayant une valeur HLB de 11 à 17, de préférence de 12 à 16, ou de 13 à 16.
  10. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit booster est un éthoxylate d'alcool provenant d'un alcool en C8 à C20 avec 50 à 200 groupes éthoxy.
  11. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit booster est présent dans une quantité de 3 à 20 % en poids, de préférence de 5 à 15 % en poids, notamment de 7 à 15 % en poids, respectivement par rapport au poids total des composants (c), (d) et (e).
  12. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que ledit sel est choisi dans le groupe consistant en sulfate de sodium, chlorure de sodium, gluconate de sodium, citrate de sodium, phosphate de trisodium, hydrogénophosphate de sodium, sulfate de potassium, chlorure de potassium, sulfate d'ammonium, chlorure d'ammonium, sulfate de magnésium, chlorure de magnésium, chlorure de calcium, acétate de calcium et acétate de magnésium, de préférence ledit sel est un acétate, notamment l'acétate de calcium et/ou l'acétate de magnésium.
  13. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que la somme des composants (c), (d) et (e) est présente dans une quantité de 2 à 20 % en poids, de préférence de 3 à 15 % en poids, de préférence encore de 3 à 10 % en poids, et notamment de 3 à 8 % en poids, ou de 4 à 8 % en poids, respectivement par rapport au poids total de la microémulsion.
  14. Microémulsion aqueuse selon l'une ou plusieurs des revendications précédentes, caractérisée en ce que la microémulsion se présente comme microémulsion bicontinue.
  15. Utilisation de la microémulsion selon l'une ou plusieurs des revendications précédentes
    comme détergent, notamment pour éliminer des taches huileuses, ou
    pour nettoyer et/ou éliminer des composés choisis dans le groupe consistant en peintures, vernis, graisses, huiles, résines, bitume, goudron, résidus de colle, matériaux d'étanchéité, traces de gomme, résidus de cosmétiques et débris de maquillage, et des produits de pyrolyse de composés organiques, notamment pour nettoyer et/ou éliminer des taches dont les composants organiques sont basés sur des polymères, par exemple, peintures, adhésifs, compositions d'étanchéité, mousses polymères, ou
    pour nettoyer des outils contaminés avec des résidus de peintures, notamment des outils pour appliquer des peintures, par exemple, pinceaux, rouleaux à peinture, ou pistolets de peinture, ou
    pour nettoyer des fours, des vitres cheminée, ou un barbecue.
  16. Procédé de nettoyage, comprenant les étapes consistant à
    a) appliquer une microémulsion selon l'une ou plusieurs des revendications précédentes sur une surface contaminée,
    b) éventuellement faire agir la microémulsion, et
    c) éliminer la contamination.
EP13710857.7A 2012-03-20 2013-03-20 Produit de nettoyage à base de microémulsion Not-in-force EP2828370B1 (fr)

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US20150045278A1 (en) 2015-02-12
JP2015510964A (ja) 2015-04-13
US9150823B2 (en) 2015-10-06
CN104220579A (zh) 2014-12-17
EP2828370A1 (fr) 2015-01-28
WO2013139842A1 (fr) 2013-09-26
DE102012204378A1 (de) 2013-09-26

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