EP2828419B1 - Formulation aqueuse, agent de surface, anti-corrosive ainsi qu' une émulsion concentrée oléagineuse miscible avec l'eau - Google Patents

Formulation aqueuse, agent de surface, anti-corrosive ainsi qu' une émulsion concentrée oléagineuse miscible avec l'eau Download PDF

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Publication number
EP2828419B1
EP2828419B1 EP13709100.5A EP13709100A EP2828419B1 EP 2828419 B1 EP2828419 B1 EP 2828419B1 EP 13709100 A EP13709100 A EP 13709100A EP 2828419 B1 EP2828419 B1 EP 2828419B1
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Prior art keywords
carbon atoms
corrosion protection
protection system
component
corrosion
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EP13709100.5A
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German (de)
English (en)
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EP2828419A1 (fr
Inventor
Andreas Temme
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL13709100T priority Critical patent/PL2828419T3/pl
Publication of EP2828419A1 publication Critical patent/EP2828419A1/fr
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • 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
    • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
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    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the corrosion protection system comprises carboxylic and / or phosphonic acids and at least one amine having at least one oxybis (alkylamine) unit.
  • Such anticorrosive systems effectively protect metal surfaces from corrosion and have high water solubility, which is indispensable for the formulation of aqueous concentrates for metalworking and metalworking fluids.
  • the present invention relates to an aqueous surface-active and corrosion-protective preparation comprising the corrosion protection system and an emulsifier system and an oily, water-miscible emulsion concentrate which, when diluted with water, provides ready-to-use corrosion protection, cleaning and cooling lubricant emulsions.
  • corrosion-prone metals such as iron, aluminum, zinc, copper or their alloys against corrosion
  • a permanent corrosion-protective coating such as a paint due to their processing condition or because of their field of application.
  • Examples include metal parts during technical processing stages such as machining or non-cutting shaping or cleaning and finished metal components such as heat exchangers or pipelines, which come into contact during their function with corrosive aqueous media.
  • the metal surfaces are brought into contact with corrosion inhibitors, which cause a temporary corrosion protection.
  • Inorganic corrosion inhibitors may be based, for example, on chromates, nitrites or phosphates, but these are more or less disadvantageous for toxicological and ecological reasons.
  • Organic corrosion inhibitors are often based on carboxylates, amines, amides or on nitrogen-containing heterocyclic compounds.
  • Carboxylic acids as such prove in practice to be insufficiently long-term effective if the pH is lowered by an acid entry into the inhibitor baths or by microbiological processes to such an extent that the carboxylic acids are present in the less active acid form instead of in the salt form.
  • Corrosion-inhibiting carboxylic acids are therefore often used in the form of their salts or as a corrosion protection system consisting of the carboxylic acid and a base.
  • Particularly well-known in the art are corrosion protection systems consisting of carboxylic acids and alkanolamines, which have an increased inhibitory effect compared to systems of carboxylic acid and alkalis based on sodium hydroxide solution or ammonia.
  • the DE 102007004325 describes an emulsifier system for the production of coolant emulsions suitable for use in the machining of light metals or aluminum alloyed metals.
  • the emulsifier system comprises a corrosion protection system consisting of light metal inhibitors such as carboxylic acids and phosphonic acids, which in addition to avoid the so-called fountain blacks contains chelating tertiary organic amine compounds having phosphonic acid groups.
  • the corrosion protection system contains alkanolamines, preferably mono- and trialkanolamines, as bases for providing particularly effective inhibiting carboxylic and phosphonic acid salts.
  • the DE 4444878 discloses a water-soluble inhibitor system based on monocarboxylic acids and aromatic hydroxy compounds with a pK s value for the Hydroxy group in the range of 7.0 to 11, wherein both components are in a certain weight ratio to each other.
  • the JP2005015617 discloses an aqueous anticorrosion composition for metalworking comprising an aliphatic carboxylic acid in combination with an amine, preferably bis (2-dimethylaminoethyl) ether or N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) , contains.
  • the DE 19747895 discloses a corrosion protection system for the neutral pH range based on a combination of one or more carboxylic acids and one or several nitrogen compounds selected from organic amines or nitrogen-containing heterocycles, wherein the nitrogen compounds have a pK a value for at least one protolysis stage is in the range 6-9 , wherein both components are in a certain weight ratio to each other.
  • Preferred nitrogen compounds may for example be selected from linear or cyclic alkylenediamines, alkylene triamines and alkylene tetraamines.
  • the object of the present invention is to provide an aqueous surface-active and corrosion-protective preparation suitable for the production of aqueous metal treatment and metalworking fluids, in particular cleaners and lubricants, that metals, in particular iron and iron alloys, in comparison with the prior art in contact with the Treatment and processing fluid more effectively protects against corrosion.
  • an aqueous surface-active and corrosion-protective preparation according to the present claim 1.
  • the inventive aqueous surface-active and corrosion-protective preparation provides excellent protection against corrosion of iron and iron alloys and of aluminum and Aluminum alloys in contact with aqueous liquids, in particular liquids for metal treatment or metalworking.
  • the corrosion protection system (I) is characterized by its good water solubility, which makes it possible to distribute the corrosion protection system in the form of highly concentrated aqueous preparations.
  • Each preparation for example a ready-to-use metal treatment or metalworking fluid or its concentrate, which contains the two components a) and b), thus comprises the corrosion protection system (I).
  • a solution of the anticorrosive system is formulated into a metalworking or metalworking fluid to impart the desired anticorrosive properties.
  • corrosion protection systems which store the components a) and b) in an aqueous phase are therefore preferred.
  • At least one amine of the following structural formula (1) is contained: wherein the radicals R 1 , R 2 , R 3 and R 4 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms and - ((CH 2 ) o -X) p -R 5 , where o is a natural whole Number in the range of 1 to 3, p is a natural integer in the range of 1 to 6, X is either an oxygen or a nitrogen atom, and R 5 is selected from hydrogen, methyl, ethyl or propyl; with m and n as natural integers in the range of 1 to 3.
  • radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) may be selected from those containing the two nitrogen atoms of the oxybis (alkylamine) moiety bridge, so that the radical R 1 and / or the radical R 2 are each structurally identical to the radical R 3 or R 4 , wherein bridging radicals R 1 or R 2 or R 3 or R 4 are selected from alkylene, polyoxyalkylenes or polyaminoalkylenes with not more than 6 carbon atoms.
  • Such a preferred bridged amine in a corrosion protection system (I) has the following general structural formula (1a): wherein the radicals R 1 and R 2 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms and - ((CH 2 ) o -X) p -R 5 , where o is a natural integer in the range of 1 to 3, p is a natural integer in the range of 1 to 6, X is either an oxygen or a nitrogen atom, and R 5 is selected from hydrogen, methyl, ethyl or propyl; with m and n as natural integers in the range of 1 to 3; and wherein q, r and s are integer numbers in the range of 1 to 3 and Z is either a carbon, oxygen or nitrogen atom.
  • amines of the structural formula (1a) for which the radicals R 1 and R 2 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms, preferably not more than 4 carbon atoms, for the m, n, q and r is 2, and s is not greater than 3, where Z is an oxygen or nitrogen atom.
  • bridged amines are N, N'-dimethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-diethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-dimethyl 1,4,10-trioxa-7,13-diazacyclopentadecane and N, N'-diethyl-1,4,10-trioxa-7,13-diazacyclopentadecane.
  • the radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) are independently selected from branched or unbranched alkyl radicals with no more as 8 carbon atoms, more preferably not more than 4 carbon atoms, wherein the natural integers m and n are equal to 2.
  • the radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) are independently selected from branched or unbranched alkyl radicals with no more as 8 carbon atoms, more preferably not more than 4 carbon atoms, wherein the natural integers m and n are equal to 2.
  • a preferred corrosion protection system (I) contains at least 50% by weight, more preferably at least 80% by weight, only those organic amines according to component b) which are selected from amines of the general structural formula (1) according to component b) , particularly preferably from such amines of general structural formula (1) according to component b), for which the radicals R 1 , R 2 , R 3 and R 4 are independently selected from branched or unbranched alkyl radicals having not more than 4 carbon atom, wherein the natural integers m and n are 2, and more preferably are selected from N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) and / or N, N, N', N '-Tetraethyl-2,2'-oxybis (ethylamine).
  • the aliphatic carboxylic acids according to component a) of the corrosion protection system (I) having at least 6 but not more than 14 carbon atoms can be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic carboxylic acids, but are preferably selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.
  • carboxylic acids according to component a) with inserted into the carbon chain oxygen heteroatoms are preferably selected ether carboxylic acids of the general formula R- (OC 2 H 4 ) n -OCH 2 COOH, where R is a linear or branched, saturated or unsaturated alkyl radical having 6 to Is 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are to be matched to one another such that the sum of the carbon and oxygen atoms is not greater than 25, neglecting the carboxyl group.
  • the ether carboxylic acids may be technical mixtures of molecules with different radicals R and different values for n. An example of this is the technical Laurylethercarbonklare, in which R for is a mixture of linear, saturated alkyl groups having 12 and 14 carbon atoms and n is about 2.5.
  • the aliphatic phosphonic acids having at least 4 but not more than 18 carbon atoms contained in the corrosion protection system (I) according to component a) may be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic phosphonic acids, but are preferably selected from saturated straight-chain or linear branched monophosphonic acids. Mixtures of different acids may be particularly advantageous, the alkyl monophosphonic acids are particularly suitable in their straight-chain form. Further preferred are alkyl monophosphonic acids having 6 to 12 carbon atoms.
  • carboxylic acids as component a) is always preferable for ecological reasons, if the use of phosphonic acids is not able to significantly improve the temporary corrosion protection in metal treatment or metalworking.
  • component a) is therefore selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, and / or carboxylic acids with into the carbon chain inserted oxygen heteroatoms having between 6 and 26 atoms in the carbon heteroatom chain, in particular ether carboxylic acids of the general formula R- (OC 2 H 4 ) n -OCH 2 COOH, wherein R is a linear or branched, saturated or unsaturated alkyl radical 6 to 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are coordinated so that the sum of the C and O atoms is neglecting the carboxyl group is not greater than 25.
  • component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.
  • the weight-based proportion of carboxylic acids according to component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular the weight-related proportion of caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, on the total amount of carboxylic acids and phosphonic acids in the corrosion protection system, including those carboxylic acids and phosphonic acids which are not compounds according to component a), at least 50 wt .-%, particularly preferably at least 80 wt .-% is.
  • components a) and b) of the corrosion protection system (I) can undergo acid-base reactions with one another and, in aqueous solution, also have a protolysis equilibrium with their respective deprotonated or protonated form.
  • the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not less than 1: 3 in order to ensure a minimum amount of the amine according to component b) is present in the corrosion protection system as ammonium salt.
  • this molar ratio is not less than 2: 3.
  • the total amount of carboxyl and / or phosphonic acid groups of components a) relative to the proportion of amines according to component b) should not exceed values for which the effectiveness of the corrosion protection is clearly evident decreases.
  • the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not greater than 5: 1, more preferably not greater than 3: 1, particularly preferably not greater than 2: 1.
  • the corrosion protection system (I) is suitable to be used in aqueous emulsions, especially in cleaning, anticorrosion and cooling lubricant emulsions, to prevent metal corrosion.
  • An advantage of using a corrosion protection system based on components a) and b) is that for a sufficient corrosion protection, a comparatively small amount of these two active components must be present in the aqueous metal working and metal treatment system.
  • the emulsifier system (II) of the aqueous surface-active and anti-corrosive preparation according to the invention additionally comprises alkoxylated fatty amines as component e) to improve the filterability of emulsions prepared from these preparations.
  • alkoxylated fatty amines consisting of one or more alkoxylated saturated and / or unsaturated aliphatic amines having an aliphatic chain length of at least 8, preferably at least 10 and more preferably at least 12, but not more than 20, preferably not more than 18 and most preferably not used more than 16 carbon atoms.
  • the fatty amines used should be ethoxylated with at least 8, preferably not more than 10, but not more than 16, preferably not more than 14 and most preferably 12 ethylene oxide units. In particular, is suitable for increasing the Filterability of ready-to-use emulsions 12 times ethoxylated cocoamine prepared from these formulations.
  • the proportion of components a) to e) of the preparation according to the invention for an application-ready anticorrosive cleaner solution is preferably in the range from 0.5 to 10% by weight, the total proportion of components a) and b) of the anticorrosion system (I) preferably being at least 0.1 wt .-% is.
  • the preparation according to the invention can also be a concentrate for the production of anticorrosion cleaner solutions in which the proportion of components a) to e) is preferably in the range from 40 to 95% by weight, the total amount of components a) and b) being of the corrosion protection system (I) in the preparation according to the invention is preferably at least 10 wt .-%.
  • the aqueous surface-active and corrosion-protective preparation may additionally be admixed with a water component of not more than 60% by weight, so that a total of one oil-containing, water-miscible emulsion concentrate for metalworking, in particular a concentrate for a coolant lubricant or anticorrosion emulsion, realized.
  • the corrosion protection system (I) and the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention are identical to those described for the corrosion protection system and the aqueous surface-active and corrosion-protective preparation according to the invention.
  • the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention as described above for the aqueous surface-active and anti-corrosive preparation, alkoxylated fatty amines as component e), preferably with a weight fraction in the concentrate of at least 1 wt .-%, more preferably at least 2 wt .-%, but preferably not more than 10 wt .-%, particularly preferably not more than 8 wt .-%.
  • the oil component (III) of the oily, water-miscible emulsion concentrate according to the invention is preferably selected from paraffinic or naphthenic mineral oils, dialkyl ethers having 12 to 20 carbon atoms and / or ester oils.
  • auxiliaries or active ingredients may be mentioned: lubricating additives in general and in particular so-called “extreme pressure” additives (so-called EP additives) and biocides in each case in an amount of preferably 0.1 to 2 wt .-% in the concentrate; Buffer systems, in particular based on boric acid, in an amount based on the particular acid form of preferably 2 to 10 wt .-% in the concentrate; Neutralizing agent based on alkanolamines, solubilizers such as glycols, glycerol or sodium cumenesulfonate each in an amount of preferably 1 to 6 wt .-% in the concentrate.
  • so-called "extreme pressure" additives so-called EP additives
  • biocides in each case in an amount of preferably 0.1 to 2 wt .-% in the concentrate
  • Buffer systems in particular based on boric acid, in an amount based on the particular acid form of preferably 2 to 10 wt .-% in the
  • the invention relates to the ready-to-use oil-in-water emulsion which is obtainable by adding from about 0.5 to about 10 parts by weight of the above-described oily, water-miscible concentrate with about 99.5 to about 90 parts by weight of water. Due to the self-emulsifying properties of the emulsion concentrate, the ready-to-use emulsion forms spontaneously upon addition of water or after slight mechanical agitation such as stirring. This emulsion can be used for example as a cleaning, corrosion protection or cooling lubricant emulsion.
  • oil-containing, water-miscible emulsion concentrate according to the invention and the ready-to-use oil-in-water emulsions preparable therefrom by dilution with water are particularly suitable for the treatment and processing of iron and iron alloys and of aluminum and aluminum alloys.
  • the mode of action of the corrosion protection system (I) is shown by way of example and compared with systems known in the prior art.
  • a corrosion protection test according to DIN 51360-2 is carried out in which gray cast iron chips (type GG25) are wetted on a round filter with freshly prepared dilute aqueous solutions containing various corrosion protection systems based on an amine and isononanoic acid.
  • Table 1 lists the compositions of concentrated aqueous corrosion protection systems (stock solutions) based on an amine and isononanoic acid.
  • stock solutions of the corrosion protection systems with an active component content of 20% by weight in water with a hardness of 20 ° dH (3.04 mmol CaCl 2 , 0.54 mmol MgSO 4 )
  • Amine component Wt .-% carboxylic acid
  • V2 triethanolamine 9.71 isononanoic 10.29 V3 N, N, N ', N'-tetramethyl-1,6-hexamethylenediamine 10.43 isononanoic 9.57
  • Table 2 shows the degree of rust formation as a function of the active content of the solutions based on the assessment of the corrosion marks on the filter paper after 2 hours exposure of the chips at 20 ° C.
  • the corrosion protection system (I) containing the amine with a Oxybis (alkylamine) unit already shows a significant corrosion protection effect from a weight fraction of 6% based on the stock solution B1. At a weight fraction of at least 7% based on the stock solution B1, only slight corrosion phenomena on the filter paper are detectable, while for the other corrosion protection systems a moderate (V3) to further strong (V1, V2) corrosion can be observed.
  • the corrosion protection system (B1) containing the amine with the oxybis (alkylamine) unit is also superior to the corrosion protection system (V3) containing the hexamethylene-bridged tertiary diamine.

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Claims (8)

  1. Préparation aqueuse tensio-active et anti-corrosion contenant, outre de l'eau
    i) un système anti-corrosion (I) comprenant
    a) des acides carboxyliques aliphatiques ayant au moins 6, mais au maximum 14 atomes de carbone et/ou des acides carboxyliques ayant des hétéro-atomes d'oxygène insérés dans la chaîne carbone, qui présentent entre 6 et 26 atomes dans la chaîne d'hétéro-atomes carbone, et/ou des acides phosphoniques aliphatiques ayant au moins 4, mais au maximum 18 atomes de carbone,
    b) au moins une amine qui présente au moins une unité d'oxybis(alkylamine) ayant des groupes amino tertiaires, dans laquelle les chaînes alkyle de cette unité sont constituées chacune d'au maximum 4 atomes de carbone, dans lequel le rapport molaire de la quantité totale de groupes d'acides carboxyliques et/ou d'acides phosphoniques des constituants a) aux unités oxybis(alkylamine) de ladite amine du constituant b) n'est pas supérieur à 5 : 1, mais au minimum égal à 1 : 3,
    ii) un système émulsifiant (II) constitué
    c) d'éthoxylates/de propoxylates d'alcools gras ayant de 8 à 18 atomes de carbone dans l'alcool, avec de 2 à 6 unités d'oxyde d'éthylène et de 4 à 8 unités oxyde de propylène et
    d) d'alcools gras et/ou des propoxylates d'alcools gras ayant de 12 à 24 atomes de carbone dans l'alcool et de 0 à 3 unités d'oxyde de propylène et/ou du résidu de distillation de ces alcools gras.
  2. Préparation selon la revendication 1, caractérisée en ce que le rapport molaire de la quantité totale de groupes d'acides carboxyliques et/ou d'acides phosphoniques des constituants a) aux unités oxybis(alkylamine) de ladite amine du constituant b) du système anti-corrosion (I) n'est pas supérieur à 3 : 1, mais au minimum égal à 2 : 3.
  3. Préparation selon l'une quelconque des revendications précédentes ou les deux revendications précédentes, caractérisée en ce qu'elle contient en tant que constituant b) du système anti-corrosion (I) au moins une amine de formule structurelle (1) suivante :
    Figure imgb0005
     dans laquelle les radicaux R1, R2, R3 et R4 sont choisis, indépendamment les uns des autres, parmi des radicaux alkyle ramifiés ou non-ramifiés ayant au maximum 8 atomes de carbone et -((CH2)x-O)y-R5, où x est un nombre entier naturel dans la plage allant de 1 à 3, y est un nombre entier naturel dans la plage allant de 1 à 6 et le radical R5 est choisi parmi l'hydrogène, le méthyle, l'éthyle ou le propyle ;
    et/ou dans laquelle les radicaux R1, R2, R3 et R4 sont choisis parmi les radicaux qui relient les deux atomes d'azote de l'unité d'oxybis(alkylamine), de sorte que le radical R1 et/ou le radical R2 sont chacun de structure identique au radical R3 ou R4, lesdits radicaux de liaison R1 ou R2 et R3 ou R4 sont choisis parmi les alkylènes, les polyoxyalkylènes ou les polyaminoalkylènes ayant au maximum 6 atomes de carbone ; m et n étant des nombres entiers naturels dans la plage allant de 1 à 3.
  4. Préparation selon la revendication 3, caractérisée en ce qu'elle contient en tant que constituant b) du système anti-corrosion (I) au moins une amine de formule structurelle (1), dans laquelle les radicaux R1, R2, R3 et R4 sont choisis, indépendamment les uns des autres, parmi les radicaux alkyle ramifiés ou non-ramifiés ayant au maximum 8, de préférence au maximum 4 atomes de carbone, et dans laquelle les nombres entiers naturels m et n sont égaux à 2.
  5. Préparation selon une ou plusieurs des revendications précédentes, caractérisée en ce que les amines du constituant b) du système anti-corrosion (I) représentent au moins 50 % en poids, de préférence au moins 80 % en poids, par rapport à la quantité totale d'amines du constituant b) du système anti-corrosion (I) et sont choisies parmi les amines de formule structurelle (I) selon l'une quelconque des revendications 3 ou 4.
  6. Préparation selon une ou plusieurs des revendications précédentes, caractérisée en ce que le constituant a) du système anti-corrosion (I) est choisi parmi les acides monocarboxyliques aliphatiques ramifiés ou non-ramifiés, lesquels sont de préférence choisis parmi l'acide caprylique, l'acide éthylhexanoïque, l'acide isononanoïque et l'acide isodécanoïque.
  7. Concentré en émulsion huileux hydrophile contenant
    i) de 2 à 20 % en poids d'un système anti-corrosion (I), comprenant
    a) des acides carboxyliques aliphatiques ayant au moins 6, mais au maximum 14 atomes de carbone et/ou des acides carboxyliques ayant des hétéro-atomes d'oxygène insérés dans la chaîne carbone, qui présentent entre 6 et 26 atomes dans la chaîne d'hétéro-atomes carbone, et/ou des acides phosphoniques aliphatiques ayant au moins 4, mais au maximum 18 atomes de carbone,
    b) au moins une amine qui présente au moins une unité d'oxybis(alkylamine) ayant des groupes amino tertiaires, dans laquelle les chaînes alkyle de cette unité sont constituées chacune d'au maximum 4 atomes de carbone, dans lequel le rapport en poids des constituants a) et b) peut varier de 1 : 0,2 à 0,3 : 1
    ii) de 2 à 50 % en poids d'un système émulsifiant (II) constitué
    c) d'éthoxylates/de propoxylates d'alcools gras ayant de 8 à 18 atomes de carbone dans l'alcool, avec de 2 à 6 unités d'oxyde d'éthylène et de 4 à 8 unités d'oxyde de propylène et
    d) d'alcools gras et/ou de propoxylates d'alcools gras ayant de 12 à 24 atomes de carbone dans l'alcool et de 0 à 3 unités d'oxyde de propylène et/ou du résidu de distillation de ces alcools gras, dans lequel le rapport en poids des constituants c) et d) peut varier de 1 : 0,3 à 0,3 : 1, et
    iii) de 5 à 50 en % poids d'un constituant huileux (III), et éventuellement d'autres adjuvants et substances actives (IV), dans lequel la somme des éléments I) à IV) équivaut à 60 à 95 % en poids, le pourcentage en poids restant représentant de l'eau.
  8. Concentré en émulsion huileux hydrophile selon la revendication 7, caractérisé en ce qu'on utilise, en tant que constituant huileux (III), de l'huile minérale paraffinique ou naphténique, de l'éther de dialkyle ayant de 12 à 20 atomes de carbone et/ou des huiles d'esters.
EP13709100.5A 2012-03-23 2013-03-13 Formulation aqueuse, agent de surface, anti-corrosive ainsi qu' une émulsion concentrée oléagineuse miscible avec l'eau Active EP2828419B1 (fr)

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