EP1652909B2 - Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use. - Google Patents

Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use. Download PDF

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Publication number
EP1652909B2
EP1652909B2 EP04024857A EP04024857A EP1652909B2 EP 1652909 B2 EP1652909 B2 EP 1652909B2 EP 04024857 A EP04024857 A EP 04024857A EP 04024857 A EP04024857 A EP 04024857A EP 1652909 B2 EP1652909 B2 EP 1652909B2
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EP
European Patent Office
Prior art keywords
weight
fatty acid
acid
concentrate
corrosion
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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Application number
EP04024857A
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German (de)
French (fr)
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EP1652909A1 (en
EP1652909B1 (en
Inventor
Helmut Theunissen
Sabine Theunissen
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Individual
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Individual
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Application filed by Individual filed Critical Individual
Priority to DE502004006426T priority Critical patent/DE502004006426D1/en
Priority to SI200430722T priority patent/SI1652909T2/en
Priority to PL04024857T priority patent/PL1652909T5/en
Priority to EP04024857A priority patent/EP1652909B2/en
Priority to ES04024857T priority patent/ES2304575T5/en
Priority to DK04024857.7T priority patent/DK1652909T4/en
Priority to PT04024857T priority patent/PT1652909E/en
Priority to AT04024857T priority patent/ATE388218T1/en
Priority to PCT/EP2005/011149 priority patent/WO2006042730A1/en
Priority to MX2007004705A priority patent/MX2007004705A/en
Priority to US11/665,160 priority patent/US7851420B2/en
Priority to AU2005296748A priority patent/AU2005296748B2/en
Priority to CN2005800358063A priority patent/CN101044230B/en
Priority to RU2007118665/04A priority patent/RU2397275C2/en
Priority to ARP050104363A priority patent/AR055503A1/en
Publication of EP1652909A1 publication Critical patent/EP1652909A1/en
Priority to HK06111658A priority patent/HK1089786A1/en
Priority to ZA200701941A priority patent/ZA200701941B/en
Publication of EP1652909B1 publication Critical patent/EP1652909B1/en
Application granted granted Critical
Priority to HR20080237T priority patent/HRP20080237T4/en
Priority to CY20081100572T priority patent/CY1108108T1/en
Publication of EP1652909B2 publication Critical patent/EP1652909B2/en
Anticipated expiration legal-status Critical
Active legal-status Critical Current

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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/04Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
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    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02Well-defined aliphatic compounds
    • C10M2203/0206Well-defined aliphatic compounds used as base material
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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    • C10M2207/125Carboxylix 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
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    • C10M2207/1273Carboxylix 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 polycarboxylic used as base material
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/1403Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings used as base material
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Definitions

  • the present invention relates to a functional fluid corrosion inhibitor, a water-miscible water-based functional fluid-containing concentrate containing this corrosion inhibitor, and the use thereof.
  • HFA fluids are liquids used as lubricants, abrasives, coolants and lubricants for metal forming and metal cutting, and more particularly as hydraulic fluids, namely, hydraulic fluids.
  • These water-based functional fluids are also referred to as HFA fluids or HFA hydraulic fluids.
  • HFA hydraulic fluids are used in particular in the hydraulic longwall mining systems. They are prepared on site by mixing from 1 to 20% by weight of a water-miscible concentrate containing the necessary active ingredients with correspondingly 99 to 80% by weight of water. The concentrates may contain as lubricants, synthetic products or those based on mineral oil.
  • the HFA hydraulic fluid obtained is either an emulsion (HFAE), including a microemulsion, with mineral or synthetic oil, or solutions (HFAS).
  • HFAE emulsion
  • HFAS HFAS
  • Such HFA hydraulic fluids have the viscosity of water and can be used in a temperature range of + 5 ° C to + 55 ° C.
  • these water-based functional fluids contain corrosion inhibitors and other auxiliaries, such as animal, vegetable, mineral and / or synthetic oils, fats , Oil or fat components as lubricants, fatty alcohols, biocides, fungicides, complexing agents, heavy metal inhibitors, nonionic or anionic emulsifiers, dispersants and defoamers.
  • corrosion inhibitors and other auxiliaries such as animal, vegetable, mineral and / or synthetic oils, fats , Oil or fat components as lubricants, fatty alcohols, biocides, fungicides, complexing agents, heavy metal inhibitors, nonionic or anionic emulsifiers, dispersants and defoamers.
  • a water-miscible coolant concentrate known which contains natural or synthetic mineral oils, emulsifiers, solubilizers, preservatives, metal inhibitors and other conventional additives and having a pH of less than 7.7 for the purpose of ensuring skin compatibility.
  • this concentrate may contain reaction products of boric acid with primary or tertiary alkanolamines, ethoxylated or propoxylated fatty acids or fatty acid alkanolamides, phosphoric acid esters, triazoles of the thiadiazoles either alone or in combination.
  • a water-mixed cooling lubricant can be produced with these concentrates, whose pH is as close to the neutral point and still does not lead to rusting of metal parts that have been processed with an aqueous solution of the coolant, these assets Concentrates and the functional fluids produced therewith based on water, especially with regard to their corrosion effect unsatisfactory.
  • these waterborne coolants when in contact with metal surfaces for extended periods of time, such as when used in hydraulic equipment, can result in corrosion of the exposed metal surfaces, particularly by pitting and the deposition of undesirable deposits.
  • EP-A-591 771 describes lubricant compositions for metal forming comprising as lubricating component an ethoxylated fatty amine or amide, an amine or amide salt, a Imidazolinsalz, a polyalkylene glycol or lanolin, as a film-forming component one or more vinyl or acrylic polymers, cellulose ethers, fatty alcohols or waxes and anticorrosive a mixture of mono and dicarboxylic acids, a fatty acid ethanolamide or a glycol derivative.
  • lubricating component an ethoxylated fatty amine or amide, an amine or amide salt, a Imidazolinsalz, a polyalkylene glycol or lanolin, as a film-forming component one or more vinyl or acrylic polymers, cellulose ethers, fatty alcohols or waxes and anticorrosive a mixture of mono and dicarboxylic acids, a fatty acid ethanolamide or a glycol derivative.
  • US-A-4391722 describes an aqueous hydraulic fluid containing a 0.15 wt .-% C21-Alkyldiethanolamid, 0.1 wt .-% benzoic acid and 0.2% by weight of an alcohol and a concentrate containing C21 diethanolamide, 0.2% ethanol and 2% benzoic acid.
  • DE-A-4323909 describes a composition of an oil / water emulsion containing an oil component, an emulsifier, a co-emulsifier (fatty alcohols), and water and an aqueous solution containing salts of aliphatic mono- or dicarboxylic acids, benzenecarboxylic acids or Arylsulfonaminocarbonsauren as a corrosion inhibitor.
  • the object of the present invention is now a corrosion inhibitor for functional fluids to improve the corrosion protection performance of such HFA fluids, namely HFA hydraulic fluids for hydraulic systems, without affecting the other requirements for such a functional fluid, in such a way that their use in large-volume and extremely costly hydraulic equipment, as described in Mining becomes possible becomes possible.
  • the invention therefore provides the corrosion inhibitor according to the main claim.
  • the subclaims relate to preferred embodiments of this subject of the invention, a water-miscible water-based functional concentrate containing this corrosion inhibitor, preferred embodiments of this concentrate and its use for the preparation of a lubricant, an abrasive, a hydraulic fluid or a water-based cooling lubricant for metal forming and metal cutting.
  • One embodiment of the invention therefore relates to a functional fluid corrosion inhibitor comprising 5 to 80% by weight of at least one fatty acid alkanolamide based on saturated or unsaturated fatty acids having 10 to 20 carbon atoms, 5 to 80% by weight of at least one alcohol having 2 to 14 carbon atoms selected from the group consisting of isopropanol, n-butanol, butyldiglycol, hexylene glycol, butyltriglycol, benzyl alcohol and phenoxyethanol and from 5 to 80% by weight of at least one aromatic monocarboxylic acid or an aliphatic dicarboxylic acid having from 10 to 12 carbon atoms selected from sebacic acid, undecanedioic acid, Dodecanedioic acid and p-tert-butylbenzoic acid group, wherein the sum of these ingredients is 100 wt .-% and the wt .-% based on the weight of the corrosion inhibitor.
  • the corrosion inhibitor according to the invention contains from 25 to 60% by weight of the at least one fatty acid alkanolamide, from 15 to 25% by weight of the at least one alcohol with from 20 to 50% by weight of the at least one aromatic monocarboxylic acid or aliphatic dicarboxylic acid of the type defined above.
  • Preferred fatty acid alkanolamides in the corrosion inhibitor according to the invention are those based on saturated or unsaturated fatty acids having 12 to 18 carbon atoms and alkanolamines having 2 to 6 carbon atoms, namely monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-2-methyl-1 propanol, 2-amino-2-ethyl-1,3-propanediol and / or diglycolamine, which is also referred to as 2-aminoethoxyethanol or ethylene glycol 2-aminoethyl ether.
  • Fatty acid alkanolamides which are particularly preferred according to the invention are coconut fatty acid alkanolamides and tall oil fatty acid monoalkanolamides, such as coconut fatty acid monoethanolamide, coconut fatty acid monopropanolamide, tall oil fatty acid monoethanolamide and tall oil fatty acid monopropanolamide and in particular also reaction products of coconut fatty acid, coconut oil, tall oil fatty acid and / or tall oil and diglycolamine.
  • the aromatic monocarboxylic acid or aliphatic dicarboxylic acid used according to the invention as the third essential constituent of the corrosion inhibitor is selected from the group consisting of sebacic acid, undecanedioic acid, dodecanedioic acid and p-tert-butylbenzoic acid. Mixtures of these acids have proven to be particularly favorable, in particular mixtures of undecanedioic acid and dodecanedioic acid in a weight ratio of 3: 1 to 1: 3 and in particular 1: 1.
  • a further subject matter of the invention is a water-miscible concentrate for water-based functional fluids and in particular for HFA hydraulic fluids containing animal, vegetable, mineral and / or synthetic oils, fats, oil or fat components as lubricants, fatty alcohols, biocides, fungicides, complexing agents, Contains heavy metal inhibitors, nonionic or anionic emulsifiers, dispersants, defoamers, corrosion inhibitors and water and conventional additives as the remainder and contains as essential ingredient of the invention 2 to 20 wt .-%, preferably 5 to 15 wt .-% of the above-defined corrosion inhibitor, wherein the weight percent are based on the weight of the water-miscible concentrate.
  • the water-miscible concentrate contains 1 to 12% by weight, more preferably 2 to 8% by weight, of at least one fatty acid alkanolamide based on saturated or unsaturated Fatty acids having 10 to 20 carbon atoms, 1 to 8 wt.% At least, more preferably 1.5 to 5 wt.% Of the alcohol having 2 to 14 carbon atoms and 1 to 8 wt.%, More preferably 1 to 5 wt. the aromatic monocarboxylic acid or aliphatic dicarboxylic acid having 10 to 12 carbon atoms.
  • the water-miscible concentrate contains a fatty acid alkanolamide based on saturated or unsaturated fatty acids having 12 to 18 carbon atoms and alkanolamines having 2 to 6 carbon atoms, wherein as alkanolamines monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-2-methyl 1-propanol, 2-amino-2-ethyl-1,3-propanediol and diglycolamine are particularly preferred.
  • the concentrate contains, as fatty acid alkanolamide, a coconut fatty acid monoalkanolamide and / or tall oil fatty acid monoalkanolamide, especially coconut fatty acid monoethanolamide, coconut fatty acid monopropanolamide, tall oil fatty acid monoethanolamide and / or tall fatty acid monopropanolamide, according to a further preferred embodiment as fatty acid alkanolamide a reaction product of coconut fatty acid, coconut oil, tall oil fatty acid and / or tall oil and diglycolamine.
  • the concentrate contains as alcohol isopropanol, n-butanol, butyl diglycol, hexylene glycol, butyl triglycol, benzyl alcohol and phenoxyethanol, these alcohols can be used individually or in the form of any mixtures.
  • the water-miscible concentrate contains as aromatic monocarboxylic acid or aliphatic dicarboxylic acid sebacic acid, undecanedioic acid, dodecanedioic acid or p-tert-butylbenzoic acid, which acids can be used individually or in the form of mixtures.
  • aromatic monocarboxylic acid or aliphatic dicarboxylic acid sebacic acid undecanedioic acid
  • dodecanedioic acid or p-tert-butylbenzoic acid which acids can be used individually or in the form of mixtures.
  • mixtures of undecanedioic acid and dodecanedioic acid in weight ratios of 3: 1 to 1: 3 and in particular of 1: 1 are particularly preferred. These mixtures have proven to be particularly advantageous with regard to the corrosion protection effect.
  • the water-miscible concentrate according to the invention may contain from 0.5 to 3% by weight of a biocidal compound selected from biocidal quaternary ammonium compounds, guanidine derivatives, O- or N-formals, O- or N-acetals, isothiazolines, isothiazolinones, aliphatic amines or diamines, 3-iodo-2-propynyl butylearbamate, bis (3-aminopropyl) dodecylamine, and mixtures thereof.
  • a biocidal compound selected from biocidal quaternary ammonium compounds, guanidine derivatives, O- or N-formals, O- or N-acetals, isothiazolines, isothiazolinones, aliphatic amines or diamines, 3-iodo-2-propynyl butylearbamate, bis (3-aminopropyl) dodecylamine, and mixtures thereof.
  • the concentrate may contain 0.5 to 3% by weight of a fungicidal pyridine derivative, preferably pyrithione or a pyrithione derivative such as 2-pyridinethiol-1-oxide sodium salt.
  • the concentrate according to the invention may contain 0.5 to 5 wt .-% ethylenediaminetetraacetic acid or its alkali metal or ammonium salts, sodium citrate, sodium gluconate, N, N'-disalicylidene and / or derivatives thereof.
  • the water-miscible concentrate according to the invention contains 1 to 8 wt .-%, more preferably 2 to 5 wt .-% of a phosphoric acid esters such as Ethylhexylphosphorklare, phosphonic, Diaminoxethylat, Triaminoxethylat, Alkylimidazolinen, Polyaminnaphthen yarnreamiden, synthetic or natural sulfonates, such as petroleum sulfonates , p-tert-butylbenzoic acid, tricarboxylic acids, neodecanoic acid, 5- or 6-carboxy-4-hyl-2-hexene-1-octanoic acid, saturated or unsaturated fatty acids, ethoxylated or propoxylated fatty acids and fatty acid alkanolamides, thiadiazole compounds, and mixtures thereof of additional anticorrosion agent selected.
  • a phosphoric acid esters such as Ethy
  • reaction product of boric acid and primary or tertiary alkanolamines may be contained in the water-miscible concentrate according to the invention as additional corrosion protection.
  • the concentrate according to the invention can furthermore contain 0.05 to 1.5% by weight of benzotriazole and / or toluyltriazole and / or derivatives thereof as heavy metal inhibitor.
  • the water-miscible concentrate contains as animal, vegetable, mineral and / or synthetic lubricant 3 to 70 wt .-% of a natural or synthetic mineral oil, 2 to 40 wt .-% of an ester oil, which are conventional synthetic ester oils to those skilled in the art, 1 to 6 wt .-% of a phosphated and / or ethoxylated alcohol and / or 2 to 35 wt .-% of a polyalkylene glycol and / or polyvinylpyrrolidone, with the proviso that this lubricant 10 to 70 wt. -% of the water-miscible concentrate.
  • an ester oil which are conventional synthetic ester oils to those skilled in the art
  • 1 to 6 wt .-% of a phosphated and / or ethoxylated alcohol and / or 2 to 35 wt .-% of a polyalkylene glycol and / or polyvinylpyrrolidone
  • the concentrate may contain from 0.05 to 1% by weight of a siloxane compound, while as emulsifier from 1 to 5% by weight of oleoyl sarcoside are preferred.
  • a dispersant 0.2 to 5 wt .-% of an acrylic polymer salt, in particular a salt of a poly (meth) acrylic acid may be contained in the concentrate.
  • the water-miscible concentrate after dilution with water to a concentrate content of 1 to 20 wt .-%, based on the resulting functional liquid, a pH of 8.4 to 9.8, preferably 9.0 to 9.5 on.
  • the invention relates to the use of the above-defined water-miscible concentrate for the production of a lubricant, an abrasive, a hydraulic fluid or a water-based cooling lubricant for metal forming and metal cutting by mixing from 1 to 20% by weight, preferably 2 to 5% by weight of the above-defined water-miscible concentrate, having 99 to 80 Wt .-%, preferably 99 to 95 wt .-% water.
  • the water-miscible concentrate according to the invention even when mixed with water having a hardness of 3 ° dH to 42 ° dH at a concentrate content of 2% HFA hydraulic fluid results in the form of emulsions, even after 600 hours at a temperature of 50 ° C are absolutely stable.
  • the corrosion inhibitor of the invention is prepared by simply mixing the ingredients.
  • the water-miscible concentrate of the present invention is prepared by first introducing the water-soluble or water-dispersible ingredients into water, then dissolving or dispersing the oil-soluble ingredients in the oil component, and then slowly adding the hydrous mixture to the mineral oil mixture.
  • the corrosion protection effect achieved with the anticorrosion agent according to the invention is determined by means of the crevice corrosion test, in accordance with DSK standard N 762 830.
  • the method of corrosion testing by means of this crevice corrosion test is published in Johnsonauf 138 (2002) No. 5, pages 208-212.
  • the method consists in that the pressure fluid or hydraulic fluid to be tested in a defined punch unit (piston-cylinder) is stored under purely static conditions for 21 days at a humidity of 95% and a test temperature of 35 ° C.
  • the gap region is formed between the cylinder inner surface and a bronze part located on the piston. On the bronze part, a commercially available sealing ring is mounted.
  • the stamp unit After a contact time with the liquid to be tested for 21 days, the stamp unit is dismantled and examined the gap area on the cylinder inner surface with respect to a corrosion formation.
  • this crevice corrosion test shows that inadequate corrosion protection in addition to a pitting and cratering also deposit-like, very different color corrosion products are deposited in the gap area on the cylinder surface. If these deposits are found in the gap area of the sealing ring on the cylinder surface, they are usually also found on the sealing ring surface and the bronze surface. In particular, smaller particles collect on the sealing lip, which are responsible for a linear corrosion in the circumferential direction of the cylinder surface.
  • crevice corrosion reference should be made to the standard DIN EN ISO 8044-3.17.
  • Water-mixable concentrates are first prepared from the constituents indicated in the following Tables 1 to 3, which are then mixed in a ratio of 2 parts by weight concentrate with 98 parts by weight of water, to form a HFA hydraulic fluid, which is examined in the above-mentioned crevice corrosion test.
  • water is initially introduced, after which potassium hydroxide is added and dissolved with stirring.
  • the particular acids used such as sebacic acid, dodecanedioic acid, undecanedioic acid or in Comparative Example E neodecanoic acid added, and it is stirred at a temperature of 50 ° C until the pH of the mixture is 7.
  • sodium citrate and monoethanolamine are added and the mixture is allowed to cool with stirring to 25 ° C.
  • a portion of the aliphatic hydrocarbon lubricant (50%) is heated in a separate vessel and then the fatty acid alkanolamides, sodium petroleum sulfonate is added with stirring and then the remaining aliphatic hydrocarbon followed by the remaining ingredients.
  • the mixture is then thoroughly mixed and, with stirring, the water-containing mixture obtained in the first stage is added to the aliphatic hydrocarbon-based mixture.
  • This gives a light brown, clear, slightly viscous concentrate, which is then mixed with water to form a water-based functional fluid (HFA hydraulic fluid) containing 2 wt .-% of the concentrate and 98 wt .-% water.
  • HFA hydraulic fluid water-based functional fluid
  • This HFA hydraulic fluid is introduced into the gap area of the stamp unit for the crevice corrosion test and statically stored for 21 days at a humidity of 95% and a temperature of 35 ° C.
  • the tester is examined with regard to the sludge in the bottom area of the outer tube, in the gap area and bronze piston area and deposits before cleaning in the inner tube and the outer tube and on tarnish after cleaning in the inner tube and in the outer tube and on solid deposits on the inner surface of the cylinder and in the gap region of the cylinder and on the surface of the bronze piston examined.
  • the HFA hydraulic fluids of the present invention do not give rise to any corrosion effects, while the products of Comparative Examples A to E do not pass the corrosion test according to DSK Standard N 762 830, since both deposits are present the cleaning on the cylinder notice, as well as solid deposits in the gap region of the cylinder and a line-shaped corrosion in the circumferential direction in the gap region of the cylinder.
  • Comparative Example E reveals that a water-based hydraulic fluid containing neodecanoic acid, ie a C 10 monocarboxylic acid, develops considerable corrosive effects and consequently unsuitable for use as HFA hydraulic fluid, while the anticorrosion agent according to the invention and the HFA hydraulic fluid containing it , which differs from the product of the prior art by the inventive selection of the particular aliphatic dicarboxylic acids, shows no corrosion effect and is readily suitable for use in, for example, hydraulic longwall mining systems.
  • neodecanoic acid ie a C 10 monocarboxylic acid

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Description

Die vorliegende Erfindung betrifft ein Korrosionsschutzmittel für funktionelle Flüssigkeiten, ein dieses Korrosionsschutzmittel enthaltendes wassermischbares Konzentrat für funktionelle Flüssigkeiten auf Wassergrundlage und dessen Verwendung.The present invention relates to a functional fluid corrosion inhibitor, a water-miscible water-based functional fluid-containing concentrate containing this corrosion inhibitor, and the use thereof.

Aufgrund ihrer Schwerentflammbarkeit und ihres geringen Umweltrisikos gewinnen funktionelle Flüssigkeiten auf Wassergrundlage zunehmend an Interesse. Bei diesen funktionellen Flüssigkeiten handelt es sich um Flüssigkeiten, die als Schmiermittel, Schleifmittel, Kühl- und Schmiermittel für die Metallumformung und die Metallzerspanung und insbesondere als Druckflüssigkeiten, namentlich als Hydraulikflüssigkeiten, eingesetzt werden. Diese funktionellen Flüssigkeiten auf Wassergrundlage werden auch als HFA-Flüssigkeiten beziehungsweise HFA-Hydraulikflüssigkeiten bezeichnet. Solche HFA-Hydraulikflüssigkeiten werden insbesondere in den hydraulischen Strebausbausystemen von Bergwerken eingesetzt. Sie werden vor Ort durch Vermischen von 1 bis 20 Gew.-% eines die notwendigen Wirkstoffe enthaltenden wassermischbaren Konzentrats mit entsprechend 99 bis 80 Gew.-% Wasser hergestellt. Die Konzentrate können als Schmierstoffe, synthetische Produkte oder solche auf Mineralölbasis enthalten. In Abhängigkeit von der Zusammensetzung des wassermischbaren Konzentrats erhält man als HFA-Hydraulikflüssigkeit entweder eine Emulsion (HFAE), einschließlich einer Mikroemulsion, mit mineralischem oder synthetischem Öl, oder Lösungen (HFAS). Solche HFA-Hydraulikflüssigkeiten besitzen die Viskosität von Wasser und können in einem Temperaturbereich von +5°C bis +55°C eingesetzt werden.Due to their low flammability and their low environmental risk, water-based functional fluids are increasingly gaining in interest. These functional fluids are liquids used as lubricants, abrasives, coolants and lubricants for metal forming and metal cutting, and more particularly as hydraulic fluids, namely, hydraulic fluids. These water-based functional fluids are also referred to as HFA fluids or HFA hydraulic fluids. Such HFA hydraulic fluids are used in particular in the hydraulic longwall mining systems. They are prepared on site by mixing from 1 to 20% by weight of a water-miscible concentrate containing the necessary active ingredients with correspondingly 99 to 80% by weight of water. The concentrates may contain as lubricants, synthetic products or those based on mineral oil. Depending on the composition of the water-miscible concentrate, the HFA hydraulic fluid obtained is either an emulsion (HFAE), including a microemulsion, with mineral or synthetic oil, or solutions (HFAS). Such HFA hydraulic fluids have the viscosity of water and can be used in a temperature range of + 5 ° C to + 55 ° C.

Wenn eine solche funktionelle Flüssigkeit auf Wassergrundlage, beziehungsweise HFA-Hydraulikflüssigkeit, keinen ausreichenden Korrosionsschutz sicherstellt, so führt dies an den mit dieser funktionellen Flüssigkeit in Kontakt stehenden Werkstoffoberflächen, namentlich der Hydraulikeinrichtungen, zur Ausbildung von Korrosion. Hierbei können insbesondere Lochkorrosion, Muldenkorrosion, Kraterbildung oder aber auch die Abscheidung von belagbildenden Korrosionsprodukten verursacht werden. Da eine derartige Korrosion namentlich beim Einsatz der HFA-Hydraulikflüssigkeit in großen hydraulischen Systemen, wie im Strebausbau von Bergwerken, unbedingt verhindert werden muß, enthalten diese wasserbasierten funktionellen Flüssigkeiten Korrosionsschutzmittel und weitere Hilfsstoffe, wie tierische, pflanzliche, mineralische und/oder synthetische Öle, Fette, Öl- oder Fettbestandteile als Schmiermittel, Fettalkohole, Biozide, Fungizide, Komplexbildner, Schwermetallinhibitoren, nichtionische oder anionische Emulgatoren, Dispergiermittel und Entschäumer.If such a water-based functional fluid, or HFA hydraulic fluid, does not ensure sufficient corrosion protection, this leads to the formation of corrosion on the material surfaces in contact with this functional fluid, namely the hydraulic devices. This can be caused in particular pitting, trough corrosion, cratering or even the deposition of coating-forming corrosion products. Since such corrosion especially in the use of HFA hydraulic fluid in large hydraulic systems, such as in the longwall mining, must be prevented, these water-based functional fluids contain corrosion inhibitors and other auxiliaries, such as animal, vegetable, mineral and / or synthetic oils, fats , Oil or fat components as lubricants, fatty alcohols, biocides, fungicides, complexing agents, heavy metal inhibitors, nonionic or anionic emulsifiers, dispersants and defoamers.

Aus der EP 1 174 489 A1 ist ein Verfahren zur Herstellung von Schneidflüssigkeiten auf Wassergrundlage bekannt, die eine Ölphase, eine wässrige Phase, ein Bakterizid oder Fungizid und Hochdruckkomponenten enthalten. Als antikorrosive und/oder bakteriostatische Mittel können diese Schneidflüssigkeiten organische Säuren, wie Sebacinsäure, enthalten.From the EP 1 174 489 A1 For example, there is known a process for preparing water-based cutting fluids containing an oil phase, an aqueous phase, a bactericide or fungicide, and high pressure components. As anticorrosive and / or bacteriostatic agents, these cutting fluids may contain organic acids such as sebacic acid.

Aus der DE 198 33 894 A1 ist ein wassermischbares Kühlschmierstoff-Konzentrat bekannt, welches natürliche oder synthetische Mineralöle, Emulgatoren, Lösungsvermittler, Konservierungsstoffe, Metallinhibitoren und andere übliche Additive enthält und zum Zwecke der Sicherstellung einer Hautverträglichkeit einen pH-Wert von unter 7,7 aufweist. Als Korrosionsschutzmittel kann dieses Konzentrat Umsetzungsprodukte von Borsäure mit primären oder tertiären Alkanolaminen, ethoxylierte oder propoxylierte Fettsäuren oder Fettsäurealkanolamide, Phosphorsäureester, Triazole der Thiadiazole entweder alleine oder in Kombination enthalten. Wenngleich in dieser Druckschrift angegeben ist, daß mit diesen Konzentraten ein wassergemischter Kühlschmierstoff hergestellt werden kann, dessen pH-Wert möglichst nahe am Neutralpunkt liegt und der trotzdem nicht zur Rostbildung bei Metallteilen führt, die mit einer wässrigen Lösung des Kühlschmierstoffes bearbeitet worden sind, vermögen diese Konzentrate und die damit hergestellten funktionellen Flüssigkeiten auf Wassergrundlage insbesondere im Hinblick auf ihre Korrosionswirkung nicht zu befriedigen. Insbesondere können diese wasserbasierten Kühlschmierstoffe, wenn sie während längerer Zeit mit Metalloberflächen in Kontakt stehen, wie es bei der Anwendung in Hydraulikeinrichtungen der Fall ist, zur Korrosion der freiliegenden Metalloberflächen führen, namentlich durch Lochfraß und die Abscheidung von unerwünschten Belägen.From the DE 198 33 894 A1 is a water-miscible coolant concentrate known which contains natural or synthetic mineral oils, emulsifiers, solubilizers, preservatives, metal inhibitors and other conventional additives and having a pH of less than 7.7 for the purpose of ensuring skin compatibility. As corrosion inhibitor, this concentrate may contain reaction products of boric acid with primary or tertiary alkanolamines, ethoxylated or propoxylated fatty acids or fatty acid alkanolamides, phosphoric acid esters, triazoles of the thiadiazoles either alone or in combination. Although it is stated in this document that a water-mixed cooling lubricant can be produced with these concentrates, whose pH is as close to the neutral point and still does not lead to rusting of metal parts that have been processed with an aqueous solution of the coolant, these assets Concentrates and the functional fluids produced therewith based on water, especially with regard to their corrosion effect unsatisfactory. In particular, these waterborne coolants, when in contact with metal surfaces for extended periods of time, such as when used in hydraulic equipment, can result in corrosion of the exposed metal surfaces, particularly by pitting and the deposition of undesirable deposits.

EP-A-591771 beschreibt Schmiermittelzusammensetzungen zur Metallumformung enthaltend als Schmierkomponente ein ethoxyliertes Fettamin oder Amid, ein Amin- oder Amidsalz, ein Imidazolinsalz, ein Polyalkylenglykol oder Lanolin, als filmbildende Komponente ein oder mehrere Vinyl- oder Acrylpolymere, Celluloseether, Fettalkohole oder Wachse und als Korrosionsschutzadditive ein Gemisch von Mono- und Dicarbonsäuren, ein Fettsäureethanolamid oder ein Glykolderivat. EP-A-591 771 describes lubricant compositions for metal forming comprising as lubricating component an ethoxylated fatty amine or amide, an amine or amide salt, a Imidazolinsalz, a polyalkylene glycol or lanolin, as a film-forming component one or more vinyl or acrylic polymers, cellulose ethers, fatty alcohols or waxes and anticorrosive a mixture of mono and dicarboxylic acids, a fatty acid ethanolamide or a glycol derivative.

US-A-4391722 beschreibt ein wäßriges Hydraulikfluid enthaltend ein 0.15 Gew.-% C21-Alkyldiethanolamid, 0.1 Gew.-% Benzoesäure und 0.2% Gew. eines Alkohols und ein Konzentrat enthaltend C21 diethanoldiamid, 0.2% Ethanol und 2% Benzoesäure. US-A-4391722 describes an aqueous hydraulic fluid containing a 0.15 wt .-% C21-Alkyldiethanolamid, 0.1 wt .-% benzoic acid and 0.2% by weight of an alcohol and a concentrate containing C21 diethanolamide, 0.2% ethanol and 2% benzoic acid.

DE-A-4323909 beschreibt eine Zusammensetzung aus einer Ol/Wasser-Emulsion enthaltend eine Öl-Komponente, eine Emulgator, einen Coemulgator (Fettalkohole), und Wasser sowie einer wäßrigen Lösung enthaltend Salze von aliphatischen Mono- oder Dicarbonsäuren, Benzolcarbonsäuren oder Arylsulfonaminocarbonsauren als Korrosionsinhibitor. DE-A-4323909 describes a composition of an oil / water emulsion containing an oil component, an emulsifier, a co-emulsifier (fatty alcohols), and water and an aqueous solution containing salts of aliphatic mono- or dicarboxylic acids, benzenecarboxylic acids or Arylsulfonaminocarbonsauren as a corrosion inhibitor.

Die Aufgabe der vorliegenden Erfindung besteht nun darin, ein Korrosionsschutzmittel für funktionelle Flüssigkeiten anzugeben, mit denen es gelingt, das Korrosionsschutzverhalten solcher HFA-Flüssigkeiten, namentlich von HFA-Hydraulikflüssigkeiten für Hydrauliksysteme ohne Beeinträchtigung der übrigen Anforderungen an eine solche funktionelle Flüssigkeit in der Weise zu verbessern, daß ihr Einsatz in großvolumigen und äußerst kostspieligen Hydraulikeinrichtungen, wie sie im Bergbau eingesetzt werden, möglich wird.The object of the present invention is now a corrosion inhibitor for functional fluids to improve the corrosion protection performance of such HFA fluids, namely HFA hydraulic fluids for hydraulic systems, without affecting the other requirements for such a functional fluid, in such a way that their use in large-volume and extremely costly hydraulic equipment, as described in Mining becomes possible becomes possible.

Es hat sich überraschenderweise gezeigt, daß es mit einer Kombination aus mindestens drei verschiedenen an sich bekannten Korrosionsschutzadditiven, gelingt, das Korrosionsschutzverhalten solcher HFA-Hydraulikflüssigkeiten in unerwartet starkem Maße zu verbessern, so daß nicht nur die Lochkorrosion, die Muldenkorrosion und die Kraterbildung, sondern auch die Abscheidung von belagbildenden Korrosionsprodukten vollständig vermieden werden kann, die man bei der Verwendung herkömmlicher HFA-Flüssigkeiten bei dem nachfolgend beschriebenen Spaltkorrosionstest entsprechend DSK Norm N 762 830 beobachtet.It has surprisingly been found that it is possible with a combination of at least three different corrosion protection additives known per se, to improve the corrosion protection behavior of such HFA hydraulic fluids in unexpectedly strong extent, so that not only the pitting, the trough corrosion and cratering, but also the deposition of scale-forming corrosion products observed when using conventional HFA fluids in the crevice corrosion test described below in accordance with DSK Standard N 762 830 can be completely avoided.

Gegenstand der Erfindung ist daher das Korrosionsschutzmittel gemäß Hauptanspruch. Die Unteransprüche betreffen bevorzugte Ausführungsformen dieses Erfindungsgegenstandes, ein dieses Korrosionsschutzmittel enthaltendes wassermischbares Konzentrat für funktionelle Flüssigkeiten auf Wassergrundlage, bevorzugte Ausführungsformen dieses Konzentrats sowie seine Verwendung für die Herstellung eines Schmiermittels, eines Schleifmittels, einer Hydraulikflüssigkeit oder eines Kühlschmiermittels auf Wassergrundlage für die Metallumformung und Metallzerspanung.The invention therefore provides the corrosion inhibitor according to the main claim. The subclaims relate to preferred embodiments of this subject of the invention, a water-miscible water-based functional concentrate containing this corrosion inhibitor, preferred embodiments of this concentrate and its use for the preparation of a lubricant, an abrasive, a hydraulic fluid or a water-based cooling lubricant for metal forming and metal cutting.

Eine Ausführungsform der Erfindung betrifft daher ein Korrosionsschutzmittel für funktionelle Flüssigkeiten, umfassend 5 bis 80 Gew.-% mindestens eines Fettsäurealkanolamids auf der Grundlage von gesättigten oder ungesättigten Fettsäuren mit 10 bis 20 Kohlenstoffatomen, 5 bis 80 Gew.-% mindestens eines Alkohols mit 2 bis 14 Kohlenstoffatomen ausgewählt aus der Isopropanol, n-Butanol, Butyldiglykol, Hexylenglykol, Butyltriglykol, Benzylalkohol und Phenoxyethanol umfassenden Gruppe und 5 bis 80 Gew.-% mindestens einer aromatischen Monocarbonsäure oder einer aliphatischen Dicarbonsäure mit 10 bis 12 Kohlenstoffatomen ausgewählt aus der Sebacinsäure, Undecandisäure, Dodecandisäure und p-tert-Butylbenzoesäure umfassenden Gruppe, wobei die Summe dieser Bestandteile 100 Gew.-% beträgt und die Gew.-% auf das Gewicht des Korrosionsschutzmittels bezogen sind.One embodiment of the invention therefore relates to a functional fluid corrosion inhibitor comprising 5 to 80% by weight of at least one fatty acid alkanolamide based on saturated or unsaturated fatty acids having 10 to 20 carbon atoms, 5 to 80% by weight of at least one alcohol having 2 to 14 carbon atoms selected from the group consisting of isopropanol, n-butanol, butyldiglycol, hexylene glycol, butyltriglycol, benzyl alcohol and phenoxyethanol and from 5 to 80% by weight of at least one aromatic monocarboxylic acid or an aliphatic dicarboxylic acid having from 10 to 12 carbon atoms selected from sebacic acid, undecanedioic acid, Dodecanedioic acid and p-tert-butylbenzoic acid group, wherein the sum of these ingredients is 100 wt .-% and the wt .-% based on the weight of the corrosion inhibitor.

Es hat sich bei Vergleichsuntersuchungen, die in den nachfolgenden Beispielen und Vergleichsbeispielen verdeutlicht werden, gezeigt, daß nur dann, wenn das Korrosionsschutzmittel die drei angegebenen notwendigen Bestandteile enthält und die aromatische Monocarbonsäure beziehungsweise die aliphatische Dicarbonsäure, die unerwünschte Korrosion vollständig vermieden werden kann, während beispielsweise bei Vorhandensein einer aliphatischen Monocarbonsäure mit 10 Kohlenstoffatomen, wie der Neodecansäure, das Auftreten von festen Ablagerungen und von Linienkorrosion nicht vermieden werden kann. Dieses Ergebnis ist zweifellos als überraschend und für den Fachmann unerwartet anzusehen.It has been found in comparative tests, which are illustrated in the following examples and comparative examples, that only when the anticorrosion agent contains the three specified necessary ingredients and the aromatic monocarboxylic acid or aliphatic dicarboxylic acid, the undesirable corrosion can be completely avoided, for example in the presence of an aliphatic monocarboxylic acid having 10 carbon atoms, such as neodecanoic acid, the occurrence of solid deposits and line corrosion can not be avoided. This result is undoubtedly surprising and unexpected to those skilled in the art.

Vorzugsweise enthält das erfindungsgemäße Korrosionsschutzmittel 25 bis 60 Gew.-% des mindestens einen Fettsäurealkanolamids, 15 bis 25 Gew.-% des mindestens einen Alkohols mit 20 bis 50 Gew.-% der mindestens einen aromatischen Monocarbonsäure oder aliphatischen Dicarbonsäure der oben definierten Art.Preferably, the corrosion inhibitor according to the invention contains from 25 to 60% by weight of the at least one fatty acid alkanolamide, from 15 to 25% by weight of the at least one alcohol with from 20 to 50% by weight of the at least one aromatic monocarboxylic acid or aliphatic dicarboxylic acid of the type defined above.

Als Fettsäurealkanolamide sind in dem erfindungsgemäßen Korrosionsschutzmittel vorzugsweise solche auf der Grundlage von gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 Kohlenstoffatomen und Alkanolaminen mit 2 bis 6 Kohlenstoffatomen, namentlich Monoethanolamin, Diethanolamin, Triethanolamin, Monopropanolamin, Monoisopropanolamin, 2-Amino-2-methyl-1-propanol, 2-Amino-2-ethyl-1,3-propandiol und/oder Diglykolamin, welches auch als 2-Aminoethoxyethanol oder Ethylenglykol-2-aminoethylether bezeichnet wird, enthalten.Preferred fatty acid alkanolamides in the corrosion inhibitor according to the invention are those based on saturated or unsaturated fatty acids having 12 to 18 carbon atoms and alkanolamines having 2 to 6 carbon atoms, namely monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-2-methyl-1 propanol, 2-amino-2-ethyl-1,3-propanediol and / or diglycolamine, which is also referred to as 2-aminoethoxyethanol or ethylene glycol 2-aminoethyl ether.

Erfindungsgemäß besonders bevorzugte Fettsäurealkanolamide sind Kokosfettsäurealkanolamide und Tallölfettsäuremonoalkanolamide, wie Kokosfettsäuremonoethanolamid, Kokosfettsäuremonopropanolamid, Tallölfettsäuremonoethanolamid und Tallölfettsäuremonopropanolamid und insbesondere auch Umsetzungsprodukte aus Kokosfettsäure, Kokosöl, Tallölfettsäure und/ oder Tallöl und Diglykolamin.Fatty acid alkanolamides which are particularly preferred according to the invention are coconut fatty acid alkanolamides and tall oil fatty acid monoalkanolamides, such as coconut fatty acid monoethanolamide, coconut fatty acid monopropanolamide, tall oil fatty acid monoethanolamide and tall oil fatty acid monopropanolamide and in particular also reaction products of coconut fatty acid, coconut oil, tall oil fatty acid and / or tall oil and diglycolamine.

Die erfindungsgemäß als dritter wesentlicher Bestandteil des Korrosionsschutzmittels eingesetzte aromatische Monocarbonsäure oder aliphatische Dicarbonsäure wird aus der Sebacinsäure, Undecandisäure, Dodecandisäure und p-tert-Butylbenzoesäure umfassenden Gruppe ausgewählt. Als besonders günstig haben sich Mischungen aus diesen Säuren herausgestellt, insbesondere Mischungen aus Undecandisäure und Dodecandisäure in einem auf das Gewicht bezogenen Mischungsverhältnis von 3:1 bis 1:3 und insbesondere 1:1.The aromatic monocarboxylic acid or aliphatic dicarboxylic acid used according to the invention as the third essential constituent of the corrosion inhibitor is selected from the group consisting of sebacic acid, undecanedioic acid, dodecanedioic acid and p-tert-butylbenzoic acid. Mixtures of these acids have proven to be particularly favorable, in particular mixtures of undecanedioic acid and dodecanedioic acid in a weight ratio of 3: 1 to 1: 3 and in particular 1: 1.

Ein weiterer Gegenstand der Erfindung ist ein wassermischbares Konzentrat für funktionelle Flüssigkeiten auf Wassergrundlage und insbesondere für HFA-Hydraulikflüssigkeiten, welches tierische, pflanzliche, mineralische und/ oder synthetische Öle, Fette, Öl- oder Fettbestandteile als Schmiermittel, Fettalkohole, Biozide, Fungizide, Komplexbildner, Schwermetallinhibitoren, nichtionische oder anionische Emulgatoren, Dispergiermittel, Entschäumer, Korrosionsschutzmittel und Wasser und übliche Zusätze als Rest enthält und als wesentlichen erfindungsgemäßen Bestandteil 2 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-% des oben definierten Korrosionsschutzmittels enthält, wobei die Gewichtsprozent auf das Gewicht des wassermischbaren Konzentrats bezogen sind.A further subject matter of the invention is a water-miscible concentrate for water-based functional fluids and in particular for HFA hydraulic fluids containing animal, vegetable, mineral and / or synthetic oils, fats, oil or fat components as lubricants, fatty alcohols, biocides, fungicides, complexing agents, Contains heavy metal inhibitors, nonionic or anionic emulsifiers, dispersants, defoamers, corrosion inhibitors and water and conventional additives as the remainder and contains as essential ingredient of the invention 2 to 20 wt .-%, preferably 5 to 15 wt .-% of the above-defined corrosion inhibitor, wherein the weight percent are based on the weight of the water-miscible concentrate.

Gemäß einer bevorzugten Ausführungsform enthält das wassermischbare Konzentrat 1 bis 12 Gew.-%, bevorzugter 2 bis 8 Gew.-% mindestens eines Fettsäurealkanolamids auf der Grundlage von gesättigten oder ungesättigten Fettsäuren mit 10 bis 20 Kohlenstoffatomen, 1 bis 8 Gew.-% mindestens, bevorzugter 1,5 bis 5 Gew.-% des Alkohols mit 2 bis 14 Kohlenstoffatomen und 1 bis 8 Gew.-%, bevorzugter 1 bis 5 Gew.-% der aromatischen Monocarbonsäure oder aliphatischen Dicarbonsäure mit 10 bis 12 Kohlenstoffatomen.According to a preferred embodiment, the water-miscible concentrate contains 1 to 12% by weight, more preferably 2 to 8% by weight, of at least one fatty acid alkanolamide based on saturated or unsaturated Fatty acids having 10 to 20 carbon atoms, 1 to 8 wt.% At least, more preferably 1.5 to 5 wt.% Of the alcohol having 2 to 14 carbon atoms and 1 to 8 wt.%, More preferably 1 to 5 wt. the aromatic monocarboxylic acid or aliphatic dicarboxylic acid having 10 to 12 carbon atoms.

In vorteilhafter Weise enthält das wassermischbare Konzentrat ein Fettsäurealkanolamid auf der Grundlage von gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 Kohlenstoffatomen und Alkanolaminen mit 2 bis 6 Kohlenstoffatomen, wobei als Alkanolamine Monoethanolamin, Diethanolamin, Triethanolamin, Monopropanolamin, Monoisopropanolamin, 2-Amino-2-methyl-1-propanol, 2-Amino-2-ethyl-1,3-propandiol und Diglykolamin besonders bevorzugt sind. Noch bevorzugter enthält das Konzentrat als Fettsäurealkanolamid ein Kokosfettsäuremonoalkanolamid und/oder Tallölfettsäuremonoalkanolamid, insbesondere Kokosfettsäuremonoethanolamid, Kokosfettsäuremonopropanolamid, Tallölfettsäuremonoethanolamid und/oder Tallfettsäuremonopropanolamid, wobei gemäß einer weiter bevorzugten Ausführungsform als Fettsäurealkanolamid ein Umsetzungsprodukt aus Kokosfettsäure, Kokosöl, Tallölfettsäure und/oder Tallöl und Diglykolamin eingesetzt wird.Advantageously, the water-miscible concentrate contains a fatty acid alkanolamide based on saturated or unsaturated fatty acids having 12 to 18 carbon atoms and alkanolamines having 2 to 6 carbon atoms, wherein as alkanolamines monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-2-methyl 1-propanol, 2-amino-2-ethyl-1,3-propanediol and diglycolamine are particularly preferred. Even more preferably, the concentrate contains, as fatty acid alkanolamide, a coconut fatty acid monoalkanolamide and / or tall oil fatty acid monoalkanolamide, especially coconut fatty acid monoethanolamide, coconut fatty acid monopropanolamide, tall oil fatty acid monoethanolamide and / or tall fatty acid monopropanolamide, according to a further preferred embodiment as fatty acid alkanolamide a reaction product of coconut fatty acid, coconut oil, tall oil fatty acid and / or tall oil and diglycolamine.

Das Konzentrat enthält als Alkohol Isopropanol, n-Butanol, Butyldiglykol, Hexylenglykol, Butyltriglykol, Benzylalkohol und Phenoxyethanol, wobei diese Alkohole einzeln oder in Form von beliebigen Mischungen eingesetzt werden können.The concentrate contains as alcohol isopropanol, n-butanol, butyl diglycol, hexylene glycol, butyl triglycol, benzyl alcohol and phenoxyethanol, these alcohols can be used individually or in the form of any mixtures.

Das wassermischbare Konzentrat enthält als aromatische Monocarbonsäure oder aliphatische Dicarbonsäure Sebacinsäure, Undecandisäure, Dodecandisäure oder p-tert-Butylbenzoesäure, wobei diese Säuren einzeln oder in Form von Mischungen eingesetzt werden können. Hierbei sind Mischungen aus Undecandisäure und Dodecandisäure in Gewichtsverhältnissen von 3:1 bis 1:3 und insbesondere von 1:1 besonders bevorzugt sind. Diese Mischungen haben sich im Hinblick auf die Korrosionsschutzwirkung als besonders vorteilhaft erwiesen.The water-miscible concentrate contains as aromatic monocarboxylic acid or aliphatic dicarboxylic acid sebacic acid, undecanedioic acid, dodecanedioic acid or p-tert-butylbenzoic acid, which acids can be used individually or in the form of mixtures. Here, mixtures of undecanedioic acid and dodecanedioic acid in weight ratios of 3: 1 to 1: 3 and in particular of 1: 1 are particularly preferred. These mixtures have proven to be particularly advantageous with regard to the corrosion protection effect.

Gemäß einer weiteren bevorzugten Ausführungsform kann das erfindungsgemäße wassermischbare Konzentrat 0,5 bis 3 Gew.-% einer bioziden Verbindung enthalten, die aus bioziden quaternären Ammoniumverbindungen, Guanidinderivaten, O- oder N-Formalen, O- oder N-Acetalen, Isothiazolinen, Isothiazolinonen, aliphatischen Aminen oder Diaminen, 3-Iod-2-propinyl-butylearbamat, Bis(3-aminopropyl)-dodecylamin und Mischungen davon ausgewählt ist. Als Fungizid oder Bakterizid kann das Konzentrat 0,5 bis 3 Gew.-% eines fungiziden Pyridinderivats, vorzugsweise Pyrithion oder ein Pyrithionderivat, wie 2-Pyridinthiol-1-oxid-Natriumsalz enthalten.According to another preferred embodiment, the water-miscible concentrate according to the invention may contain from 0.5 to 3% by weight of a biocidal compound selected from biocidal quaternary ammonium compounds, guanidine derivatives, O- or N-formals, O- or N-acetals, isothiazolines, isothiazolinones, aliphatic amines or diamines, 3-iodo-2-propynyl butylearbamate, bis (3-aminopropyl) dodecylamine, and mixtures thereof. As a fungicide or bactericide, the concentrate may contain 0.5 to 3% by weight of a fungicidal pyridine derivative, preferably pyrithione or a pyrithione derivative such as 2-pyridinethiol-1-oxide sodium salt.

Als Komplexbildner kann das erfindungsgemäße Konzentrat 0,5 bis 5 Gew.-% Ethylendiamintetraessigsäure oder deren Alkali- oder Ammoniumsalze, Natriumcitrat, Natriumgluconat, N,N'-Disalicyliden und/oder Derivate davon enthalten.As a complexing agent, the concentrate according to the invention may contain 0.5 to 5 wt .-% ethylenediaminetetraacetic acid or its alkali metal or ammonium salts, sodium citrate, sodium gluconate, N, N'-disalicylidene and / or derivatives thereof.

Gemäß einer weiteren vorteilhaften Ausführungsform enthält das erfindungsgemäße wassermischbare Konzentrat 1 bis 8 Gew.-%, bevorzugter 2 bis 5 Gew.-% eines aus Phosphorsäureestern, wie Ethylhexylphosphorsäure, Phosphonsäurederivaten, Diaminoxethylat, Triaminoxethylat, Alkylimidazolinen, Polyaminnaphthensäureamiden, synthetischen oder natürlichen Sulfonaten, wie Erdölsulfonaten, p-tert-Butylbenzoesäure, Tricarbonsäuren, Neodecansäure, 5- oder 6-Carboxy-4-hehyl-2-hexen-1-octansäure, gesättigten oder ungesättigten Fettsäuren, ethoxylierten oder propoxylierten Fettsäuren und Fettsäurealkanolamiden, Thiadiazolverbindungen und Mischungen davon ausgewählten zusätzlichen Korrosionsschutzmittels.According to a further advantageous embodiment, the water-miscible concentrate according to the invention contains 1 to 8 wt .-%, more preferably 2 to 5 wt .-% of a phosphoric acid esters such as Ethylhexylphosphorsäure, phosphonic, Diaminoxethylat, Triaminoxethylat, Alkylimidazolinen, Polyaminnaphthensäureamiden, synthetic or natural sulfonates, such as petroleum sulfonates , p-tert-butylbenzoic acid, tricarboxylic acids, neodecanoic acid, 5- or 6-carboxy-4-hyl-2-hexene-1-octanoic acid, saturated or unsaturated fatty acids, ethoxylated or propoxylated fatty acids and fatty acid alkanolamides, thiadiazole compounds, and mixtures thereof of additional anticorrosion agent selected.

Weiterhin kann als zusätzliches Korrosionsschutzmittel 3 bis 25 Gew.-% eines Umsetzungsprodukts aus Borsäure und primären oder tertiären Alkanolaminen in dem erfindungsgemäßen wassermischbaren Konzentrat enthalten sein.Furthermore, 3 to 25 wt .-% of a reaction product of boric acid and primary or tertiary alkanolamines may be contained in the water-miscible concentrate according to the invention as additional corrosion protection.

Das erfindungsgemäße Konzentrat kann weiterhin 0,05 bis 1,5 Gew.-% Benzotriazol und/oder Toluyltriazol und/oder Derivate davon als Schwermetallinhibitor enthalten.The concentrate according to the invention can furthermore contain 0.05 to 1.5% by weight of benzotriazole and / or toluyltriazole and / or derivatives thereof as heavy metal inhibitor.

Erfindungsgemäß enthält das mit Wasser mischbare Konzentrat als tierisches, pflanzliches, mineralisches und/oder synthetisches Schmiermittel 3 bis 70 Gew.-% eines natürlichen oder synthetischen Mineralöls, 2 bis 40 Gew.-% eines Esteröls, bei dem es sich um übliche synthetische Esteröle handelt, die dem Fachmann geläufig sind, 1 bis 6 Gew.-% eines phosphatierten und/oder ethoxylierten Alkohols und/oder 2 bis 35 Gew.-% eines Polyalkylenglykols und/oder Polyvinylpyrrolidons, mit der Maßgabe, daß dieses Schmiermittel 10 bis 70 Gew.-% des wassermischbaren Konzentrats ausmacht.According to the invention, the water-miscible concentrate contains as animal, vegetable, mineral and / or synthetic lubricant 3 to 70 wt .-% of a natural or synthetic mineral oil, 2 to 40 wt .-% of an ester oil, which are conventional synthetic ester oils to those skilled in the art, 1 to 6 wt .-% of a phosphated and / or ethoxylated alcohol and / or 2 to 35 wt .-% of a polyalkylene glycol and / or polyvinylpyrrolidone, with the proviso that this lubricant 10 to 70 wt. -% of the water-miscible concentrate.

Als Entschäumer kann das Konzentrat 0,05 bis 1 Gew.-% einer Siloxanverbindung enthalten, während als Emulgator 1 bis 5 Gew.-% Oleoylsarcosid bevorzugt sind. Als Dispergiermittel können 0,2 bis 5 Gew.-% eines Acrylpolymersalzes, insbesondere eines Salzes einer Poly(meth)acrylsäure in dem Konzentrat enthalten sein.As defoamer, the concentrate may contain from 0.05 to 1% by weight of a siloxane compound, while as emulsifier from 1 to 5% by weight of oleoyl sarcoside are preferred. As a dispersant, 0.2 to 5 wt .-% of an acrylic polymer salt, in particular a salt of a poly (meth) acrylic acid may be contained in the concentrate.

Gemäß einer bevorzugten Ausführungsform weist das wassermischbare Konzentrat nach dem Verdünnen mit Wasser auf einen Konzentratgehalt von 1 bis 20 Gew.-%, bezogen auf die erhaltene funktionelle Flüssigkeit, einen pH-Wert von 8,4 bis 9,8, vorzugsweise von 9,0 bis 9,5 auf.According to a preferred embodiment, the water-miscible concentrate after dilution with water to a concentrate content of 1 to 20 wt .-%, based on the resulting functional liquid, a pH of 8.4 to 9.8, preferably 9.0 to 9.5 on.

Gemäß einer weiteren Ausführungsform betrifft die Erfindung die Verwendung des oben definierten wassermischbaren Konzentrats für die Herstellung eines Schmiermittels, eines Schleifmittels, einer Hydraulikflüssigkeit oder eines Kühlschmiermittels auf Wassergrundlage für die Metallumformung und die Metallzerspanung durch Vermischen von 1 bis 20 Gew.-%, vorzugsweise 2 bis 5 Gew.-% des oben definierten wassermischbaren Konzentrats, mit 99 bis 80 Gew.-%, vorzugsweise 99 bis 95 Gew.-% Wasser. Unter spanloser Metallumformung ist im Rahmen der erfindungsgemäßen Verwendung das Tiefziehen. Kaltfließpressen oder Walzen zu verstehen, während die spanende Metallverarbeitungen das Drehen, Fräsen, Bohren und Schleifen von Metallen umfaßt.According to a further embodiment, the invention relates to the use of the above-defined water-miscible concentrate for the production of a lubricant, an abrasive, a hydraulic fluid or a water-based cooling lubricant for metal forming and metal cutting by mixing from 1 to 20% by weight, preferably 2 to 5% by weight of the above-defined water-miscible concentrate, having 99 to 80 Wt .-%, preferably 99 to 95 wt .-% water. Under non-cutting metal forming in the context of the inventive use deep drawing. Cold extrusion or rolling, while the metal cutting operations include turning, milling, drilling and grinding of metals.

Es hat sich überraschenderweise gezeigt, daß das erfindungsgemäße wassermischbare Konzentrat auch beim Vermischen mit Wasser mit einer Härte von 3°dH bis 42°dH bei einem Konzentratanteil von 2% HFA-Hydraulikflüssigkeit in Form von Emulsionen ergibt, die auch nach 600 Stunden bei einer Temperatur von 50°C absolut stabil sind.It has surprisingly been found that the water-miscible concentrate according to the invention even when mixed with water having a hardness of 3 ° dH to 42 ° dH at a concentrate content of 2% HFA hydraulic fluid results in the form of emulsions, even after 600 hours at a temperature of 50 ° C are absolutely stable.

Das erfindungsgemäße Korrosionsschutzmittel wird durch einfaches Vermischen der Bestandteile hergestellt. Das wassermischbare Konzentrat der vorliegenden Erfindung wird dadurch hergestellt, daß man die in Wasser löslichen beziehungsweise in Wasser dispergierbaren Bestandteile zunächst in Wasser einbringt, dann die öllöslichen Bestandteile in der Ölkomponente löst oder dispergiert und dann die wasserhaltige Mischung langsam der Mineralölmischung zusetzt.The corrosion inhibitor of the invention is prepared by simply mixing the ingredients. The water-miscible concentrate of the present invention is prepared by first introducing the water-soluble or water-dispersible ingredients into water, then dissolving or dispersing the oil-soluble ingredients in the oil component, and then slowly adding the hydrous mixture to the mineral oil mixture.

Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung.The following examples serve to further illustrate the invention.

In den Beispielen und den Vergleichsbeispielen wird der mit dem erfindungsgemäßen Korrosionsschutzmittel erzielte Korrosionsschutzeffekt mit Hilfe des Spaltkorrosionstests, entsprechend der DSK Norm N 762 830 bestimmt. Das Verfahren der Korrosionsprüfung mit Hilfe dieses Spaltkorrosionstests ist veröffentlicht in Glückauf 138 (2002) Nr. 5, Seiten 208-212. Das Verfahren besteht darin, daß die zu prüfende Druckflüssigkeit oder Hydraulikflüssigkeit in einer definierten Stempeleinheit (Kolben-Zylinder) unter rein statischen Bedingungen während 21 Tagen bei einer Luftfeuchtigkeit von 95% und einer Prüftemperatur von 35°C gelagert wird. Der Spaltbereich ist zwischen der Zylinderinnenoberfläche und einem auf dem Kolben befindlichen Bronzeteil ausgebildet. Auf dem Bronzeteil ist ein handelsüblicher Dichtring aufgezogen. Nach einer Kontaktzeit mit der zu prüfenden Flüssigkeit während 21 Tagen wird die Stempeleinheit demontiert und der Spaltbereich auf der Zylinderinnenoberfläche im Hinblick auf eine Korrosionsausbildung untersucht. Bei diesem Spaltkorrosionstest zeigt sich, daß bei unzureichendem Korrosionsschutz neben einer Lochkorrosion und Kraterbildungen auch belagsähnliche, farblich sehr unterschiedliche Korrosionsprodukte im Spaltbereich auf der Zylinderoberfläche abgelagert werden. Wenn sich diese Beläge im Spaltbereich des Dichtrings auf der Zylinderoberfläche finden, so finden sie sich in der Regel auch auf der Dichtringoberfläche und der Bronzeoberfläche. Insbesondere sammeln sich an der Dichtlippe kleinere Partikel an, die für eine linienförmige Korrosion in Umfangsrichtung der Zylinderoberfläche verantwortlich sind. Im Hinblick auf die Definition des Begriffes "Spaltkorrosion" ist auf die Norm DIN EN ISO 8044-3.17 zu verweisen.In the examples and the comparative examples, the corrosion protection effect achieved with the anticorrosion agent according to the invention is determined by means of the crevice corrosion test, in accordance with DSK standard N 762 830. The method of corrosion testing by means of this crevice corrosion test is published in Glückauf 138 (2002) No. 5, pages 208-212. The method consists in that the pressure fluid or hydraulic fluid to be tested in a defined punch unit (piston-cylinder) is stored under purely static conditions for 21 days at a humidity of 95% and a test temperature of 35 ° C. The gap region is formed between the cylinder inner surface and a bronze part located on the piston. On the bronze part, a commercially available sealing ring is mounted. After a contact time with the liquid to be tested for 21 days, the stamp unit is dismantled and examined the gap area on the cylinder inner surface with respect to a corrosion formation. In this crevice corrosion test shows that inadequate corrosion protection in addition to a pitting and cratering also deposit-like, very different color corrosion products are deposited in the gap area on the cylinder surface. If these deposits are found in the gap area of the sealing ring on the cylinder surface, they are usually also found on the sealing ring surface and the bronze surface. In particular, smaller particles collect on the sealing lip, which are responsible for a linear corrosion in the circumferential direction of the cylinder surface. With regard to the definition of the term "crevice corrosion", reference should be made to the standard DIN EN ISO 8044-3.17.

Beispiele 1 bis 5 und Vergleichsbeispiele A bis EExamples 1 to 5 and Comparative Examples A to E

Aus den in den nachfolgenden Tabellen 1 bis 3 angegebenen Bestandteilen werden zunächst wassermischbare Konzentrate hergestellt, die dann im Verhältnis von 2 Gewichtsteilen Konzentrat mit 98 Gewichtsteilen Wasser vermischt werden, unter Bildung einer HFA-Hydraulikflüssigkeit, die bei dem oben angesprochenen Spaltkorrosionstest untersucht wird.Water-mixable concentrates are first prepared from the constituents indicated in the following Tables 1 to 3, which are then mixed in a ratio of 2 parts by weight concentrate with 98 parts by weight of water, to form a HFA hydraulic fluid, which is examined in the above-mentioned crevice corrosion test.

Für die Herstellung der wassermischbaren Konzentrate wird zunächst Wasser vorgelegt, wonach Kaliumhydroxid zugegeben und unter Rühren gelöst wird. Anschließend werden die jeweils verwendeten Säuren, wie Sebacinsäure, Dodecandisäure, Undecandisäure beziehungsweise im Vergleichsbeispiel E Neodecansäure, zugesetzt, und es wird so lange bei einer Temperatur von 50°C gerührt, bis der pH-Wert der Mischung bei 7 liegt. Anschließend werden Natriumcitrat und Monoethanolamin zugesetzt und man läßt die Mischung unter Rühren auf 25°C abkühlen.For the preparation of the water-mixable concentrates, water is initially introduced, after which potassium hydroxide is added and dissolved with stirring. Subsequently, the particular acids used, such as sebacic acid, dodecanedioic acid, undecanedioic acid or in Comparative Example E neodecanoic acid added, and it is stirred at a temperature of 50 ° C until the pH of the mixture is 7. Subsequently, sodium citrate and monoethanolamine are added and the mixture is allowed to cool with stirring to 25 ° C.

In einem getrennten Gefäß erwärmt man einen Teil des als Schmierstoff eingesetzten aliphatischen Kohlenwasserstoffs (50%) und gibt anschließend die Fettsäurealkanolamide, Natriumpetrolsulfonat unter Rühren zu und anschlie-ßend den verbliebenen aliphatischen Kohlenwasserstoff, gefolgt von den restlichen Bestandteilen. Anschließend mischt man gut durch und gibt unter Rühren die in der ersten Stufe erhaltene wasserhaltige Mischung zu der Mischung auf der Grundlage von aliphatischen Kohlenwasserstoffs zu. Man erhält ein hellbraunes, klares, leicht viskoses Konzentrat, welches dann mit Wasser vermischt wird unter Bildung einer funktionellen Flüssigkeit auf Wassergrundlage (HFA-Hydraulikflüssigkeit) mit einem Gehalt von 2 Gew.-% des Konzentrats und 98 Gew.-% Wasser. Diese HFA-Hydraulikflüssigkeit wird in den Spaltbereich der Stempeleinheit für den Spaltkorrosionstest eingebracht und während 21 Tagen bei einer Luftfeuchtigkeit von 95% und einer Temperatur von 35°C statisch gelagert. Nach der Öffnung der Stempeleinheit und dem Entfernen der darin enthaltenen HFA-Hydaulikflüssigkeit wird die Prüfeinrichtung im Hinblick auf die Verschlammung im Bodenbereich des Außenrohrs, im Spaltbereich und im Bronzekolbenbereich untersucht und auf Ablagerungen vor der Reinigung im Innenrohr und im Außenrohr und auf Anlauffarbe nach der Reinigung im Innenrohr und im Außenrohr und auf feste Ablagerungen an der Innenfläche des Zylinders und im Spaltbereich des Zylinders sowie an der Oberfläche des Bronzekolbens untersucht.A portion of the aliphatic hydrocarbon lubricant (50%) is heated in a separate vessel and then the fatty acid alkanolamides, sodium petroleum sulfonate is added with stirring and then the remaining aliphatic hydrocarbon followed by the remaining ingredients. The mixture is then thoroughly mixed and, with stirring, the water-containing mixture obtained in the first stage is added to the aliphatic hydrocarbon-based mixture. This gives a light brown, clear, slightly viscous concentrate, which is then mixed with water to form a water-based functional fluid (HFA hydraulic fluid) containing 2 wt .-% of the concentrate and 98 wt .-% water. This HFA hydraulic fluid is introduced into the gap area of the stamp unit for the crevice corrosion test and statically stored for 21 days at a humidity of 95% and a temperature of 35 ° C. After opening the stamp unit and removing the HFA-Hydaulikflüssigkeit contained therein, the tester is examined with regard to the sludge in the bottom area of the outer tube, in the gap area and bronze piston area and deposits before cleaning in the inner tube and the outer tube and on tarnish after cleaning in the inner tube and in the outer tube and on solid deposits on the inner surface of the cylinder and in the gap region of the cylinder and on the surface of the bronze piston examined.

Wie in den nachfolgenden Tabellen 1 bis 3 angegeben ist, ergeben sich mit den HFA-Hydraulikflüssigkeiten nach der vorliegenden Erfindung keinerlei Korrosionseffekte, während die Produkte der Vergleichsbeispiele A bis E den Korrosionstest entsprechend der DSK Norm N 762 830 nicht bestehen, da sich sowohl Ablagerungen vor der Reinigung am Zylinder feststellen lassen, ebenso wie feste Ablagerungen im Spaltbereich des Zylinders und eine linienförmige Korrosion in Umfangsrichtung im Spaltbereich des Zylinders. Tabelle 1 Beispiel 1 Vergleich A Beispiel 2 Vergleich B Bestandteile Gew.-% Gew.-% Gew.-% Gew.-% Wasser 28,0 31,6 28,0 32,0 Totuyltriazol/Benzotriazol 0,5 0,5 0,5 0,5 Fettalkoholpolyglykolether 3,6 3.6 3,6 3,6 Oleoylsarkosid 1,8 1,8 1,8 1,8 Hexahydrotriazin 1,2 1,2 1,2 1,2 aliphat. Kohlenwasserstoff Siedebereich <200°C (BNS 4) 42,8 42,8 42,8 42,8 Synthetisches Natriumpetrolsulfonat 1,8 1,8 1,8 1,8 Kaliumhydroxid 1,3 1,3 1,3 Natriumcitrat 0,9 0,9 0,9 0,9 Triäthanolamin rein Oleylethercarbosäure 5 EO 1,8 1,8 1,8 1,8 5-, 6-Carboxy-4-hexyl-2-cyclohexen-1-octansäure Polysiloxan-Entschäumer 0,25 0,25 0,25 0,25 Monoethanolamin 2,6 2,6 2,6 2,6 Tallölfettsäure 2-Ethylhexylphosphorsäure 3-Jod-2Propinylbutylcarbamat 0,35 0,35 0,35 0,35 Bis(3-aminopropyl)-dodecyl-amin 0,5 0,5 0,5 0,5 Kokosfettsäurealkanolamid 3,0 3,0 Tallölfettsäurealkanolamid 6,3 6,3 3,3 3.3 n-Butanol 0,9 0,9 0,9 Benzylalkohol 2,7 2,7 2,7 Butyldiglykol Sebacinsäure Dodecandisäure 1,35 1,35 1,35 Undecandisäure 1,35 1,35 1,35 Neodecansäure (C10 Monocarbonsäure) Summe 100,00 100,00 100,00 100,00 pH-Wert nach dem Verdünnen 9,3 8,8 9,2 9,4 Spaltkorrosionstest gemäß DSK N 762 830 keine Korrosion Ablagerungen im Zylinder, feste Ablagerungen, Linienkorrosion keine Korrosion Ablagerungen im Zylinder, feste Ablagerungen, Linienkorrosion Tabelle 2 Beispiel 3 Vergleich C Beispiel 4 Vergleich D Bestandteile Gew.-% Gew.-% Gew.-% Gew.-% Wasser 25,7 30,1 59,0 62.5 Toluyltriazol/Benzotriazol 0,2 0,2 0,2 0,2 Fettalkoholpolyglykolether 3,6 3,6 3,0 3,0 Oleoylsarkosid 1,8 1,8 1,0 1,0 Hexahydrotriazin 0,5 0,5 1,0 1,0 aliphat. Kohlenwasserstoff Siedebereich <200°C (BNS 4) 42,8 42,8 13,0 13,0 Synthetisches Natriumpetrolsul- 1,8 1,8 1,0 1,0 Kaliumhydroxid 1,0 1,0 1,0 1,0 Natriumcitrat 0,9 0,9 1,0 1,0 Triäthanolamin rein Oleylethercarbonsäure 5 EO 1,8 1,8 2,0 2,0 5-, 6-Carboxy-4-hexyl-2-cyclohexen-1-octansäure 0,75 0,75 Polysiloxan-Entschäumer 0,25 0,25 0,5 0,5 Monoethanolamin 4,3 4,3 3,8 3,8 Tallöliettsäure 0,8 0,8 2-Ethylhexylphosphorsäure 2,0 2,0 3,0 3,0 3-Jod-2Propinylbutylcarbamat Bis(3-aminopropyl)-dodecyl-amin 0,5 0,5 Koltosfettsäurealkanolamid 5,0 5,0 5,0 5,0 Tallölfeftsäurealkanolamid n-Butanol 0,9 1,0 Benzylalkohol 2,5 2,5 Butyldiglykol 1,0 Sebacinsäure 1,0 1,0 Dodecandisäure 1,0 1,0 Undecandisäure 1,0 1,0 1,0 1,0 Neodecansäure (C10 Monocarbonsäure) Summe 100,00 100,00 100,0 100,0 pH-Wert nach dem Verdünnen 9,40 9,40 9,2 8,6 Spaltkorrosionstest gemäß DSK N 762 830 keine Korrosion Ablagerungen im Zylinder, feste Ablagerungen, Linienkorrosion keine Korrosion Ablagerungen im Zylinder, feste Ablagerungen, Linienkorrosion Tabelle 3 Beispiel 5 Vergleich E Bestandteile Gew.-% Gew.-% Wasser 61,5 61,5 Toluyltriazol/Benzotriazol 0,2 0,2 Fettalkoholpolyglykolether 3,0 3,0 Oleoylsarkosid 1,0 1,0 Hexahydrotriazin 1,0 1,0 aliphat. Kohlenwasserstoff Siedebereich <200°C (BNS 4) 13,0 13,0 Synthetisches Natriumpetrolsulfonat 1,0 1,0 Kaliumhydroxid 1,0 1,0 Natriumcitrat 1,0 1,0 Triäthanolamin rein 2,0 2,0 Oleylethercarbonsäure 5 EO 2,0 2,0 5-, 6-Carboxy-4-hexyl-2-cyclohexen-1-octansäure Polysiloxan-Entschäumer 0,5 0,5 Monoethanolamin 0,3 0,3 Tallölfettsäure 2-Ethylhexylphosphorsäure 3-Jod-2Propinylbutylcarbamat Bis(3-aminopropyl)-dodecylamin kokosfettsäurealkanolamid 5,0 5,0 Tallölfettsänrealkanolamid n-Butanol 1,0 1,0 Benzylalkohol 1,5 1,5 Butyldiglykol 3,0 3,0 Sebacinsäure Dodecandisäure 1,0 Undecandisäure 1,0 Neodecansäure (C10 Monocarbonsäure) 2,0 Summe 100,00 100,00 pH-Wert nach dem Verdünnen 8,9 9,0 Spaltkorrosionstest gemäß DSK N 762 830 keine Korrosion Ablagerungen im Zylinder, feste Ablagerungen, Linienkorrosion As indicated in Tables 1 to 3 below, the HFA hydraulic fluids of the present invention do not give rise to any corrosion effects, while the products of Comparative Examples A to E do not pass the corrosion test according to DSK Standard N 762 830, since both deposits are present the cleaning on the cylinder notice, as well as solid deposits in the gap region of the cylinder and a line-shaped corrosion in the circumferential direction in the gap region of the cylinder. Table 1 example 1 Comparison A Example 2 Comparison B ingredients Wt .-% Wt .-% Wt .-% Wt .-% water 28.0 31.6 28.0 32.0 Totuyltriazol / benzotriazole 0.5 0.5 0.5 0.5 Fettalkoholpolyglykolether 3.6 3.6 3.6 3.6 Oleoylsarkosid 1.8 1.8 1.8 1.8 hexahydrotriazine 1.2 1.2 1.2 1.2 aliphatic. Hydrocarbon boiling range <200 ° C (BNS 4) 42.8 42.8 42.8 42.8 Synthetic sodium petrol sulfonate 1.8 1.8 1.8 1.8 potassium hydroxide 1.3 1.3 1.3 sodium citrate 0.9 0.9 0.9 0.9 Triethanolamine pure Oleyl ether carboxylic acid 5 EO 1.8 1.8 1.8 1.8 5-, 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid Polysiloxane defoamers 0.25 0.25 0.25 0.25 Monoethanolamine 2.6 2.6 2.6 2.6 tall oil fatty acid 2-ethylhexyl phosphoric acid 3 Iodine 2Propinylbutylcarbamat 0.35 0.35 0.35 0.35 Bis (3-aminopropyl) dodecyl-amine 0.5 0.5 0.5 0.5 Kokosfettsäurealkanolamid 3.0 3.0 Tallölfettsäurealkanolamid 6.3 6.3 3.3 3.3 n-butanol 0.9 0.9 0.9 benzyl alcohol 2.7 2.7 2.7 diglycol sebacic dodecanedioic 1.35 1.35 1.35 undecanoic 1.35 1.35 1.35 Neodecanoic acid (C 10 monocarboxylic acid) total 100.00 100.00 100.00 100.00 pH after dilution 9.3 8.8 9.2 9.4 Crevice corrosion test according to DSK N 762 830 no corrosion Deposits in the cylinder, solid deposits, line corrosion no corrosion Deposits in the cylinder, solid deposits, line corrosion Table 2 Example 3 Comparison C Example 4 Comparison D ingredients Wt .-% Wt .-% Wt .-% Wt .-% water 25.7 30.1 59.0 62.5 Tolyltriazole / benzotriazole 0.2 0.2 0.2 0.2 Fettalkoholpolyglykolether 3.6 3.6 3.0 3.0 Oleoylsarkosid 1.8 1.8 1.0 1.0 hexahydrotriazine 0.5 0.5 1.0 1.0 aliphatic. Hydrocarbon boiling range <200 ° C (BNS 4) 42.8 42.8 13.0 13.0 Synthetic Sodium Petroleum Sulphate 1.8 1.8 1.0 1.0 potassium hydroxide 1.0 1.0 1.0 1.0 sodium citrate 0.9 0.9 1.0 1.0 Triethanolamine pure Oleyl ether carboxylic acid 5 EO 1.8 1.8 2.0 2.0 5-, 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid 0.75 0.75 Polysiloxane defoamers 0.25 0.25 0.5 0.5 Monoethanolamine 4.3 4.3 3.8 3.8 Tallöliettsäure 0.8 0.8 2-ethylhexyl phosphoric acid 2.0 2.0 3.0 3.0 3 Iodine 2Propinylbutylcarbamat Bis (3-aminopropyl) -dodecyl-amine 0.5 0.5 Koltosfettsäurealkanolamid 5.0 5.0 5.0 5.0 Tallölfeftsäurealkanolamid n-butanol 0.9 1.0 benzyl alcohol 2.5 2.5 diglycol 1.0 sebacic 1.0 1.0 dodecanedioic 1.0 1.0 undecanoic 1.0 1.0 1.0 1.0 Neodecanoic acid (C 10 monocarboxylic acid) total 100.00 100.00 100.0 100.0 pH after dilution 9.40 9.40 9.2 8.6 Crevice corrosion test according to DSK N 762 830 no corrosion Deposits in the cylinder, solid deposits, line corrosion no corrosion Deposits in the cylinder, solid deposits, line corrosion Table 3 Example 5 Comparison E ingredients Wt .-% Wt .-% water 61.5 61.5 Tolyltriazole / benzotriazole 0.2 0.2 Fettalkoholpolyglykolether 3.0 3.0 Oleoylsarkosid 1.0 1.0 hexahydrotriazine 1.0 1.0 aliphatic. Hydrocarbon boiling range <200 ° C (BNS 4) 13.0 13.0 Synthetic sodium petrol sulfonate 1.0 1.0 potassium hydroxide 1.0 1.0 sodium citrate 1.0 1.0 Triethanolamine pure 2.0 2.0 Oleyl ether carboxylic acid 5 EO 2.0 2.0 5-, 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid Polysiloxane defoamers 0.5 0.5 Monoethanolamine 0.3 0.3 tall oil fatty acid 2-ethylhexyl phosphoric acid 3 Iodine 2Propinylbutylcarbamat Bis (3-aminopropyl) dodecylamine kokosfettsäurealkanolamid 5.0 5.0 Tallölfettsänrealkanolamid n-butanol 1.0 1.0 benzyl alcohol 1.5 1.5 diglycol 3.0 3.0 sebacic dodecanedioic 1.0 undecanoic 1.0 Neodecanoic acid (C 10 monocarboxylic acid) 2.0 total 100.00 100.00 pH after dilution 8.9 9.0 Crevice corrosion test according to DSK N 762 830 no corrosion Deposits in the cylinder, solid deposits, line corrosion

Namentlich das Vergleichsbeispiel E läßt erkennen, daß eine Hydraulikflüssigkeit auf Wassergrundlage, die Neodecansäure, also eine C10-Monocarbonsäure enthält, erhebliche Korrosionswirkungen entfaltet und demzufolge für die Anwendung als HFA-Hydraulikflüssigkeit ungeeignet ist, während das erfindungsgemäße Korrosionsschutzmittel und die es enthaltende HFA-Hydraulikflüssigkeit, welche sich durch die erfindungsgemäße Auswahl der besonderen aliphatischen Dicarbonsäuren von dem Produkt des Standes der Technik unterscheidet, keinerlei Korrosionswirkung zeigt und ohne weiteres für den Einsatz in beispielsweise hydraulischen Strebausbausystemen für den Bergbau geeignet ist.In particular, Comparative Example E reveals that a water-based hydraulic fluid containing neodecanoic acid, ie a C 10 monocarboxylic acid, develops considerable corrosive effects and consequently unsuitable for use as HFA hydraulic fluid, while the anticorrosion agent according to the invention and the HFA hydraulic fluid containing it , which differs from the product of the prior art by the inventive selection of the particular aliphatic dicarboxylic acids, shows no corrosion effect and is readily suitable for use in, for example, hydraulic longwall mining systems.

Dieses Ergebnis der sprunghaften Verbesserung der Korrosionsschutzwirkung durch die erfindungsgemäße Kombination aus dem definierten Fettsäurealkanolamid, dem definierten Alkohol und der definierten aromatischen Monocarbonsäure beziehungsweise den definierten aliphatischen Dicarbonsäuren, ist überraschend und in keiner Weise zu erwarten gewesen.This result of the abrupt improvement of the corrosion protection effect by the combination according to the invention of the defined fatty acid alkanolamide, the defined alcohol and the defined aromatic monocarboxylic acid or the defined aliphatic dicarboxylic acids, has been surprising and was not to be expected in any way.

Claims (27)

  1. Corrosion protectant for functional fluids, comprising 5 to 80 weight % of at least one fatty acid alkanolamide based on saturated or unsaturated fatty acids with 10 to 20 carbon atoms, 5 to 80 weight % of at least one alcohol with 2 to 14 carbon atoms selected from the group comprising isopropanol, n-butanol, butyl diglycol, hexylene glycol, butyl triglycol, benzyl alcohol, and phenoxyethanol, and 5 to 80 weight % of at least one aromatic monocarboxylic acid or an aliphatic dicarboxylic acid with 10 to 12 carbon atoms selected from the group comprising sebacic acid, undecanedioic acid, dodecanedioic acid, and p-tert-butylbenzoic acid, where the sum of these components is 100 weight % and the weight % is relative to the weight of the corrosion protectant.
  2. Corrosion protectant as in claim 1, characterized in that it contains 25 to 60 weight % of at least one fatty acid alkanolamide, 15 to 25 weight % of at least one alcohol, and 20 to 50 weight % of at least one aromatic monocarboxylic acid or aliphatic dicarboxylic acid, and the sum of these components is 100 weight %.
  3. Corrosion protectant as in claim 1 or 2, characterized in that it contains fatty acid alkanolamides based on saturated or unsaturated fatty acids with 12 to 18 carbon atoms and alkanolamines with 2 to 6 carbon atoms.
  4. Corrosion protectant as in claim 3, characterized in that it contains fatty acid alkanolamides based on saturated or unsaturated fatty acids with 12 to 18 carbon atoms and monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propandiol and/or diglycolamine.
  5. Corrosion protectant as in claim 4, characterized in that it contains coco fatty acid monoalkanolamide and/or tall oil fatty acid monoalkanolamide as the fatty acid alkanolamide.
  6. Corrosion protectant as in claim 5, characterized in that it contains a reaction product of coco fatty acid, coconut oil, tall oil fatty acid, and/or tall oil and diglycolamine as the fatty acid alkanolamide.
  7. Corrosion protectant as in claim 5, characterized in that it contains coco fatty acid monoethanolamide, coco fatty acid monopropanolamide, tall oil fatty acid monoethanolamide and/or tall oil fatty acid monopropanolamide as the fatty acid alkanolamide.
  8. Water-soluble concentrate for aqueous functional fluids containing animal, vegetable, mineral, and/or synthetic oils, fats, oil or fat components as a lubricant, fatty alcohols, biocides, fungicides, complexing agents, heavy metal inhibitors, nonionic or anionic emulsifiers, dispergents, anti-foaming agents, corrosion protectant, and water, and typical additives as a remainder, characterized in that it contains as a corrosion protectant 2 to 20 weight %, preferably 5 to 15 weight %, of the corrosion protectant as in one of the claims 1 through 7, and the weight % is relative to the weight of the concentrate.
  9. Concentrate as in claim 8, characterized in that it contains 1 to 12 weight % of at least one fatty acid alkanolamide based on saturated or unsaturated fatty acids with 10 to 20 carbon atoms, 1 to 8 weight % of at least one alcohol with 2 to 14 carbon atoms, and 1 to 8 weight % of at least one aromatic monocarboxylic acid or aliphatic dicarboxylic acid with 10 to 12 carbon atoms.
  10. Concentrate as in claim 9, characterized in that it contains 2 to 8 weight % of at least one fatty acid alkanolamide, 1.5 to 5 weight % of at least one alcohol, and 1 to 5 weight % of at least one aromatic monocarboxylic acid or aliphatic dicarboxylic acid.
  11. Concentrate as in at least one of the claims 8 through 10, characterized in that it contains fatty acid alkanolamides based on saturated or unsaturated fatty acids with 12 to 18 carbon atoms and alkanolamines with 2 to 6 carbon atoms.
  12. Concentrate as in claim 11, characterized in that it contains fatty acid alkanolamides based on saturated or unsaturated fatty acids with 12 to 18 carbon atoms and monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propandiol and/or diglycolamine.
  13. Concentrate as in claim 11, characterized in that it contains coco fatty acid monoalkanolamide and/or tall oil fatty acid monoalkanolamide as the fatty acid alkanolamide.
  14. Concentrate as in claim 13, characterized in that it contains a reaction product of coco fatty acid, coconut oil, tall oil fatty acid, and/or tall oil and diglycolamine as the fatty acid alkanolamide.
  15. Concentrate as in claim 13, characterized in that it contains coco fatty acid monoethanolamide, coco fatty acid monopropanolamide, tall oil fatty acid monoethanolamide and/or tall oil fatty acid monopropanolamide as the fatty acid alkanolamide.
  16. Concentrate as in at least one of the claims 8 to 15, characterized in that it contains 0.5 to 3 weight % of a biocidal compound that is selected from biocidal quaternary ammonium compounds, guanidine derivates, O- or N-formals, O- or N-acetals, isothiazolines, isothiazolinones, aliphatic amines or diamines, 3-iodine-2-propinyl-butyl carbamate, bis(3-aminopropyl)-dodecylamine and mixtures thereof.
  17. Concentrate as in at least one of the claims 8 to 16, characterized in that it contains 0.5 to 3 weight % of a fungicidal pyridine derivate, preferably pyrithion or a pyrithion derivate such as 2-pyridinthiol-1-oxide sodium salt as a fungicide or bactericide.
  18. Concentrate as in at least one of the claims 8 to 17, characterized in that it contains 0.5 to 5 weight % of ethylenediaminetetraacetic acid or its alkali or ammonium salts, sodium citrate, sodium gluconate, N,N'-disalicylidene, and/or derivates of them as a complexing agent.
  19. Concentrate as in at least one of the claims 8 to 18, characterized in that it contains 1 to 8 weight %, preferably 2 to 5 weight % of an additional corrosion protectant selected from phosphoric acid esters, such as ethylhexylphosphoric acid, phosphonic acid derivatives, diamine oxethylate, triamine oxethylate, alkylimidazolines, polyaminenaphthalenic acid amides, synthetic or natural sulfonates, such as petroleum sulfonates, p-tert-butyl benzoic acid, tricarboxylic acids, neodecanoic acids, 5 or 6-carboxy-4-hexyl-2-hexene-1-octane acid, saturated or unsaturated fatty acids, ethoxylated or propoxylated fatty acids and fatty acid alkanolamides, thiadiazole compounds, and mixtures of these.
  20. Concentrate as in at least one of the claims 8 to 19, characterized in that it contains 3 to 25 weight % of a reaction product from boric acid and primary or tertiary alkanolamines as an additional corrosion protectant.
  21. Concentrate as in at least one of the claims 8 to 20, characterized in that it contains 0.05 to 1.5 weight % benzotriazole and/or toluyltriazole and/or derivatives thereof as a heavy metal inhibitor.
  22. Concentrate as in at least one of the claims 8 to 21, characterized in that it contains 3 to 70 weight % of a natural or synthetic mineral oil; 2 to 40 weight % of an ester oil; 1 to 6 weight % of a phospated and/or ethyloxylated alcohol and/or 2 to 35 weight % of a polyalkylene glycol and/or polyvinylpyrrolidone as an animal, vegetable, mineral, and/or synthetic lubricant, with the requirement that this lubricant makes up 10 to 70 weight % of the concentrate.
  23. Concentrate as in at least one of the claims 8 to 22, characterized in that it contains 0.05 to 1 weight % of a siloxane compound as a defoamer.
  24. Concentrate as in at least one of the claims 8 to 23, characterized in that it contains 1 to 5 weight % oleoylsarcoside and/or ethoxylated oleylethercarboxylic acid as an emulsifier.
  25. Concentrate as in at least one of the claims 8 to 24, characterized in that it contains 0.2 to 5 weight % of an acrylic polymer salt as a dispersant, in particular a salt of a poly(meth)acrylic acid.
  26. Concentrate as in at least one of the claims 8 to 25, characterized in that it has a pH value of 8.4 to 9.8, preferably 9.0 to 9.5, after diluting with water to a concentration of 1 to 20 weight % relative to the functional fluid obtained.
  27. Use of the water-soluble concentrate as in at least one of the claims 8 through 26 for the manufacture of a lubricant, an abrasive, a hydraulic fluid, and a coolant/lubricant on an aqueous basis for metal forming and metal cutting, by mixing from 1 to 20 weight % with 99 to 80 weight % of water.
EP04024857A 2004-10-19 2004-10-19 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use. Active EP1652909B2 (en)

Priority Applications (19)

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DE502004006426T DE502004006426D1 (en) 2004-10-19 2004-10-19 Corrosion inhibitor for functional fluids, water-miscible concentrate and its use
SI200430722T SI1652909T2 (en) 2004-10-19 2004-10-19 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use.
PL04024857T PL1652909T5 (en) 2004-10-19 2004-10-19 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use.
EP04024857A EP1652909B2 (en) 2004-10-19 2004-10-19 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use.
ES04024857T ES2304575T5 (en) 2004-10-19 2004-10-19 CORROSION INHIBITOR FOR FUNCTIONAL FLUIDS, CONCENTRATE OF MISCIBLE LUBRICANT IN WATER AND ITS USE.
DK04024857.7T DK1652909T4 (en) 2004-10-19 2004-10-19 Corrosion protection agent for functional liquids, water miscible concentrate and use thereof
PT04024857T PT1652909E (en) 2004-10-19 2004-10-19 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use.
AT04024857T ATE388218T1 (en) 2004-10-19 2004-10-19 CORROSION PROTECTION AGENT FOR FUNCTIONAL LIQUIDS, WATER-MIXABLE CONCENTRATE AND USE THEREOF
MX2007004705A MX2007004705A (en) 2004-10-19 2005-10-17 Corrosion protection agent for functional fluids water-miscible concentrate and use thereof.
RU2007118665/04A RU2397275C2 (en) 2004-10-19 2005-10-17 Anticorrosion agent for functional fluids, water-miscible concentrate and use thereof
PCT/EP2005/011149 WO2006042730A1 (en) 2004-10-19 2005-10-17 Corrosion protection agent for functional fluids water-miscible concentrate and use thereof
US11/665,160 US7851420B2 (en) 2004-10-19 2005-10-17 Corrosion protection agent for functional fluids water-miscible concentrate and use thereof
AU2005296748A AU2005296748B2 (en) 2004-10-19 2005-10-17 Corrosion protection agent for functional fluids water-miscible concentrate and use thereof
CN2005800358063A CN101044230B (en) 2004-10-19 2005-10-17 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use
ARP050104363A AR055503A1 (en) 2004-10-19 2005-10-19 ANTI-CORROSIVE FOR FUNCTIONAL LIQUIDS CONCENTRATED MISCIBLE WITH WATER AND ITS USE
HK06111658A HK1089786A1 (en) 2004-10-19 2006-10-23 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use
ZA200701941A ZA200701941B (en) 2004-10-19 2007-03-06 Corrosion protection agent for functional fluids water-miscible concentrate and use thereof
HR20080237T HRP20080237T4 (en) 2004-10-19 2008-05-29 Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use
CY20081100572T CY1108108T1 (en) 2004-10-19 2008-06-02 PROTECTIVE MEASURES AGAINST CORROSION Corrosion-proof liquid condensate which may be mixed with water and used

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US20070298983A1 (en) 2007-12-27
AU2005296748B2 (en) 2010-09-09
DE502004006426D1 (en) 2008-04-17
HRP20080237T3 (en) 2008-06-30
PT1652909E (en) 2008-06-09
SI1652909T1 (en) 2008-08-31
ZA200701941B (en) 2008-10-29
AR055503A1 (en) 2007-08-22
US7851420B2 (en) 2010-12-14
AU2005296748A1 (en) 2006-04-27
RU2397275C2 (en) 2010-08-20
WO2006042730A1 (en) 2006-04-27
ES2304575T5 (en) 2011-10-18
RU2007118665A (en) 2008-11-27
SI1652909T2 (en) 2011-09-30
ES2304575T3 (en) 2008-10-16
MX2007004705A (en) 2007-09-07
PL1652909T3 (en) 2008-08-29
CY1108108T1 (en) 2014-02-12
HRP20080237T4 (en) 2011-08-31
EP1652909A1 (en) 2006-05-03
DK1652909T4 (en) 2011-08-15
HK1089786A1 (en) 2006-12-08
PL1652909T5 (en) 2011-09-30
CN101044230A (en) 2007-09-26
DK1652909T3 (en) 2008-07-07
EP1652909B1 (en) 2008-03-05
CN101044230B (en) 2010-11-10

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