EP2111440A1 - Réfrigérant lubrifiant à grand pouvoir dispersant pour l'usinage par enlèvement de copeaux par voie humide de métaux légers - Google Patents

Réfrigérant lubrifiant à grand pouvoir dispersant pour l'usinage par enlèvement de copeaux par voie humide de métaux légers

Info

Publication number
EP2111440A1
EP2111440A1 EP07821718A EP07821718A EP2111440A1 EP 2111440 A1 EP2111440 A1 EP 2111440A1 EP 07821718 A EP07821718 A EP 07821718A EP 07821718 A EP07821718 A EP 07821718A EP 2111440 A1 EP2111440 A1 EP 2111440A1
Authority
EP
European Patent Office
Prior art keywords
water
oil
emulsion concentrate
weight
emulsion
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.)
Withdrawn
Application number
EP07821718A
Other languages
German (de)
English (en)
Inventor
Thomas Molz
Florian Bauer
Markus Wunderlich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2111440A1 publication Critical patent/EP2111440A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C10N2050/011—Oil-in-water

Definitions

  • the invention relates to an oil-containing, water-miscible emulsion concentrate for the production of low-foaming oil-in-water emulsions, suitable for various technical metalworking processes in soft and hard water as cleaning, corrosion protection or cooling lubricant emulsions of light metals, especially magnesium and magnesium alloys , suitable.
  • the emulsifier system therefore contains, according to the invention, alkoxylated fatty amines, which significantly improve the dispersibility and the filterability of the application solutions of the emulsion concentrates.
  • Anti-corrosive emulsions are used as passivation agents for the temporary protection of metallic workpieces from atmospheric, corrosion-causing influences. They contain essentially non-polar or polar oils, emulsifiers, corrosion inhibitors and water. Commercial systems are based on oil concentrates containing emulsifiers and corrosion inhibitors but little or no water. The emulsifiers and corrosion inhibitors used must therefore be oil-soluble. For the preparation of oil-in-water emulsions ("O / W emulsions”) which are used in water-diluted form, such systems must be self-emulsifying.
  • O / W emulsions oil-in-water emulsions
  • Coolant emulsions which are used in the non-cutting or machining of metallic workpieces, have a composition similar to anti-corrosive emulsions, since they also have to show a corrosion-inhibiting effect. By adding suitable lubricating additives, the lubricating effect can be improved. All these types of emulsion have in common that they tend to foam because of the emulsifiers used. Foaming tendency is particularly pronounced when the emulsifier system contains anionic surfactants. When used in hard water, the foaming tendency is reduced by the fact that the anionic surfactants can form sparingly soluble salts with calcium ions, which have an antifoaming effect. In soft to medium-hard water, ie in water with less than 12 ° dH and in particular less than 8 ° dH, such emulsions are at least not applicable because of the high foam tendency when working in the spray process.
  • DE-A-19956237 discloses a low-foaming emulsifier system which can be used in both soft and hard water and has sufficient stability especially at high water hardness, consisting of a) ethoxylates / propoxylates of fatty alcohols having 8 to 18 carbon atoms in Alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units, b) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 C atoms in the alcohol and 0 to 3 propylene oxide units and / or distillation residue of these fatty alcohols and c) ether carboxylic acids of the general formula (I) or their anions,
  • R is a saturated or unsaturated, linear or branched alkyl radical having 5 to 22 C atoms
  • A is hydrogen or a methyl group
  • the corrosion protection system of the emulsion concentrate in addition to the typically used carboxylic acids for the treatment of light metals such as aluminum and magnesium and their alloys
  • alkylphosphonic having 4 to 18 carbon atoms must contain in order to significantly reduce the corrosive dissolution of the metallic workpiece.
  • the suppression of corrosion and thus inevitably occurring especially in the processing of non-precious metal workpieces hydrogen evolution is also important for safety and process engineering reasons.
  • Corrosion protection systems for light metals based on oil-in-water emulsions must also largely prevent the occurrence of tempering inks of the so-called “fountain blackened", which is a dark coloration of the aluminum-containing metallic materials in contact with the aqueous emulsion because there is largely irreversible discoloration of the surface of the material caused by superficial pickling operations, typically in the processing of aluminum, aluminum alloys and aluminum alloyed metals in aqueous systems.
  • the emulsion in a cooling lubricant system for separating the abrasion, so suspended finely divided material particles, via a fine filtration with a pore size of less than 50 microns by high pressure pumps (> 200 bar) circulated, so that the filter system by the precipitation of dissolved metal salts at insufficient dispersibility of the emulsion is overloaded in no time.
  • a premature overloading of the fine filtration system in the so-called care level of the cooling lubricant circuit is, however, absolutely necessary for procedural reasons and because of the high costs incurred for the use of new fine filters or their reprocessing.
  • the invention therefore has the object to provide an oil-containing, water-miscible emulsion concentrate, which is suitable for various technical metalworking processes in soft and hard water as a cleaning, corrosion protection or cooling lubricant emulsion for light metals such as aluminum and magnesium and their alloys, with a high Dispersibility and excellent filterability of the application solutions of the emulsion concentrate is ensured at the same time high metal salt load.
  • an emulsifier system containing a) ethoxylates / propoxylates of fatty alcohols having 8 to 18 carbon atoms in the alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and b) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 carbon atoms in the alcohol and 0 to 3 propylene oxide units and / or the distillation residue of these fatty alcohols and (IM) a corrosion protection system comprising a) straight-chain and / or branched carboxylic acids and / or phosphonic acids having 6 to 12 carbon atoms, characterized in that the emulsifier system (II) additionally contains one or more alkoxylated fatty amines (Il c).
  • alkoxylated fatty amines are preferred in the oil-containing, water-miscible emulsion concentrate consisting of one or more alkoxylated saturated and / or unsaturated aliphatic amines having an aliphatic chain length of at least 8, preferably at least 10 and more preferably at least 12, but not more than 20, preferably not more than 18 and more preferably not more than 16 carbon atoms.
  • component (IIc) fatty amines should be used which are ethoxylated with at least 8, preferably not more than 10, but not more than 16, preferably not more than 14 and most preferably 12 ethylene oxide units.
  • the oil-containing, water-miscible emulsion concentrate contains 12 times ethoxylated cocoamine to increase the filterability of an application solution of the concentrate as alkoxylated fatty amine (IIc).
  • the proportion of the oil component (I), the emulsifier system (II) and the corrosion protection system (III) on the oil-containing, water-miscible emulsion concentrate is variable depending on the type of metal working, the object underlying the invention being achieved by emulsion concentrates containing i) 5 to 50% by weight of the oil component (I), ii) from 2 to 50% by weight of the emulsifier system (II) containing the components Il a to Il b, the weight ratio of the components a: b being 1: 0.3 to 0.3: 1, and a weight proportion of the alkoxylated fatty amines (Il c) on the emulsion concentrate of at least 1 wt.%, Preferably at least 2 wt.%, But not more than 10 wt .-%, preferably not more than 8 wt .-%, iii) 2 to 15 wt .-% of the corrosion protection system (III), and optionally other excipients and active
  • fatty alcohol ethoxylates / propoxylates must be present which carry both 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units.
  • These more hydrophilic components are to be combined with the more hydrophobic components (II b) unalkoxylated fatty alcohols having 12 to 24 carbon atoms, their distillation residue or their alkoxylation with up to an average of at most 3 propylene oxide units.
  • the stated approximate weight ratio is to be observed. Distillation residue of fatty alcohols having 12 to 24 carbon atoms by Cognis Germany GmbH & Co. KG, Dusseldorf, sold under the name Pernil ® RU.
  • the chelating organic amine compounds (III b) according to the general structural formula (B) are particularly suitable for preventing the "blackened” metalworking in the emulsion concentrate.
  • n is at least 1, but not greater than 8 and preferably 3
  • the substituents X are independently selected from hydrogen atoms, alkali metal cations, ammonium ions, quaternary ammonium compounds or aliphatic radicals having not more than 4 carbon atoms, preferably from Hydrogen atoms and alkali metal cations.
  • nitrilotris methylenephosphonic acid
  • ethylenediamine tetrakis- methylenephosphonic acid
  • diethylenetriaminepentakis- methylenephosphonic acid
  • triethylenetetraminehexakis- methylenephosphonic acid
  • tetraethylenepentamineheptakis- methylenephosphonic acid
  • pentaethylenehexamine-oktakis- methylenephosphonic acid
  • hexaethyleneheptamine nonakis- methylenephosphonic acid
  • heptaethyleneoctamine decakis methylenephosphonic acid
  • the chelate-forming amine compounds (IM b) should be present in the emulsion concentrate in concentrations which, on the one hand, have an inhibiting effect on the discoloration of the material to be processed and, on the other hand, are still acceptable for reasons of economy.
  • the lower concentration limit at which just a positive effect of the inhibitor according to the invention is detectable is given by about 0.05 wt .-% of the chelating amine compounds (III b) on the emulsion concentrate. As the proportion of inhibitor increases, the performance, ie the suppression of the "fountain black", becomes more significant, with a maximum performance amounting to about 0.5% by weight.
  • the upper limit for the proportion of chelating amine compounds (IIIb) is about 2% by weight of the emulsion concentrate for efficiency and cost reasons.
  • the corrosion-inhibiting carboxylic acids and / or phosphonic acids (III a) contained in the corrosion protection system (III) of the emulsion concentrate, as already mentioned, can be straight-chain or branched. Mixtures of different acids may be particularly advantageous, the alkylphosphonic acids are particularly suitable in their straight-chain form.
  • alkylphosphonic acids having 4 to 18 carbon atoms, more preferably having 6 to 12 carbon atoms, or in each case their salts in an amount of 0.1 to 4, preferably from 0.2 to 2 parts by weight of the emulsion concentrate.
  • carboxylic acids are caprylic acid, ethylhexanoic acid, isononanoic acid and isodecanoic acid.
  • anticorrosive emulsions usually have neutral to basic pH values, it is preferable to use the inhibitors containing acid groups at least partially in neutralized form, ie as salts.
  • Particularly suitable as a basic component for neutralization are potassium hydroxide solution and / or alkanolamines, the latter enhancing the corrosion inhibitor effect.
  • dialkanolamines is less preferred. Instead, monoalkanolamines or trialkanolamines or preferably mixtures thereof are used. In particular, ethanolamines are used.
  • the corrosion protection system additionally preferably contains non-ferrous metal inhibitors. These may be selected from the group of triazoles, in particular from benzotriazoles and tolyltriazoles.
  • the emulsion concentrate then preferably contains about 0.1 to 1 part by weight of non-ferrous metal inhibitors.
  • emulsion concentrates which form low-foam emulsions as aqueous application solution largely independently of the water hardness are accessible in that the emulsifier system (II) additionally contains ether carboxylic acids (II d) or their anions of the general formula (C), RO- (CHA-CH 2 -O) n - (CH 2 ) m -COOH (C)
  • R is a saturated or unsaturated, linear or branched alkyl radical having 5 to 22 C atoms
  • A is hydrogen or a methyl group
  • n is a number in the range of 1 to 15 and m is a number in the range of 1 to 3
  • the weight ratio a: b: d of the constituents of the emulsifier system (II) except the ethoxylated fatty amines (Il c) is between 1: 0.3: 0.1 and 1: 4: 1, more preferably in the range of 1: 1: 0.1 to 1: 3: 0.5.
  • a in the general formula (C) is preferably hydrogen, i. the ether carboxylic acids of the general formula (C) preferably contain ethylene oxide groups.
  • m is preferably 1, i. the ether carboxylic acids are preferably acetyl-terminated.
  • the ether carboxylic acids of general formula (C) can be constructed very differently.
  • they may be ether carboxylic acids derived from a fatty alcohol mixture containing 12 to 14 carbon atoms in the alkyl group which has been ethoxylated with an average of 2.5 ethylene oxide units and subsequently acetyl terminated.
  • the acetyl termination can be carried out, for example, by reaction of the fatty alcohol ethoxylates with chloroacetic acid.
  • Such products are commercially available.
  • ether carboxylic acids are acetyl-terminated ether carboxylic acids of oleyl alcohol which has been ethoxylated on average with 9 ethylene oxide units, of caprylic alcohol which has been ethoxylated on average with 8 ethylene oxide units or of hexyl alcohol which has been ethoxylated on average with 6 ethylene oxide units.
  • These ether carboxylic acids can be used each alone, but also in admixture with each other. In the latter case, the quantities of the ether carboxylic acid refer to the mixture of these acids.
  • the ether carboxylic acids can be used as such or in the form of their alkali metal salts, for example the sodium salts.
  • the emulsion concentrate according to the invention can be obtained by adding the appropriate parts by weight of an oil component to the anticorrosive and emulsifier system described above.
  • an oil component such as a Concentrate by mixing together the oil component (I), the individual emulsifiers of the emulsifier (II) and the components of the corrosion protection system (III) in any order.
  • oil component (I) non-polar or polar oils of petrochemical or native origin (based on vegetable or animal oils or fats) can be used. Furthermore, synthetic oil components are suitable. Examples of usable oil components are paraffinic or naphthenic mineral oil, dialkyl ethers having 12 to 20 carbon atoms and / or ester oils.
  • emulsion concentrates according to the invention which have a considerable buffer capacity so that the pH is permanently stable even in the case of increased hydrogen evolution, which can not be completely suppressed in the processing of light metals such as magnesium and / or aluminum alloys, even in the presence of the corrosion protection system hold.
  • Particularly suitable for this purpose are boric acid-containing emulsion concentrates and, as already mentioned, concentrates which contain alkanolamines as a pH-stabilizing organic compound class.
  • the oily, water-miscible emulsion concentrate therefore contains as auxiliary and active ingredient (IV) a buffer system based on boric acid / borate, preferably in an amount based on the equivalent amount of boric acid of 2 to 10 parts by weight of the emulsion concentrate.
  • the emulsion concentrate may contain triethanolamine as further auxiliary and active ingredient (IV), preferably in an amount of 1 to 6 parts by weight of the emulsion concentrate.
  • auxiliary and active ingredient IV
  • lubricating additives in general and in particular so-called “extreme pressure" additives (so-called EP additives), preservatives, solubilizers such as glycols, glycerol or sodium cumenesulfonate.
  • biocides such as 3,3 ' -Methylenebis (5-methyl-1, 3-oxazolidine) and / or iodine-2-propynyl-N-butylcarbamate can be added, which extend the life of the emulsion.
  • the proportion by weight of the components in the emulsion concentrate which in this sense constitute auxiliaries or active ingredients in the emulsion concentrate is at least 0.1% by weight and is not greater than 2 parts by weight.
  • the proportion by weight of the solubiliser glycerol on the emulsion concentrate should be at least 1, but not exceed 6 parts by weight.
  • the present invention relates to the ready-to-use oil-in-water emulsion obtainable by mixing about 0.5 to 10 parts by weight of an oily, water-miscible emulsion concentrate having about 99.5 to 90 parts by weight of water. Due to the self-emulsifying properties of the emulsion concentrate, the ready-to-use emulsion forms spontaneously upon addition of water or after slight mechanical agitation such as stirring.
  • This emulsion can be used for example as a cleaning, corrosion protection or cooling lubricant emulsion.
  • the emulsions can be prepared with water of any hardness, d. H.
  • emulsions are sufficiently low-foaming to be sprayed at any temperature. They also show the required long-term stability.
  • the pH of the ready-to-use oil-in-water emulsion prepared in this manner is not greater than 10, preferably not greater than 9.5 and not less than 8, preferably not less than 8.5. If the buffered boric acid emulsion concentrate is used to formulate the application solution, the pH remains stable in the preferred range mentioned above, even with long metal working times and a long service life of the emulsion. Oil-in-water emulsions of the emulsion concentrate according to the invention are outstandingly suitable as a cooling lubricant emulsion in the machining of light metals. In this case, light metals are understood as meaning, in particular, aluminum and magnesium and in each case their alloys, which consist of more than 50 atomic percent of aluminum or magnesium.
  • non-ferrous metals in particular of copper and its alloys, for example brass or bronze, or of material surfaces which are at least partially non-ferrous metal surfaces, such oil-in-water emulsions can be used, provided they contain the non-ferrous metal inhibitors mentioned above ,
  • Such emulsions have the advantage that they are suitable for the processing of components from virtually all of the metals and metal alloys occurring in equipment and vehicle construction. Therefore, when processing different types of metal, the emulsion does not have to be changed.
  • an exemplary base recipe of an emulsion concentrate according to the underlying invention divided according to oil components (I), emulsifier system (II), corrosion protection system (IM) and auxiliaries and active ingredients (IV) refer, wherein the alkoxylated fatty amines (Il c ) are not included.
  • each 50 g of the emulsion concentrate which contains a corresponding proportion of ethoxylated cocoamine, mixed with water hardness 20 ° dH (DIN 51360) up to a total amount of the application solution of 1000 g ,
  • a solution A is prepared by dissolving 39 g of calcium chloride hexahydrate with demineralized water to a volume of one liter.
  • a solution B is prepared by dissolving 44 g of magnesium sulfate heptahydrate with demineralized water to a volume of one liter. Take 17 ml of solution A and 3 ml of solution B and add 980 ml of demineralized water.
  • composition of the basis of an emulsion concentrate to which the alkoxylated fatty amine according to the invention according to Table 2 is admixed is admixed.
  • EO / PO ethylene oxide or propylene oxide units
  • Emulsion Concentrate of Table 1 The proportion by weight of cocoamine (FA%) is the amount of cocoamine (FA) based on the total amount of the emulsion concentrate according to Tab. 1 including all components X listed there, including water and the respective amount of cocoamine (FA ):
  • the throughput time t D as a measure of the filterability of the application solution is already significantly reduced by about 40% compared to a cocoamine (12 EO) -free application solution (BV1) even at a weight fraction of 1% by weight.
  • the optimum filterability of the use solution is achieved with a cocoamine (12 EO) content for the test series of about 2% by weight (B3) listed in Table 4.
  • B3 2% by weight
  • Table 3 now sets forth the exemplary inventive chelating amine compounds (B6-B9) according to the invention contained in the emulsion concentrate in a further aspect of the invention and the light metal inhibitors used in the concentrate in the comparative examples (V1-V3).
  • 5% by weight of application solutions are prepared starting from the emulsion concentrate according to Table 1 in DIN 51360-water in which the emulsion concentrate additionally contains the particular inhibitor with a weight fraction of 0.5% by weight.
  • Aluminum-alloyed magnesium sheets (AZ91) are then immersed in half in these 5% strength by weight application solutions of the emulsion concentrates with the respective inhibitors the appearance of the so-called "fountain blacks" after a short exposure time t A and indicates the maximum exposure time t E after which the respective maximum observed blackening occurs.
  • the assessment of the "blackened black” takes place on an
  • Table 4 clearly shows that the chelating amine compounds (IIIb) according to the invention have a markedly delayed (B6) or even almost completely suppress the occurrence of the "fountain black" (B1-B9) compared to the inhibitor-free oil-in-water emulsion (BV1)
  • tertiary amine B6 prevents a fast discoloration of the magnesium alloy, however, after 24 hours of exposure the sheet has a "fountain black", which is also found in the inhibitor-free application solution.
  • B6 is therefore only conditionally and exclusively for short machining processes and can with the inhibitors V1 and V2, z.
  • the typical light metal inhibitor Octane phosphonic acid (V1) do not compete because they are able to reduce the occurring "fountain blacks" in total.
  • non-tertiary amine compounds such as aminomethylphosphonic acid (V3) leads to inferior results with respect to the inhibitor of "fountain blackened” especially in the case of a short exposure time in comparison with the inhibitor B6 according to the invention, which is a tertiary amine compound.
  • B9 in turn suppress the unwanted discoloration of the workpiece almost completely even up to an exposure time of 48 h and are far superior to the inhibitors V1-V3 used in the comparative examples.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un concentré émusionnable huileux et miscible à l'eau comprenant (I) une composante huile (II) un système émulsifiant contenant a) des éthoxylats/propoxylats d'alcools gras avec 8 à 18 atomes de carbone dans l'alcool avec 2 à 6 unités d'oxyde d'éthylène et 4 à 8 unités d'oxyde de propylène et b) des alcools gras et/ou des propoxylats d'alcools gras avec 12 à 24 atomes de carbone dans l'alcool et 0 à 3 unités d'oxyde de propylène et/ou le résidu de distillat de ces alcools gras et (III) un système de protection anticorrosion contenant a) des acides carboxyliques et/ou des acides phosphoniques à chaîne droite et/ou ramifiée avec 6 à 12 atomes de carbone, caractérisé en ce que le système émulsifiant (II) contient, en plus, au moins un amine gras alcoxylé (II c ). L'invention concerne également une émulsion huile-eau comme solution d'application du concentré émulsionnable pour l'usinage de métaux légers, notamment d'aluminium et de magnésium tout comme leurs alliages et l'utilisation de cette émulsion comme émulsion de nettoyage, de protection anticorrosion et de réfrigérant lubrifiant, notamment lors de l'usinage de métaux par enlèvement de copeaux.
EP07821718A 2007-01-23 2007-10-23 Réfrigérant lubrifiant à grand pouvoir dispersant pour l'usinage par enlèvement de copeaux par voie humide de métaux légers Withdrawn EP2111440A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007004292A DE102007004292A1 (de) 2007-01-23 2007-01-23 Kühlschmierstoff für die wässrige Zerspanung von Leichtmetallen mit hohem Dispergiervermögen
PCT/EP2007/061354 WO2008089858A1 (fr) 2007-01-23 2007-10-23 Réfrigérant lubrifiant à grand pouvoir dispersant pour l'usinage par enlèvement de copeaux par voie humide de métaux légers

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EP2111440A1 true EP2111440A1 (fr) 2009-10-28

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EP (1) EP2111440A1 (fr)
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BR112012003705B1 (pt) 2009-08-18 2018-08-07 The Lubrizol Corporation Composição lubrificante contendo um agente antidesgaste
ES2421184T3 (es) 2009-10-01 2013-08-29 Rhein Chemie Rheinau Gmbh Uso de aditivos de protección frente a la corrosión para la protección de aluminio y/o aleaciones de aluminio para procedimientos de acabado
DE102012003224A1 (de) 2012-02-20 2013-08-22 Sasol Germany Gmbh Bohrspülflüssigkeit, Verwendung und Verfahren unter Verwendung der Bohrspülflüssigkeit
EP3156518A1 (fr) * 2015-10-14 2017-04-19 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Composition inhibitrice de corrosion pour alliages de magnésium ou magnésium

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DE19747895A1 (de) * 1997-10-30 1999-05-06 Henkel Kgaa Metallbehandlungsflüssigkeit für den neutralen pH-Bereich
US5900392A (en) * 1998-07-24 1999-05-04 Loeffler Chemical Corporation Aqueous belt lubricant composition based on fatty alkyl propylene tettramines and fatty alcohol polyglycol ethers and method for lubricating belt conveyor systems
DE19956237A1 (de) 1999-11-23 2001-05-31 Henkel Kgaa Emulgatorsystem und dieses enthaltende Metallbearbeitungsemulsion

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WO2008089858A1 (fr) 2008-07-31

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