EP2487227B1 - Composition d'agent lubrifiant de déformage, notamment pour le déformage à froid de pièces métalliques - Google Patents

Composition d'agent lubrifiant de déformage, notamment pour le déformage à froid de pièces métalliques Download PDF

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Publication number
EP2487227B1
EP2487227B1 EP12000782.8A EP12000782A EP2487227B1 EP 2487227 B1 EP2487227 B1 EP 2487227B1 EP 12000782 A EP12000782 A EP 12000782A EP 2487227 B1 EP2487227 B1 EP 2487227B1
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EP
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Prior art keywords
fatty acid
amount ranging
composition
amount
acid ester
Prior art date
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EP12000782.8A
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German (de)
English (en)
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EP2487227A1 (fr
Inventor
Hans Schreiber
Ulrich Brochheuser
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GKN Driveline International GmbH
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GKN Driveline International GmbH
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Priority to PL12000782T priority Critical patent/PL2487227T3/pl
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy 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
    • 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
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • 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
    • 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
    • C10M2215/20—Containing nitrogen-to-oxygen bonds
    • C10M2215/202—Containing nitrogen-to-oxygen bonds containing nitro 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • 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
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • 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
    • C10N2040/243—Cold working
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to a forming lubricating composition, in particular for the cold forming of metallic parts, as well as a process for their preparation, a process for coating to be formed, in particular metallic, parts, as well as a process for the production of formed parts, in particular metallic parts.
  • thermoplastics By forming in particular metals, but also thermoplastics, plastically brought into a different form.
  • cold and hot forming During cold forming, the deformation takes place below the recrystallization temperature of the material used, in the hot forming, however, there is regularly recrystallization of the material, which counteracts a solidification of the same.
  • forming There are various types of forming such as pressure forming, tension forming, tensile forming, bending, shear forming and possibly also other forming processes. The forming takes place, for example, by rolling, free-forming, including swaging and driving, impressions, compression, deep-drawing, bending, and the like.
  • lubricants In order to reduce the friction as well as the forces to be used during forming, a wide variety of types of lubricants are used.
  • two types of lubricants are used, namely on the one hand, those which are liquid, and others, as such, which form a solid film on the parts to be formed.
  • the disadvantage of the liquid lubricant is especially in the problem of processing, be it by film formation on floors, for example, whereby the risk of accidents is increased, be it by other contaminants of the immediate environment of the forming.
  • there are basically problems with regard to the uniformity of the transformations since the coating carried out by liquid lubricants is in motion during the forming process.
  • US 4,212,750 discloses a waterborne metalworking lubricant including water soluble polyalkylene glycols, a water emulsifiable high pressure lubricant component which may be a chloroparaffin or a sulfuric or chlorofatty acid ester, and a nonionic or anionic emulsifier for the high pressure lubricant.
  • the reshaping lubricant composition according to the invention has the great advantage that, as tests have shown by means of cup-backward extrusion (NRFP), these lead to a reduction of the stamping force to be applied during forming by up to 30 kN in comparison to conventional lubricants, with error-free, In particular scarf-free formed parts can be obtained.
  • NRFP cup-backward extrusion
  • the scope of the forming lubricant composition according to the invention is extended compared to those known from the prior art.
  • the achievable friction coefficients are reduced by about 10%.
  • no so-called conversion layer is formed after application of this composition, so that an immediate transformation can take place.
  • the EP (Extreme Pressure) additive included in the composition of the invention is preferably contained therein in an amount ranging from about 20% to about 28% by weight.
  • the EP additive is inventively selected from a group consisting of phosphoric acid esters, more preferably alkylated or ethoxylated phosphoric acid esters.
  • the preferred phosphoric acid esters can be selected from a group comprising primary, secondary and / or tertiary esters of orthophosphoric acid, and are preferably secondary or tertiary phosphoric acid esters.
  • the phosphoric acid esters are preferably prepared in a reaction of phosphoric acid with straight-chain or branched alkyl alcohols having 1 to 12 carbon atoms and / or fatty alcohols having 12 to 24 carbon atoms.
  • phosphoric acid esters prepared in this way which have been subjected to ethoxylation, that is, in which at least one, preferably at least two -CH 2 -CH 2 -O groups have been inserted into the alkyl radical or fatty alcohol radical.
  • suitable phosphoric esters as EP additives for the purposes of the present invention are di-2-ethylhexyl phosphoric esters and ethoxylated fatty alcohol phosphoric esters.
  • the fatty acids or fatty acid esters used in the forming lubricant composition according to the invention can fulfill various functions. They can act as Reibwertverminderer, as control oil, or in specific embodiments as a further EP additive in addition to another EP additive, in particular as described above, act.
  • the at least one fatty acid or fatty acid ester is employed in the composition of the present invention in an amount ranging from 8% to 55% by weight, preferably from about 20% to about 51% by weight. -%, based on the total amount of the composition.
  • the at least one fatty acid or the at least one fatty acid ester is to be used as a coefficient of friction reduction, these are preferably present in the composition according to the invention in an amount in a range of about 5% by weight, preferably from about 8% by weight to about 15 Wt .-%, preferably up to about 10 wt .-%, based on the total amount of the composition.
  • Fric- tion-reducing fatty acids and / or fatty acid esters are preferably selected from a group comprising at least monounsaturated (free) fatty acids or fatty acid esters, also alkylated, in particular methylated, or ethoxylated, having at least monounsaturated fatty acid residues, and are preferably free fatty acids which are at least monounsaturated.
  • the (free) fatty acids or fatty acid esters have in their fatty acid radical preferably 12 to 22, more preferably up to 20 carbon atoms, preferably 16 to 20 carbon atoms.
  • linoleic acid or linseed oil and oleic acid in particular in the form of crude oleic acid, tallow fatty acids, tall oil and / or tall oil fatty acid, where olein can also comprise palmitic and stearic acid in addition to oleic acid, as well as glycerol mono- and dioleates in addition to trioleates , or derivatives of said substances, in particular alkylated, in particular methylated, or ethoxylated. Also, mixtures of the substances mentioned are possible.
  • linseed oil or derivatives of linseed oil that is, for example, methylated or ethoxylated linseed oil, linoleic or linolenic acid, alone and in admixture, optionally also with the addition of oleic acid and / or tall oil or tall oil fatty acid, as fatty acid or in the form of derivatives, in particular in the form of alkyl fatty acid esters.
  • the fatty acid and / or the fatty acid ester is selected as Reibwertverminderer selected from a group comprising fatty acids or fatty acid esters having 16 to 24 carbon atoms. More preferably, the fatty acid and / or fatty acid esters are at least monounsaturated, more preferably selected from a group comprising oleic acid, linoleic acid and / or linolenic acid and / or tall oil fatty acid, individually or in admixture, or their corresponding fatty acid esters when using fatty acid esters. Particularly preferably, at least some of the fatty acids and / or fatty acid esters used have conjugated double bonds.
  • control oil preferably in addition to or in combination with other control oils
  • these are preferably selected from a group comprising at least monounsaturated fatty acids and / or fatty acid esters, preferably comprising monounsaturated Fatty acid esters, in particular ethoxylated, more preferably those having an alkyl radical having 1 to 6 carbon atoms.
  • Particularly preferred are alkyloleates, more preferably methyloleate.
  • fatty acids and / or fatty acid esters used as (single) control oils they are in the composition preferably in an amount in a range of about 4 Ges .-% to about 45 wt .-%, preferably up to about 30 wt .-%, based on the total amount of the composition present.
  • the fatty acid and / or fatty acid ester is advantageously present in an amount ranging from about 3% to about 15% by weight, preferably up to 8% by weight, based on the total amount of the composition, of this.
  • the at least monounsaturated fatty acid and / or fatty acid esters as control oil, as defined above, may also be sulfurized, but are preferably unsulfurized. Preferably, these have 12 to 22 carbon atoms in the fatty acid or the fatty acid radical.
  • the proportion of at least monounsaturated fatty acid or fatty acid ester is at least about 80 wt .-%, preferably at least about 90 wt .-%, to about 99 wt .-%, preferably up to about 95 wt .-%, based on the total fatty acid or the Automatfettklareester.
  • the at least one fatty acid and / or fatty acid ester fulfill the function of a (further) EP additive, then these are advantageously selected from a group comprising at least monounsaturated fatty acids and / or fatty acid esters, more preferably at least partially sulfurized, more advantageously at least partially sulphurized with a sulfur content in a range from about 5% to about 30%, preferably from about 8% to about 20% by weight, based on the total amount of the fatty acid and / or fatty acid ester.
  • Sulfurated fatty acid esters which can be used as an EP additive, preferably have straight-chain or branched alkyl radicals having 1 to 12 carbon atoms.
  • fatty acids and / or fatty acid esters are used as further EP additives in the composition according to the invention, they are present in the composition according to the invention in an amount ranging from about 7% by weight to about 30% by weight, more preferably in one range from about 7.5% to about 26% by weight, based on the total amount of the composition.
  • the composition according to the invention comprises at least one free, at least monounsaturated fatty acid and / or at least one at least monounsaturated fatty acid esters, preferably both at least one free, at least monounsaturated fatty acid and at least one at least monounsaturated fatty acid ester.
  • at least one fatty acid or the at least one fatty acid ester is used in a composition as an adjusting oil and also as an EP additive, these may optionally be chemically identical, depending on the further constituents of the composition.
  • a fatty acid ester is used as the control oil, it is preferably non-sulfurized and further preferably has a kinematic viscosity in a range from about 5 to about 15 cSt (corresponding to about 5 to about 15 mm 2 / s -1 ), measured according to DIN 51562 at 40 ° C, on, when used as an EP additive, it is preferably used sulfurized, preferably with a kinematic viscosity in a range of about 16 to about 250 cSt (corresponding to about 16 to about 250 mm 2 / s ), preferably from about 18 to about 150 cSt (corresponding to about 18 to about 150 mm 2 / s -1 ), measured according to DIN 51562 at 40 ° C.
  • the amine-containing buffering agent according to the composition of the invention is advantageously in a range from about 8% to about 15% by weight, more preferably in a range from about 9% to about 14% by weight, in the present invention Composition present, based in each case on the total amount of the composition.
  • the amine-containing buffering agent is advantageously selected from a group comprising fatty amines, in particular fatty amines having a fatty acid radical having at least one unsaturated carbon-carbon double bond. Further advantageously, the amine-containing buffering agent is selected from a group comprising ethoxylated fatty amines, wherein at least one, preferably at least two -CH 2 -CH 2 -O-groups are included in the fatty amine.
  • buffering agents in the context of the present invention are soya oil and rapeseed fatty amines obtained from rapeseed oil and soybean oil, as well as oleic amines (oleylamines), particularly preferably ethoxylated fatty amines of the substances mentioned.
  • oleic amines oleylamines
  • tertiary ethoxylated fatty amines but also primary and secondary fatty amines, in particular ethoxylated, are excluded in the context of the present invention as a buffering agent.
  • the wetting agent further comprised by the composition according to the invention is advantageously present therein in an amount in the range of about 3 From about 10% to about 10% by weight, more preferably from about 4% to about 9% by weight, based on the total amount of the composition.
  • the wetting agent is selected from a group consisting of alkylbenzenesulfonic acids or their salts, in particular dodecylbenzenesulfonic acid, in particular in the form of salts, but also in free form. Particularly preferred is the use of amine salts of alkylbenzenesulfonic acids, more preferably the use of triethanolamine dodecylbenzylsulfonate.
  • the inorganic phosphates and / or amine phosphates are preferably contained therein in an amount ranging from about 6% to about 12% by weight, based on the total amount of the composition.
  • Amine phosphates to be used in the context of the present invention are more preferably primary amine phosphates, even more preferably primary amine phosphates having a tertiary amine radical which preferably has straight-chain alkyl radicals having 1 to 12 or 2 to 6 carbon atoms, preferably methyl, ethyl, propyl radicals.
  • primary triethanolamine phosphate for the purposes of the present invention, particular preference is given to primary triethanolamine phosphate.
  • the amine phosphate is prepared immediately prior to preparation of the composition of the invention from a tertiary amine, for example triethanolamine, and aqueous phosphoric acid.
  • Inorganic phosphates which may be employed in the composition of the present invention include, for example, primary sodium phosphate, primary calcium phosphate or primary strontium phosphate, which are preferably prepared in situ from phosphoric acid and the corresponding alkali or alkaline earth carbonate.
  • the composition according to the invention furthermore advantageously comprises at least one control oil, preferably not based on, in particular, at least monounsaturated fatty acids and / or fatty acid esters, in an amount of from 12% by weight to 30% by weight, more preferably in an amount of approximately 16% by weight to about 25% by weight, based on the total amount of the composition.
  • the control oil is selected from a group consisting of at least one polythylene glycol.
  • derivatives of the polyethylene glycol having an average molecular weight in a range of about 10,000 to about 40,000, more preferably about 21,000 to about 38,000, even more preferably about 24,000 to about 36,000.
  • polyethylene glycol fatty acid ester derivatives more preferably those which have at least one unsaturated double bond in the fatty acid radical, more preferably polyethylene glycol monooleate.
  • Polyethylene glycol fatty acid derivatives, especially monooleates are preferably employed having a molecular weight in a range of from about 100 to about 2000, more preferably from about 200 to 1000, even more preferably in a range from about 300 to about 700.
  • the polythylene glycol derivatives used have the general formula R 3 O - [- R 1 -OR 2 -O] n -H, but can also be used as block polymers having the general formula R 3 O - (- R 1 -O-) x - (- R 2 -O) x -H be formed.
  • the radical R 3 may be an alkyl radical having 1 to 24 carbon atoms, but may also be a fatty acid ester having 12 to 22 carbon atoms, also partially unsaturated, preferably having at least one carbon-carbon double bond.
  • the composition according to the invention particularly preferably has an actuating oil based on at least one polyethylene glycol derivative, as described above, and an (at least) monounsaturated (free) fatty acid or fatty acid ester acting as an adjusting oil.
  • the at least one fatty acid and / or fatty acid ester in an amount of preferably 4 wt .-% to about 8 wt .-% in the mixture according to the invention, and the control oil based on a polyethylene glycol in an amount of about 15 wt. -% to about 25 wt .-%, each based on the total amount of the composition.
  • At least one fatty acid ester preferably an at least monounsaturated fatty acid ester, is used, more preferably an alkyl oleate, even more preferably methyl oleate.
  • the polyethylene glycol is advantageously selected from a group comprising polyethylene glycols esterified with fatty acids, even more preferably polyethylene glycol monooleate.
  • esters of carboxylic acids having 2 to 6 carbon atoms particular preference being given to ethyl esters and propane esters.
  • alkyl esters are particularly preferably esterified with tertiary alkylol radicals, for example trimethylol or triethylol radicals.
  • tertiary alkylol radicals for example trimethylol or triethylol radicals.
  • Particular preference is given to using a trimethylolpropane ester.
  • weight% ranges what has been said above for other control oils, in particular based on at least monounsaturated fatty acids and / or fatty acid esters, applies.
  • the composition according to the invention furthermore advantageously comprises a reaction accelerator in an amount of from 0.05% by weight to about 2.5% by weight, more preferably in an amount of from about 0.1% by weight to about 2% by weight. , even more preferably in an amount of about 0.15% to about 0.5% by weight, based in each case on the total amount of the composition.
  • the reaction accelerator is selected from a group consisting of benzoic acid or its salts, and is preferably 3,5 dinitrobenzoic acid.
  • derivatives such as salts of benzoic acid, for example triethanolamine salts of 3,5-dinitrobenzoic acid, can also be used, or else salts of nitroacids, in particular of nitrosulfonic acids.
  • the present invention further relates to a process for the preparation of a composition according to the invention as described above, characterized in that a mixture of EP additive, buffering agent and wetting agent is presented, in this mixture inorganic phosphates and / or amine phosphates is added, and then the at least one / e monounsaturated fatty acid and / or fatty acid esters is added.
  • a reaction accelerator is added before admixing inorganic phosphates and / or amine phosphates. More preferably, in the inventive method after admixture of the inorganic phosphates and / or amine phosphates, at least one control oil is added.
  • the control oil is selected from a group comprising at least one polyethylene glycol or at least one fatty acid and / or fatty acid esters, as described above.
  • Sulfurized fatty acids or fatty acid esters are used as EP additives in particular, these are presented together with the wetting agent, the buffering agent and the actual EP additive, which is not based on fatty acids and / or fatty acid esters. If a fatty acid and / or fatty acid ester is added as a friction-reducing agent, it is preferably added after addition of phosphoric acid and / or at least one of its derivatives.
  • control oil in the form of at least one fatty acid and / or fatty acid ester or in the form of an alkyl ester is present, it is preferably added last to the mixture and the desired viscosity of the mixture according to the invention is set therewith.
  • the present invention relates to a method for coating, in particular metallic, parts, with the composition according to the invention, wherein by a suitable method, for example by dipping, spraying or application by means of a application tool, for example a roll or a cloth, the composition is applied to the parts to be formed. After application, superfluous lubricant is allowed to drip off, and the thus coated part to be formed is stored, for example, in the bunker of a forming device.
  • the present invention relates to a method for forming metallic parts using the composition according to the invention, wherein the composition according to the invention is applied to the parts to be formed prior to forming and this part to be reshaped is subsequently formed. After reshaping any residues from the formed part removed, which can be done especially by hand wiping.
  • the forces to be reduced in forming by use of the composition according to the invention in comparison with the use of such known from the prior art composition, as well as the measured coefficients of friction.
  • PEG-MO polyethylene glycol monooleate
  • Ligalube PEG 400 MO obtained from the company Peter Greven GmbH & Co. KG, Bad Wegeifel, Germany , used as control oil.
  • the EP additive used was a di-2-ethylhexyl phosphoric acid ester, available under the product name Hordaphos MDAH, Clariant GmbH, Frankfurt / Main, Germany, hereinafter referred to as Hordaphos, or an ethoxylated fatty alcohol phosphoric acid ester, available under the name Lubrophos LB 400 E, from the company Rhodia, purchased from the company CH Erbslöh KG, Krefeld, Germany, hereinafter referred to as "Lubrophos" used.
  • Linseed oil fatty acid obtained from the company Carroux bottlesgesellschaft mbH, Geesthacht, Germany, was used as a friction value reducer, hereinafter referred to as "L ⁇ FS".
  • the control oil used was methyl oleate, obtained from the company FB Silbermann GmbH & Co., Gablingen, Germany, hereinafter referred to as "MO”.
  • the EP additive used was sulfurated olein, available under the name "Becrosan GO 10" from the company Lubrizol France, Rouen, France, which contains about 9% by weight of sulfur (hereinafter “becrosan”), or a sulfurized fatty acid methyl ester, available under the name “Additin RC 2818” from RheinChemie Rheinau GmbH, Mannheim, Germany, used, which contains about 18 wt .-%, based on the total amount of the fatty acid ethyl ester, sulfur and a content of at least monounsaturated fatty acid in the total fatty acid of about 90 wt .-% (hereinafter called "additin”).
  • Buffering agent used was either an ethoxylated soybean safflower, available under the name “Berol 302" from Akzo Nobel Surface Chemistry AB, Stenungsund, Sweden, and obtained from Julius Hoesch GmbH & Co. KG, Dueren, Germany, hereinafter "Berol”. called, an ethoxylated oleinamine, available under the name “Genamin O 20” from Clariant GmbH, Frankfurt / Main, Germany, hereinafter referred to as “Genamin”, or an ethoxylated oleylamine, available under the name Ethomeen OV / 17 from the company Akzo Nobel Surface Chemistry AB, Stenungsund, Sweden, and used by the company Julius Hoesch GmbH & Co. KG, Düren, Germany, hereinafter referred to as "Ethomeen” used.
  • Wetting agent used was a triethanolamine salt of dodecylbenzenesulfonic acid, available under the name "Marlopon AT 50", obtained from Brenntag AG, Mülheim / Ruhr, Germany, hereinafter referred to as "Marlopon”, or a dodecylbenzenesulfonic acid designated lumoic acid A, available from Julius Hoesch GmbH & Co. KG, Düren, Germany, from Zschimmerer & Schwarz, hereinafter referred to as "luma acid”.
  • the amine phosphate used was primary triethanolamine phosphate (hereinafter referred to as TEAP), which was prepared immediately before preparation of the composition from five parts of triethanolamine, one part of water and four parts of 80% strength aqueous phosphoric acid by means of mixtures in a stainless steel container and cold stirring thereof. also primary alkali or alkaline earth metal phosphates, prepared in situ from phosphoric acid and the corresponding alkali or alkaline earth metal derivative.
  • TEAP primary triethanolamine phosphate
  • reaction accelerator either 3,5-dinitrobenzoic acid from Sigma-Aldrich Chemie GmbH, Steinheim, Germany, hereinafter referred to as "DNB”, or a triethanolamine salt thereof, prepared by mixing triethanolamine and 3,5-dinitrobenzoic acid under stirring for clarity, hereafter referred to as "TEM DNB”.
  • control oil used was a trimethylolpropane ester with the name “Priolube 3999” from Unichema, obtained from Croda GmbH, Nettetal, Germany, hereinafter referred to as "priolube”.
  • the mixtures A to H listed above in Table 1 were prepared as described above, these were subsequently cross-cut the mixture and before filling by means of a colloid mill and filled through a filter with a gap width of 30 microns.
  • the lubricant IRMCO Fluid 980 680 available on the company Ibi oil free division GmbH, Dirmstein, Germany, was used.
  • cup-reverse flow-compression tests were carried out with mixture F and the comparative forming lubricant on cylindrical blanks with a diameter of 19.95 mm and a height of 25 mm from a case hardening steel C15 (with the German material standard 1.0401).
  • a forming machine such a May-Pressenbau GmbH was used with the type designation MKN2-600 / 14F.
  • the specimens were immersed in the mixture F or the comparative forming lubricant, drained, and then placed in the press. Force-displacement diagrams were recorded and the specimens subsequently examined. In total, up to eight specimens were subjected to reshaping.
  • the force-displacement diagrams of specimens treated with mixture F showed that a stamping force of about 350 kN on average had to be used, whereas in the comparison-conversion lubricant forces of about 375 kN on average had to be used.
  • the specimens treated with the comparative forming lubricant exhibited scoring after forming and were therefore not optically perfect.
  • mixtures G and HI were used to produce monoblock shafts with stepped toothing consisting of a cylindrical body of 25CrMo4 with a total length of 42.5 cm and a maximum diameter of 29.64 mm.
  • compositions G and H after coating the specimens with the compositions G and H, they were additionally treated with a hammer oil with the name "Ilocut460" from BP Europe SE, Mönchengladbach, Germany. Again, force-displacement diagrams, in this case the pulling force, were recorded, whereby the forming force was almost constant at 180 kN for mixture H and at 175 kN for mixture H.
  • the diameter of a controllable and temperature-controlled die in the forming tool was 20 mm.
  • a forming machine of May-Pressenbau GmbH with the name MKN 2-600 / 14F, a double-column toggle press was used.
  • the specimens were coated with the mixture G and H in a dip bath, then allowed to drain, and then placed in the forming tool.
  • the DCET tests showed a reduction of the coefficient of friction in the mixture I over mixture G by more than 20%.
  • the force to be applied could be about 5 kN to 7 kN for the mixture H after taking force-force diagrams F are lowered.
  • the pond depth ratios in the mixture H were always less than 2, based on a total of seven sample bodies examined, whereas in the case of the mixture G this was the case only for two sample bodies.
  • compositions according to the invention By means of the composition according to the invention and the processes according to the invention, it is thus possible to advantageously shape, in particular, metallic parts by reducing the forces to be applied and the coefficients of friction, especially even in the case of complicated transformations, thereby considerably expanding the field of application of the compositions according to the invention in comparison with those of the prior art is.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (11)

  1. Composition d'agent lubrifiant de formage, comprenant
    - au moins un additif EP, choisi dans un groupe composé d'esters de l'acide phosphorique, en une quantité comprise dans une plage de 15 % en poids à 30 % en poids,
    - au moins un acide gras ou un ester d'acide gras au moins une fois insaturé, en une quantité comprise dans une plage de 8 % en poids à 55 % en poids,
    - au moins un agent tampon aminé, en une quantité comprise dans une plage de 7 % en poids à 20 % en poids,
    - au moins un agent mouillant, choisi dans le groupe composé des acides alkylbenzolsulfoniques ou de leurs sels, en une quantité comprise dans une plage de 2 % en poids à 12 % en poids,
    - des phosphates inorganiques et/ou des phosphates d'amine, en une quantité comprise dans une plage de 5 % en poids à 15 % en poids,
    dans laquelle les plages de pourcentage en poids sont chaque fois rapportées à la quantité totale de la composition d'agent lubrifiant de formage.
  2. Composition selon la revendication 1, comprenant en outre au moins une huile de fluxage en une quantité comprise dans une plage de 12 % en poids à 30 % en poids, rapportée à la quantité totale de la composition.
  3. Composition selon la revendication 2, caractérisée en ce que l'huile de fluxage est choisie dans un groupe composé d'au moins un polyéthylène glycol.
  4. Composition selon l'une quelconque des revendications précédentes, comprenant en outre au moins un accélérateur de réaction, choisi dans un groupe composé de l'acide benzoïque ou de ses sels, en une quantité de 0,05 % en poids à 2,5 % en poids, rapportée à la quantité totale de la composition.
  5. Composition selon l'une quelconque des revendications précédentes, comprenant en outre au moins un acide gras libre, au moins une fois insaturé et/ou au moins un ester d'acide gras au moins une fois insaturé, dans laquelle l'acide gras et/ou l'ester d'acide gras est sulfuré avec une teneur en soufre en une quantité de 5 % en poids à 30 % en poids, rapportée à la quantité totale de l'acide gras et/ou de l'ester d'acide gras.
  6. Composition selon l'une quelconque des revendications 1 à 5, comprenant
    - au moins un additif EP à base d'un ester de l'acide phosphorique, en une quantité comprise dans une plage de 20 % en poids à 28 % en poids;
    - au moins un acide gras et/ou un ester d'acide gras au moins partiellement sulfuré, en une quantité comprise dans une plage de 8 % en poids à 15 % en poids;
    - au moins une amine grasse éthoxylée comme agent tampon, en une quantité comprise dans une plage de 7 % en poids à 15 % en poids;
    - au moins un sel d'un acide alkylbenzolsulfonique comme agent mouillant, en une quantité comprise dans une plage de 6 % en poids à 10 % en poids;
    - comme huile de fluxage au moins un polyéthylène glycol, en une quantité comprise dans une plage de 15 % en poids à 25 % en poids avec un poids moléculaire moyen compris dans une plage de 100 à 2000; ainsi que
    - au moins un phosphate d'amine primaire, en une quantité comprise dans une plage de 6 % en poids à 10 % en poids;
    - au moins un ester d'acide gras au moins une fois insaturé, en une quantité comprise dans une plage de 3 % en poids à 8 % en poids;
    - au moins un acide gras avec 16 à 22 atomes de carbone, au moins une fois insaturé, en une quantité comprise dans une plage de 8 % en poids à 15 % en poids;
    - au moins un accélérateur de réaction, choisi dans un groupe composé de l'acide benzoïque et de ses sels, en une quantité de 0,1 % en poids à 0,3 % en poids;
    dans laquelle les pourcentages en poids sont chaque fois rapportés à la quantité totale de la composition.
  7. Procédé de fabrication de compositions selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on prépare un mélange d'additif EP, d'agent tampon et d'agent mouillant, on y ajoute des phosphates inorganiques et/ou des phosphates d'amine, puis on ajoute au moins un acide gras et/ou un ester d'acide gras au moins une fois insaturé.
  8. Procédé selon la revendication 7, caractérisé en ce que l'on ajoute un accélérateur de réaction avant l'addition des phosphates inorganiques et/ou des phosphates d'amine.
  9. Procédé selon une des revendications 7 ou 8, caractérisé en ce que l'on ajoute au moins une huile de fluxage après l'addition des phosphates inorganiques et/ou des phosphates d'amine.
  10. Procédé de revêtement de pièces à former avec une composition selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on dépose la composition sur les pièces à former au moyen d'un procédé approprié.
  11. Procédé de fabrication de pièces formées, caractérisé en ce que l'on dépose une composition selon l'une quelconque des revendications 1 à 6 avant le formage sur la pièce à former et on forme ensuite cette dernière.
EP12000782.8A 2011-02-10 2012-02-07 Composition d'agent lubrifiant de déformage, notamment pour le déformage à froid de pièces métalliques Active EP2487227B1 (fr)

Priority Applications (1)

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PL12000782T PL2487227T3 (pl) 2011-02-10 2012-02-07 Kompozycja środka smarnego do obróbki plastycznej, w szczególności do obróbki plastycznej na zimno części metalowych

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EP2487227B1 true EP2487227B1 (fr) 2018-11-28

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EP (1) EP2487227B1 (fr)
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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212750A (en) * 1977-12-15 1980-07-15 Lubrication Technology, Inc. Metal working lubricant
DE19934182A1 (de) * 1999-07-21 2001-01-25 Cognis Deutschland Gmbh Schwefelhaltige Schmierstoffe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TOSHIHIDE OHMORI ET AL: "A Cold Forging Oil Containing Phosphorus Type EP Additives", TRIBOLOGY TRANSACT, THE SOCIETY, PARK RIDGE, IL, US, vol. 34, no. 3, 1 January 1991 (1991-01-01), pages 458 - 464, XP009191776, ISSN: 1040-2004 *

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