EP2311928A2 - Solution aqueuse contenant un ester d'acide phosphorique organique pour la fabrication d'une tôle métallique revêtue de lubrifiant ayant des propriétés de déformation améliorées - Google Patents

Solution aqueuse contenant un ester d'acide phosphorique organique pour la fabrication d'une tôle métallique revêtue de lubrifiant ayant des propriétés de déformation améliorées Download PDF

Info

Publication number
EP2311928A2
EP2311928A2 EP10180973A EP10180973A EP2311928A2 EP 2311928 A2 EP2311928 A2 EP 2311928A2 EP 10180973 A EP10180973 A EP 10180973A EP 10180973 A EP10180973 A EP 10180973A EP 2311928 A2 EP2311928 A2 EP 2311928A2
Authority
EP
European Patent Office
Prior art keywords
aqueous solution
phosphoric acid
acid ester
solution according
organic
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Withdrawn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
EP10180973A
Other languages
German (de)
English (en)
Other versions
EP2311928A3 (fr
Inventor
Reinhard Wormuth
Dirk Liese
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.)
ThyssenKrupp Steel Europe AG
BP Europe SE
Original Assignee
ThyssenKrupp Steel Europe AG
BP Europe SE
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 ThyssenKrupp Steel Europe AG, BP Europe SE filed Critical ThyssenKrupp Steel Europe AG
Publication of EP2311928A2 publication Critical patent/EP2311928A2/fr
Publication of EP2311928A3 publication Critical patent/EP2311928A3/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • B21D22/201—Work-pieces; preparation of the work-pieces, e.g. lubricating, coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C10M2201/08—Inorganic acids or salts 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
    • 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
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2223/0405—Phosphate esters used as base material
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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
    • C10N2050/023—Multi-layer lubricant coatings
    • 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
    • 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
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

Definitions

  • the invention relates to a lubricant-coated metal sheet or a blank thereof with improved Umformeigens ⁇ chaften, wherein the lubricant is in particular a corrosion protection oil, Pre-Lube and / or Dry-Lube.
  • the invention further relates to a method for producing such a metal sheet or sheet metal blank and their use for the production of metal bodies by forming, in particular by deep drawing.
  • metal sheets for. As steel sheets, it is customary to equip them immediately after the production and coating process and before delivery to the metalworking industry with a temporary corrosion protection for storage and transport. This is usually done by applying a corrosion-inhibiting lubricant immediately before winding the sheet, such as a corrosion protection oil, a pre-Lubes or a dry Lubes. If the metal sheet for further processing by forming such as deep drawing is determined, the lubricants used in addition to corrosion-inhibiting substances may contain other specially tailored to the particular forming process excipients improve the tribological properties of the sheet during the forming process. Such coated metal sheets are used for example in the automotive industry in the manufacture of bodies made of metal sheets by deep drawing.
  • a method of cold-forming metal sheets in which the deep-drawing sheet and / or the deep-drawing die are treated with an aqueous solution of an inorganic alkali phosphate and then deep-drawn in the presence of a deep-drawing oil.
  • a disadvantage of the method is that the alkali phosphate used and the soaps formed after deep drawing is not completely free from residue to remove from the sheet.
  • a lubricant composition for non-cutting cold working of metals which contains a finely dispersed water-soluble inorganic salt such as borax to improve the tribological properties.
  • a disadvantage of this lubricant composition is that its lubricity is not constant since The salt is not evenly distributed over the surface, which disturbs the deep drawing process.
  • Prelubes contain Ziehosscher, which are introduced into the approximately 1 micron thick oil layer. However, only the direct steel tool interface in the range of a few nanometers is tribologically active.
  • This document relates to an application in the acidic pH range.
  • the use in the acidic area is disadvantageous because it has a negative effect on safety at work and brings with it the risk of chemical burn of machine components.
  • the metal sheet should be easy to clean after the forming process and without leaving any residue.
  • the production of the lubricant-coated metal sheet should finally be feasible easily and without high investment in existing manufacturing facilities.
  • a metal sheet or a sheet metal blank with a coating of lubricant in particular a corrosion protection oil, pre-lube and / or dry lube
  • the metal sheet or sheet metal blank comprises a layer containing by applying an organic phosphoric acid ester Solution is formed on the metallic surface of the sheet.
  • the lubricant-coated metal sheets according to the invention have excellent tribological properties as a result of their layer formed by the phosphoric acid ester. Compared with lubricant-coated metal sheets without such a layer, the metal sheets according to the invention have a reduced coefficient of friction. Finally, the metal sheets according to the invention can easily be cleaned with existing degreasing systems after the forming process, wherein both the lubricant-containing and the layer formed by the phosphoric acid ester can be removed without residue from the surface of the sheet without any problems.
  • the metal sheets which can be used according to the invention may be any metal sheets from which metal bodies can be produced by deformation, in particular by cold forming. Particularly suitable metal sheets are steel sheets.
  • the metal sheets which can be used according to the invention can be coated or uncoated.
  • uncoated metal sheet for example, uncoated sheet, in particular contigeglühtes uncoated sheet comes into question.
  • coated metal sheets are in particular electrolytically coated sheet, in particular electrolytically galvanized sheet, and hot-dip galvanized and galvanized sheets in question.
  • the metal sheets preferably have a thickness of 0.05 to 5 mm, in particular from 0.5 to 1.5 mm.
  • the metal sheets and sheet metal blanks according to the invention are coated with a lubricant which is intended, at least temporarily, to protect the sheets from undesired environmental influences, in particular from corrosion phenomena, after production.
  • a lubricant which is intended, at least temporarily, to protect the sheets from undesired environmental influences, in particular from corrosion phenomena, after production.
  • the selection of the lubricant is not limited; Rather, any fat or oil-containing substances or the like as well as dry lubricant such as graphite come into question.
  • the inventively employable lubricants preferably contain corrosion inhibitors.
  • the lubricant may contain other additives, in particular additives to improve the drawing properties of the sheets.
  • a corrosion protection oil is used as the lubricant.
  • Such corrosion protection oils are well known to the skilled person and usually contain a base oil having an aromatic content ⁇ 10% and a corrosion inhibitor such. B. calcium sulfonates.
  • the corrosion protection oils may contain antioxidants to prevent oil aging and Thixotropiesentner to reduce dripping losses in oiled metal sheets.
  • a so-called pre-lube is used as the lubricant.
  • Pre-lubes are corrosion protection oils with improved drawing properties and as such are well known to those skilled in the art.
  • the improvement of the drawing properties is achieved by adding further additives, eg. As esters, achieved.
  • a so-called dry lubricant is used as the lubricant.
  • Dry lubricants are wax and / or acrylate based thin films with similar properties to pre-lubes and as such are well known to those skilled in the art.
  • dry lubricants offer the possibility of producing difficult drawn parts in the press shop without any additional lubrication. drip loss coated sheets are completely avoided.
  • Dry Lubricants can be applied after melting, for example, electrostatically or by means of a roller coater.
  • a layer is formed on the metallic surface of the sheet, which is obtainable by applying an organic phosphoric acid ester on the metallic surface of the sheet.
  • the layer formed by phosphoric acid ester contains, as further component, a water-soluble organic sulfur compound and / or an organic molybdenum compound.
  • Particularly suitable organic sulfur compounds according to the invention are thiadiazoles, dithiocarbamates and / or dithiopropionates and their salts and derivatives.
  • organic sulfur compounds are, for example, sodium 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and salts and derivatives thereof, sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate and / or monoethanolamine dithiopropionate.
  • Suitable organic molybdenum compounds according to the invention are obtainable, for example, by reacting molybdenum trioxide and / or molybdic acid with an amine and / or alkanolamine.
  • the layer containing phosphoric ester contains as further component at least one inorganic compound selected from the group consisting of polyphosphates, borates, molybdates and tungstates.
  • Particularly suitable inorganic compounds according to the invention are, for example, ammonium tripolyphosphate, sodium tetraborate, ammonium molybdate, sodium tungstate, potassium tungstate and / or sodium tungstate.
  • the organic phosphoric acid ester and any other components in the form of an aqueous solution are applied to the metal sheet. After application, the metal sheet is preferably dried.
  • the layer formed by phosphoric acid ester may be formed in any thicknesses. However, this is preferably formed as a very thin layer, in particular as a line in the nanometer range.
  • a lubricant-containing layer is formed directly on the layer formed by phosphoric acid ester.
  • the lubricant-containing layer preferably contains a corrosion protection oil, pre-lube and / or dry lube.
  • the lubricant-containing layer contains a corrosion protection oil.
  • the lubricant-containing layer may be formed in any thicknesses. Particularly good tribological properties can be achieved if the lubricant-containing layer in a thickness of 0.3 to 3.0 g / m 2 , in particular 1 to 2 g / m 2 is formed.
  • the lubricant-containing layer is matched to the layer containing phosphoric acid ester, as containing components which are also contained in the layer containing phosphoric acid ester.
  • the lubricant-containing layer contains at least one organic phosphoric acid ester as defined above in an amount of from 0.01 to 50% by weight, in particular from 0.05 to 10% by weight.
  • the lubricant-containing layer comprises a water-soluble organic sulfur compound as defined above in an amount of 0.005 to 50% by weight, especially 0.01 to 30% by weight, and / or an organic molybdenum compound as defined above in an amount from 0.005 to 50 wt.%, In particular 0.01 to 30 wt.% Contains.
  • the lubricant contains an inorganic compound as defined above in an amount of 0.005 to 50% by weight, in particular 0.01 to 30% by weight.
  • the application of the solution containing the organic phosphoric acid ester can be carried out by any known to the expert measures such as dipping, spraying, brushing or doctoring.
  • the application of the solution containing phosphoric acid can be carried out, for example, in the coating of the sheet in the rinsing bath of a coating plant or in the cooling of the sheet in the bath of a water cooling plant.
  • the application of the solution containing phosphoric acid ester is preferably carried out in the rinsing bath of a coating installation.
  • the rinsing bath is preferably downstream of the metallic coating process (eg electrolytic galvanizing) as a one-stage no-rinse aftertreatment.
  • the rinsing bath can be followed by further production steps.
  • the metal sheet may be dried after the rinsing bath in a suitable dryer and / or subsequently coated with a lubricant (eg by electrostatic lubrication).
  • the phosphoric acid ester-containing solution is preferably applied as an aqueous solution.
  • the solution preferably contains the organic phosphoric acid ester in an amount of 0.1 to 15% by weight, in particular 3 to 8% by weight.
  • the pH of the solution is preferably adjusted to a value of 6.5 to 11, in particular 7.5 to 9.5.
  • the solution contains as another component as described above a water-soluble organic sulfur compound, in particular one of the compounds described above, and / or an organic molybdenum compound, in particular one of the compounds described above, and / or one of the inorganic compounds described above contains.
  • the water-soluble organic sulfur compound (s) and / or organic molybdenum compound (s) are preferably contained in the solution in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight on the amount of phosphoric acid ester.
  • the inorganic compound (s) are contained in the solution in an amount of 1 to 50% by weight, especially 5 to 10% by weight, based on the amount of phosphoric acid ester.
  • the lubricant used is preferably a corrosion protection oil, pre-lube and / or dry lube as described above.
  • the lubricant In terms of its composition so far matched to the phosphoric acid ester-containing solution than that as described above contains components (eg., Organic phosphoric acid ester, water-soluble organic sulfur compound, organic molybdenum compound and / or inorganic compound), which are also included in the solution containing phosphoric acid ester.
  • the lubricant is preferably applied in an amount of 0.3 to 3 g / m 2 , in particular 1 to 2 g / m 2 .
  • the invention accordingly also comprises the use of a solution containing an organic phosphoric acid ester as described above for the treatment of metal surfaces.
  • the invention further provides an aqueous solution for treating metal surfaces comprising an organic phosphoric acid ester and a water-soluble organic sulfur compound and / or an organic molybdenum compound, all compounds as described above, and a concentrate for producing such a solution.
  • Electrolytically galvanized steel sheets of 1 mm thickness were treated by dipping with an aqueous solution of the composition shown below, dried, and then coated with 1.5 g / m 2 Pre-Lube. To determine the drawing power, the coefficient of friction was then determined in the draw-bed test.
  • the reference for the coefficient of friction was a sample of the electrolytically galvanized steel sheet, which was not treated with an aqueous solution. The coefficient of friction of this reference sample was set at 100%.
  • An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric ester mixture of (CH 3 -O) PO (OH) 2 and (OH) PO (O-CH 3 ) 2 .
  • the sheet was dried and then coated with 1.5 g / m 2 Pre-Lube. The coefficient of friction was 88%.
  • An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric ester mixture of (C 4 H 9 -O) PO (OH) 2 and (OH) PO (OC 4 H 9 ) 2.
  • the sheet was dried and then washed with 1.5 g / m 2 pre-lube coated. The coefficient of friction was 58%.
  • An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric acid ester mixture of (C 8 H 17 -O) PO (OH) 2 and (OH) PO (OC 8 H 17 ) 2 .
  • the sheet was dried and then coated with 1.5 g / m 2 Pre-Lube. The friction coefficient was 90%.
  • An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric acid ester mixture of (CH 3 - [O-CH 2 CH 2 ] 3 -C 12 H 24 -O) PO (OH) 2 and (HO) PO (CH 3 - [O-CH 2 CH 2 ] 3 -C 12 H 24 -O) 2 .
  • the sheet was dried and then coated with 1.5 g / m 2 Pre-Lube. The friction coefficient was 92%.
  • thermoforming working range of an electrolytically galvanized sheet according to the invention produced according to Example 2 was compared with the reference sample without pretreatment.
  • the results of this study are in Fig. 1 shown.
  • An electrolytically galvanized steel sheet was treated with a 5% sodium tetraborate solution, dried and then coated with 1.5 g / m 2 Pre-Lube.
  • the friction coefficient was 90%.
  • An electrolytically galvanized steel sheet was treated with a 5% phosphoric acid solution, dried and then coated with 1.5 g / m 2 of Pre-Lube.
  • the friction coefficient was 95%.
  • the results show that the metal sheets according to the invention which have been treated with a solution of phosphoric acid ester have significantly improved tribological properties as well as an increased deep drawing working range compared to metal sheets which have not been subjected to such a treatment.
  • the Metal sheets according to the invention were also easy to clean and completely residue-free in a conventional degreasing system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP10180973A 2002-12-03 2003-12-02 Solution aqueuse contenant un ester d'acide phosphorique organique pour la fabrication d'une tôle métallique revêtue de lubrifiant ayant des propriétés de déformation améliorées Withdrawn EP2311928A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10256639A DE10256639A1 (de) 2002-12-03 2002-12-03 Schmierstoffbeschichtetes Metallblech mit verbesserten Umformeigenschaften
EP03782275A EP1567623A2 (fr) 2002-12-03 2003-12-02 Tole metallique a revetement lubrifiant et a proprietes de deformation ameliorees

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP03782275.6 Division 2003-12-02

Publications (2)

Publication Number Publication Date
EP2311928A2 true EP2311928A2 (fr) 2011-04-20
EP2311928A3 EP2311928A3 (fr) 2011-09-07

Family

ID=32335959

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10180973A Withdrawn EP2311928A3 (fr) 2002-12-03 2003-12-02 Solution aqueuse contenant un ester d'acide phosphorique organique pour la fabrication d'une tôle métallique revêtue de lubrifiant ayant des propriétés de déformation améliorées
EP03782275A Withdrawn EP1567623A2 (fr) 2002-12-03 2003-12-02 Tole metallique a revetement lubrifiant et a proprietes de deformation ameliorees

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP03782275A Withdrawn EP1567623A2 (fr) 2002-12-03 2003-12-02 Tole metallique a revetement lubrifiant et a proprietes de deformation ameliorees

Country Status (10)

Country Link
US (1) US7727942B2 (fr)
EP (2) EP2311928A3 (fr)
KR (1) KR101177088B1 (fr)
CN (1) CN100572511C (fr)
AU (1) AU2003289934B2 (fr)
CA (1) CA2508716C (fr)
DE (1) DE10256639A1 (fr)
RU (1) RU2343223C2 (fr)
UA (1) UA86583C2 (fr)
WO (1) WO2004050808A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2937411A1 (fr) * 2014-04-25 2015-10-28 Voestalpine Stahl GmbH Tôle et procédé destiné à l'amélioration de la déformabilité d'une tôle
DE102018209737A1 (de) * 2018-06-18 2019-12-19 Thyssenkrupp Ag Trennschicht für die Warmumformung
WO2020064548A1 (fr) 2018-09-24 2020-04-02 Thyssenkrupp Steel Europe Ag Procédé d'amélioration de l'aptitude à la phosphatation de surfaces métalliques pourvues d'un pré-traitement ou d'un post-traitement temporaire

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070141266A1 (en) * 2005-12-21 2007-06-21 Greenlee Greg T Construction hardware and method of reducing corrosion thereof
KR100985269B1 (ko) * 2007-11-19 2010-10-04 주식회사 포스코 연속 소둔 중 강재 표면의 석출 물질 저감용 코팅재 및코팅 방법
US8092618B2 (en) * 2009-10-21 2012-01-10 Nalco Company Surface passivation technique for reduction of fouling
WO2012150105A1 (fr) 2011-04-08 2012-11-08 Micronic Mydata AB Composition de pâte à souder contenant des corps solides
US9975206B2 (en) 2011-04-08 2018-05-22 Micronic Mydata AB Composition of solid-containing paste
DE102011077654B4 (de) * 2011-06-16 2020-12-03 BSH Hausgeräte GmbH Verfahren zur Herstellung eines Blechteils durch Umformen
PL2851452T3 (pl) * 2013-09-19 2019-10-31 Fuchs Petrolub Se Nieorganiczna powłoka funkcyjna na stali ocynkowanej ogniowo jako pomocna przy formowaniu
MX2016010837A (es) * 2014-02-21 2016-10-28 Nihon Parkerizing Composicion para material equipado con pelicula lubricante, electrolisis catodica de corriente directa, y metodo para produccion de la misma.
KR101691040B1 (ko) * 2015-08-28 2016-12-29 (주) 엠에스텍 드로잉 가공 장치
DE102016209375B4 (de) * 2016-05-31 2020-11-19 BSH Hausgeräte GmbH Verfahren zum Umformen eines Edelstahlfeinblechs unter Verwendung einer Atmosphärendruckplasmaschicht
CN106191848A (zh) * 2016-08-31 2016-12-07 常熟市强盛电力设备有限责任公司 异步电机转子
CN108048163B (zh) * 2018-01-19 2021-02-26 东莞理工学院 一种荒氨酸基均三嗪衍生物多功能润滑油添加剂及其制备方法与应用
WO2019200323A1 (fr) 2018-04-13 2019-10-17 Molecular Surface Technologies, Llc Fixation électrochimique d'acides phosphoniques à des substrats métalliques et dispositifs médicaux ostéoconducteurs les contenant
US11767596B2 (en) 2019-07-29 2023-09-26 Ecolab Usa Inc. Oil soluble molybdenum complexes for inhibiting high temperature corrosion and related applications in petroleum refineries
EP4004149A1 (fr) 2019-07-29 2022-06-01 Ecolab USA Inc. Complexes de molybdène solubles dans l'huile servant d'inhibiteurs d'encrassement à haute température

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142540A (en) 1983-06-29 1985-01-23 Barbara Hayday Skin massaging device
US4880552A (en) * 1987-04-24 1989-11-14 Societe Nationale Elf Aquitaine (Production) Water-soluble additives having extreme pressure effect for aqueous functional fluids, functional fluids and concentrated aqueous compositions containing the additives
EP0489105B1 (fr) 1989-09-11 1994-06-22 Sollac Procede d'amelioration de l'emboutissabilite d'une tole ou d'un flan de tole metallique
US5650097A (en) * 1994-06-13 1997-07-22 E. I. Du Pont De Nemours And Company Corrosion inhibitor composition for steel
EP1123969A1 (fr) * 2000-02-08 2001-08-16 Mobil Oil Francaise Composition soluble dans l'eau pour le laminage à froid d'aluminium et d'aliages d'aluminium

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1402760B2 (de) 1961-06-13 1971-03-11 Metallgesellschaft AG, 6000 Frank fürt Ueberzug zur erleichterung der kaltverformung metallischer werkstuecke
FR1332533A (fr) * 1961-06-13 1963-07-19 Parker Ste Continentale Procédé pour faciliter le formage à froid des métaux sans enlèvement de copeaux
GB1053616A (fr) * 1963-03-06
FR1421796A (fr) 1964-08-20 1965-12-17 Parker Ste Continentale Agent lubrifiant pour le formage à froid sans copeaux des métaux
US3734784A (en) * 1970-01-14 1973-05-22 S Bereday Treating aluminum surfaces
US4017335A (en) * 1975-10-30 1977-04-12 Economics Laboratory, Inc. Liquid phosphatizing composition and use thereof
US4313836A (en) * 1980-12-01 1982-02-02 Basf Wyandotte Corporation Water-based hydraulic fluid and metalworking lubricant
JPS59227990A (ja) * 1983-06-10 1984-12-21 Kao Corp 水可溶性金属加工用潤滑剤組成物
JPS60130693A (ja) * 1983-12-19 1985-07-12 Hitachi Ltd 金属加工用潤滑油及びその使用方法
JPS60202196A (ja) * 1984-03-28 1985-10-12 Hitachi Ltd 金属の塑性加工法
US4878963A (en) * 1986-09-18 1989-11-07 Sanchem, Inc. Corrosion resistant aluminum coating composition
JPS63109175A (ja) 1986-10-27 1988-05-13 Kawasaki Steel Corp 塗料密着性に優れたりん酸塩処理法
US5064500A (en) * 1987-06-01 1991-11-12 Henkel Corporation Surface conditioner for formed metal surfaces
US4846898A (en) * 1988-05-05 1989-07-11 Amax Inc. Method of rendering aluminum base metal resistant to water staining
US5137647A (en) * 1991-12-09 1992-08-11 R. T. Vanderbilt Company, Inc. Organic molybdenum complexes
DE69332618T2 (de) * 1992-04-21 2003-11-13 Baker Hughes Inc Reaktionsprodukt von Stickstoffbasen und Phosphatestern als Korrosionsinhibitor
JPH0790635A (ja) * 1993-09-20 1995-04-04 Nissan Motor Co Ltd 防錆油
US5706684A (en) * 1995-10-03 1998-01-13 Cincinnati Milacron Inc. Metalworking process
US6478885B1 (en) * 1998-05-08 2002-11-12 Henkel Corporation Phosphating processes and products therefrom with improved mechanical formability
DE19833894A1 (de) * 1998-07-28 2000-02-03 Fuchs Dea Schmierstoffe Gmbh & Wassermischbares Kühlschmierstoff-Konzentrat
DE19854231A1 (de) 1998-11-24 2000-05-25 Bsh Bosch Siemens Hausgeraete Mehrtemperaturen-Kältegerät
DE10007625A1 (de) * 2000-02-18 2001-08-23 Henkel Kgaa Schmiermittel zur Umformung von Metallen
FR2809117B1 (fr) * 2000-05-19 2002-07-05 Atofina Lubrifiant aqueux multifonctionnel a base d'acide dithiodiglycolique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142540A (en) 1983-06-29 1985-01-23 Barbara Hayday Skin massaging device
US4880552A (en) * 1987-04-24 1989-11-14 Societe Nationale Elf Aquitaine (Production) Water-soluble additives having extreme pressure effect for aqueous functional fluids, functional fluids and concentrated aqueous compositions containing the additives
EP0489105B1 (fr) 1989-09-11 1994-06-22 Sollac Procede d'amelioration de l'emboutissabilite d'une tole ou d'un flan de tole metallique
US5650097A (en) * 1994-06-13 1997-07-22 E. I. Du Pont De Nemours And Company Corrosion inhibitor composition for steel
EP1123969A1 (fr) * 2000-02-08 2001-08-16 Mobil Oil Francaise Composition soluble dans l'eau pour le laminage à froid d'aluminium et d'aliages d'aluminium

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BYERS: "Metalworking fluids", 1994, MARCEL DECKER, pages: 136 - 140
MORTIER; ORSZULIK: "Chemistry and Technology of Lubricants, 2. Aufl.", 1997, CHAPMANN & HALL, pages: 253 - 260
NACHTMANN: "Lubricants and lubrication in metalworking aperations", 1985, MARCEL DECKER, pages: 81 - 105

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2937411A1 (fr) * 2014-04-25 2015-10-28 Voestalpine Stahl GmbH Tôle et procédé destiné à l'amélioration de la déformabilité d'une tôle
WO2015162304A1 (fr) * 2014-04-25 2015-10-29 Voestalpine Stahl Gmbh Tôle et procédé d'amélioration de la transformabilité d'une tôle
DE102018209737A1 (de) * 2018-06-18 2019-12-19 Thyssenkrupp Ag Trennschicht für die Warmumformung
WO2020064548A1 (fr) 2018-09-24 2020-04-02 Thyssenkrupp Steel Europe Ag Procédé d'amélioration de l'aptitude à la phosphatation de surfaces métalliques pourvues d'un pré-traitement ou d'un post-traitement temporaire

Also Published As

Publication number Publication date
US7727942B2 (en) 2010-06-01
EP1567623A2 (fr) 2005-08-31
UA86583C2 (ru) 2009-05-12
CA2508716C (fr) 2012-07-17
AU2003289934A1 (en) 2004-06-23
WO2004050808A3 (fr) 2005-02-24
US20060100112A1 (en) 2006-05-11
EP2311928A3 (fr) 2011-09-07
CA2508716A1 (fr) 2004-06-17
RU2343223C2 (ru) 2009-01-10
CN100572511C (zh) 2009-12-23
DE10256639A1 (de) 2004-06-24
WO2004050808A2 (fr) 2004-06-17
CN1742074A (zh) 2006-03-01
KR101177088B1 (ko) 2012-08-27
AU2003289934B2 (en) 2010-02-18
RU2005120742A (ru) 2006-06-10
KR20050101312A (ko) 2005-10-21

Similar Documents

Publication Publication Date Title
EP2311928A2 (fr) Solution aqueuse contenant un ester d'acide phosphorique organique pour la fabrication d'une tôle métallique revêtue de lubrifiant ayant des propriétés de déformation améliorées
EP2238227B1 (fr) Procédé d'enduction de surfaces métalliques avec une couche de phosphate puis avec une couche de lubrifiant polymère
EP2247701B1 (fr) Procédé d'enduction de surfaces métalliques avec une composition de lubrifiant contenant des cires
EP2238228B1 (fr) Procédé d'enduction de surfaces métalliques avec une composition de lubrifiant
EP2995674B1 (fr) Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage
EP2683848A1 (fr) Produit d'acier plat, procédé de fabrication d'un produit d'acier plat et procédé de fabrication d'une pièce structurale
EP2215285B1 (fr) Phosphatation au zirconium de pièces métalliques, en particulier en fer
DE1954040A1 (de) Schmiermittel zur Metallbearbeitung und Verfahren zur Vorbehandlung von Metallen
EP0270836B1 (fr) Procédé d'étirage de fils
DE2545500A1 (de) Schmiermittel zur metallbearbeitung und verfahren zur auftragung
EP2851452B1 (fr) Couche fonctionnelle anorganique sur de l'acier galavanisé à chaud
EP0186823A2 (fr) Procédé pour faciliter la déformation à froid
EP0024062B1 (fr) Lubrifiant réactif et procédé pour la préparation de métaux pour la déformation à froid
DE60214221T2 (de) Verfahren zum bearbeiten oder verformen von metallen in gegenwart von wässrigen gleitmitteln auf basis von methansulfonsäuresalzen
EP0231524B1 (fr) Application d'acides alkylbenzoylacryliques comme inhibiteurs de corrosion
EP3405600B1 (fr) Procédé de fabrication d'un produit en acier doté d'un revêtement de zinc et d'une couche active tribilogiquement appliquée sur celui-ci ainsi que produit en acier obtenu de maniere correspondante
DE102007061109B4 (de) Behandlungslösung zum Beschichten eines Stahlbandes, ein Verfahren zum Aufbringen derselben sowie ein Stahlband mit einer Beschichtung erhalten aus der Behandlungslösung zur Verbesserung des Umformverhaltens
EP0947519B1 (fr) Lubrifiant a base d'eau, contenant du soufre comme atome de coordination et leur utilisation
DE3006921A1 (de) Verfahren zum schmieren eines zu bearbeitenden metallischen werkstoffes und schmiermittel zur durchfuehrung des verfahrens
EP0200167A2 (fr) Procédé pour faciliter la formation à froid
EP0135193B1 (fr) Lubrifiant pour le traitement de métal
DE60306569T2 (de) Beschichtungslösung für Metalle und Metalllegierungen
US6852678B2 (en) Water-based lubricants containing sulfur as a coordinating atom and uses thereof
DE3124348A1 (de) Verfahren zur entfernung von phosphat- und/oder reaktionsschmiermittelschichten
DE1519023C3 (de) Filmbildner für Schutzüberzüge auf Metallen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AC Divisional application: reference to earlier application

Ref document number: 1567623

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

RIC1 Information provided on ipc code assigned before grant

Ipc: C10M 173/02 20060101AFI20110729BHEP

Ipc: C10N 40/24 20060101ALN20110729BHEP

Ipc: C10N 50/02 20060101ALN20110729BHEP

17P Request for examination filed

Effective date: 20120307

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BP EUROPA SE

Owner name: THYSSENKRUPP STEEL EUROPE AG

17Q First examination report despatched

Effective date: 20131205

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140617