EP1567623A2 - Lubricant coated sheet metal with improved deformation properties - Google Patents

Lubricant coated sheet metal with improved deformation properties

Info

Publication number
EP1567623A2
EP1567623A2 EP03782275A EP03782275A EP1567623A2 EP 1567623 A2 EP1567623 A2 EP 1567623A2 EP 03782275 A EP03782275 A EP 03782275A EP 03782275 A EP03782275 A EP 03782275A EP 1567623 A2 EP1567623 A2 EP 1567623A2
Authority
EP
European Patent Office
Prior art keywords
sheet metal
phosphoric acid
sheet
acid ester
lubricant
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Withdrawn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
EP03782275A
Other languages
German (de)
French (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
Castrol Industrie GmbH
ThyssenKrupp Stahl AG
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 Castrol Industrie GmbH, ThyssenKrupp Stahl AG, ThyssenKrupp Steel Europe AG, BP Europe SE filed Critical Castrol Industrie GmbH
Priority to EP10180973A priority Critical patent/EP2311928A3/en
Publication of EP1567623A2 publication Critical patent/EP1567623A2/en
Withdrawn legal-status Critical Current

Links

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 forming properties, the lubricant being in particular an anti-corrosion 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 the use thereof for producing metal bodies by forming, in particular by deep drawing.
  • metal sheets e.g. B. steel sheets
  • a temporary corrosion protection for storage and transport immediately after the manufacturing or coating process and before delivery to the metalworking industry. This is usually done by applying a corrosion-inhibiting lubricant immediately before winding the sheet, such as an anti-corrosion oil, a pre-lube or a dry-lube.
  • a corrosion-inhibiting lubricant immediately before winding the sheet, such as an anti-corrosion oil, a pre-lube or a dry-lube.
  • the lubricants used may contain, in addition to corrosion-inhibiting substances, other auxiliaries which are specifically tailored to the respective forming process and which improve the tribological properties of the sheet during the forming process.
  • Metal sheets coated in this way are used, for example, in the automotive industry in the production of bodies from metal sheets by deep drawing.
  • EP 0 489 105 B1 discloses a process for cold deep drawing of metal sheets in which the sheet to be deep drawn and / or the deep drawing tool is treated with an aqueous solution of an inorganic alkali metal phosphate and then deep drawn in the presence of a deep drawing oil.
  • the salt deposited on the sheet forms a soap under the pressure and temperature conditions of deep-drawing by reaction with the deep-drawing oil, which causes a reduction in the coefficient of friction.
  • a disadvantage of the process is that the alkali metal phosphate used and the soaps formed cannot be completely removed from the sheet after the deep-drawing process.
  • Lubricant composition known for non-cutting cold forming of metals, which contains a finely dispersed water-soluble inorganic salt such as borax to improve the tribological properties.
  • the disadvantage of this lubricant composition is that its lubricity is not constant because the salt is not evenly distributed over the surface, which interferes with the deep-drawing process.
  • Prelubes contain drawing aids, which are placed in the approx. 1 ⁇ m thick oil layer.
  • drawing aids which are placed in the approx. 1 ⁇ m thick oil layer.
  • only the direct steel-tool interface in the range of a few nanometers is tribologically active.
  • the invention was based on the object, a lubricant-coated metal sheet for the production of To provide metal bodies by forming with improved tribological properties.
  • the metal sheet should be easy to clean after the forming process and without leaving any residues. After all, the production of the lubricant-coated metal sheet should be simple and can be carried out in existing production plants without high capital expenditure.
  • a sheet metal or a sheet metal blank with a coating of lubricant, in particular an anti-corrosion oil, pre-lube and / or dry lube the sheet metal or the sheet metal blank comprising a layer which is applied 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 due to their layer formed by the phosphoric acid ester. Compared to 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 be easily cleaned with existing degreasing systems after the shaping process, both the lubricant-containing layer and the layer formed by the phosphoric acid ester being easily removable from the surface of the sheet without residue.
  • the metal sheets which can be used according to the invention can be any metal sheets from which metal bodies can be produced by forming, in particular by cold forming. Steel sheets are particularly suitable metal sheets.
  • the metal sheets that can be used according to the invention can be coated or uncoated.
  • an uncoated metal sheet for example, uncoated thin sheet, in particular conti-annealed uncoated thin sheet, can be used.
  • Coated metal sheets are in particular electrolytically coated sheet, in particular electrolytically galvanized sheet, and hot-dip galvanized and galvanized sheets.
  • the metal sheets preferably have a thickness of 0.05 to 5 mm, in particular 0.5 to 1.5 mm.
  • the metal sheets and sheet metal blanks according to the invention are coated with a lubricant which, at least temporarily, is intended to protect the sheets from undesired environmental influences, in particular from corrosion, after production.
  • a lubricant which, at least temporarily, is intended to protect the sheets from undesired environmental influences, in particular from corrosion, after production.
  • the choice of lubricant is not limited; Rather, any greasy or oily substances or the like as well as dry lubricants such as graphite come into question.
  • the lubricants that can be used according to the invention preferably contain corrosion inhibitors.
  • the lubricants can contain other additives, in particular additives to improve the drawing properties of the sheets.
  • Lubricants of this type for the metalworking industry are generally known to the person skilled in the art and are described, for example, in demomann “Lubricants and lubrication in metalworking operations ,,, Marcel Decker, New York, 1985, pages 81 to 105; Byers “Metalworking fluids”, Marcel Decker, New York, 1994, pages 136 to 140 and Mortier, Orszulik “Chemistry and Technology of Lubricants", 2nd edition, Chapmann & Hall, London, 1997, pages 253 to 260 ,
  • an anti-corrosion oil is used as the lubricant.
  • corrosion protection oils are well known to the person skilled in the art and usually contain a base oil with an aromatic content ⁇ 10% and a corrosion inhibitor such as, for. B. Calcium sulfonate.
  • the anti-corrosion oils can contain antioxidants to prevent oil aging and thixotropic agents to reduce dripping losses on oiled 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 generally known to the person skilled in the art.
  • the improvement in the drawing properties is achieved by adding further additives, e.g. B. of esters.
  • a so-called dry lubricant is used as the lubricant.
  • Dry lubricants are wax and / or acrylate-based thin films with properties similar to Pre-Lubes and as such are generally known to the person skilled in the art.
  • dry lubricants offer the possibility of producing difficult drawn parts in the press shop without additional greasing. Drip drained coated sheets are completely avoided.
  • dry lubricants can be applied, for example, electrostatically or using a roll coater.
  • a layer is formed on the metallic surface of the sheet, which can be obtained by applying an organic phosphoric acid ester to the metallic surface of the sheet.
  • Organic phosphoric acid esters which can be used according to the invention are in particular compounds of the general formula
  • R for is a straight-chain or branched alkyl group having 1 to 14, in particular 1 to 8, carbon atoms
  • R ' is a straight-chain or branched alkylene group having 1 to 14, in particular 1 to 8 carbon atoms
  • R and R ' can each be the same or different and n is a number from 0 to 3, with the proviso that n is not 0 when X is exclusively hydrogen.
  • the layer formed by phosphoric acid esters contains as a further component a water-soluble organic sulfur compound and / or an organic molybdenum compound.
  • Organic sulfur compounds suitable according to the invention are in particular 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.
  • Organic molybdenum compounds suitable according to the invention can be obtained, for example, by reacting molybdenum trioxide and / or molybdic acid with an amine and / or alkanolamine.
  • the layer containing phosphoric acid ester contains as a further component at least one inorganic compound selected from the group consisting of polyphosphates, borates, molybdates and tungstates.
  • Inorganic compounds which are particularly suitable 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 are preferably applied to the metal sheet in the form of an aqueous solution. After the application, the metal sheet is preferably dried.
  • the layer formed by phosphoric acid esters can be formed in any thickness. However, this is preferably formed as a very thin layer, in particular as a line in the nanomer range.
  • a layer containing lubricant is formed directly on the layer formed by phosphoric acid esters.
  • the lubricant-containing layer preferably contains an anti-corrosion oil, pre-lube and / or dry-lube.
  • the layer containing lubricant preferably contains an anti-corrosion oil.
  • the layer containing lubricant can be formed in any thickness. Particularly good tribological properties can be achieved if the layer containing lubricant is formed in a thickness of 0.3 to 3.0 g / m 2 , in particular 1 to 2 g / m 2 .
  • the layer containing lubricant is matched to the extent that the layer containing phosphoric acid ester is used, than that it contains components which are also contained in the layer containing phosphoric acid ester.
  • the layer containing lubricant contains at least one organic phosphoric acid ester as defined above in an amount of 0.01 to 50% by weight, in particular 0.05 to 10% by weight.
  • the lubricant-containing layer contains a water-soluble organic sulfur compound as defined above in an amount of 0.005 to 50% by weight, in particular 0.01 to 30% by weight, and / or an organic molybdenum compound in an amount contains from 0.005 to 50% by weight, in particular 0.01 to 30% by weight.
  • 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 invention further relates to a method for producing the metal sheet or sheet metal blank according to the invention, comprising the following steps:
  • the solution containing the organic phosphoric acid ester can be applied by any measures known to the person skilled in the art, such as dipping, spraying, brushing or knife coating.
  • the solution containing phosphoric acid esters can be applied when coating the sheet in the rinsing bath of a coating system or when cooling the sheet in the bath of a water cooling system.
  • the solution containing phosphoric acid esters is preferably applied in the rinsing bath of a coating system.
  • the rinsing bath is preferably connected as a one-stage no-rinse after-treatment after the metallic coating process (e.g. electrolytic galvanizing). Further production steps can be added to the rinsing bath within a production system.
  • the metal sheet can be dried in a suitable dryer after the rinsing bath and / or subsequently coated with a lubricant (for example by electrostatic oiling).
  • the solution containing phosphoric acid esters 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 from 6.5 to 11, in particular 7.5 to 9.5.
  • the solution contains, as a further 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 present in the solution in an amount of 1 to 50% by weight, in particular 5 to 25% by weight on the amount of phosphoric acid ester included.
  • the inorganic compound (s) are present in the solution in an amount of 1 to 50% by weight, in particular 5 to 10% by weight, based on the amount of phosphoric acid ester.
  • A is preferably used as the lubricant
  • Corrosion protection oil Pre-Lube and / or Dry-Lube used as described above.
  • the lubricant is preferred its composition is matched to the solution containing phosphoric acid esters to the extent that it contains components (e.g. organic phosphoric acid esters, water-soluble organic sulfur compounds, organic molybdenum compounds and / or inorganic compounds) as described above, which are also contained in the solution containing phosphoric acid esters.
  • 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 includes the use of a solution containing an organic phosphoric acid ester as described above for the treatment of metal surfaces.
  • the invention further relates to an aqueous solution for the treatment of metal surfaces containing 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 with a thickness of 1 mm were treated by dipping with an aqueous solution of the composition given below, dried, and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was then determined in the draw bed test to determine the drawing power.
  • An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric acid ester mixture of (CH 3 -0) PO (OH) 2 and (OH) PO (0-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 mixture of phosphoric acid esters of (C 4 H 9 -0) PO (OH) 2 and (OH) PO (0-C 4 H 9 ) 2.
  • the sheet was dried and then coated with 1.5 g / m 2 Pre-Lube. 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 -0) PO (OH) 2 and (OH) PO (0-C B H 17 ) 2 .
  • the sheet was dried and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was 90%.
  • An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar mixture of phosphoric acid esters of (CH 3 - [0-CH 2 CH 2 ] 3 -C 12 H 24 -0) PO (OH) 2 and (HO) PO (CH 3 - [0-CH 2 CH 2 ] 3 -C 12 H 24 -0) 2 treated.
  • the sheet was dried and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was 92%.
  • 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 coefficient of friction 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 pre-lube.
  • the coefficient of friction was 95%.
  • the results show that the metal sheets according to the invention, which were treated with a phosphoric acid ester solution, have significantly improved tribological properties and an enlarged 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 and completely residue-free to clean in a conventional degreasing system.

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Abstract

The invention relates to sheet metal or a sheet metal blank provided with a lubricant coating, especially an anti-corrosion oil of the Pre-Lube or Dry Lube variety. The sheet metal or sheet metal blank comprises a layer which is formed by applying a solution containing an organic phosphoric acid ester to the metal surface of the sheet metal. Sheet metal provided with said coating has excellent tribological properties.

Description

Schmierstoffbeschichtetes Metallblech mit verbesserten Lubricant coated metal sheet with improved
Umformeigenschaftenformability
Die Erfindung betrifft ein schmierstoffbeschichtetes Metallblech oder einen Zuschnitt hiervon mit verbesserten Umformeigenschaften, wobei der Schmierstoff insbesondere ein Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube ist. Die Erfindung betrifft ferner ein Verfahren zur Herstellung eines solchen Metallblechs oder Metallblechzuschnitts sowie deren Verwendung zur Herstellung von Metallkörpern durch Umformung, insbesondere durch Tiefziehen.The invention relates to a lubricant-coated metal sheet or a blank thereof with improved forming properties, the lubricant being in particular an anti-corrosion 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 the use thereof for producing metal bodies by forming, in particular by deep drawing.
Bei der Herstellung von Metallblechen, z. B. Stahlblechen, ist es üblich, diese unmittelbar nach dem Herstellungs- bzw. Beschichtungsverfahren und vor Auslieferung an die metallverarbeitende Industrie mit einem temporären Korrosionsschutz für Lagerung und Transport auszustatten. Dies erfolgt in der Regel durch Aufbringen eines korrosionshemmenden Schmierstoffes unmittelbar vor dem Aufspulen des Bleches, etwa eines Korrosionsschutzöls, eines Pre-Lubes oder eines Dry- Lubes. Wenn das Metallblech zur Weiterverarbeitung durch Umformung wie etwa Tiefziehen bestimmt ist, können die eingesetzten Schmierstoffe neben korrosionshemmenden Substanzen weitere, speziell auf den jeweiligen Umformvorgang abgestimmte Hilfsstoffe enthalten, welche die tribologischen Eigenschaften des Bleches beim Umformvorgang verbessern. Derartig beschichtete Metallbleche finden beispielsweise in der Automobilindustrie bei der Herstellung von Karosserien aus Metallblechen durch Tiefziehen Verwendung.In the manufacture of metal sheets, e.g. B. steel sheets, it is common to provide them with a temporary corrosion protection for storage and transport immediately after the manufacturing or coating process and before delivery to the metalworking industry. This is usually done by applying a corrosion-inhibiting lubricant immediately before winding the sheet, such as an anti-corrosion oil, a pre-lube or a dry-lube. If the metal sheet is intended for further processing by forming, such as deep drawing, the lubricants used may contain, in addition to corrosion-inhibiting substances, other auxiliaries which are specifically tailored to the respective forming process and which improve the tribological properties of the sheet during the forming process. Metal sheets coated in this way are used, for example, in the automotive industry in the production of bodies from metal sheets by deep drawing.
Beim Einsatz von Schmierstoffen für den temporären Korrosionsschutz und zur Verbesserung der Umformeigenschaften ist insbesondere zu beachten, dass diese nach dem Umformvorgang leicht und vollständig vom Blech entfernbar sind.When using lubricants for temporary corrosion protection and to improve the forming properties, it is particularly important to note that they can be easily and completely removed from the sheet after the forming process.
Aus der EP 0 489 105 Bl ist ein Verfahren zum Kalttiefziehen von Metallblechen bekannt, in dem das tiefzuziehende Blech und/oder das Tiefziehwerkzeug mit einer wässrigen Lösung eines anorganischen Alkaliphosphats behandelt und anschließend in Gegenwart eines Tiefziehöls tiefgezogen wird. Das auf dem Blech abgelagerte Salz bildet unter den Druck- und Temperaturbedingungen des Tiefziehens durch Reaktion mit dem Tiefziehöl eine Seife, welche eine Verringerung des Reibungskoeffizienten bewirkt. Nachteilig an dem Verfahren ist, dass das eingesetzte Alkaliphosphat und die gebildeten Seifen nach dem Tiefziehen nicht völlig rückstandsfrei von dem Blech zu entfernen ist.EP 0 489 105 B1 discloses a process for cold deep drawing of metal sheets in which the sheet to be deep drawn and / or the deep drawing tool is treated with an aqueous solution of an inorganic alkali metal phosphate and then deep drawn in the presence of a deep drawing oil. The salt deposited on the sheet forms a soap under the pressure and temperature conditions of deep-drawing by reaction with the deep-drawing oil, which causes a reduction in the coefficient of friction. A disadvantage of the process is that the alkali metal phosphate used and the soaps formed cannot be completely removed from the sheet after the deep-drawing process.
Aus der CH 441 594 ist ferner eineFrom CH 441 594 is also one
SchmierstoffZusammensetzung zur spanlosen Kaltverformung von Metallen bekannt, welche zur Verbesserung der tribologischen Eigenschaften ein fein dispergiertes wasserlösliches anorganisches Salz wie Borax enthält. Nachteilig an dieser SchmierstoffZusammensetzung ist, dass dessen Schmierfähigkeit nicht konstant ist, da sich das Salz nicht gleichmäßig über die Oberfläche verteilt, was den Tiefziehvorgang stört.Lubricant composition known for non-cutting cold forming of metals, which contains a finely dispersed water-soluble inorganic salt such as borax to improve the tribological properties. The disadvantage of this lubricant composition is that its lubricity is not constant because the salt is not evenly distributed over the surface, which interferes with the deep-drawing process.
Bei der Produktion von einseitig elektrolytisch verzinktem Feinblech hat sich eine Dünnstphosphatierung bzw. Boraxpassivierung mit einem Schichtgewicht von ca. 10 mg/m2 als vorteilhaft hinsichtlich tribologischer Eigenschaften herausgestellt. Beide Produkte können in den vorhandenen Spülbädern der Verzinkungslinien appliziert werden. Sie haben aber den Nachteil, dass sie die Phosphatierung im Automobilwerk beeinträchtigen können.In the production of sheet metal electrolytically galvanized on one side, thin phosphating or borax passivation with a layer weight of approx. 10 mg / m 2 has proven to be advantageous with regard to tribological properties. Both products can be applied in the existing rinse baths of the galvanizing lines. However, they have the disadvantage that they can impair phosphating in the automobile plant.
Der Idee, die tribologischen Eigenschaften von Stahlband direkt auf der Stahloberfläche zu beeinflussen, wird durch den Einsatz von Prelubes Rechnung getragen. Prelubes enthalten Ziehhilfsstoffe, welche in die ca. 1 μm dicke Olschicht eingebracht werden. Tribologisch aktiv ist aber nur das direkte Stahl-Werkzeug-Interface im Bereich weniger Nanometer.The idea of influencing the tribological properties of steel strips directly on the steel surface is taken into account by using prelubes. Prelubes contain drawing aids, which are placed in the approx. 1 μm thick oil layer. However, only the direct steel-tool interface in the range of a few nanometers is tribologically active.
Schließlich ist allgemein bekannt, zur Verbesserung der tribologischen Eigenschaften eine Oberflächenbehandlung des tiefzuziehenden Bleches durchzuführen. Insbesondere sind chemische Verfahren zur Oberflächenbehandlung wie beispielsweise die Phosphortierung bekannt, durch welche der Reibungskoeffizient Blech/Werkzeug reduziert und somit die Formgebung des Blechzuschnitts begünstigt wird. Eine solche Behandlung ist jedoch teuer und lässt sich nicht auf alle tiefzuziehenden Bleche anwenden.Finally, it is generally known to carry out a surface treatment of the sheet to be deep-drawn to improve the tribological properties. In particular, chemical methods for surface treatment, such as phosphor coating, are known, by means of which the coefficient of friction of the sheet / tool is reduced and thus the shaping of the sheet blank is favored. However, such a treatment is expensive and cannot be applied to all deep-drawn sheets.
Der Erfindung lag die Aufgabe zugrunde, ein schmierstoffbeschichtetes Metallblech zur Herstellung von Metallkörpern durch Umformung mit verbesserten tribologischen Eigenschaften bereitzustellen. Das Metallblech soll nach dem Umformvorgang leicht und ohne Verbleib von jeglichen Rückständen zu reinigen sein. Die Herstellung des schmierstoffbeschichteten Metallblechs soll schließlich einfach und ohne hohen Investitionsaufwand in bestehenden Herstellungsanlagen durchführbar sein.The invention was based on the object, a lubricant-coated metal sheet for the production of To provide metal bodies by forming with improved tribological properties. The metal sheet should be easy to clean after the forming process and without leaving any residues. After all, the production of the lubricant-coated metal sheet should be simple and can be carried out in existing production plants without high capital expenditure.
Diese Aufgabe wird erfindungsgemäß durch ein Metallblech oder einen Metallblechzuschnitt mit einer Beschichtung aus Schmierstoff, insbesondere einem Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube, gelöst, wobei das Metallblech oder der Metallblechzuschnitt eine Schicht umfasst, welche durch Aufbringen einer einen organischen Phosphorsäureester enthaltenden Lösung auf die metallische Oberfläche des Blechs gebildet ist.This object is achieved according to the invention by a sheet metal or a sheet metal blank with a coating of lubricant, in particular an anti-corrosion oil, pre-lube and / or dry lube, the sheet metal or the sheet metal blank comprising a layer which is applied by applying an organic phosphoric acid ester Solution is formed on the metallic surface of the sheet.
Überraschend wurde gefunden, dass die erfindungsgemäßen schmierstoffbeschichteten Metallbleche infolge ihrer durch den Phosphorsäureester gebildeten Schicht ausgezeichnete tribologische Eigenschaften aufweisen. Gegenüber schmierstoffbeschichteten Metallblechen ohne eine solche Schicht weisen die erfindungsgemäßen Metallbleche einen verringerten Reibungskoeffizienten auf. Schließlich lassen sich die erfindungsgemäßen Metallbleche nach dem Umformvorgang leicht mit bestehenden Entfettungsanlagen reinigen, wobei sowohl die Schmierstoff enthaltende, als auch die durch den Phosphorsäureester gebildete Schicht rückstandsfrei von der Oberfläche des Blechs problemlos entfernbar ist. Bei den erfindungsgemäß einsetzbaren Metallblechen kann es sich um beliebige Metallbleche handeln, aus denen sich durch Umformung, insbesondere durch Kaltformen, Metallkörper herstellen lassen. Besonders geeignete Metallbleche sind Stahlbleche. Die erfindungsgemäß einsetzbaren Metallbleche können beschichtet oder unbeschichtet sein. Als unbeschichtetes Metallblech kommt beispielsweise unbeschichtetes Feinblech, insbesondere contigeglühtes unbeschichtetes Feinblech, in Frage. Als beschichtete Metallbleche kommen insbesondere elektrolytisch beschichtetes Blech, insbesondere elektrolytisch verzinktes Blech, und feuerverzinkte und galvanealed Bleche in Frage. Die Metallbleche weisen vorzugsweise eine Dicke von 0,05 bis 5 mm, insbesondere von 0,5 bis 1,5 mm auf.Surprisingly, it was found that the lubricant-coated metal sheets according to the invention have excellent tribological properties due to their layer formed by the phosphoric acid ester. Compared to 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 be easily cleaned with existing degreasing systems after the shaping process, both the lubricant-containing layer and the layer formed by the phosphoric acid ester being easily removable from the surface of the sheet without residue. The metal sheets which can be used according to the invention can be any metal sheets from which metal bodies can be produced by forming, in particular by cold forming. Steel sheets are particularly suitable metal sheets. The metal sheets that can be used according to the invention can be coated or uncoated. As an uncoated metal sheet, for example, uncoated thin sheet, in particular conti-annealed uncoated thin sheet, can be used. Coated metal sheets are in particular electrolytically coated sheet, in particular electrolytically galvanized sheet, and hot-dip galvanized and galvanized sheets. The metal sheets preferably have a thickness of 0.05 to 5 mm, in particular 0.5 to 1.5 mm.
Die erfindungsgemäßen Metallbleche und Metallblechzuschnitte sind mit einem Schmierstoff beschichtet, welches die Bleche nach der Herstellung zumindest temporär vor unerwünschten Umwelteinflüssen, insbesondere vor Korrosionserscheinungen, schützen soll. Die Auswahl des Schmierstoffs ist nicht beschränkt; es kommen vielmehr jegliche fett- oder ölhaltige Substanzen oder dergleichen sowie Trocken-Schmierstoff wie Graphit in Frage. Die erfindungsgemäß einsetzbaren Schmierstoffe enthalten vorzugsweise Korrosionsinhibitoren. Daneben können die Schmierstoff noch weitere Zusatzstoffe enthalten, insbesondere Zusatzstoffe zur Verbesserung der Zieheigenschaften der Bleche.The metal sheets and sheet metal blanks according to the invention are coated with a lubricant which, at least temporarily, is intended to protect the sheets from undesired environmental influences, in particular from corrosion, after production. The choice of lubricant is not limited; Rather, any greasy or oily substances or the like as well as dry lubricants such as graphite come into question. The lubricants that can be used according to the invention preferably contain corrosion inhibitors. In addition, the lubricants can contain other additives, in particular additives to improve the drawing properties of the sheets.
Derartige Schmierstoffe für die metallverarbeitende Industrie sind dem Fachmann allgemein bekannt und beispielsweise in Nachtmann „Lubricants and lubrication in metalworking operations,, , Marcel Decker, New York, 1985, Seiten 81 bis 105; Byers „Metalworking fluids,, , Marcel Decker, New York, 1994, Seiten 136 bis 140 und Mortier, Orszulik „ Chemistry and Technology of Lubricants,, , 2. Aufl., Chapmann & Hall, London, 1997, Seiten 253 bis 260 beschrieben.Lubricants of this type for the metalworking industry are generally known to the person skilled in the art and are described, for example, in Nachtmann “Lubricants and lubrication in metalworking operations ,,, Marcel Decker, New York, 1985, pages 81 to 105; Byers "Metalworking fluids", Marcel Decker, New York, 1994, pages 136 to 140 and Mortier, Orszulik "Chemistry and Technology of Lubricants", 2nd edition, Chapmann & Hall, London, 1997, pages 253 to 260 ,
Gemäß einer bevorzugten Ausführungsform der Erfindung wird als Schmierstoff ein Korrosionsschutzöl eingesetzt. Derartige Korrosionsschutzöle sind dem Fachmann allgemein bekannt und enthalten üblicherweise ein Grundöl mit einem Aromatengehalt < 10 % und einen Korrosionsinhibitor wie z . B . Calciumsulfonat . Daneben können die Korrosionsschutzöle Antioxidantien zur Verhinderung von Ölalterung sowie Thixotropiebildner zur Reduzierung von Abtropf erlusten bei eingeölten Blechen enthalten.According to a preferred embodiment of the invention, an anti-corrosion oil is used as the lubricant. Such corrosion protection oils are well known to the person skilled in the art and usually contain a base oil with an aromatic content <10% and a corrosion inhibitor such as, for. B. Calcium sulfonate. In addition, the anti-corrosion oils can contain antioxidants to prevent oil aging and thixotropic agents to reduce dripping losses on oiled sheets.
Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung wird als Schmierstoff ein sogenannter Pre-Lube eingesetzt. Pre-Lubes sind Korrosionsschutzöle mit verbesserten Zieheigenschaften und als solche dem Fachmann allgemein bekannt. Die Verbesserung der Zieheigenschaften wird durch Zugabe von weiteren Additiven, z. B. von Estern, erreicht.According to a further preferred embodiment of the invention, a so-called pre-lube is used as the lubricant. Pre-lubes are corrosion protection oils with improved drawing properties and as such are generally known to the person skilled in the art. The improvement in the drawing properties is achieved by adding further additives, e.g. B. of esters.
Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung wird als Schmierstoff ein sogenannter Dry Lubricant eingesetzt. Dry Lubricants sind wachs- und/oder acrylatbasierte dünne Filme mit ähnlichen Eigenschaften wie Pre-Lubes und sind als solche dem Fachmann allgemein bekannt. Zusätzlich bieten Dry Lubricants die Möglichkeit, schwierige Ziehteile im Presswerk ohne weitere Zusatzbefettung herzustellen. Abtropf erluste beschichteter Bleche werden vollständig vermieden. Dry Lubricants können nach dem Aufschmelzen beispielsweise elektrostatisch oder mittels Rollcoater appliziert werden.According to a further preferred embodiment of the invention, a so-called dry lubricant is used as the lubricant. Dry lubricants are wax and / or acrylate-based thin films with properties similar to Pre-Lubes and as such are generally known to the person skilled in the art. In addition, dry lubricants offer the possibility of producing difficult drawn parts in the press shop without additional greasing. Drip drained coated sheets are completely avoided. After melting, dry lubricants can be applied, for example, electrostatically or using a roll coater.
Erfindungsgemäß ist auf der metallischen Oberfläche des Blechs eine Schicht ausgebildet, welche erhältlich ist durch Aufbringen eines organischen Phosphorsäureesters auf die metallische Oberfläche des Blechs.According to the invention, a layer is formed on the metallic surface of the sheet, which can be obtained by applying an organic phosphoric acid ester to the metallic surface of the sheet.
Erfindungsgemäß einsetzbare organische Phosphorsäureester sind insbesondere Verbindungen der allgemeinen FormelOrganic phosphoric acid esters which can be used according to the invention are in particular compounds of the general formula
X3-nP04Rn,X 3 - n P0 4 R n ,
worin X für Wasserstoff, Na, K, -NH2, -NHR, -NR2, -NH(R'-OH), -N(R'-OH)2 oder -NR(R'-OH), R für eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 14, insbesondere 1 bis 8 Kohlenstoffatomen steht, R' eine geradkettige oder verzweigte Alkylengruppe mit 1 bis 14, insbesondere 1 bis 8 Kohlenstoffatomen bedeutet, wobei ein oder mehrere Wasserstoffatome in R und R' durch eine polymere oder oligomere Gruppe -Y-R substituiert sein können, worin Y für (CH2-CH2-0-)ra oder (CH2-CH(CH3) -0-)m mit m = 1 bis ∞ und insbesondere m = 1 bis 10 steht, R und R' jeweils gleich oder verschieden sein können und n eine Zahl von 0 bis 3 ist, mit der Maßgabe, dass n nicht 0 ist, wenn X ausschließlich für Wasserstoff steht.where X is hydrogen, Na, K, -NH 2 , -NHR, -NR 2 , -NH (R'-OH), -N (R'-OH) 2 or -NR (R'-OH), R for is a straight-chain or branched alkyl group having 1 to 14, in particular 1 to 8, carbon atoms, R 'is a straight-chain or branched alkylene group having 1 to 14, in particular 1 to 8 carbon atoms, one or more hydrogen atoms in R and R' being represented by a polymeric or oligomeric group -YR can be substituted, in which Y represents (CH 2 -CH 2 -0-) ra or (CH 2 -CH (CH 3 ) -0-) m with m = 1 to ∞ and in particular m = 1 to 10 is, R and R 'can each be the same or different and n is a number from 0 to 3, with the proviso that n is not 0 when X is exclusively hydrogen.
Besonders gute Ergebnisse werden erzielt, wenn als organischer Phosphorsäureester eine Verbindung der oben genannten Formel mit X = H, R = C4H9 und n = 1 oder 2 eingesetzt wird. Besonders bevorzugt ist ferner ein äquimolares Gemisch aus (C4H9-0) PO (OH) 2 und (OH)PO(0-C4H9)2.Particularly good results are achieved when a compound of the above formula with X = H, R = C 4 H 9 and n = 1 or 2 is used as the organic phosphoric acid ester is used. An equimolar mixture of (C 4 H 9 -0) PO (OH) 2 and (OH) PO (0-C 4 H 9 ) 2 is also particularly preferred.
Gemäß einer bevorzugten Ausführungsform der Erfindung enthält die durch Phosphorsäureester gebildete Schicht als weitere Komponente eine wasserlösliche organische Schwefelverbindung und/oder eine organische Molybdänverbindung .According to a preferred embodiment of the invention, the layer formed by phosphoric acid esters contains as a further component a water-soluble organic sulfur compound and / or an organic molybdenum compound.
Erfindungsgemäß geeignete organische Schwefelverbindungen sind insbesondere Thiadiazole, Dithiocarbamate und/oder Dithiopropionate sowie deren Salze und Derivate.Organic sulfur compounds suitable according to the invention are in particular thiadiazoles, dithiocarbamates and / or dithiopropionates and their salts and derivatives.
Besonders geeignete organische Schwefelverbindungen sind beispielsweise Natrium-2-mercaptobenzothiazol, 2,5- Dimercapto-1, 3 , 4-thiadiazol sowie Salze und Derivate davon, Natriumdimethyldithiocarbamat , Kaliumdimethyldithiocarbamat und/oder Monoethanolamindithiopropionat .Particularly suitable 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.
Erfindungsgemäß geeignete organische Molybdänverbindungen sind beispielsweise durch Umsetzung von Molybdäntrioxid und/oder Molybdänsäure mit einem Amin und/oder Alkanolamin erhältlich.Organic molybdenum compounds suitable according to the invention can be obtained, for example, by reacting molybdenum trioxide and / or molybdic acid with an amine and / or alkanolamine.
Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung enthält die Phosphorsäureester enthaltende Schicht als weitere Komponente mindestens eine anorganische Verbindung ausgewählt aus der Gruppe bestehend aus Polyphosphaten, Boraten, Molybdaten und Wolframaten. Erfindungsgemäß besonders geeignete anorganische Verbindungen sind beispielsweise Ammoniumtripolyphosphat, Natriumtetraborat, Ammoniummolybdat, Natriumwolframat , Kaliumwolframat und/oder Natriumwolframat.According to a further preferred embodiment of the invention, the layer containing phosphoric acid ester contains as a further component at least one inorganic compound selected from the group consisting of polyphosphates, borates, molybdates and tungstates. Inorganic compounds which are particularly suitable according to the invention are, for example, ammonium tripolyphosphate, sodium tetraborate, ammonium molybdate, sodium tungstate, potassium tungstate and / or sodium tungstate.
Vorzugsweise werden der organische Phosphorsäureester und etwaige weitere Komponenten in Form einer wäßrigen Lösung auf das Metallblech aufgebracht. Nach dem Aufbringen wird das Metallblech vorzugsweise getrocknet.The organic phosphoric acid ester and any other components are preferably applied to the metal sheet in the form of an aqueous solution. After the application, the metal sheet is preferably dried.
Die durch Phosphorsäureester gebildete Schicht kann in beliebigen Dicken ausgebildet sein. Bevorzugt wird diese jedoch als sehr dünne Schicht, insbesondere als Strich im Nanomerbereich, ausgebildet.The layer formed by phosphoric acid esters can be formed in any thickness. However, this is preferably formed as a very thin layer, in particular as a line in the nanomer range.
Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung wird eine Schmierstoff enthaltende Schicht unmittelbar auf der durch Phosphorsäureester gebildeten Schicht ausgebildet. Die Schmierstoff enthaltende Schicht enthält bevorzugt ein Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube. Vorzugsweise enthält die Schmierstoff enthaltende Schicht ein Korrosionsschutzöl .According to a further preferred embodiment of the invention, a layer containing lubricant is formed directly on the layer formed by phosphoric acid esters. The lubricant-containing layer preferably contains an anti-corrosion oil, pre-lube and / or dry-lube. The layer containing lubricant preferably contains an anti-corrosion oil.
Die Schmierstoff enthaltende Schicht kann in beliebigen Dicken ausgebildet sein. Besonders gute tribologische Eigenschaften lassen sich erzielen, wenn die Schmierstoff enthaltende Schicht in einer Dicke von 0,3 bis 3,0 g/m2 , insbesondere 1 bis 2 g/m2, ausgebildet ist.The layer containing lubricant can be formed in any thickness. Particularly good tribological properties can be achieved if the layer containing lubricant is formed in a thickness of 0.3 to 3.0 g / m 2 , in particular 1 to 2 g / m 2 .
Als besonders vorteilhaft hat sich erwiesen, wenn die Schmierstoff enthaltende Schicht insoweit auf die Phosphorsäureester enthaltende Schicht abgestimmt ist, als dass sie Komponenten enthält, welche auch in der Phosphorsäureester enthaltenden Schicht enthalten sind.It has proven to be particularly advantageous if the layer containing lubricant is matched to the extent that the layer containing phosphoric acid ester is used, than that it contains components which are also contained in the layer containing phosphoric acid ester.
Es wurde gefunden, dass durch diese Maßnahme ein synergistischer Effekt eintritt und die tribologischen Eigenschaften des Blechs weiter verbessert werden.It was found that this measure has a synergistic effect and further improves the tribological properties of the sheet.
So ist es vorteilhaft, wenn die Schmierstoff enthaltende Schicht mindestens einen organischen Phosphorsäureester wie oben definiert in einer Menge von 0,01 bis 50 Gew.%, insbesondere 0,05 bis 10 Gew.%, enthält.It is advantageous if the layer containing lubricant contains at least one organic phosphoric acid ester as defined above in an amount of 0.01 to 50% by weight, in particular 0.05 to 10% by weight.
Ferner ist es vorteilhaft, wenn die Schmierstoff enthaltende Schicht eine wasserlösliche organische Schwefelverbindung wie oben definiert in einer Menge von 0,005 bis 50 Gew.%, insbesondere 0,01 bis 30 Gew.%, und/oder eine organische Molybdänverbindung wie oben definiert in einer Menge von 0,005 bis 50 Gew.%, insbesondere 0,01 bis 30 Gew.%, enthält.It is also advantageous if the lubricant-containing layer contains a water-soluble organic sulfur compound as defined above in an amount of 0.005 to 50% by weight, in particular 0.01 to 30% by weight, and / or an organic molybdenum compound in an amount contains from 0.005 to 50% by weight, in particular 0.01 to 30% by weight.
Schließlich ist es vorteilhaft, wenn der Schmierstoff eine anorganische Verbindung wie oben definiert in einer Menge von 0,005 bis 50 Gew.%, insbesondere 0,01 bis 30 Gew.%, enthält.Finally, it is advantageous if 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.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung des erfindungsgemäßen Metallblechs oder Metallblechzuschnitts umfassend folgende Schritte:The invention further relates to a method for producing the metal sheet or sheet metal blank according to the invention, comprising the following steps:
Aufbringen einer Lösung enthaltend einen organischen Phosphorsäureester auf die Ober- und/oder Unterseite des Blechs und Aufbringen eines Schmierstoffs auf das so beschichtete Blech.Applying a solution containing an organic phosphoric acid ester to the top and / or bottom of the sheet and Applying a lubricant to the coated sheet.
Das Aufbringen der Lösung enthaltend den organischen Phosphorsäureester kann durch beliebige, dem Fachmann bekannte Maßnahmen wie Tauchen, Sprühen, Streichen oder Rakeln erfolgen.The solution containing the organic phosphoric acid ester can be applied by any measures known to the person skilled in the art, such as dipping, spraying, brushing or knife coating.
Der Arbeitsvorgang kann bequem in die bestehenden Arbeitsabläufe bei der Herstellung von Metallblechen integriert werden. So kann das Aufbringen der Phosphorsäureester enthaltenden Lösung beispielsweise bei der Beschichtung des Blechs im Spülbad einer Beschichtungsanlage oder bei der Kühlung des Blechs im Bad einer Wasserkühlanlage erfolgen. Vorzugsweise erfolgt das Aufbringen der Phosphorsäureester enthaltenden Lösung im Spülbad einer Beschichtungsanlage. Das Spülbad ist dabei vorzugsweise als einstufige No-Rinse-Nachbehandlung dem metallischen BeschichtungsVorgang (z. B. elektrolytische Verzinkung) nachgeschaltet. Innerhalb einer Produktionsanlage können dem Spülbad weitere Produktionsschritte nachgeschaltet werden. Insbesondere kann das Metallblech nach dem Spülbad in einem geeigneten Trockner getrocknet werden und/oder anschließend mit einem Schmierstoff (z. B. durch elektrostatische BeÖlung) beschichtet werden.The work process can be easily integrated into the existing work processes in the production of metal sheets. For example, the solution containing phosphoric acid esters can be applied when coating the sheet in the rinsing bath of a coating system or when cooling the sheet in the bath of a water cooling system. The solution containing phosphoric acid esters is preferably applied in the rinsing bath of a coating system. The rinsing bath is preferably connected as a one-stage no-rinse after-treatment after the metallic coating process (e.g. electrolytic galvanizing). Further production steps can be added to the rinsing bath within a production system. In particular, the metal sheet can be dried in a suitable dryer after the rinsing bath and / or subsequently coated with a lubricant (for example by electrostatic oiling).
Die Phosphorsäureester enthaltende Lösung wird vorzugsweise als wässrige Lösung aufgebracht. Die Lösung enthält den organischen Phosphorsäureester vorzugsweise in einer Menge von 0,1 bis 15 Gew.%, insbesondere 3 bis 8 Gew.%.The solution containing phosphoric acid esters 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.
Der pH der Lösung wird vorzugsweise auf einen Wert von 6,5 bis 11, insbesondere 7,5 bis 9,5 eingestellt.The pH of the solution is preferably adjusted to a value from 6.5 to 11, in particular 7.5 to 9.5.
Gemäß einer bevorzugten Ausführungsform der Erfindung enthält die Lösung als weitere Komponente wie oben beschrieben eine wasserlösliche organische Schwefelverbindung, insbesondere eine der zuvor beschriebenen Verbindungen, und/oder eine organische Molybdänverbindung, insbesondere eine der zuvor beschriebenen Verbindungen, und/oder eine der zuvor beschriebenen anorganischen Verbindungen enthält . Die wasserlösliche (n) organische (n) Schwefelverbindung (en) und/oder organische (n) Molybdänverbindung (en) sind in der Lösung vorzugsweise in einer Menge von 1 bis 50 Gew.%, insbesondere von 5 bis 25 Gew.%, bezogen auf die Menge an Phosphorsäureester, enthalten.According to a preferred embodiment of the invention, the solution contains, as a further 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 present in the solution in an amount of 1 to 50% by weight, in particular 5 to 25% by weight on the amount of phosphoric acid ester included.
Die anorganische (n) Verbindung (en) sind in der Lösung in einer Menge von 1 bis 50 Gew.%, insbesondere von 5 bis 10 Gew.%, bezogen auf die Menge an Phosphorsäureester, enthalten.The inorganic compound (s) are present in the solution in an amount of 1 to 50% by weight, in particular 5 to 10% by weight, based on the amount of phosphoric acid ester.
Vor dem Aufbringen des Schmierstoffs ist es vorteilhaft, das Blech zu trocknen.Before applying the lubricant, it is advantageous to dry the sheet.
Als Schmierstoff wird vorzugsweise einA is preferably used as the lubricant
Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube wie oben beschrieben eingesetzt. Vorzugsweise ist der Schmierstoff hinsichtlich seiner Zusammensetzung insoweit auf die Phosphorsaureester enthaltende Lösung abgestimmt, als dass er wie vorstehend beschrieben Komponenten (z. B. organische Phosphorsaureester, wasserlösliche organische Schwefelverbindung, organische Molybdänverbindung und/oder anorganische Verbindung) enthält, welche auch in der Phosphorsaureester enthaltenden Lösung enthalten sind.Corrosion protection oil, Pre-Lube and / or Dry-Lube used as described above. The lubricant is preferred its composition is matched to the solution containing phosphoric acid esters to the extent that it contains components (e.g. organic phosphoric acid esters, water-soluble organic sulfur compounds, organic molybdenum compounds and / or inorganic compounds) as described above, which are also contained in the solution containing phosphoric acid esters.
Der Schmierstoff wird vorzugsweise in einer Menge von 0,3 bis 3 g/m2, insbesondere 1 bis 2 g/m2 aufgebracht.The lubricant is preferably applied in an amount of 0.3 to 3 g / m 2 , in particular 1 to 2 g / m 2 .
Die Erfindung umfaßt demgemäß auch die Verwendung einer Lösung enthaltend einen organischen Phosphorsaureester wie zuvor beschrieben zur Behandlung von Metalloberflächen.The invention accordingly also includes the use of a solution containing an organic phosphoric acid ester as described above for the treatment of metal surfaces.
Gegenstand der Erfindung ist ferner eine wäßrige Lösung zur Behandlung von Metalloberflächen enthaltend einen organischen Phosphorsaureester und eine wasserlösliche organische Schwefelverbindung und/oder eine organische Molybdänverbindung, sämtliche Verbindungen wie zuvor beschrieben, sowie ein Konzentrat zur Herstellung einer solchen Lösung.The invention further relates to an aqueous solution for the treatment of metal surfaces containing 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.
Schließlich umfaßt die Verwendung des erfindungsgemäßen Metallblechs oder Metallblechzuschnitts zur Herstellung von Metallkörpern durch Umformen, insbesondere durch Tiefziehen.Finally, the use of the metal sheet or sheet metal blank according to the invention for the production of metal bodies by forming, in particular by deep drawing.
Nachfolgend wird die Erfindung anhand eines Ausführungsbeispiels näher beschrieben. Elektrolytisch verzinkte Stahlbleche einer Dicke von 1 mm wurden durch Tauchen mit einer wässrigen Lösung der nachstehend angegebenen Zusammensetzung behandelt, getrocknet, und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Zur Bestimmung der Ziehleistung wurde anschließend die Reibzahl im Draw-Bed-Test bestimmt. Als Referenz für die Reibzahl diente eine Probe des elektrolytisch verzinkten Stahlblechs, welche nicht mit einer wässrigen Lösung behandelt wurde. Die Reibzahl dieser Referenzprobe wurde auf 100 % gesetzt.The invention is described in more detail below using an exemplary embodiment. Electrolytically galvanized steel sheets with a thickness of 1 mm were treated by dipping with an aqueous solution of the composition given below, dried, and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was then determined in the draw bed test to determine the drawing power. A sample of the electrolytically galvanized steel sheet, which was not treated with an aqueous solution, served as a reference for the coefficient of friction. The coefficient of friction of this reference sample was set to 100%.
Beispiel 1example 1
Ein elektrolytisch verzinktes Stahlblech wurde mit einer 5 %igen Lösung eines äquimolaren Phosphorsäureester- Gemischs aus (CH3-0) PO (OH) 2 und (OH) PO (0-CH3) 2 behandelt. Das Blech wurde getrocknet und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Die Reibzahl betrug 88 %.An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric acid ester mixture of (CH 3 -0) PO (OH) 2 and (OH) PO (0-CH 3 ) 2 . The sheet was dried and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was 88%.
Gegenüber der Referenzprobe ohne Vorbehandlung wurde eine Reduktion der Reibzahl um 12 % festgestellt.Compared to the reference sample without pretreatment, the coefficient of friction was reduced by 12%.
Beispiel 2Example 2
Ein elektrolytisch verzinktes Stahlblech wurde mit einer 5 %igen Lösung eines äquimolaren Phosphorsäureester- Gemischs aus (C4H9-0) PO (OH) 2 und (OH) PO (0-C4H9) 2 behandelt Das Blech wurde getrocknet und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Die Reibzahl betrug 58 %.An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar mixture of phosphoric acid esters of (C 4 H 9 -0) PO (OH) 2 and (OH) PO (0-C 4 H 9 ) 2. The sheet was dried and then coated with 1.5 g / m 2 Pre-Lube. The coefficient of friction was 58%.
Gegenüber der Referenzprobe ohne Vorbehandlung wurde eine Reduktion der Reibzahl um 42 % festgestellt. Beispiel 3Compared to the reference sample without pretreatment, the coefficient of friction was reduced by 42%. Example 3
Ein elektrolytisch verzinktes Stahlblech wurde mit einer 5 %igen Lösung eines äquimolaren Phosphorsäureester- Gemischs aus (C8H17-0) PO (OH) 2 und (OH) PO (0-CBH17) 2 behandelt. Das Blech wurde getrocknet und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Die Reibzahl betrug 90 %.An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar phosphoric acid ester mixture of (C 8 H 17 -0) PO (OH) 2 and (OH) PO (0-C B H 17 ) 2 . The sheet was dried and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was 90%.
Gegenüber der Referenzprobe ohne Vorbehandlung wurde eine Reduktion der Reibzahl um 10 % festgestellt.Compared to the reference sample without pretreatment, the coefficient of friction was reduced by 10%.
Beispiel 4Example 4
Ein elektrolytisch verzinktes Stahlblech wurde mit einer 5 %igen Lösung eines äquimolaren Phosphorsäureester- Gemischs aus (CH3- [0-CH2CH2] 3-C12H24-0) PO (OH) 2 und (HO)PO(CH3- [0-CH2CH2]3-C12H24-0)2 behandelt. Das Blech wurde getrocknet und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Die Reibzahl betrug 92 %.An electrolytically galvanized steel sheet was treated with a 5% solution of an equimolar mixture of phosphoric acid esters of (CH 3 - [0-CH 2 CH 2 ] 3 -C 12 H 24 -0) PO (OH) 2 and (HO) PO (CH 3 - [0-CH 2 CH 2 ] 3 -C 12 H 24 -0) 2 treated. The sheet was dried and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was 92%.
Gegenüber der Referenzprobe ohne Vorbehandlung wurde eine Reduktion der Reibzahl um 8 % festgestellt.Compared to the reference sample without pretreatment, the coefficient of friction was reduced by 8%.
Beispiel 5Example 5
In diesem Beispiel wurde der Tiefzieh-Arbeitsbereich eines gemäß Beispiel 2 hergestellten erfindungsgemäßen elektrolytisch verzinkten Feinblechs gegenüber der Referenzprobe ohne Vorbehandlung untersucht . Die Ergebnisse dieser Untersuchung sind in Fig. 1 dargestellt. Die Ergebnisse zeigen, dass das erfindungsgemäß beschichtete Feinblech (Fig. lb) einen deutlich größeren Tiefzieh-Arbeitsbereich aufweist, als die Referenzprobe ohne Vorbehandlung (Fig. la) .In this example, the deep-drawing working area of an electrolytically galvanized thin sheet according to the invention produced according to Example 2 compared to the reference sample without pretreatment was examined. The results of this investigation are shown in Fig. 1. The results show that the thin sheet coated according to the invention (FIG. 1b) has a significantly larger deep-drawing work area than the reference sample without pretreatment (FIG. 1a).
Vergleichsbeispiel 1Comparative Example 1
Ein elektrolytisch verzinktes Stahlblech wurde mit einer 5 %igen Natriumtetraborat-Lösung behandelt, getrocknet und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Die Reibzahl betrug 90 %.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 coefficient of friction was 90%.
Gegenüber der Referenzprobe ohne Vorbehandlung wurde eine Reduktion der Reibzahl um 10 % festgestellt.Compared to the reference sample without pretreatment, the coefficient of friction was reduced by 10%.
Vergleichsbeispiel 2Comparative Example 2
Ein elektrolytisch verzinktes Stahlblech wurde mit einer 5 %igen Phosphorsäurelösung behandelt, getrocknet und anschließend mit 1,5 g/m2 Pre-Lube beschichtet. Die Reibzahl betrug 95 %.An electrolytically galvanized steel sheet was treated with a 5% phosphoric acid solution, dried and then coated with 1.5 g / m 2 pre-lube. The coefficient of friction was 95%.
Gegenüber der Referenzprobe ohne Vorbehandlung wurde eine Reduktion der Reibzahl um 5 % festgestellt.Compared to the reference sample without pretreatment, the coefficient of friction was reduced by 5%.
Die Ergebnisse zeigen, dass die erfindungsgemäßen Metallbleche, die mit einer Phosphorsäureester-Lösung behandelt wurden, gegenüber Metallblechen, die keine derartige Behandlung unterzogen wurden, deutlich verbesserte tribologische Eigenschaften sowie einen vergrößerten Tiefzieh-Arbeitsbereich aufweisen. Die erfindungsgemäßen Metallbleche waren ferner leicht und völlig rückstandsfrei in einer üblichen Entfettungsanlage zu reinigen. The results show that the metal sheets according to the invention, which were treated with a phosphoric acid ester solution, have significantly improved tribological properties and an enlarged 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 and completely residue-free to clean in a conventional degreasing system.

Claims

Patentansprüche claims
1. Metallblech oder Metallblechzuschnitt mit einer Beschichtung aus Schmierstoff, insbesondere einem Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube, dadurch gekennzeichnet, dass das Metallblech oder der Metallblechzuschnitt eine Schicht umfasst, welche durch Aufbringen einer einen organischen Phosphorsaureester enthaltenden Lösung auf die metallische Oberfläche des Blechs gebildet ist.1. sheet metal or sheet metal blank with a coating of lubricant, in particular an anti-corrosion oil, pre-lube and / or dry lube, characterized in that the sheet metal or sheet metal blank comprises a layer which is applied to the metallic by applying a solution containing an organic phosphoric acid ester Surface of the sheet is formed.
2. Metallblech oder Metallblechzuschnitt nach Anspruch 1, dadurch gekennzeichnet, dass der organische Phosphorsaureester eine Verbindung der allgemeinen Formel2. Sheet metal or sheet metal blank according to claim 1, characterized in that the organic phosphoric acid ester is a compound of the general formula
ist, worin X für Wasserstoff, Na, K, -NH2, -NHR, -NR2, -NH(R'-OH), -N(R'-0H)2 oder -NR(R'-OH), R für eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 14, insbesondere 1 bis 8 Kohlenstoffatomen steht, R' eine geradkettige oder verzweigte Alkylengruppe mit 1 bis 14, insbesondere 1 bis 8 Kohlenstoffatomen bedeutet, wobei ein oder mehrere Wasserstoffatome in R und R' durch eine polymere oder oligomere Gruppe -Y-R substituiert sein können, worin Y für (CH2-CH2-0-)ra oder (CH2-CH (CH3) -0-) m mit m = 1 bis ∞ und insbesondere m = 1 bis 10 steht, R und R' jeweils gleich oder verschieden sein können und n eine Zahl von 0 bis 3 ist, mit der Maßgabe, dass n nicht 0 ist, wenn X ausschließlich für Wasserstoff steht.where X is hydrogen, Na, K, -NH 2 , -NHR, -NR 2 , -NH (R'-OH), -N (R'-0H) 2 or -NR (R'-OH), R represents a straight-chain or branched alkyl group having 1 to 14, in particular 1 to 8, carbon atoms, R 'is a straight-chain or branched alkylene group having 1 to 14, in particular 1 to 8, carbon atoms, one or more hydrogen atoms in R and R' being represented by a polymeric or oligomeric group -YR can be substituted, in which Y represents (CH 2 -CH 2 -0-) ra or (CH 2 -CH (CH 3 ) -0-) m with m = 1 to ∞ and in particular m = 1 to 10, R and R 'can each be the same or different and n is a number from 0 to 3, with the proviso that when X is exclusively hydrogen, n is not 0.
3. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der organische Phosphorsaureester ein Gemisch aus3. sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the organic phosphoric acid ester is a mixture of
(C4H9-0)OP(OH)2 und (OH) P (0-C4H9) 2 ist.(C 4 H 9 -0) OP (OH) 2 and (OH) P (0-C 4 H 9 ) 2 .
4. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die Phosphorsaureester enthaltende Lösung als weitere Komponente eine wasserlösliche organische Schwefelverbindung und/oder eine organische Molybdänverbindung enthält.4. sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the solution containing phosphoric acid ester contains as a further component a water-soluble organic sulfur compound and / or an organic molybdenum compound.
5. Metallblech oder Metallblechzuschnitt nach Anspruch 4, dadurch gekennzeichnet, dass die organische Schwefelverbindung ausgewählt ist aus der Gruppe bestehend aus Thiadiazolen, Dithiocarbamaten und Dithiopropionaten sowie Salzen und Derivaten davon.5. sheet metal or sheet metal blank according to claim 4, characterized in that the organic sulfur compound is selected from the group consisting of thiadiazoles, dithiocarbamates and dithiopropionates, and salts and derivatives thereof.
6. Metallblech oder Metallblechzuschnitt nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass die organische Schwefelverbindung ausgewählt ist aus der Gruppe bestehend aus Natrium-2-mercaptobenzothiazol, 2,5- Dimercapto-1, 3, 4-thiadiazol sowie Salze und Derivate davon, Natriumdimethyldithiocarbamat, Kaliumdimethyldithiocarbamat und Monoethanolamindithiopropionat .6. sheet metal or sheet metal blank according to claim 4 or 5, characterized in that the organic sulfur compound is selected from the group consisting of sodium 2-mercaptobenzothiazole, 2,5-dimercapto-1, 3, 4-thiadiazole and salts and derivatives thereof, Sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate and monoethanolamine dithiopropionate.
7. Metallblech oder Metallblechzuschnitt nach Anspruch 6, dadurch gekennzeichnet, dass die organische Molybdänverbindung durch Umsetzung von Molybdäntrioxid und/oder Molybdänsäure mit einem Amin und/oder Alkanolamin erhältlich ist.7. sheet metal or sheet metal blank according to claim 6, characterized in that the organic molybdenum compound by reaction of molybdenum trioxide and / or molybdic acid with an amine and / or alkanolamine is available.
8. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die Phosphorsaureester enthaltende Lösung als weitere Komponente mindestens eine anorganische Verbindung ausgewählt aus der Gruppe bestehend aus Polyphosphaten, Boraten, Molybdaten und Wolframaten enthält.8. sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the solution containing phosphoric acid ester contains as a further component at least one inorganic compound selected from the group consisting of polyphosphates, borates, molybdate and tungstates.
9. Metallblech oder Metallblechzuschnitt nach Anspruch 8, dadurch gekennzeichnet, dass die anorganische Verbindung ausgewählt ist aus der Gruppe bestehend aus Ammoniumtripolyphosphat, Natriumtetraborat , Ammoniummolybdat, Natriumwolframat, Kaliumwolframat und Natriumwolframat .9. sheet metal or sheet metal blank according to claim 8, characterized in that the inorganic compound is selected from the group consisting of ammonium tripolyphosphate, sodium tetraborate, ammonium molybdate, sodium tungstate, potassium tungstate and sodium tungstate.
10. Metallblech oder Metallblechzuschnitt nach Anspruch10. sheet metal or sheet metal blank according to claim
I, dadurch gekennzeichnet, dass die durch die Phosphorsaureester enthaltende Lösung gebildete Schicht als dünner Strich im Nanobereich ausgebildet ist.I, characterized in that the layer formed by the solution containing phosphoric acid esters is formed as a thin line in the nano range.
11. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass auf der durch den Phosphorsaureester gebildeten Schicht eine Schicht enthaltend Schmierstoff, insbesondere ein Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube, ausgebildet ist.11. Sheet metal or sheet metal blank according to one of the preceding claims, characterized in that a layer containing lubricant, in particular an anti-corrosion oil, pre-lube and / or dry-lube, is formed on the layer formed by the phosphoric acid ester.
12. Metallblech oder Metallblechzuschnitt nach Anspruch12. sheet metal or sheet metal blank according to claim
II, dadurch gekennzeichnet, dass die Schmierstoff enthaltende Schicht in einer Dicke von 0,3 bis 3,0 g/m2, insbesondere 1 bis 2 g/m2, ausgebildet ist. II, characterized in that the lubricant-containing layer is formed in a thickness of 0.3 to 3.0 g / m 2 , in particular 1 to 2 g / m 2 .
13. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Schmierstoff einen organischen Phosphorsaureester wie oben definiert in einer Menge von 0,01 bis 50 Gew.%, insbesondere von 0,05 bis 10 Gew.%, enthält.13. Sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the lubricant contains an organic phosphoric acid ester as defined above in an amount of 0.01 to 50 wt.%, In particular 0.05 to 10 wt.%.
14. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Schmierstoff eine wasserlösliche organische Schwefelverbindung wie oben definiert in einer Menge von 0.005 bis 30 Gew.%, insbesondere 0,01 bis 5 Gew.%, enthält .14. Sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the lubricant contains a water-soluble organic sulfur compound as defined above in an amount of 0.005 to 30% by weight, in particular 0.01 to 5% by weight.
15. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Schmierstoff eine organische Molybdänverbindung wie oben definiert in einer Menge von 0.005 bis 30 Gew.%, insbesondere 0,01 bis 5 Gew.%, enthält.15. Sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the lubricant contains an organic molybdenum compound as defined above in an amount of 0.005 to 30% by weight, in particular 0.01 to 5% by weight.
16. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Schmierstoff eine anorganische Verbindung wie oben definiert in einer Menge von 0.005 bis 30 Gew.%, insbesondere 0,01 bis 5 Gew.%, enthält.16. Sheet metal or sheet metal blank according to one of the preceding claims, characterized in that the lubricant contains an inorganic compound as defined above in an amount of 0.005 to 30% by weight, in particular 0.01 to 5% by weight.
17. Metallblech oder Metallblechzuschnitt nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass das Blech ein beschichtetes oder unbeschichtetes Stahlblech ist. 17. Metal sheet or sheet metal blank according to one of the preceding claims, characterized in that the sheet is a coated or uncoated steel sheet.
18. Verfahren zur Herstellung eines Metallblechs oder Metallblechzuschnitts nach einem der Ansprüche 1 bis 17, gekennzeichnet durch folgende Schritte :18. A method for producing a metal sheet or sheet metal blank according to one of claims 1 to 17, characterized by the following steps:
Aufbringen einer Lösung enthaltend einen organischen Phosphorsaureester auf die Ober- und/oder Unterseite des Blechs undApplying a solution containing an organic phosphoric acid ester to the top and / or bottom of the sheet and
Aufbringen eines Schmierstoffs auf das so beschichtete Blech.Applying a lubricant to the coated sheet.
19. Verfahren nach Anspruch 18, dadurch gekennzeichnet, dass das Aufbringen der Lösung enthaltend den organischen Phosphorsaureester durch Tauchen, Sprühen, Streichen oder Rakeln erfolgt .19. The method according to claim 18, characterized in that the application of the solution containing the organic phosphoric acid ester is carried out by dipping, spraying, brushing or knife coating.
20. Verfahren nach Anspruch 18 oder 19, dadurch gekennzeichnet, dass das Aufbringen der Lösung enthaltend den organischen Phosphorsaureester bei der Beschichtung des Blechs im Spülbad einer Beschichtungsanlage oder bei der Kühlung des Blechs im Bad einer Wasserkühlanlage erfolgt .20. The method according to claim 18 or 19, characterized in that the application of the solution containing the organic phosphoric acid ester takes place in the coating of the sheet in the rinsing bath of a coating system or in the cooling of the sheet in the bath of a water cooling system.
21. Verfahren nach einem der Ansprüche 18 bis 20, dadurch gekennzeichnet, dass eine wässrige Lösung des organischen Phosphorsäureesters aufgebracht wird.21. The method according to any one of claims 18 to 20, characterized in that an aqueous solution of the organic phosphoric acid ester is applied.
22. Verfahren nach einem der Ansprüche 18 bis 21, dadurch gekennzeichnet, dass eine Lösung aufgebracht wird, welche den organischen Phosphorsaureester in einer Konzentration von 0,1 bis 15 Gew.%, insbesondere 3 bis 8 % enthält. 22. The method according to any one of claims 18 to 21, characterized in that a solution is applied which contains the organic phosphoric acid ester in a concentration of 0.1 to 15% by weight, in particular 3 to 8%.
23. Verfahren nach einem der Ansprüche 18 bis 22, dadurch gekennzeichnet, dass der pH der23. The method according to any one of claims 18 to 22, characterized in that the pH of the
Phosphorsaureester enthaltenden Lösung auf einen Wert von 6,5 bis 11, insbesondere 7,5 bis 9,5 eingestellt wird.Solution containing phosphoric acid ester is adjusted to a value of 6.5 to 11, in particular 7.5 to 9.5.
24. Verfahren nach einem der Ansprüche 18 bis 23, dadurch gekennzeichnet, dass eine Lösung aufgebracht wird, welche als weitere Komponente eine wasserlösliche organische Schwefelverbindung, insbesondere eine der in Anspruch 5 oder 6 beschriebenen Verbindungen, und/oder eine organische Molybdänverbindung, insbesondere eine der in Anspruch 7 beschriebenen Verbindungen, enthält.24. The method according to any one of claims 18 to 23, characterized in that a solution is applied which, as a further component, a water-soluble organic sulfur compound, in particular one of the compounds described in claim 5 or 6, and / or an organic molybdenum compound, in particular one of the contains compounds described in claim 7.
25. Verfahren nach Anspruch 24, dadurch gekennzeichnet, dass eine Lösung aufgebracht wird, welche die wasserlösliche (n) organische (n) Schwefelverbindung (en) und/oder organische (n) Molybdänverbindung (en) in einer Menge von 1 bis 50 Gew.%, insbesondere 5 bis 25 Gew.%, bezogen auf die Menge an Phosphorsaureester, enthält.25. The method according to claim 24, characterized in that a solution is applied which the water-soluble organic sulfur compound (s) and / or organic molybdenum compound (s) in an amount of 1 to 50 wt. %, in particular 5 to 25% by weight, based on the amount of phosphoric acid ester.
26. Verfahren nach einem der Ansprüche 18 bis 25, dadurch gekennzeichnet, dass eine Lösung aufgebracht wird, welche als weitere Komponente mindestens eine der in den Ansprüchen 8 und 9 beschriebenen anorganischen Verbindungen enthält .26. The method according to any one of claims 18 to 25, characterized in that a solution is applied which contains at least one of the inorganic compounds described in claims 8 and 9 as a further component.
27. Verfahren nach Anspruch 26, dadurch gekennzeichnet, dass eine Lösung aufgebracht wird, welche die anorganische (n) Verbindung (en) in einer Menge von 1 bis 50 Gew.%, insbesondere von 5 bis 10 Gew.%, bezogen auf die Menge an Phosphorsaureester, enthält. 27. The method according to claim 26, characterized in that a solution is applied which contains the inorganic compound (s) in an amount of 1 to 50% by weight, in particular 5 to 10% by weight, based on the amount on phosphoric acid ester.
28. Verfahren nach einem der Ansprüche 18 bis 27, dadurch gekennzeichnet, dass das Blech vor dem Aufbringen des Schmierstoffs getrocknet wird.28. The method according to any one of claims 18 to 27, characterized in that the sheet is dried before the lubricant is applied.
29. Verfahren nach einem der Ansprüche 18 bis 28, dadurch gekennzeichnet, dass als Schmierstoff ein Korrosionsschutzöl, Pre-Lube und/oder Dry-Lube eingesetzt wird.29. The method according to any one of claims 18 to 28, characterized in that an anti-corrosion oil, pre-lube and / or dry-lube is used as the lubricant.
30. Verfahren nach einem der Ansprüche 18 bis 29, dadurch gekennzeichnet, dass der Schmierstoff in einer Menge von 0,3 bis 3 g/m2, insbesondere 1 bis 2 g/m2 aufgebracht wird.30. The method according to any one of claims 18 to 29, characterized in that the lubricant is applied in an amount of 0.3 to 3 g / m 2 , in particular 1 to 2 g / m 2 .
31. Verwendung einer Lösung enthaltend einen organischen Phosphorsaureester, insbesondere einen der in Anspruch 2 oder 3 beschriebenen organischen Phosphorsaureester, zur Behandlung von Metalloberflächen.31. Use of a solution containing an organic phosphoric acid ester, in particular one of the organic phosphoric acid esters described in claim 2 or 3, for the treatment of metal surfaces.
32. Wäßrige Lösung zur Behandlung von Metalloberflächen enthaltend einen organischen Phosphorsaureester, insbesondere eine der in Anspruch 2 oder 3 beschriebenen Verbindungen, und eine wasserlösliche organische Schwefelverbindung, insbesondere eine der in Anspruch 5 oder 6 beschriebenen Verbindungen, und/oder eine organische Molybdänverbindung, insbesondere eine der in Anspruch 7 beschriebenen Verbindungen.32. Aqueous solution for the treatment of metal surfaces containing an organic phosphoric acid ester, in particular one of the compounds described in claim 2 or 3, and a water-soluble organic sulfur compound, in particular one of the compounds described in claim 5 or 6, and / or an organic molybdenum compound, in particular one of the compounds described in claim 7.
33. Wäßrige Lösung nach Anspruch 32, dadurch gekennzeichnet, dass diese als weitere Komponente eine der in Anspruch 8 oder 9 beschriebenen anorganischen Verbindungen enthält . 33. Aqueous solution according to claim 32, characterized in that it contains as a further component one of the inorganic compounds described in claim 8 or 9.
34. Konzentrat zur Herstellung einer Lösung zur Behandlung von Metalloberflächen gemäß Anspruch 32 oder 33.34. Concentrate for the preparation of a solution for the treatment of metal surfaces according to claim 32 or 33.
35. Verwendung eines Metallblechs oder35. Use of a metal sheet or
Metallblechzuschnitts nach einem der Ansprüche 1 bis 17 zur Herstellung von Metallkörpern durch Umformen, insbesondere durch Tiefziehen. Sheet metal blank according to one of claims 1 to 17 for the production of metal bodies by forming, in particular by deep drawing.
EP03782275A 2002-12-03 2003-12-02 Lubricant coated sheet metal with improved deformation properties Withdrawn EP1567623A2 (en)

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DE10256639A DE10256639A1 (en) 2002-12-03 2002-12-03 Lubricant-coated metal sheet with improved forming properties
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PCT/EP2003/013557 WO2004050808A2 (en) 2002-12-03 2003-12-02 Lubricant coated sheet metal with improved deformation properties

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UA86583C2 (en) 2009-05-12
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AU2003289934B2 (en) 2010-02-18
AU2003289934A1 (en) 2004-06-23
EP2311928A2 (en) 2011-04-20
EP2311928A3 (en) 2011-09-07
DE10256639A1 (en) 2004-06-24
CA2508716C (en) 2012-07-17
WO2004050808A3 (en) 2005-02-24
CN100572511C (en) 2009-12-23
CA2508716A1 (en) 2004-06-17
RU2343223C2 (en) 2009-01-10
KR20050101312A (en) 2005-10-21
US20060100112A1 (en) 2006-05-11
US7727942B2 (en) 2010-06-01
KR101177088B1 (en) 2012-08-27
WO2004050808A2 (en) 2004-06-17

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