EP2612957A1 - Procédé de production d'une tôle d'acier laminée à froid, tôle d'acier laminée à froid, et élément de véhicule - Google Patents

Procédé de production d'une tôle d'acier laminée à froid, tôle d'acier laminée à froid, et élément de véhicule Download PDF

Info

Publication number
EP2612957A1
EP2612957A1 EP11821649.8A EP11821649A EP2612957A1 EP 2612957 A1 EP2612957 A1 EP 2612957A1 EP 11821649 A EP11821649 A EP 11821649A EP 2612957 A1 EP2612957 A1 EP 2612957A1
Authority
EP
European Patent Office
Prior art keywords
steel sheet
acid
cold
mass
rolled steel
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.)
Granted
Application number
EP11821649.8A
Other languages
German (de)
English (en)
Other versions
EP2612957A4 (fr
EP2612957B1 (fr
Inventor
Hiroyuki Masuoka
Satoru Ando
Shunsuke Yamamoto
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.)
JFE Steel Corp
Original Assignee
JFE Steel Corp
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 JFE Steel Corp filed Critical JFE Steel Corp
Publication of EP2612957A1 publication Critical patent/EP2612957A1/fr
Publication of EP2612957A4 publication Critical patent/EP2612957A4/fr
Application granted granted Critical
Publication of EP2612957B1 publication Critical patent/EP2612957B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0269—Cleaning
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/081—Iron or steel solutions containing H2SO4
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/085—Iron or steel solutions containing HNO3
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/02—Rolling special iron alloys, e.g. stainless steel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • This invention relates to a method of producing a cold-rolled steel sheet as well as a cold-rolled steel sheet and a member for automobile, and more particularly to a method of producing a cold-rolled steel sheet being excellent in not only the phosphate treatability but also the corrosion resistance after coating as evaluated by a hot salt water immersion test or a composite cycle corrosion test, a cold-rolled steel sheet produced by this method as well as a member for automobile using the cold-rolled steel sheet.
  • the cold-rolled steel sheet according to the invention can be preferably used in a high-strength cold-rolled steel sheet containing Si and having a tensile strength TS of not less than 590 MPa.
  • the Si-containing oxide considerably deteriorates the phosphate treatability
  • the high-strength cold-rolled steel sheets containing a great amount of Si have problems that the phosphate treatability is poor but the coating peeling is easily caused to deteriorate the corrosion resistance after the coating as compared with the commonly used steel sheets when the steels sheet after electrodeposition coating is subjected to severer corrosion environment as in a hot salt water immersion test or a composite cycle corrosion test repeating cycle of wetting-drying.
  • Patent Document 1 proposes a high-strength cold-rolled steel sheet obtained by heating a slab at a temperature of higher than 1200°C in hot rolling, descaling under high pressure, polishing the surface of the hot-rolled steel sheet with a nylon brush containing abrasion grains prior to pickling and then immersing in a bath of 9% hydrochloric acid twice to perform pickling to lower the Si concentration on the surface of the steel sheet.
  • Patent Document 2 proposes a high-strength cold-rolled steel sheet wherein the corrosion resistance is improved by rendering line width of Si-containing linear oxide observed in 1-10 ⁇ m from the surface of the steel sheet into not more than 300 nm.
  • the Si-containing oxide is formed on the surface of the steel sheet by annealing after cold rolling, so that the improvement of the corrosion resistance after coating is not desired.
  • the high-strength cold-rolled steel sheet disclosed in Patent Document 2 there is no problem in the corrosion resistance under corrosion environment as in a salt spray test defined according to JIS Z2371, but sufficient corrosion resistance after coating is not obtained under severer corrosion environment as in a hot salt water immersion test or a composite cycle corrosion test. That is, the high-strength cold-rolled steel sheet having an excellent corrosion resistance after coating can not be obtained only by reducing the Si concentration on the surface of the steel sheet after hot rolling or by reducing the Si-containing linear oxide.
  • Patent Document 3 discloses a technique wherein the Si-containing oxide enriched on the surface of the steel sheet by annealing step or the like is removed by pickling and further an S-based compound is applied to the surface to enhance the reactivity with a phosphate treating solution to thereby improve the phosphate treatability.
  • Patent Document 4 discloses a technique wherein a P-based compound is applied instead of the S-based compound of the above technique.
  • the invention is made in view of considering the above problems inherent to the cold-rolled steel sheet containing a great amount of Si and is to provide a method of producing a cold-rolled steel sheet being excellent in not only the phosphate treatability even when using a phosphate treating solution at a lower temperature but also in the corrosion resistance after coating as evaluated by a hot salt water immersion test or a composite cycle corrosion test, a cold-rolled steel sheet produced by this method as well as a member for automobile using the cold-rolled steel sheet.
  • the inventors have made detailed analysis on surface properties of steel sheets after annealing in order to solve the above problems and various studies on a method of enhancing the reactivity between the surface of the steel sheet and the phosphate treating solution.
  • it has been found that it is very important to subject the continuously annealed steel sheet surface to strong pickling after the cold rolling to thereby remove Si-containing oxide layer formed on the surface of the steel sheet during the annealing but also reduce a ratio of covering the surface of the steel sheet with an iron-based oxide formed on the steel sheet surface by the strong pickling, and consequently the invention has been accomplished.
  • the invention proposes a method of producing a cold-rolled steel sheet, comprising steps of cold rolling a steel sheet, continuously annealing, pickling and further repickling it.
  • the repickling in the production method of the invention is characterized in that a non-oxidizable acid is used instead of an acid used in the pickling prior to the repickling.
  • the non-oxidizable acid in the production method of the invention is characterized to be any of hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, formic acid, acetic acid, citric acid, hydrofluoric acid, oxalic acid and a mixed acid of two or more thereof.
  • the non-oxidizable acid in the production method of the invention is characterized to be any of hydrochloric acid with a concentration of 0.1-50 g/L, sulfuric acid with a concentration of 0.1-150 g/L and a mixed acid of 0.1-20 g/L of hydrochloric acid and 0.1-60 g/L of sulfuric acid.
  • the production method of the invention is characterized in that the repickling is carried out at a temperature of a repickling solution of 20-70°C for 1-30 seconds.
  • the production method of the invention is characterized in that the pickling is carried out with any of nitric acid, hydrochloric acid, hydrofluoric acid, sulfuric acid and a mixed acid of two or more thereof.
  • the production method of the invention is characterized in that the pickling is carried out with any of a mixed acid of nitric acid and hydrochloric acid wherein a concentration of nitric acid is more than 50 g/L but not more than 200 g/L and a ratio (HCl/HNO 3 of hydrochloric acid concentration to nitric acid concentration is 0.01-1.0, or a mixed acid of nitric acid and hydrofluoric acid wherein a concentration of nitric acid is more than 50 g/L but not more than 200 g/L and a ratio (HF/HNO 3 ) of hydrofluoric acid concentration to nitric acid concentration is 0.01-1.0.
  • a mixed acid of nitric acid and hydrochloric acid wherein a concentration of nitric acid is more than 50 g/L but not more than 200 g/L and a ratio (HF/HNO 3 ) of hydrofluoric acid concentration to nitric acid concentration is 0.01-1.0.
  • the steel sheet in the production method of the invention is characterized by comprising 0.5-3.0 mass% of Si.
  • the steel sheet in the production method of the invention is characterized by having a chemical composition comprising, in addition to Si, C: 0.01-0.30 mass%, Mn: 1.0-7.5 mass%, P: not more than 0.05 mass%, S: not more than 0.01 mass%, Al: not more than 0.06 mass% and the remainder being Fe and inevitable impurities.
  • the steel sheet in the production method of the invention is characterized by containing, in addition to the above chemical composition, one or more selected from Nb: not more than 0.3 mass%, Ti: not more than 0.3 mass%, V: not more than 0.3 mass%, Mo: not more than 0.3 mass%, Cr: not more than 0.5 mass%, B: not more than 0.006 mass% and N: not more than 0.008 mass%.
  • the steel sheet in the production method of the invention is characterized by containing, in addition to the aforementioned chemical composition, one or more selected from Ni: not more than 2.0 mass%, Cu: not more than 2.0 mass%, Ca: not more than 0.1 mass% and REM: not more than 0.1 mass%.
  • the invention is a cold-rolled steel sheet produced by any one of the aforementioned methods, characterized in that a Si-containing oxide layer is removed from a surface layer of the steel sheet by pickling after continuous annealing and a surface covering ratio of an iron-based oxide existing on the surface of the steel sheet after repickling is not more than 40%.
  • the cold-rolled steel sheet of the invention is characterized in that a maximum thickness of the iron-based oxide existing on the steel sheet surface after repickling is not more than 150 nm.
  • the invention is a member for automobiles, characterized by using a cold-rolled steel sheet as described in any one of the above.
  • a cold-rolled steel sheet which is excellent in the phosphate treatability even when Si is contained as large as 0.5-3.0 mass% and when using a phosphate treating solution at a lower temperature but also is excellent in the corrosion resistance after coating under severer corrosion environment as in a hot salt water immersion test or a composite cycle corrosion test. According to the invention, therefore, it is possible to largely improve the phosphate treatability and corrosion resistance after coating in the high-strength cold-rolled steel sheets containing a greater amount of Si and having a tensile strength TS of not less than 590 MPa, so that it can be preferably used in strong members and the like in a vehicle body of an automobile.
  • the Si-containing oxide is formed not only the surface of the steel sheet but also in the interior of the steel matrix, it is known that the oxide obstructs the etching property on the surface of the steel sheet in the phosphate treatment (treatment with zinc phosphate) made as an underlaying treatment for electrodeposition coating and badly affects the formation of sound phosphate treated coating.
  • the lowering of the temperature of the phosphate treating solution is proceeding for the purpose of reducing the sludge amount generated in the phosphate treatment and the running cost, and hence the phosphate treatment is carried out under a condition that the reactivity of the phosphate treating solution to the steel sheet is considerably low as compared with the conventional technique.
  • the change of the phosphate treating condition is not particularly questioned by the improvement of the surface adjusting technique or the like in the conventionally used common steel sheets having a less addition amount of an alloy.
  • the steel sheet having a greater addition amount of alloying component particularly a high-strength cold-rolled steel sheet attempted to increase the strength by adding a greater amount of Si, however, the influence of changing the phosphate treating condition as mentioned above is very large.
  • the cold-rolled steel sheet having a greater amount of Si therefore, it is required that the surface of the steel sheet itself is activated in correspondence with the deterioration of the phosphate treating condition to enhance the reactivity with the phosphate treating solution.
  • the inventors have made various investigations on a method of improving the phosphate treatability for corresponding to the deterioration of the phosphate treating condition as mentioned above. As a result, it has been found out that it is effective to conduct strong pickling of the surface of the cold-rolled steel sheet after continuous annealing with nitric acid or the like as a pickling solution to remove a Si-containing oxide layer formed on the surface of the steel sheet by continuous annealing and the like after cold rolling.
  • Si-containing oxide used herein means SiO 2 or Si-Mn base composite oxide formed on the surface of the steel sheet or along crystal grain boundary inside the steel sheet in the slab heating or after hot rolling or in annealing after cold rolling.
  • the thickness of the layer containing these Si-containing oxides varied depending upon components of the steel sheet or the annealing condition (temperature, time, atmosphere), but is usually about 1 ⁇ m from the surface of the steel sheet.
  • the term "removal of the Si-containing oxide layer" according to the invention means that the pickling is carried out to remove the Si-containing oxide layer to a level that peaks of Si, O do not appear when the surface of the steel sheet is analyzed in depth direction by means of GDS (glow discharge optical emission spectroscopy).
  • the reason why a strong acid such as nitric acid or the like is used as the pickling solution is due to the fact that among the Si-containing oxides, Si-Mn based composite oxide is easily dissolved in an acid, but SiO 2 is hardly soluble, and in order to remove the latter, the Si-containing oxide on the surface of the steel sheet should be removed together with the steel matrix.
  • the phosphate treatability is largely improved by removing the Si-containing oxide layer existing on the steel sheet surface through strong pickling with nitric acid or the like after the continuous annealing but the phosphate treatability may be deteriorated at moments.
  • the cause is further investigated, it is newly found that although the Si-containing oxide layer is removed by the strong pickling with nitric acid or the like, Fe dissolved from the surface of the steel sheet by the pickling separately produces an iron-based oxide, which is settled and precipitated on the surface of the steel sheet so as to cover the steel sheet surface to thereby deteriorate the phosphate treatability.
  • the inventors have found that the phosphate treatability is more improved and the corrosion resistance is further improved when the maximum thickness of the iron-based oxide is not more than 150 nm in addition to the fact that the covering ratio of the iron-based oxide generated on the surface of the steel sheet by pickling is not more than 40% and that it is effective as means for attaining the above to conduct the repickling by properly increasing the concentration of the acid used in the repickling.
  • the iron-based oxide in the invention means an oxide composed mainly of iron wherein an atomic concentration ratio of iron is not less than 30% as an element other than oxygen constituting the oxide.
  • the iron-based oxide is existent on the surface of the steel sheet at an uneven thickness, which is different from a natural oxide film existing uniformly and in layer at a thickness of few nm.
  • the iron-based oxide generated on the surface of the cold-rolled steel sheet is confirmed to be amorphous from the observation by means of a transmission electron microscope (TEM) and analysis results of diffraction pattern (analytical diagram) through an electron diffractometry.
  • TEM transmission electron microscope
  • analysis results of diffraction pattern analytical diagram
  • Si is an element effective for attaining the increase of the strength of the steel because the effect of enhancing the strength of steel (solid-solution strengthening ability) is large without largely damaging the workability, but is also an element adversely exerting on the phosphate treatability and the corrosion resistance after coating.
  • Si is added as means for attaining a high strength, the addition of not less than 0.5 mass% is necessary. If the Si content is less than 0.5 mass%, the influence due to the deterioration of the phosphate treating conditions is less. On the other hand, when the Si content exceeds 3.0 mass%, the hot rolling property and cold rolling property are largely deteriorated, which is adversely influenced on the productivity and leads to the deterioration of ductility of the steel sheet itself. Therefore, Si is added within a range of 0.5-3.0 mass%. Preferably, it is a range of 0.8-2.5 mass%.
  • the cold-rolled steel sheet of the invention is an essential feature to include Si in the above range.
  • the other components are acceptable as far as they are included within composition ranges in the common cold-rolled steel sheet, and are not particularly limited.
  • the cold-rolled steel sheet of the invention is preferable to have the following component composition when it is applied to a high-strength cold-rolled steel sheet having a tensile strength of not less than 590 MPa for use in vehicle bodies for automobiles and so on.
  • C is an element effective for enhancing the strength of steel and further is an element effective for producing residual austenite having an effect of TRIP (Transformation Induced Plasticity), bainite and martensite.
  • TRIP Transformation Induced Plasticity
  • bainite and martensite.
  • C content is not less than 0.01 mass%, the above effect is obtained, while when C content is not more than 0.30 mass%, the deterioration of the weldability is not caused. Therefore, C is added preferably within a range of 0.01-0.3 mass%, more preferably within a range of 0.10-0.20 mass%.
  • Mn is an element having an action for solid-solution strengthening steel to increase the strength and enhance the hardenability and promoting the formation of residual austenite, bainite and martensite. Such effects are developed by the addition of not less than 1.0 mass%. On the other hand, when Mn content is not more than 7.5 mass%, the above effect is obtained without the increase of the cost. Therefore, Mn is added preferably within a range of 1.0-7.5 mass%, more preferably within a range of 2.0-5.0 mass%.
  • P is an element damaging no drawability though the solid-solution strengthening ability is large and is also an element effective for attaining a high strength, so that it is preferable to be included in an amount of not less than 0.005 mass%.
  • P is an element damaging the spot weldability, but there is no problem when it is not more than 0.05 mass%. Therefore, P is preferably not more than 0.05 mass%, more preferably not more than 0.02 mass%.
  • S is an impurity element inevitably incorporated, and is a harmful element which is precipitated in steel as MnS to deteriorate the stretch-flanging property.
  • S is preferably not more than 0.01 mass%, more preferably not more than 0.005 mass%, further preferably not more than 0.003 mass%.
  • Al is an element added as a deoxidizer at steel-making step, and is also an element effective for separating non-metallic inclusion, which deteriorates the stretch-flanging property, as a slug, so that it is preferable to be included in an amount of not less than 0.01 mass%.
  • Al content is not more than 0.06 mass%, the above effect is obtained without the increase of cost for material. Therefore, Al is preferable to be not more than 0.06 mass%, More preferably, it is a range of 0.02-0.06 mass%.
  • the cold-rolled steel sheet of the invention may contain one or more selected from Nb: not more than 0.3 mass%, Ti: not more than 0.3 mass%, V: not more than 0.3 mass%, Mo: not more than 0.3 mass%, Cr: not more than 0.5 mass%, B: not more than 0.006 mass% and N: not more than 0.008 mass%.
  • Nb, Ti and V are elements forming carbide and nitride to suppress ferrite growth at a heating stage in the annealing and finely divide the structure to improve the formability, particularly stretch-flanging property, and also Mo, Cr and B are elements improving the hardenability of steel and promoting the formation of bainite and martensite, so that they can be added within the above ranges.
  • N is an element forming nitrides with Nb, Ti and V or solid-soluting in steel to contribute to the increase of the strength of steel, so that when it is not more than 0.008 mass%, a greater amount of the nitride is not formed, and hence the breakage due to the formation of voids in the press forming can be suppressed to obtain the above effect.
  • the cold-rolled steel sheet of the invention may contain one or more selected from Ni: not more than 2.0 mass%, Cu: not more than 2.0 mass%, Ca: not more than 0.1 mass% and REM: not more than 0.1 mass%.
  • Ni and Cu promote the formation of the low-temperature transformation phase to develop the effect of increasing the strength of steel, so that they can be added within the above ranges.
  • Ca and REM are elements controlling the form of the sulfide base inclusion to improve the stretch-flanging property of the steel sheet, so that they can be added within the above ranges.
  • the remainder other than the above components is Fe and inevitable impurities. However, other components may be optionally added within a scope of not damaging the action and effect of the invention.
  • the cold-rolled steel sheet of the invention is necessary to have a steel sheet surface obtained after the removal of Si-containing oxide layer such as SiO 2 or Si-Mn based composite oxide formed on the surface layer of the steel sheet during annealing. For this end, it is necessary to conduct strong pickling with nitric acid or the like to dissolve and remove the Si-containing oxide formed on the surface of the steel sheet and in the grain boundary portion in the vicinity of the surface together with the steel matrix.
  • the ratio of covering the surface of the steel sheet with iron-based oxide generated on the steel sheet surface by the strong pickling with nitric acid or the like is not more than 85% as an area ratio in addition to the removal of the Si-containing oxide layer.
  • the surface covering ratio exceeds 85%, the dissolving reaction of iron in the phosphate treatment is inhibited to suppress the crystal growth of phosphate such as zinc phosphate or the like.
  • the covering ratio of not more than 85% is insufficient in cold-rolled steel sheets used in applications requiring an extremely severe corrosion resistance after coating such as leg members for vehicle bodies particularly subjected to severe corrosion, so that it should be further reduced to not more than 40%, preferably not more than 35%.
  • the surface covering ratio of the iron-based oxide is determined as follows:
  • a steel slab of Steel symbol G shown in Table 3 of the following example is subjected to hot rolling, cold rolling and continuous annealing under conditions of No. 8 in Table 4 of the following example to obtain a cold-rolled steel sheet of 1.8 mm in thickness, and then the cold-rolled steel sheet after the continuous annealing is subjected to pickling and repickling under conditions shown in Table 1, washed with water, dried and subjected to 0.7% temper rolling to obtain two cold-rolled steel sheets of Nos. a and b having different iron-based oxide amounts on their steel sheet surfaces. Then, the cold-rolled steel sheet of No. a is a standard sample having a large amount of iron-based oxide and the cold-rolled steel sheet of No.
  • FIG. 1 shows photographs of reflection electron images of steel sheets Nos. a and b
  • FIG. 2 shows a histogram of pixel number to a gray value in the photographs of the reflection electron images of the steel sheets Nos. a and b.
  • a gray value (Y point) corresponding to an intersecting point (X point) of the histograms of Nos. a and b shown in FIG. 2 is defined as a threshold value.
  • the surface covering ratio of the iron-based oxide in the steel sheets Nos. a and b is determined with the above threshold value, it is 85.3% in the steel sheet No. a and 25.8% in the steel sheet No. b.
  • the maximum thickness of the iron-based oxide is not more than 150 nm in addition that the covering ratio of the iron-based oxide produced on the steel sheet surface by repickling is not more than 40%.
  • the maximum thickness of the iron-based oxide is not more than 150 nm, the dissolving reaction of iron through the phosphate treatment is not inhibited locally and also the precipitation of crystal of phosphate such as zinc phosphate or the like is not inhibited locally. More preferably, it is not more than 130 nm.
  • the maximum thickness of the iron-based oxide is measured as follows. First, 10 extraction replicas are prepared from the surface of the steel sheet after the pickling by a focused ion beam (FIB) work for observing a section of about 8 ⁇ m relative to the widthwise direction of the steel sheet. Then, the section of 8 ⁇ m in the each replica is continuously shot by means of a transmission electron microscope (TEM) provided with an energy dispersion type X-ray spectrometer (EDX) capable of checking local information of the section at an acceleration voltage of 200 kV and a magnification of 100000 times.
  • TEM transmission electron microscope
  • EDX energy dispersion type X-ray spectrometer
  • FIG. 3 is a photograph showing a section of a covering layer existing on the surface of the steel sheet and generated by pickling as observed by TEM
  • the covering layer is an iron-based oxide composed mainly of iron. Therefore, the interval between a line A showing a surface of the steel sheet and a line B showing a thickest portion of an oxide layer shown by the photograph of the section in FIG. 3 is measured with respect to the 10 replicas, and a maximum thickness among them is a maximum thickness of the iron-based oxide. Moreover, the size and numbers of the replicas, measuring conditions by TEM and the like as mentioned above are merely exemplified, and may be properly modified as a matter of course.
  • the production method of the cold-rolled steel sheet according to the invention will be described below.
  • the production method of the cold-rolled steel sheet of the invention is necessary to be a method wherein a steel material (slab) having Si: 0.5-3.0 mass% is heated, hot rolled, cold rolled, continuously annealed and then strong-pickled with nitric acid or the like to remove Si-containing oxide layer on a surface layer portion of the steel sheet and further repickled to render a surface covering ratio of an iron-based oxide not more than 40% generated on the steel sheet surface by the above strong pickling.
  • the cold-rolled steel sheet after the annealing is strongly pickled with nitric acid or the like, whereby the Si-containing oxide layer on the surface of the steel sheet is removed with the steel matrix.
  • Si-Mn based composite oxide among the Si-containing oxides is easily dissolved in an acid, but SiO 2 is insoluble in an acid. Therefore, in order to remove the Si-containing oxide including SiO 2 , it is necessary to remove the oxide layer together with the steel matrix of the steel sheet by the strong pickling.
  • the acid usable in the strong pickling can be preferably used nitric acid as a strong oxidizable acid, but hydrofluoric acid, hydrochloric acid, sulfuric acid or the like may be used as long as the Si-containing oxide layer can be removed, so that the kind of the acid is particularly no matter. Also, it is effective to add a pickling promoting agent to the acid, or to co-use an electrolytic treatment to promote the dissolution of the steel matrix.
  • a temperature of the pickling solution is 20-70°C and a pickling time is 3-30 seconds.
  • the iron-based oxide is dissolved and removed by further repickling the steel sheet pickled after the continuous annealing with a non-oxidizable acid.
  • the non-oxidizable acid usable in the repickling includes hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, formic acid, acetic acid, citric acid, hydrofluoric acid, oxalic acid and a mixed acid of two or more thereof. Any of these may be used, but hydrochloric acid or sulfuring acid commonly used in the iron-making industry may be preferably used. Among them, hydrochloric acid is preferable because it is a volatile acid and hardly remains a residue on the steel sheet surface after washing with water different from sulfuric acid retaining sulfuric acid root and is large in the effect of breaking the oxide by chloride ion. Also, a mixed acid of hydrochloric acid and sulfuric acid may be used.
  • hydrochloric acid When hydrochloric acid is used as the pickling solution in the repickling, it is preferable that a concentration of hydrochloric acid is 0.1-50 g/L, while in case of using sulfuric acid, it is preferable that a concentration of sulfuric acid is 0.1-150 g/L. Also, when the mixed acid of hydrochloric acid and sulfuric acid is used in the repickling, it is preferable to use a mixed acid having a hydrochloric acid concentration of 0.1-20 g/L and a sulfuric acid concentration of 0.1-60 g/L.
  • the repickling of the invention is preferable to be conducted at a temperature of a repickling solution of 20-70°C for a treating time of 1-30 seconds even in case of using any of the repickling solutions.
  • concentration of the repickling solution is more than the above lower limit and the liquid temperature is not lower than 20°C and the treating time is not less than 1 second, it is sufficient to remove the iron-based oxide existing on the steel sheet surface, while when the concentration of the repickling solution is not more than the above upper limit and the temperature is not higher than 70°C and the treating time is not more than 30 seconds, the dissolution of the steel sheet surface becomes not excessive and a new surface oxide film is not formed.
  • the maximum thickness of the iron-based oxide existing on the steel sheet surface after the pickling is surely thinned to not more than 150 nm.
  • the concentration of hydrochloric acid is 3-50 g/L, while when sulfuric acid is used in the repickling, the concentration of sulfuric acid is 8-150 g/L.
  • a mixed acid having a hydrochloric acid concentration of 3-20 g/L and a sulfuric acid concentration of 8-60 g/L.
  • the iron-based oxide can be surely thinned to not more than 150 nm, whereby the phosphate treatability and the corrosion resistance after coating are improved.
  • the acid concentration is within the above range, the dissolution of the steel sheet surface becomes not excessive, and hence new surface oxide film is never formed.
  • the cold-rolled steel sheet wherein the covering ratio of the steel sheet surface with the iron-based oxide is made to not more than 40% by pickling and repickling after the continuous annealing as mentioned above, or alternately the cold-rolled steel sheet, wherein the maximum thickness of the iron-based oxide is made to not more than 150 nm, is subsequently subjected to usual treating steps such as temper rolling and the like to provide products.
  • a steel comprising C: 0.125 mass%, Si: 1.5 mass%, Mn: 2.6 mass%, P: 0.019 mass%, S: 0.008 mass%, Al: 0.040 mass% and the remainder being Fe and inevitable impurities is prepared according to common refining process such as melting in a converter, degassing treatment and the like and continuously cast into a steel material (slab). Then, the slab is reheated to a temperature of 1150-1170°C, hot rolled at a terminating temperature of finish rolling of 850-880°C and coiled at a temperature of 500-550°C to obtain a hot-rolled steel sheet having a thickness of 3 ⁇ 5mm.
  • the hot-rolled steel sheet is pickled to remove scales and thereafter cold rolled to obtain a cold-rolled steel sheet having a thickness of 1.8 mm.
  • the cold-rolled steel sheet is subjected to such a continuous annealing that it is heated to a soaking temperature of 750-780°C and held at this temperature for 40-50 seconds and then cooled at a rate of 20-30°C/second from the soaking temperature to a cooling stop temperature of 350-400°C and held at the cooling stop temperature range for 100-120 seconds, and then the steel sheet is pickled and further repickled under conditions shown in Table 2, washed with water, dried and subjected to a temper rolling at a stretching ratio of 0.7% to obtain cold-rolled steel sheets Nos. 1-85 shown in Table 2.
  • a test specimen is sampled from each of the above cold-rolled steel sheets and observed at 5 fields of the steel sheet surface with a scanning type electron micrcope of ultra-low acceleration voltage (ULV-SEM; made by SEISS; ULTRA 55) at an acceleration voltage of 2 kV, an operating distance of 3.0 mm and a magnification of 1000 times. And analyzed with an energy dispersion X-ray spectrometer (EDX; made by Thermo Fisher; NSS 312E) to obtain a reflection electron image.
  • the reflection electron image is binarized with an image analyzing software (Image J) with respect to gray value (Y-point) corresponding to intersect point (X-point) and threshold value defined in histograms of the aforementioned standard samples Nos. a and b to measure an area ratio of a black portion.
  • the values measured at 5 fields are averaged as a surface covering ratio of iron-based oxide.
  • a test specimen is sampled from each of the above cold-rolled steel sheets and subjected to a phosphate treatment and a coating treatment under the following conditions and then subjected to three corrosion tests of hot salt water immersion test, salt water spray test and composite cycle corrosion test to evaluate a corrosion resistance after coating. Further, a distribution of O, Si, Mn and Fe in depth direction on the surface of the test specimen sampled from each cold-rolled steel sheet is measured with GDS.
  • test specimen sampled from each cold-rolled steel sheet is subjected to a phosphate treatment with a degreasing agent: FC-E2011, a surface regulator: PL-X and a phosphate treating agent: PALBOND PB-L3065, which are made by Nihon Parkerizing Co., Ltd., so as to provide a phosphate coating adhered amount of 1.7-3.0 g/m 2 under two conditions of the following standard condition and comparative condition of lowering the phosphate treating temperature to a low temperature.
  • a degreasing agent FC-E2011
  • PL-X a surface regulator
  • PALBOND PB-L3065 which are made by Nihon Parkerizing Co., Ltd.
  • the surface of the test specimen subjected to the phosphate treatment is electrodeposited with an electrodeposition paint : V-50 made by Nippon Paint Co., Ltd. so as to have a coating thickness of 25 ⁇ m and then subjected to the following three corrosion tests.
  • a test of peeling off the tape is carried out to measure a maximum peeled full width combining either side of the cut flaw portion.
  • the corrosion resistance can be evaluated to be good in the hot slat water immersion test.
  • the maximum peeled full width is not more than 4.0 mm, the corrosion resistance can be evaluated to be good in the salt water spray test.
  • test results are also shown in Table 2.
  • the steel sheets of Invention Examples subjected to the pickling and repickling under the conditions adequate for the invention after the continuous annealing are small in the maximum peeled full width on all of the hot salt water immersion test, salt water spray test and composite cycle corrosion test and show the good corrosion resistance after coating.
  • all of the cold-rolled steel sheets having the surface covering ratio of the iron-based oxide of not more than 40% are excellent in the corrosion resistance after coating under severe corrosion environment.
  • FIG. 5 shows the profile in depth direction of O, Si, Mn and Fe as surface-analyzed with GDS with respect to the test specimens of Comparative Example No. 1 and Invention Example No. 9 in Table 2.
  • Each of steels A-X having a chemical composition shown in Table 3 is prepared according to common refining process such as melting in a converter, degassing treatment and the like and continuously cast into a steel slab.
  • the steel slab is hot rolled under hot rolling conditions shown in Table 4 to obtain a hot-rolled steel sheet having a thickness of 3-4 mm, which is pickled to remove scales on the surface of the steel sheet and thereafter cold rolled to obtain a cold-rolled steel sheet having a thickness of 1.8 mm.
  • the cold-rolled steel sheet is continuously annealed under the conditions shown in Table 4, pickled and repickled under conditions shown in Table 5, washed with water, dried and subjected to a temper rolling at a stretching ratio of 0.7% to obtain cold-rolled steel sheets Nos. 1-39.
  • a test specimen is sampled from each of the cold-rolled steel sheets and subjected to the following tensile test and test for the corrosion resistance after coating after the surface covering ratio of iron-based oxide on the steel sheet surface after the repickling is measured in the same manner as in Example 1. Also, the distribution in depth direction of O, Si, Mn and Fe on the surface of the test specimen sampled from each of the cold-rolled steel sheets is measured with GDS.
  • test specimen is prepared by subjecting the test specimen sampled from each of the cold-rolled steel sheet to phosphate treatment and electrodeposition under the same conditions as in Example 1 and then subjected to three corrosion tests of hot salt water immersion test, salt water spray test (SST) and composite cycle corrosion test (CCT) likewise Example 1 to evaluate the corrosion resistance after coating.
  • SST salt water spray test
  • CCT composite cycle corrosion test
  • a steel comprising C: 0.125 mass%, Si: 1.5 mass%, Mn: 2.6 mass%, P: 0.019 mass%, S: 0.008 mass%, Al: 0.040 mass% and the remainder being Fe and inevitable impurities is melted and continuously cast into a steel material (slab).
  • the slab is reheated to a temperature of 1150-1170°C, hot rolled at a terminating temperature of finish rolling of 850-880°C and coiled at a temperature of 500-550°C to obtain a hot-rolled steel sheet having a thickness of 3-4 mm..
  • the hot-rolled steel sheet is pickled to remove scales and thereafter cold rolled to obtain a cold-rolled steel sheet having a thickness of 1.8 mm.
  • the cold-rolled steel sheet is subjected to such a continuous annealing that it is heated to a soaking temperature of 750-780°C and held at this temperature for 40-50 seconds and then cooled at a rate of 20-30°C/second from the soaking temperature to a cooling stop temperature of 350-400°C and held at the cooling stop temperature range for 100-120 seconds, and then the steel sheet is pickled and repickled under conditions shown in Table 6, washed with water, dried and subjected to a temper rolling at a stretching ratio of 0.7% to obtain cold-rolled steel sheets Nos. 1-61 shown in Table 6.
  • a test specimen is sampled from each of the above cold-rolled steel sheets to measure a surface covering ratio and maximum thickness of iron-based oxide generated on the surface of the steel sheet by pickling through the aforementioned methods.
  • test specimen is sampled from each of the above cold-rolled steel sheets and subjected to phosphate treatment and coating treatment under the following conditions and then subjected to three corrosion tests of hot salt water immersion test, salt water spray test and composite cycle corrosion test to evaluate the corrosion resistance after coating. Further, the distribution in depth direction of O, Si, Mn and Fe on the surface of the test specimen sampled from each of the cold-rolled steel sheets is measured with GDS.
  • test specimen sampled from each cold-rolled steel sheet is subjected to a phosphate treatment with a degreasing agent: FC-E2011, a surface regulator: PL-X and a phosphate treating agent: PALBOND PB-L3065, which are made by Nihon Parkerizing Co., Ltd., so as to provide a phosphate coating adhered amount of 1.7-3.0 g/m2 under two conditions of the following standard condition and comparative condition of lowering the phosphate treating temperature to a low temperature.
  • a degreasing agent FC-E2011
  • PL-X a surface regulator
  • PALBOND PB-L3065 which are made by Nihon Parkerizing Co., Ltd.
  • the surface of the test specimen subjected to the phosphate treatment is electrodeposited with an electrodeposition paint : V-50 made by Nippon Paint Co., Ltd. so as to have a coating thickness of 25 ⁇ m and then subjected to the following three corrosion tests under more strict conditions than the one with Example 1.
  • the maximum peeled full width is not more than 4.0 mm, the corrosion resistance can be evaluated to be good in the salt water spray test.
  • the cold-rolled steel sheets produced according to the invention not only are excellent in the corrosion resistance after coating but also have a high strength and a good workability, so that they can be preferably used as not only a starting material used in members of the automotive vehicle body but also a starting material for applications requiring the same properties such as household electrical goods, building members and so on.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)
EP11821649.8A 2010-08-31 2011-08-25 Procédé de production d'une tôle d'acier laminée à froid ainsi que d'une tôle d'acier laminée à froid et éléments de véhicule Active EP2612957B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010193182 2010-08-31
JP2010266125 2010-11-30
JP2011177861A JP5729211B2 (ja) 2010-08-31 2011-08-16 冷延鋼板の製造方法、冷延鋼板および自動車部材
PCT/JP2011/069193 WO2012029632A1 (fr) 2010-08-31 2011-08-25 Procédé de production d'une tôle d'acier laminée à froid, tôle d'acier laminée à froid, et élément de véhicule

Publications (3)

Publication Number Publication Date
EP2612957A1 true EP2612957A1 (fr) 2013-07-10
EP2612957A4 EP2612957A4 (fr) 2015-04-08
EP2612957B1 EP2612957B1 (fr) 2021-04-14

Family

ID=45772724

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11821649.8A Active EP2612957B1 (fr) 2010-08-31 2011-08-25 Procédé de production d'une tôle d'acier laminée à froid ainsi que d'une tôle d'acier laminée à froid et éléments de véhicule

Country Status (9)

Country Link
US (1) US20130149526A1 (fr)
EP (1) EP2612957B1 (fr)
JP (1) JP5729211B2 (fr)
KR (1) KR101502213B1 (fr)
CN (1) CN102959130B (fr)
BR (1) BR112013004853A2 (fr)
MX (1) MX348689B (fr)
TW (1) TWI527934B (fr)
WO (1) WO2012029632A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2612956A4 (fr) * 2010-08-31 2015-03-18 Jfe Steel Corp Procédé de production d'une tôle d'acier laminée à froid, tôle d'acier laminée à froid, et élément véhicule
EP2821515A4 (fr) * 2012-02-28 2015-08-05 Jfe Steel Corp Tôle d'acier laminée à froid, à haute résistance et contenant du si, procédé de production associé et élément de véhicule
EP3115482A1 (fr) * 2014-03-04 2017-01-11 JFE Steel Corporation Tôle d'acier laminée à froid, procédé de fabrication s'y rapportant et pièce de voiture
EP3272892A4 (fr) * 2015-03-18 2018-01-24 JFE Steel Corporation Tôle d'acier laminée à froid à haute résistance et son procédé de fabrication
EP3418417A4 (fr) * 2016-02-18 2019-01-02 JFE Steel Corporation Tôle en acier laminée à froid hautement résistante
US11248277B2 (en) 2017-05-19 2022-02-15 Jfe Steel Corporation Method for manufacturing high-strength galvanized steel sheet

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5919920B2 (ja) * 2011-03-28 2016-05-18 Ｊｆｅスチール株式会社 Ｓｉ含有冷延鋼板の製造方法及び装置
JP2013237912A (ja) * 2012-05-16 2013-11-28 Nippon Steel & Sumitomo Metal Corp 化成処理性に優れた高張力冷延鋼帯とその製造方法
JP5962541B2 (ja) * 2012-07-23 2016-08-03 Ｊｆｅスチール株式会社 高強度鋼板の製造方法
JP5962543B2 (ja) * 2012-07-23 2016-08-03 Ｊｆｅスチール株式会社 高強度鋼板の製造方法
JP5962542B2 (ja) * 2012-07-23 2016-08-03 Ｊｆｅスチール株式会社 高強度鋼板の製造方法
JP6102902B2 (ja) * 2014-03-05 2017-03-29 Ｊｆｅスチール株式会社 冷延鋼板、その製造方法、高強度溶融亜鉛めっき鋼板及び高強度合金化溶融亜鉛めっき鋼板
KR102110187B1 (ko) * 2014-05-14 2020-05-14 카르스젠 테라퓨틱스 리미티드 키메라 항원 수용체 단백질을 코딩하는 핵산 및 키메라 항원 수용체 단백질을 발현하는 t 림프구
JP6137089B2 (ja) 2014-09-02 2017-05-31 Ｊｆｅスチール株式会社 冷延鋼板の製造方法および冷延鋼板の製造設備
CN105483549B (zh) * 2014-09-19 2017-07-21 鞍钢股份有限公司 一种宽薄规格汽车用高强度冷轧钢板及生产方法
JP6041079B1 (ja) * 2015-07-08 2016-12-07 Ｊｆｅスチール株式会社 冷延鋼帯の製造方法及び製造設備
US20180298503A1 (en) * 2015-07-08 2018-10-18 Jfe Steel Corporation Method of producing cold rolled steel strip and production system for cold rolled steel strip
MX2018009968A (es) * 2016-02-18 2018-11-09 Jfe Steel Corp Lamina de acero laminada en frio de alta resistencia.
DE102016117508B4 (de) * 2016-09-16 2019-10-10 Salzgitter Flachstahl Gmbh Verfahren zur Herstellung eines Stahlflachprodukts aus einem mittelmanganhaltigen Stahl und ein derartiges Stahlflachprodukt
KR101889193B1 (ko) * 2016-12-22 2018-08-16 주식회사 포스코 내식성 및 가공성이 우수한 냉연강판 및 그 제조방법
JP6191810B1 (ja) * 2017-03-24 2017-09-06 新日鐵住金株式会社 鋼板の製造方法
KR101951936B1 (ko) * 2017-08-24 2019-02-25 주식회사포스코 고강도 냉연강판의 제조방법
CN107974631B (zh) * 2017-12-01 2019-07-30 安徽工业大学 一种多维度增强增塑生产高强塑积超高强度第三代汽车用钢的方法
CN107937690A (zh) * 2017-12-28 2018-04-20 滁州宝岛特种冷轧带钢有限公司 一种冷轧带钢的热处理工艺
CN108031717A (zh) * 2017-12-28 2018-05-15 滁州宝岛特种冷轧带钢有限公司 一种冷轧带钢表面的酸洗除磷方法
JP6962451B2 (ja) 2018-03-30 2021-11-05 Ｊｆｅスチール株式会社 冷延鋼板およびその製造方法
US20210395895A1 (en) * 2018-11-09 2021-12-23 Jfe Steel Corporation Cold rolled steel sheet for zirconium-based chemical conversion treatment, method for producing same, zirconium-based chemical conversion-treated steel sheet, and method for producing same
KR102178809B1 (ko) * 2018-11-30 2020-11-13 주식회사 포스코 내산용 열연강판 및 그 제조방법
CN110987993A (zh) * 2019-12-17 2020-04-10 中国地质大学（武汉） 一种原位有机质定量统计分析方法
CN111923515A (zh) * 2020-09-11 2020-11-13 长虹美菱股份有限公司 一种冷轧钢板表面3d拉丝结构及表面3d拉丝工艺
CN112522716A (zh) * 2020-12-01 2021-03-19 苏州阿诺医疗器械有限公司 一种用于铰刀的酸洗钝化工艺
US20240018617A1 (en) 2021-02-02 2024-01-18 Nippon Steel Corporation Thin steel sheet
WO2022201686A1 (fr) 2021-03-26 2022-09-29 Ｊｆｅスチール株式会社 Procédé de production de tôle d'acier recuite et décapée
CN116917546A (zh) * 2021-03-26 2023-10-20 杰富意钢铁株式会社 退火酸洗钢板的制造方法
CN114214491A (zh) * 2021-12-23 2022-03-22 盐城吉研智能科技有限公司 一种提高灰口铸铁零部件抗腐蚀能力的方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL269606A (fr) * 1960-10-15
JPS6052737A (ja) * 1983-09-01 1985-03-26 Kawasaki Steel Corp 酸濃度測定用酸洗液サンプリング装置
DE19532278B4 (de) * 1995-09-01 2006-07-27 Bwg Bergwerk- Und Walzwerk-Maschinenbau Gmbh Verfahren zur Herstellung eines kaltgewalzten Bandes in einem Durchlauf
FR2775205B1 (fr) * 1998-02-25 2000-03-24 Usinor Installation de fabrication de bandes d'acier inoxydable laminees a froid
JP3356112B2 (ja) * 1999-04-27 2002-12-09 住友金属工業株式会社 酸濃度自動制御装置および酸濃度自動制御方法
KR100358287B1 (ko) * 2000-06-15 2002-10-25 현대하이스코 주식회사 표면성이 우수한 자동차용 냉연강판 제조방법
KR20020047581A (ko) * 2000-12-13 2002-06-22 이구택 내식성이 향상되는 페라이트계 스테인레스 냉연강판의제조방법
JP4175463B2 (ja) * 2001-04-09 2008-11-05 エイケイ・スティール・プロパティーズ・インコーポレイテッド ステンレス鋼等級のための過酸化水素酸洗計画
KR20070087240A (ko) * 2001-06-15 2007-08-27 신닛뽄세이테쯔 카부시키카이샤 고강도 알루미늄계 합금 도금 강판의 열간 프레스 방법
KR100949694B1 (ko) * 2002-03-29 2010-03-29 제이에프이 스틸 가부시키가이샤 초미세입자 조직을 갖는 냉연강판 및 그 제조방법
JP4221984B2 (ja) * 2002-09-20 2009-02-12 Ｊｆｅスチール株式会社 極めて良好な表面光沢度を有するマルテンサイト系ステンレス鋼冷間圧延‐焼鈍‐酸洗鋼帯
JP3990349B2 (ja) 2002-12-10 2007-10-10 新日本製鐵株式会社 塗装後耐食性に優れた良加工性高強度冷延鋼板
JP4739653B2 (ja) 2003-02-17 2011-08-03 株式会社神戸製鋼所 高強度冷延鋼板
JP4422498B2 (ja) * 2004-01-15 2010-02-24 三菱日立製鉄機械株式会社 連続酸洗設備
JP4335737B2 (ja) * 2004-04-27 2009-09-30 住友金属工業株式会社 Ｓｉ含有鋼板の製造方法
JP4510688B2 (ja) * 2005-04-20 2010-07-28 新日本製鐵株式会社 高強度高延性合金化溶融亜鉛メッキ鋼板の製造方法
JP4510697B2 (ja) * 2005-05-18 2010-07-28 新日本製鐵株式会社 Ｐ添加鋼板の合金化溶融亜鉛メッキ方法
JP5168793B2 (ja) 2006-02-16 2013-03-27 Ｊｆｅスチール株式会社 塗装後耐食性に優れた高強度冷延鋼板の製造方法
JP4725374B2 (ja) 2006-03-14 2011-07-13 Ｊｆｅスチール株式会社 成形性、化成処理性および塗装後耐食性に優れた高強度冷延鋼板およびその製造方法
JP4804996B2 (ja) * 2006-04-07 2011-11-02 新日本製鐵株式会社 加工性、パウダリング性、摺動性の良好な合金化溶融亜鉛メッキ鋼板の製造方法
ITMI20062187A1 (it) * 2006-11-14 2008-05-15 Sviluppo Materiali Spa Processo di ricottura e decapaggio
DE102008005605A1 (de) * 2008-01-22 2009-07-23 Thyssenkrupp Steel Ag Verfahren zum Beschichten eines 6 - 30 Gew. % Mn enthaltenden warm- oder kaltgewalzten Stahlflachprodukts mit einer metallischen Schutzschicht
JP5233346B2 (ja) * 2008-03-19 2013-07-10 Ｊｆｅスチール株式会社 化成処理性および塗装後耐食性に優れる高強度冷延鋼板およびその製造方法
JP5919920B2 (ja) * 2011-03-28 2016-05-18 Ｊｆｅスチール株式会社 Ｓｉ含有冷延鋼板の製造方法及び装置

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2612956A4 (fr) * 2010-08-31 2015-03-18 Jfe Steel Corp Procédé de production d'une tôle d'acier laminée à froid, tôle d'acier laminée à froid, et élément véhicule
EP2821515A4 (fr) * 2012-02-28 2015-08-05 Jfe Steel Corp Tôle d'acier laminée à froid, à haute résistance et contenant du si, procédé de production associé et élément de véhicule
US10174430B2 (en) 2012-02-28 2019-01-08 Jfe Steel Corporation Si-containing high strength cold rolled steel sheet, method of producing the same, and automotive members
EP3115482A1 (fr) * 2014-03-04 2017-01-11 JFE Steel Corporation Tôle d'acier laminée à froid, procédé de fabrication s'y rapportant et pièce de voiture
EP3115482A4 (fr) * 2014-03-04 2017-05-10 JFE Steel Corporation Tôle d'acier laminée à froid, procédé de fabrication s'y rapportant et pièce de voiture
EP3272892A4 (fr) * 2015-03-18 2018-01-24 JFE Steel Corporation Tôle d'acier laminée à froid à haute résistance et son procédé de fabrication
EP3418417A4 (fr) * 2016-02-18 2019-01-02 JFE Steel Corporation Tôle en acier laminée à froid hautement résistante
US11008635B2 (en) 2016-02-18 2021-05-18 Jfe Steel Corporation High-strength cold-rolled steel sheet
US11248277B2 (en) 2017-05-19 2022-02-15 Jfe Steel Corporation Method for manufacturing high-strength galvanized steel sheet

Also Published As

Publication number Publication date
EP2612957A4 (fr) 2015-04-08
WO2012029632A1 (fr) 2012-03-08
TWI527934B (zh) 2016-04-01
KR101502213B1 (ko) 2015-03-12
EP2612957B1 (fr) 2021-04-14
JP5729211B2 (ja) 2015-06-03
CN102959130A (zh) 2013-03-06
TW201224216A (en) 2012-06-16
US20130149526A1 (en) 2013-06-13
BR112013004853A2 (pt) 2016-06-07
CN102959130B (zh) 2016-06-01
MX348689B (es) 2017-06-26
MX2013000619A (es) 2013-05-28
JP2012132092A (ja) 2012-07-12
KR20130031285A (ko) 2013-03-28

Similar Documents

Publication Publication Date Title
EP2612957B1 (fr) Procédé de production d'une tôle d'acier laminée à froid ainsi que d'une tôle d'acier laminée à froid et éléments de véhicule
EP2612956B1 (fr) Procédé de production d'une tôle d'acier laminée à froid, tôle d'acier laminée à froid, et élément véhicule
CN111511945B (zh) 高强度冷轧钢板及其制造方法
EP3190211B1 (fr) Tôle d'acier laminée à froid, procédé de production de tôle d'acier laminée à froid, élément d'automobile, et équipement de production de tôle d'acier laminée à froid
EP3399064B1 (fr) Tôle en acier laminée à froid hautement résistante
KR102529040B1 (ko) 열연 강판 및 그 제조 방법
EP2902520A1 (fr) Feuille d'acier laminée à chaud et son procédé de production
CN108699648B (zh) 高强度冷轧钢板
CN112955575B (zh) 高强度构件、高强度构件的制造方法和高强度构件用钢板的制造方法
EP2821515A1 (fr) Tôle d'acier laminée à froid, à haute résistance et contenant du si, procédé de production associé et élément de véhicule
JP5835545B2 (ja) Ｓｉ含有熱延鋼板の製造方法
JP5835547B2 (ja) Ｓｉ含有冷延鋼板の製造方法
EP3115482B1 (fr) Tôle d'acier laminée à froid, procédé de fabrication s'y rapportant et pièce de voiture
JP5682366B2 (ja) Ｓｉ含有冷延鋼板の製造方法
EP4269644A1 (fr) Tôle d'acier laminée à froid et son procédé de fabrication
EP4269643A1 (fr) Tôle d'acier laminée à froid et procédé de fabrication de celle-ci

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130325

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/58 20060101ALI20150205BHEP

Ipc: C22C 38/00 20060101ALI20150205BHEP

Ipc: C23G 1/08 20060101AFI20150205BHEP

Ipc: B21B 3/02 20060101ALI20150205BHEP

Ipc: C21D 9/46 20060101ALI20150205BHEP

Ipc: C22C 38/02 20060101ALI20150205BHEP

RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150305

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180327

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011070700

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23G0001080000

Ipc: C21D0008020000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/38 20060101ALI20201111BHEP

Ipc: C22C 38/22 20060101ALI20201111BHEP

Ipc: C22C 38/04 20060101ALI20201111BHEP

Ipc: B21B 3/02 20060101ALI20201111BHEP

Ipc: C22C 38/34 20060101ALI20201111BHEP

Ipc: C22C 38/14 20060101ALI20201111BHEP

Ipc: C23G 1/00 20060101ALI20201111BHEP

Ipc: C22C 38/00 20060101ALI20201111BHEP

Ipc: C22C 38/16 20060101ALI20201111BHEP

Ipc: C21D 8/02 20060101AFI20201111BHEP

Ipc: C22C 38/12 20060101ALI20201111BHEP

Ipc: C22C 38/06 20060101ALI20201111BHEP

Ipc: C22C 38/02 20060101ALI20201111BHEP

Ipc: C23G 1/08 20060101ALI20201111BHEP

Ipc: C22C 38/32 20060101ALI20201111BHEP

Ipc: C22C 38/08 20060101ALI20201111BHEP

INTG Intention to grant announced

Effective date: 20201203

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011070700

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1382440

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1382440

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210414

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210714

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210814

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210715

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210816

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210714

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011070700

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220117

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210814

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210825

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210825

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110825

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230706

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210414

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240702

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240702

Year of fee payment: 14