WO2022091851A1 - 溶融Ａｌ－Ｚｎ－Ｓｉ－Ｍｇ－Ｓｒ系めっき鋼板、表面処理鋼板及び塗装鋼板 - Google Patents

溶融Ａｌ－Ｚｎ－Ｓｉ－Ｍｇ－Ｓｒ系めっき鋼板、表面処理鋼板及び塗装鋼板 Download PDF

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WO2022091851A1
WO2022091851A1 PCT/JP2021/038480 JP2021038480W WO2022091851A1 WO 2022091851 A1 WO2022091851 A1 WO 2022091851A1 JP 2021038480 W JP2021038480 W JP 2021038480W WO 2022091851 A1 WO2022091851 A1 WO 2022091851A1
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compound
mass
steel sheet
film
resin
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PCT/JP2021/038480
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English (en)
French (fr)
Japanese (ja)
Inventor
昌浩 吉田
章一郎 平
利彦 大居
純久 岩野
洋平 佐藤
史嵩 菅野
聡 安藤
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Ｊｆｅスチール株式会社
Ｊｆｅ鋼板株式会社
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Priority claimed from JP2021150581A external-priority patent/JP7097491B2/ja
Priority claimed from JP2021150576A external-priority patent/JP7097489B2/ja
Priority claimed from JP2021150585A external-priority patent/JP7097493B2/ja
Application filed by Ｊｆｅスチール株式会社, Ｊｆｅ鋼板株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to KR1020237015482A priority Critical patent/KR20230082045A/ko
Priority to CN202180073469.6A priority patent/CN116507754A/zh
Priority to AU2021368356A priority patent/AU2021368356A1/en
Publication of WO2022091851A1 publication Critical patent/WO2022091851A1/ja

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    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • 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
    • C23C22/06—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 acidic solutions with pH less than 6
    • C23C22/40—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • the present invention relates to a molten Al-Zn-Si-Mg-Sr-based plated steel sheet, a surface-treated steel sheet and a coated steel sheet having stable and excellent corrosion resistance.
  • hot-dip Al-Zn-based plated steel sheets represented by 55% Al-Zn-based steel sheets exhibit high corrosion resistance among hot-dip galvanized steel sheets because they have both the sacrificial corrosion resistance of Zn and the high corrosion resistance of Al. Has been done. Therefore, due to its excellent corrosion resistance, hot-dip Al-Zn plated steel sheets are mainly used in the field of building materials such as roofs and walls that are exposed to the outdoors for a long period of time, and in the field of civil engineering and construction such as guardrails, wiring pipes, and noise barriers. ..
  • the plating film of the molten Al-Zn-based plated steel sheet consists of the portion where Al containing Zn oversaturated is solidified into a dendrite ( ⁇ -Al phase) and the Zn-Al eutectic structure existing in the dendrite gap (interdrendlite). It is characterized by having a structure in which a plurality of ⁇ -Al phases are laminated in the film thickness direction of the plating film. Due to such a characteristic film structure, the corrosion progress path from the surface becomes complicated, so that the corrosion does not easily proceed, and the hot-dip Al-Zn-based plated steel sheet becomes a hot-dip galvanized steel sheet having the same plating film thickness. It is also known that better corrosion resistance can be achieved.
  • Patent Document 1 contains an Al-Zn-Si alloy containing Mg in a plating film, and the Al-Zn-Si alloy is described as described above.
  • Si-Mg-Sr based plated steel sheets are disclosed. Further, in Patent Document 2, the plating film contains at least one of 2 to 10% Mg and 0.01 to 10% Ca to improve corrosion resistance and protect the base steel sheet after it is exposed. A hot-dip Al-Zn-Si-Mg-Sr-based plated steel sheet for the purpose of enhancing the above is disclosed. Further, in Patent Document 3, Mg: 1 to 15%, Si: 2 to 15%, Zn: 11 to 25% are contained in mass%, and the balance forms a coating layer composed of Al and unavoidable impurities.
  • Patent Document 4 discloses a molten Al-Zn-Si-Mg-Sr-based plated steel sheet in which wrinkle-like unevenness defects are suppressed by containing 0.01 to 10% Sr in the plating film.
  • Patent Document 5 also discloses a molten Al-Zn-Si-Mg-Sr-based plated steel sheet in which mottled defects are suppressed by containing 500 to 3000 ppm of Sr in the plating film. Techniques for improving the view are disclosed.
  • Patent Document 4 discloses a molten Al-Zn-Si-Mg-based plated steel sheet in which wrinkle-like unevenness defects are suppressed by containing 0.01 to 10% Sr in the plating film.
  • Patent Document 5 also discloses a molten Al-Zn-Si-Mg-based plated steel sheet in which mottled defects are suppressed by containing 500 to 3000 ppm of Sr in the plating film.
  • Patent Document 6 discloses a molten Al-Zn-Si-Mg-based plated steel sheet in which 0.001 to 1.0% of Sr is contained in the plating film to achieve both surface appearance and corrosion resistance.
  • Patent Document 7 also describes a molten Al-Zn-Si-Mg-based plated steel sheet in which 0.001 to 1.0% of Sr is contained in the plating film to achieve both surface appearance and corrosion resistance between the flat plate portion and the processed portion. Is disclosed.
  • Patent Document 8 also discloses a molten Al-Zn-Si-Mg-based plated steel sheet that achieves both surface appearance and corrosion resistance by containing 0.01 to 0.2% Sr in the plating film. ..
  • Patent Document 9 discloses a molten Al-Zn-Si-Mg-based plated steel sheet having improved corrosion resistance by controlling the Si and Mg concentrations in the plating film at a specific ratio.
  • Patent Document 10 describes molten Al-Zn-Si in which the mass ratio of Mg in the Si-Mg phase to the total amount of Mg in the plating layer is optimized for the purpose of improving the white rust resistance of the processed portion. -Mg-based plated steel sheets are disclosed.
  • Patent Document 11 blackening resistance and white rust resistance are improved by forming a chemical conversion film containing a urethane resin on the plating film of a molten Al-Zn-Si-Mg-based plated steel sheet.
  • the technology is disclosed.
  • a coated steel sheet in which a chemical conversion film, primer coating film, topcoat coating film, etc. is formed on the surface of a molten Al-Zn-based plated steel sheet can be bent 90 degrees or 180 degrees by press forming, roll forming, or embossing. Various processing is applied, and long-term coating film durability is required.
  • the molten Al-Zn-based plated steel sheet forms a chromate-containing chemical conversion film
  • the primer coating film also contains a chromate-based rust-preventive pigment, and on top of that, a heat-curable polyester-based film.
  • Patent Document 12 describes aluminum-zinc alloy plating containing Al, Zn, Si and Mg on the surface of a steel material and adjusting the content of these elements.
  • the layer ( ⁇ ) is plated, and a film ( ⁇ ) containing at least one compound (A) selected from a titanium compound and a zirconium compound as a film-forming component is formed as an upper layer thereof, and an aluminum-zinc alloy plated layer ( ⁇ ) is formed.
  • a surface-treated hot-dip plated steel material in which the mass ratio of the Si—Mg phase in ⁇ ) to the total amount of Mg in the plating layer is adjusted to 3% or more is disclosed.
  • Patent Documents 1 to 3 the technique of containing Mg in the plating film as disclosed in Patent Documents 1 to 3 does not always bring about the improvement of corrosion resistance uniquely.
  • the corrosion resistance is improved only by containing Mg in the plating component, but the metal phase constituting the plating film is formed. -The characteristics of the intermetallic compound phase were not taken into consideration, and it was not possible to uniformly talk about the superiority or inferiority of corrosion resistance.
  • the coated steel sheet has long-term coating film durability performance in a state where it has been subjected to various processing such as 90 degree bending and 180 degree bending by press forming, roll forming, embossing, etc.
  • various processing such as 90 degree bending and 180 degree bending by press forming, roll forming, embossing, etc.
  • Patent Document 12 can always obtain stable corrosion resistance and surface appearance after processing.
  • the corrosion resistance of the coated steel sheet is affected by the corrosion resistance of the plated steel sheet used as the base, and as for the surface appearance, the height difference of the unevenness of the wrinkle-like defect is as much as several tens of ⁇ m. Even if the surface is smoothed, the unevenness is not completely eliminated, and it is considered that the appearance of the coated steel sheet cannot be improved.
  • the coating film becomes thin in the convex portion, there is a concern that the corrosion resistance is locally deteriorated. Therefore, in order to obtain a coated steel sheet having excellent corrosion resistance and surface appearance, it is important to improve the corrosion resistance and surface appearance of the underlying plated steel sheet.
  • an object of the present invention to provide a molten Al-Zn-Si-Mg-Sr-based plated steel sheet having stable and excellent corrosion resistance and good surface appearance. Another object of the present invention is to provide a surface-treated steel sheet having stable and excellent corrosion resistance and white rust resistance. Further, it is an object of the present invention to provide a coated steel sheet having stable and excellent corrosion resistance and corrosion resistance of a processed portion.
  • the present inventors have made Mg 2 Si phase, Mg Zn 2 phase, and Si formed in the plating film of the molten Al-Zn-Si-Mg-Sr-based plated steel sheet.
  • the phase it was found that the amount of precipitation increases or decreases depending on the balance of each component in the plating film and the formation conditions of the plating film, the abundance ratio changes, and one of the phases may not precipitate depending on the balance of the composition. ..
  • the corrosion resistance of the molten Al-Zn-Si-Mg-Sr-based plated steel sheet changes depending on the abundance ratio of these phases, and the corrosion resistance is stably improved especially when the Si phase is smaller than that of the Mg 2 Si phase.
  • a general method such as a scanning electron microscope is used to observe the secondary electron image or backscattered electron image of the plating film from the surface or cross section. It is known that it is very difficult to distinguish the difference between the phases.
  • Mg 2 Si phase and Si phase that influence macroscopic information such as corrosion resistance and appearance.
  • the present inventors focused on the X-ray diffraction method and quantified the phase abundance ratio by using the intensity ratio of specific diffraction peaks for the Mg 2 Si phase and the Si phase. Furthermore, it was found that when the Mg 2 Si phase and the Si phase satisfy a specific abundance ratio in the plating film, stable and excellent corrosion resistance can be realized. Furthermore, the present inventors controlled the abundance ratio of Mg 2 Si phase, Si phase, etc. in the molten Al-Zn-Si-Mg-Sr-based plated steel sheet, and then controlled the Sr concentration in the bath. It was also found that a plated steel sheet with excellent surface appearance can be obtained by reliably suppressing the occurrence of wrinkle-like uneven defects.
  • the present inventors also studied the chemical conversion film formed on the plating film, and formed the chemical conversion film from a specific resin and a specific metal compound to form a plating film of the chemical conversion film. It was also found that the affinity of the white rust and the rust preventive effect were enhanced, and the stable improvement of the white rust resistance was improved.
  • the present inventors have also studied the chemical conversion film and the primer coating film formed on the plating film, and while forming the chemical conversion film with a specific resin and a specific inorganic compound, the primer coating film is formed. It has also been found that, by being composed of a specific polyester resin and an inorganic compound, the barrier property and adhesion of the coating film can be enhanced, and excellent post-processing corrosion resistance can be realized even if it is chromate-free.
  • the present invention has been made based on the above findings, and the gist thereof is as follows.
  • 1. A molten Al-Zn-Si-Mg-Sr-based plated steel sheet with a plating film.
  • the plating film contains Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass, Mg: 1.0 to 10.0% by mass and Sr: 0.01 to 1.0% by mass, and the balance is composed of Zn and unavoidable impurities.
  • Si (111): Diffraction intensity of Si (111) plane (plane spacing d 0.3135 nm)
  • Mg 2 Si (111): Diffraction intensity of Mg 2 Si (111) plane (plane spacing d 0.3668 nm)
  • Si (111) 0 ⁇ ⁇ ⁇ (2)
  • Si (111): Diffraction intensity of Si (111) plane (plane spacing d 0.3135 nm)
  • a surface-treated steel sheet comprising the plating film according to any one of 1 to 5 and a chemical conversion film formed on the plating film.
  • the chemical conversion film comprises at least one resin selected from epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin, and P compound, Si compound and Co.
  • a surface treatment comprising at least one metal compound selected from a compound, a Ni compound, a Zn compound, an Al compound, an Mg compound, a V compound, a Mo compound, a Zr compound, a Ti compound and a Ca compound. Steel plate.
  • the chemical conversion film contains (a): an anionic polyurethane resin having an ester bond and (b): an epoxy resin having a bisphenol skeleton in a total amount of 30 to 50% by mass, and contains the (a) and the (b).
  • the ratio ((a): (b)) is in the range of 3:97 to 60:40 in mass ratio, 2 to 10% by mass of vanadium compound, 40 to 60% by mass of zirconium compound and 0.5 to 0.5.
  • the coating film has at least a primer coating film, and the primer coating film contains a polyester resin having a urethane bond and an inorganic compound containing a vanadium compound, a phosphoric acid compound and magnesium oxide. , Painted steel plate.
  • the present invention it is possible to provide a molten Al-Zn-Si-Mg-Sr-based plated steel sheet having stably excellent corrosion resistance and good surface appearance. Further, according to the present invention, it is possible to stably provide a surface-treated steel sheet having excellent corrosion resistance and white rust resistance. Further, according to the present invention, it is possible to stably provide a coated steel sheet having excellent corrosion resistance and corrosion resistance of a processed portion.
  • the molten Al-Zn-Si-Mg-Sr-based plated steel sheet of the present invention has a plating film on the surface of the steel sheet.
  • the plating film contains Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass, Mg: 1.0 to 10.0% by mass and Sr: 0.01 to 1.0% by mass, and the balance is from Zn and unavoidable impurities.
  • the Al content in the plating film is 45 to 65% by mass, preferably 50 to 60% by mass, from the viewpoint of the balance between corrosion resistance and operation. This is because if the Al content in the plating film is at least 45% by mass, dendrite solidification of Al occurs, and a plating film structure mainly composed of the dendrite solidified structure of the ⁇ -Al phase can be obtained.
  • the corrosion progress path becomes complicated and the corrosion resistance of the plating film itself is improved. Further, the more the dendrite portions of the ⁇ -Al phase are laminated, the more complicated the corrosion progress path becomes, and the more difficult it is for corrosion to reach the base steel sheet.
  • the corrosion resistance is improved, and the Al content is 50 mass. % Or more is preferable.
  • the Al content in the plating film exceeds 65% by mass, most of Zn changes to a structure that is solid-dissolved in ⁇ -Al, and the dissolution reaction of the ⁇ -Al phase cannot be suppressed, so that Al-Zn -The corrosion resistance of Si-Mg-Sr plating deteriorates. Therefore, the Al content in the plating film needs to be 65% by mass or less, preferably 60% by mass or less.
  • Si in the plating film mainly suppresses the growth of the Fe-Al-based and / or Fe-Al-Si-based interfacial alloy layer generated at the interface with the underlying steel sheet, and does not deteriorate the adhesion between the plating film and the steel sheet.
  • Added for the purpose When a steel plate is actually immersed in an Al-Zn-based plating bath containing Si, Fe on the surface of the steel plate and Al or Si in the bath undergo an alloying reaction, and Fe-Al-based and / or Fe-Al-Si-based.
  • the metal-metal compound layer is formed at the base steel plate / plating film interface.
  • the Fe-Al-Si alloy has a slower growth rate than the Fe-Al alloy, so the ratio of the Fe-Al-Si alloy is high.
  • the higher the value the more the growth of the entire interfacial alloy layer is suppressed. Therefore, the Si content in the plating film needs to be 1.0% by mass or more.
  • the Si content in the plating film exceeds 4.0% by mass, not only the above-mentioned growth suppressing effect of the interfacial alloy layer is saturated, but also corrosion is promoted due to the presence of an excess Si phase in the plating film. Therefore, the Si content should be 4.0% or less.
  • the content of Si in the plating film is preferably 3.0% or less from the viewpoint of suppressing the presence of an excessive Si phase.
  • the Si content is preferably 1.0 to 3.0% by mass from the viewpoint of easily satisfying the relational expression (1) described later in relation to the Mg content described later.
  • the plating film contains 1.0 to 10.0% of Mg.
  • Mg in the plating film, the above-mentioned Si can be present in the form of an intermetallic compound of Mg 2 Si phase, and the promotion of corrosion can be suppressed.
  • MgZn 2 phase which is an intermetallic compound, is also formed in the plating film, and the effect of further improving the corrosion resistance can be obtained.
  • Mg content in the plating film is less than 1.0% by mass, Mg is used for solid solution to the ⁇ -Al phase, which is the main phase, rather than the formation of the intermetallic compounds (Mg 2 Si, MgZn 2 ). Therefore, sufficient corrosion resistance cannot be ensured.
  • the Mg content in the plating film is set to 10.0% or less.
  • the Mg content in the plating film is preferably 5.0% by mass or less from the viewpoint of suppressing the generation of dross during plating formation and facilitating the management of the plating bath. From the viewpoint of easily satisfying the relational expression (1) described later in relation to the Si content, the Mg content is preferably 3.0% by mass, and compatibility with dross suppression is taken into consideration. Then, it is more preferable to set the Mg content to 3.0 to 5.0% by mass.
  • the above intermetallic compounds dissolve preferentially over the ⁇ -Al phase, resulting in the formation of near the corrosive products.
  • the effect of improving the protective effect of the plating film is more reliably expressed when Si in the plating film exists as the Mg 2 Si phase instead of the Si phase, so that the abundance ratio of the Si phase to the Mg 2 Si phase is lowered. Is considered to be effective.
  • the abundance ratio of Mg 2 Si and Si in the plating film has a relationship (1): Si (111) / Mg 2 Si (111) ⁇ 0.8 using the diffraction peak intensity obtained by the X-ray diffractometry. It is necessary to satisfy, but when the abundance ratio of Mg 2 Si and Si in the plating film does not satisfy the relationship (1), that is, when Si (111) / Mg 2 Si (111)> 0.8, the plating is performed. Since the amount of Si phase present in the film increases, it is not possible to obtain the above-mentioned Mg-rich environment in the vicinity of corrosion products, and it becomes difficult to obtain the effect of improving the protective effect of the plating film.
  • the abundance ratio of Si to Mg 2 Si (Si (111) / Mg 2 Si (111)) is preferably 0.5 or less, more preferably 0.3 or less, and 0.2 or less. Is particularly preferable.
  • the composition of the plating film tentatively satisfies the range of the present invention (Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass, Mg: Even if it contains 1.0 to 10.0% by mass and Sr: 0.01 to 1.0% by mass, and the balance consists of Zn and unavoidable impurities), the abundance ratio of Mg 2 Si and Si does not satisfy the relationship (1).
  • the effect of improving the protective effect of the plating film according to the present invention cannot be sufficiently obtained.
  • Mg 2 Si (111) is (111) of Mg 2 Si.
  • Diffraction intensity of the plane (plane spacing d 0.3668 nm).
  • Si (111) / Mg 2 Si (111) can be obtained.
  • the amount of plating film (amount to scrape off the plating film) required for powder X-ray diffraction measurement is 0.1 g or more from the viewpoint of accurately measuring Si (111) and Mg 2 Si (111). It may be sufficient, preferably 0.3 g or more.
  • the plating film when the plating film is scraped off, steel plate components other than the plating film may be contained in the powder, but these intermetallic compound phases are contained only in the plating film, and the above-mentioned peak strength can be obtained. It has no effect. Further, the reason why the plating film is powdered and X-ray diffraction is performed is that when X-ray diffraction is performed on the plating film formed on the plated steel sheet, it is affected by the plane orientation of the solidification structure of the plating film and has the correct phase ratio. This is because it is difficult to perform the calculation.
  • the diffraction intensity of Si in the plating film by the X-ray diffraction method is increased from the viewpoint that the corrosion resistance can be improved more stably. It is preferable to satisfy the following relationship (2).
  • Si (111) 0 ⁇ ⁇ ⁇ (2)
  • Si (111): Diffractive intensity of Si (111) plane (plane spacing d 0.3135 nm)
  • the Si phase is present as a cathode site, so that the surroundings Since it is known to promote the dissolution of the ⁇ -Al phase, reducing the Si phase is also effective from the viewpoint of suppressing the dissolution of the ⁇ -Al phase, and among them, Si as described in the relationship (2).
  • a phase-free film (setting the diffraction peak intensity of Si (111) to zero) is the most excellent for stabilizing corrosion resistance.
  • the method for measuring the diffraction peak intensity of the (111) plane of Si by X-ray diffraction is as described above.
  • the method for satisfying the above-mentioned relationship (1) and relationship (2) is not particularly limited.
  • the balance between the Si content, the Mg content and the Al content in the plating film is adjusted to obtain Mg 2 Si and Si.
  • the abundance ratio (diffraction intensity of Mg 2 Si (111) and Si (111)) can be controlled.
  • the balance between the Si content, the Mg content and the Al content in the plating film does not necessarily satisfy the relationship (1) and the relationship (2) if the content ratio is set to a certain level. For example, it is necessary to change the content ratio of Mg and Al depending on the content (mass%) of Si.
  • the conditions for forming the plating film (for example, cooling conditions after plating) can be adjusted.
  • the diffraction intensity of Mg 2 Si (111) and Si (111) can be controlled so as to satisfy the relationship (1) and the relationship (2).
  • the plating film contains 0.01 to 1.0% by mass of Sr.
  • Sr When the plating film contains Sr, it is possible to more reliably suppress the occurrence of surface defects such as wrinkle-like uneven defects, and it is possible to realize good surface appearance.
  • the wrinkle-like defect is a wrinkle-like uneven defect formed on the surface of the plating film, and is observed as a whitish streak on the surface of the plating film. Such wrinkle-like defects are likely to occur when a large amount of Mg is added to the plating film.
  • the plating film contains 0.01 to 1.0% by mass of Sr, but when the Sr content in the plating film is less than 0.01% by mass, the effect of improving the appearance cannot be obtained, and the Sr in the plating film is not obtained. If the content exceeds 1.0% by mass, Sr is excessively incorporated into the interfacial alloy layer, which adversely affects the plating adhesion and the like. From the same viewpoint, the Sr content in the plating film is preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.4% by mass.
  • the abundance ratios of Si and Mg 2 Si in the above-mentioned plating film satisfy the relationship (1), and the plating film is 0.01 to 0.01. Contains 1.0% by mass of Sr. Thereby, the effect of improving the surface appearance by the above-mentioned Sr can be further enjoyed.
  • the cause of this is not clear, but it is presumed that when the amount of Si in the plating film increases, oxidation of the plating surface layer is difficult to be suppressed in the first place, which affects the effect of improving the appearance when Sr is added. ..
  • the molten Al-Zn-Si-Mg-Sr-based plated steel sheet of the present invention contains Zn and unavoidable impurities.
  • the unavoidable impurities contain Fe.
  • This Fe is inevitably contained in the plating bath due to elution of the steel sheet and the equipment in the bath, and is supplied by diffusion from the base steel sheet during the formation of the interfacial alloy layer, and as a result, it is inevitably contained in the plating film. Will be included.
  • the Fe content in the plating film is usually about 0.3 to 2.0% by mass.
  • Other unavoidable impurities include Cr, Ni, Cu and the like.
  • the total content of the unavoidable impurities is not particularly limited, but if it is excessively contained, it may affect various characteristics of the plated steel sheet, so that the total content is preferably 5.0% by mass or less.
  • the plating film can improve the stability of the corrosion product and delay the progress of corrosion in the same manner as the above-mentioned Mg, Cr and Mn in total of 0.01 to 10% by mass.
  • V, Mo, Ti, Ca, Ni, Co, Sb and B are preferably selected from one or more. The reason why the total content of the above-mentioned components is set to 0.01 to 10% by mass is that a sufficient corrosion delay effect can be obtained and the effect is not saturated.
  • the amount of the plating film adhered is preferably 45 to 120 g / m 2 per side from the viewpoint of satisfying various characteristics.
  • the adhesion amount of the plating film is 45 g / m 2 or more, sufficient corrosion resistance can be obtained even for applications that require long-term corrosion resistance such as building materials, and the adhesion amount of the plating film is 120 g / m / m. This is because when m 2 or less, excellent corrosion resistance can be realized while suppressing the occurrence of plating cracks during processing.
  • the amount of the plating film adhered is more preferably 45 to 100 g / m 2 .
  • the amount of the plating film adhered is calculated from the difference in the weight of the steel sheet before and after peeling by dissolving and peeling the plating film of a specific area with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H0401: 2013, for example. Can be derived.
  • it can be determined by sealing with tape so that the plating surface of the non-target surface is not exposed, and then performing the above-mentioned dissolution.
  • the component composition of the plating film can be confirmed, for example, by immersing the plating film in hydrochloric acid or the like to dissolve the plating film, and confirming the solution by ICP emission spectroscopic analysis, atomic absorption spectroscopy, or the like.
  • This method is merely an example, and any method can be used as long as the component composition of the plating film can be accurately quantified, and the method is not particularly limited.
  • the plating film of the molten Al-Zn-Si-Mg-Sr-based plated steel sheet obtained by the present invention has almost the same composition as the plating bath as a whole. Therefore, the composition of the plating film can be controlled accurately by controlling the composition of the plating bath.
  • the base steel sheet constituting the molten Al-Zn-Si-Mg-Sr-based plated steel sheet of the present invention is not particularly limited, and is a cold-rolled steel sheet, a hot-rolled steel sheet, or the like, depending on the required performance and specifications. Can be used as appropriate.
  • the method for obtaining the base steel plate is not particularly limited.
  • a steel sheet that has undergone a hot-rolling step and a pickling step can be used, and in the case of the cold-rolled steel sheet, it can be manufactured by further adding a cold-rolling step.
  • the method for producing the molten Al-Zn-Si-Mg-Sr-based plated steel sheet of the present invention is not particularly limited.
  • it can be manufactured by washing, heating, and immersing the base steel sheet in a plating bath in a continuous hot-dip plating facility.
  • recrystallization annealing is performed to control the structure of the base steel sheet itself, and in order to prevent oxidation of the steel sheet and reduce a trace amount of oxide film existing on the surface, a nitrogen-hydrogen atmosphere, etc. Heating in the reducing atmosphere of is effective.
  • the composition of the plating film is almost the same as the composition of the plating bath as a whole. Therefore, it contains Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass, Mg: 1.0 to 10.0% by mass and Sr: 0.01 to 1.0% by mass, and the balance is from Zn, Fe and unavoidable impurities. Those having the above composition can be used.
  • the bath temperature of the plating bath is not particularly limited, but is preferably in the temperature range of (melting point + 20 ° C.) to 650 ° C.
  • the lower limit of the bath temperature is set to a melting point of + 20 ° C., because the bath temperature must be equal to or higher than the freezing point in order to perform the hot-dip plating treatment. This is to prevent coagulation due to a local decrease in bath temperature.
  • the upper limit of the bath temperature is set to 650 ° C. If the temperature exceeds 650 ° C, rapid cooling of the plating film becomes difficult, and the interfacial alloy layer formed between the plating film and the steel sheet may become thick. Because.
  • the temperature of the base steel plate that penetrates into the plating bath is not particularly limited, but from the viewpoint of ensuring the plating characteristics and preventing the change in the bath temperature in the continuous hot-dip plating operation, the plating bath is described. It is preferable to control the temperature within ⁇ 20 ° C.
  • the immersion time of the steel sheet in the plating bath is 0.5 seconds or more. This is because if it takes less than 0.5 seconds, a sufficient plating film may not be formed on the surface of the base steel sheet.
  • the upper limit of the dipping time is not particularly limited, but it is preferably within 8 seconds because the interfacial alloy layer formed between the plating film and the steel sheet may become thicker if the dipping time is lengthened.
  • the precipitation start temperature of the simple substance Si phase and Mg2Si in the plating film is 500 to 490 ° C for the simple substance Si phase and 520 to 500 ° C for Mg2Si. Therefore, by increasing the residence time in the temperature range of 520 to 500 ° C where only Mg2Si precipitates, the precipitation of Mg2Si is promoted and the precipitation of the simple substance Si phase is suppressed. This is because it is easier to fill.
  • the molten Al-Zn-Si-Mg-Sr-based plated steel sheet can form a coating film on the plating film directly or via an intermediate layer, depending on the required performance.
  • the method for forming the coating film is not particularly limited and can be appropriately selected according to the required performance.
  • a forming method such as roll coater coating, curtain flow coating, spray coating and the like can be mentioned.
  • After painting a paint containing an organic resin it is possible to heat and dry it by means such as hot air drying, infrared heating, and induction heating to form a coating film.
  • the intermediate layer is not particularly limited as long as it is a layer formed between the plating film of the hot-dip galvanized steel sheet and the coating film.
  • the surface-treated steel sheet of the present invention includes a plating film on the surface of the steel sheet and a chemical conversion film formed on the plating film.
  • the composition of the plating film is the same as that of the above-mentioned plating film of the hot-dip Al-Zn-Si-Mg-Sr-based plated steel sheet of the present invention.
  • a chemical conversion film is formed on the above-mentioned plating film.
  • the chemical conversion film may be formed on at least one side of the surface-treated steel sheet, and may be formed on both sides of the surface-treated steel sheet depending on the application and required performance.
  • the chemical conversion film is selected from at least one of epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin.
  • One kind of resin and at least one kind of metal selected from P compound, Si compound, Co compound, Ni compound, Zn compound, Al compound, Mg compound, V compound, Mo compound, Zr compound, Ti compound and Ca compound. It is characterized by containing a compound and.
  • the resin constituting the chemical conversion film is selected from among epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin from the viewpoint of improving corrosion resistance. At least one selected is used. From the same viewpoint, the resin preferably contains at least one of urethane resin and acrylic resin.
  • the resin constituting the chemical conversion film also includes an addition polymer of the above-mentioned resin.
  • the epoxy resin is, for example, a glycidyl etherified epoxy resin such as bisphenol A type, bisphenol F type, or novolak type, or a bisphenol A type epoxy resin to which propylene oxide, ethylene oxide, or polyalkylene glycol is added.
  • a glycidyl etherified product, an aliphatic epoxy resin, an alicyclic epoxy resin, a polyether epoxy resin, or the like can be used.
  • urethane resin for example, an oil-modified polyurethane resin, an alkyd-based polyurethane resin, a polyester-based polyurethane resin, a polyether-based polyurethane resin, a polycarbonate-based polyurethane resin, or the like can be used.
  • acrylic resin for example, polyacrylic acid and its copolymer, polyacrylic acid ester and its copolymer, polymethacrylic acid and its copolymer, polymethacrylic acid ester and its copolymer, urethane-acrylic acid.
  • examples thereof include copolymers (or urethane-modified acrylic resins) and styrene-acrylic acid copolymers, and those obtained by modifying these resins with other alkyd resins, epoxy resins, phenol resins and the like can be used.
  • acrylic silicon resin examples include a resin having a hydrolyzable alkoxysilyl group at the side chain or the end of an acrylic copolymer as a main agent, to which a curing agent is added. Further, when an acrylic silicone resin is used, excellent weather resistance can be expected in addition to corrosion resistance.
  • an oil-modified alkyd resin for example, an oil-modified alkyd resin, a rosin-modified alkyd resin, a phenol-modified alkyd resin, a styrene-modified alkyd resin, a silicon-modified alkyd resin, an acrylic-modified alkyd resin, an oil-free alkyd resin, a high-molecular-weight oil-free alkyd resin, and the like.
  • an oil-modified alkyd resin for example, an oil-modified alkyd resin, a rosin-modified alkyd resin, a phenol-modified alkyd resin, a styrene-modified alkyd resin, a silicon-modified alkyd resin, an acrylic-modified alkyd resin, an oil-free alkyd resin, a high-molecular-weight oil-free alkyd resin, and the like.
  • the polyester resin is a polycondensate synthesized by dehydrating and condensing a polyvalent carboxylic acid and a polyalcohol to form an ester bond.
  • the polyvalent carboxylic acid include terephthalic acid, 2, 6-Naphthalenedicarboxylic acid and the like are used, and examples of the polyalcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like.
  • examples of the polyester include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Further, acrylic-modified polyester resins can also be used.
  • the polyalkylene resin may be, for example, an ethylene-based copolymer such as an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or a carboxyl-modified polyolefin resin, an ethylene-unsaturated carboxylic acid copolymer, or an ethylene-based ionomer. Further, those obtained by modifying these resins with other alkyd resins, epoxy resins, phenol resins and the like can be used.
  • an ethylene-based copolymer such as an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or a carboxyl-modified polyolefin resin, an ethylene-unsaturated carboxylic acid copolymer, or an ethylene-based ionomer.
  • the amino resin is a thermosetting resin produced by the reaction of an amine or an amide compound with an aldehyde, and examples thereof include melamine resin, guanamine resin, and thiourea resin, but from the viewpoint of corrosion resistance, weather resistance, adhesion, and the like. , It is preferable to use a melamine resin.
  • the melamine resin is not particularly limited, and examples thereof include butylated melamine resin, methylated melamine resin, and aqueous melamine resin.
  • fluororesin examples include fluoroolefin polymers and copolymers of fluoroolefins with alkyl vinyl ethers, synchroalkyl vinyl ethers, carboxylic acid-modified vinyl esters, hydroxyalkylallyl ethers, tetrafluoropropyl vinyl ethers and the like. When these fluororesins are used, not only corrosion resistance but also excellent weather resistance and excellent hydrophobicity can be expected.
  • a curing agent for the purpose of improving corrosion resistance and processability.
  • the curing agent include urea resin (butylated urea resin, etc.), melamine resin (butylated melamine resin, butyl etherified melamine resin, etc.), butylated urea / melamine resin, amino resin such as benzoguanamine resin, blocked isocyanate, and oxazoline compound. Phenol resin or the like can be used as appropriate.
  • the metal compounds constituting the chemical conversion film among P compounds, Si compounds, Co compounds, Ni compounds, Zn compounds, Al compounds, Mg compounds, V compounds, Mo compounds, Zr compounds, Ti compounds and Ca compounds. At least one selected from is used. From the same viewpoint, the metal compound preferably contains at least one of a P compound, a Si compound and a V compound.
  • the P compound can be contained in the chemical conversion film to improve corrosion resistance and sweat resistance.
  • the P compound is a compound containing P, and can contain, for example, one or two or more selected from inorganic phosphoric acid, organic phosphoric acid and salts thereof.
  • the inorganic phosphoric acid includes phosphoric acid, primary phosphate, secondary phosphate, tertiary phosphate, pyrophosphoric acid, pyrophosphate, tripolyphosphoric acid, tripolyphosphate, phosphite, and subphosphoric acid. It is preferable to use one or more selected from acid salt, hypophosphite, and hypophosphite.
  • phosphonic acid phosphonic acid compound
  • the phosphonic acid it is preferable to use one or more selected from nitrilotris methylenephosphonic acid, phosphonobtantricarboxylic acid, methyldiphosphonic acid, methylenephosphonic acid, and ethylidene diphosphonic acid.
  • the salt is preferably a salt of Group 1 to Group 13 elements in the periodic table, more preferably a metal salt, and an alkali metal salt and an alkaline earth. It is preferably one or more selected from among the metal salts.
  • the chemical conversion treatment liquid containing the above P compound When the chemical conversion treatment liquid containing the above P compound is applied to a molten Al-Zn-Si-Mg-based plated steel sheet, the surface of the plating film is etched by the action of the P compound, and Al, Zn, which are constituent elements of the plating film, A concentrated layer in which Si and Mg are incorporated is formed on the plating film side of the chemical conversion film. By forming the concentrated layer, the bond between the chemical conversion film and the surface of the plating film is strengthened, and the adhesion of the chemical conversion film is improved.
  • the concentration of the P compound in the chemical conversion treatment liquid is not particularly limited, but may be 0.25% by mass to 5% by mass.
  • the concentration of the P compound is less than 0.25% by mass, the etching effect is insufficient and the adhesion to the plating interface is lowered, not only the corrosion resistance of the flat surface portion is lowered, but also the plating generated in the defective portion, the cut end face portion, the processing, etc. Corrosion resistance and sweat resistance of damaged parts of the film may also decrease.
  • the concentration of the P compound is preferably 0.35% by mass or more, more preferably 0.50% by mass or more.
  • the concentration of the P compound exceeds 5% by mass, not only the life of the chemical conversion treatment liquid is shortened, but also the appearance when the film is formed tends to be uneven, and the amount of P eluted from the chemical conversion film.
  • the concentration of the P compound is preferably 3.5% by mass or less, more preferably 2.5% by mass or less.
  • the content of the P compound in the chemical conversion film for example, by applying and drying a chemical conversion treatment solution having a concentration of the P compound of 0.25% by mass to 5% by mass, P adheres to the chemical conversion film after drying.
  • the amount can be 5 to 100 mg / m 2 .
  • the Si compound is a component that forms a skeleton that forms a chemical conversion film together with the resin, and can enhance the affinity with the plating film and uniformly form the chemical conversion film.
  • the Si compound is a compound containing Si, and preferably contains, for example, one or more selected from silica, trialkoxysilane, tetraalkoxysilane, and a silane coupling agent.
  • the silica is not particularly limited and any silica can be used.
  • the silica for example, at least one of wet silica and dry silica can be used.
  • the colloidal silica which is a kind of the wet silica for example, Snowtex O, C, N, S, 20, OS, OXS, NS and the like manufactured by Nissan Chemical Industries, Ltd. can be preferably used.
  • the dry silica for example, AEROSIL 50, 130, 200, 300, 380 manufactured by Nippon Aerosil Co., Ltd. can be preferably used.
  • trialkoxysilane any one can be used without particular limitation.
  • the general formula: R 1 Si (OR 2 ) 3 (in the formula, R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R 2 is an alkyl group having the same or different carbon atoms of 1 to 5 carbon atoms. ) Is preferably used.
  • Examples of such trialkoxysilanes include trimethoxysilane, triethoxysilane, and methyltriethoxysilane.
  • tetraalkoxysilane any one can be used without particular limitation.
  • R is an alkyl group having the same or different carbon atoms of 1 to 5.
  • tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.
  • any one can be used without particular limitation.
  • the Si compound By containing the Si compound in the chemical conversion film, the Si compound is dehydrated and condensed to form an amorphous chemical conversion film having a siloxane bond having a high barrier effect that shields the corrosive factor. Further, by binding with the above-mentioned resin, a chemical conversion film having a higher barrier property is formed. Furthermore, in a corroded environment, dense and stable corrosion products are formed in the defective parts and damaged parts of the plating and film caused by processing, and the combined effect with the plating film also has the effect of suppressing the corrosion of the underlying steel sheet. be. From the viewpoint of having a high effect of forming a stable corrosion product, it is preferable to use at least one of colloidal silica and dry silica as the Si compound.
  • the concentration of the Si compound in the chemical conversion treatment liquid for forming the chemical conversion film is 0.2% by mass to 9.5% by mass.
  • concentration of the Si compound in the chemical conversion treatment liquid is 0.2% by mass or more, the barrier effect due to the siloxane bond can be obtained, and as a result, in addition to the corrosion resistance of the flat surface portion, the damage caused by the defective portion, the cut portion, the processing and the like can be obtained. Corrosion resistance and sweat resistance in the part are improved.
  • the concentration of the Si compound is 9.5% by mass or less, the life of the chemical conversion treatment liquid can be extended.
  • the Co compound and the Ni compound can be contained in the chemical conversion film to improve blackening resistance. It is considered that this is because Co and Ni have the effect of delaying the elution of the water-soluble component from the film in a corrosive environment. Further, the Co and the Ni are elements that are less likely to be oxidized than Al, Zn, Si, Mg and the like. Therefore, by concentrating at least one of the Co compound and the Ni compound at the interface between the chemical conversion film and the plating film (forming a concentrated layer), the concentrated layer becomes a barrier against corrosion. As a result, blackening resistance can be improved.
  • Co By using a chemical conversion treatment liquid containing the Co compound, Co can be contained in the chemical conversion film and incorporated into the concentrated layer. It is preferable to use a cobalt salt as the Co compound. As the cobalt salt, it is more preferable to use 1 or 2 or more selected from cobalt sulfate, cobalt carbonate and cobalt chloride. Further, by using a chemical conversion treatment liquid containing the Ni compound, Ni can be contained in the chemical conversion film and incorporated into the concentrated layer. It is preferable to use a nickel salt as the Ni compound. As the nickel salt, it is more preferable to use 1 or 2 or more selected from nickel sulfate, nickel carbonate and nickel chloride.
  • the concentration of the Co compound and / or the Ni compound in the chemical conversion treatment liquid is not particularly limited, but may be 0.25% by mass to 5% by mass in total.
  • concentration of the Co compound and / or the Ni compound is less than 0.25% by mass, the interfacial concentrated layer becomes non-uniform, and not only the corrosion resistance of the flat surface portion is lowered, but also the plating caused by the defective portion, the cut end face portion, the processing, etc. And the corrosion resistance of the damaged part of the film may also decrease. From the same viewpoint, it is preferably 0.5% by mass or more, more preferably 0.75% by mass or more.
  • the concentration of the Co compound and / or the Ni compound exceeds 5% by mass, the appearance when the film is formed tends to be non-uniform, and the corrosion resistance may decrease. From the same viewpoint, it is preferably 4.0% by mass or less, more preferably 3.0% by mass or less.
  • a chemical conversion treatment solution having a total concentration of the Co compound and / or Ni compound of 0.25% by mass to 5% by mass, the total amount of Co and Ni adhered to the dried chemical conversion film is 5 to 100 mg. Can be / m 2 .
  • a concentrated layer containing at least one of Al, Zn and Mg can be formed on the plating film side of the chemical conversion coating. ..
  • the formed concentrated layer can improve the corrosion resistance.
  • the Al compound, the Zn compound, and the Mg compound are not particularly limited as long as they are compounds containing Al, Zn, and Mg, respectively, but are preferably inorganic compounds, and salts, chlorides, and the like. It is preferably an oxide or a hydroxide.
  • Examples of the Al compound include one or more selected from aluminum sulfate, aluminum carbonate, aluminum chloride, aluminum oxide and aluminum hydroxide.
  • Examples of the Zn compound include one or more selected from zinc sulfate, zinc carbonate, zinc chloride, zinc oxide and zinc hydroxide.
  • Examples of the Mg compound include one or more selected from magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium oxide and magnesium hydroxide.
  • the concentration of the Al compound, Zn compound and / or Mg compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.25% by mass to 5% by mass in total.
  • the total concentration is 0.25% by mass or more, the concentrated layer can be formed more effectively, and as a result, the corrosion resistance can be further improved.
  • the total concentration is 5% by mass or less, the appearance of the chemical conversion film becomes more uniform, and the corrosion resistance of the flat surface portion, the defective portion, the damaged portion of the plating or the film caused by processing, etc. is further improved.
  • V When the V compound is contained in the chemical conversion film, V is appropriately eluted in a corrosive environment and combined with zinc ions and the like of plating components that are also eluted in a corrosive environment to form a dense protective film. ..
  • the formed protective film can further enhance the corrosion resistance not only to the flat surface portion of the steel sheet but also to the defective portion, the damaged portion of the plating film caused by processing, the corrosion progressing from the cut end face to the flat surface portion, and the like.
  • the V compound is a V-containing compound, and examples thereof include one or more selected from sodium metavanadate, vanadyl sulfate, and vanadium acetylacetonate.
  • the V compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.05% by mass to 4% by mass.
  • concentration of the V compound is 0.05% by mass or more, it is easy to elute in a corrosive environment to form a protective film, and the corrosion resistance of the defective part, the cut end face part, and the damaged part of the plating film caused by processing is improved. improves.
  • concentration of the V compound exceeds 4% by mass, the appearance when the chemical conversion film is formed tends to be non-uniform, and the blackening resistance is also lowered.
  • the Mo compound is a compound containing Mo and can be obtained by adding one or both of molybdic acid and molybdate to the chemical conversion treatment liquid.
  • the molybdate include one or more selected from sodium molybdate, potassium molybdate, magnesium molybdate, and zinc molybdate.
  • the concentration of the Mo compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.01% by mass to 3% by mass.
  • concentration of the Mo compound is 0.01% by mass or more, the formation of oxygen-deficient zinc oxide is further suppressed, and the blackening resistance can be further improved.
  • concentration of the Mo compound is 3% by mass or less, the life of the chemical conversion treatment liquid is further extended, and the corrosion resistance can be further improved.
  • the corrosion factor is less likely to permeate the chemical conversion film, and the corrosion resistance can be improved.
  • the Zr compound is a compound containing Zr, and for example, one or more selected from zirconyl acetate, zirconyl sulfate, potassium zirconyl carbonate, sodium zirconyl carbonate and ammonium zirconyl carbonate can be used.
  • the organic titanium chelate compound is suitable because when the chemical conversion treatment liquid is dried to form a film, the film is densified and more excellent corrosion resistance can be obtained.
  • the Ti compound is a compound containing Ti, and is one or more selected from, for example, titanium sulfate, titanium chloride, titanium hydroxide, titanium acetylacetonate, titanium octylene glycolate, and titanium ethylacetoacetate. Can be used.
  • the concentration of the Zr compound and / or the Ti compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.2% by mass to 20% by mass in total.
  • the concentration of the Zr compound and / or the Ti compound is 0.2% by mass or more, the effect of suppressing the permeation of the corrosive factor is enhanced, and not only the corrosion resistance of the flat surface portion but also the defect portion, the cut end face portion, and the plating film damage due to processing are damaged. The corrosion resistance of the part can be further improved.
  • the total concentration of the Zr compound and / or the Ti compound is 20% by mass or less, the life of the chemical conversion treatment liquid can be further extended.
  • the Ca compound is a compound containing Ca, and examples thereof include an oxide of Ca, a nitrate of Ca, a sulfate of Ca, and an intermetallic compound containing Ca. More specifically, examples of the Ca compound include CaO, CaCO 3 , Ca (OH) 2 , Ca (NO 3 ) 2.4H 2 O, CaSO 4.2H 2 O and the like.
  • the content of the Ca compound in the chemical conversion film is not particularly limited.
  • the chemical conversion film can contain various known components usually used in the paint field, if necessary.
  • various surface conditioners such as leveling agents and defoamers, dispersants, anti-settling agents, ultraviolet absorbers, light stabilizers, silane coupling agents, various additives such as titanate coupling agents, coloring pigments, and extender pigments.
  • Various pigments such as bright materials, curing catalysts, organic solvents, lubricants and the like.
  • the chemical conversion film does not contain harmful components such as hexavalent chromium, trivalent chromium and fluorine. This is because the chemical conversion treatment liquid for forming the chemical conversion film does not contain these harmful components, so that the safety is high and the amount is small to the environment.
  • the amount of the chemical conversion film adhered is not particularly limited.
  • the adhesion amount of the chemical conversion film is preferably 0.1 to 3.0 g / m 2 , preferably 0.5 to 2.5 g / m 2 . It is more preferable to do so. Corrosion resistance can be ensured more reliably by setting the adhesion amount of the chemical conversion film to 0.1 g / m 2 or more, and cracking or peeling of the chemical conversion film by setting the adhesion amount of the chemical conversion film to 3.0 g / m 2 or less. Can be prevented.
  • the amount of the chemical conversion film adhered may be obtained by a method appropriately selected from existing methods such as a method of measuring the abundance of an element whose content in the film is known in advance by fluorescent X-ray analysis of the film. ..
  • the method for forming the chemical conversion film is not particularly limited, and can be appropriately selected according to the required performance, manufacturing equipment, and the like.
  • a chemical conversion treatment liquid is continuously applied onto the plating film with a roll coater or the like, and then, using hot air or induction heating, the plate temperature reaches about 60 to 200 ° C. (Peak Metal Temperature: PMT). It can be formed by drying.
  • PMT Peak Metal Temperature
  • a known method such as an airless spray, an electrostatic spray, a curtain flow coater or the like can be appropriately adopted in addition to the roll coater.
  • the chemical conversion film may be either a single-layer film or a multi-layer film as long as it contains the resin and the metal compound, and is not particularly limited.
  • the surface-treated steel sheet of the present invention can also form a coating film on the chemical conversion film, if necessary.
  • the coated steel sheet of the present invention is a coated steel sheet in which a coating film is formed directly on the plating film or via a chemical conversion film.
  • the composition of the plating film is the same as that of the above-mentioned plating film of the hot-dip Al-Zn-Si-Mg-Sr-based plated steel sheet of the present invention.
  • the coated steel sheet of the present invention can form a chemical conversion film on the plating film.
  • the chemical conversion film may be formed on at least one side of the coated steel sheet, and may be formed on both sides of the coated steel sheet depending on the application and required performance.
  • the chemical conversion film contains (a): an anionic polyurethane resin having an ester bond and (b): an epoxy resin having a bisphenol skeleton in a total amount of 30 to 50% by mass.
  • a resin component having a content ratio ((a): (b)) of a) and the (b) in the range of 3:97 to 60:40 by mass ratio, and a vanadium compound of 2 to 10% by mass, 40 to It is characterized by containing an inorganic compound containing 60% by mass of a zirconium compound and 0.5 to 5% by mass of a fluorine compound.
  • the resin component constituting the chemical conversion film contains (a): an anionic polyurethane resin having an ester bond and (b): an epoxy resin having a bisphenol skeleton.
  • the anionic polyurethane resin having the (a) ester bond a resin obtained by copolymerizing a polyester polyol with a diisocyanate or a polyisocyanate having two or more isocyanate groups and a dimethylolalkyl acid is obtained.
  • a chemical conversion treatment liquid can be obtained by dispersing it in a liquid such as water by a known method.
  • the polyester polyol includes a polyester obtained by a dehydration condensation reaction from a glycol component and an acid component such as an ester-forming derivative of hydroxylcarboxylic acid, a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone, and these.
  • Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylene diisocyanate, diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2-diphenylmethane diisocyanate, and triphenyl.
  • aromatic polyisocyanate examples include methanetriisocyanate, polymethylene polyphenyl polyisocyanate, naphthalenediocyanate, and derivatives thereof (for example, prepolymers obtained by reaction with polyols, modified polyisocyanates such as carbodiimide compounds of diphenylmethane diisocyanate, etc.).
  • dimethylolalkyl acid examples include dimethylolalkyl acids having 2 to 6 carbon atoms, and more specifically, dimethylolethaneic acid, dimethylolpropaneic acid, dimethylolbutanoic acid, and dimethylolheptan. Acids and dimethylolhexaneic acid and the like can be mentioned.
  • the epoxy resin having the (b) bisphenol skeleton a known epoxy resin can be used.
  • a known epoxy resin can be used.
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin and the like can be mentioned.
  • These epoxy resins can be obtained by reacting bisphenol compounds such as bisphenol A, bisphenol F, bisphenol AD, and bisphenol S with epichlorohydrin in the presence of an alkaline catalyst.
  • the component [A] preferably contains a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, and more preferably contains a bisphenol A type epoxy resin.
  • the epoxy resin having the (b) bisphenol skeleton can be dispersed in a liquid such as water by a known method to obtain a chemical conversion treatment liquid.
  • the resin component acts as a binder for the chemical conversion film, but the anionic polyurethane resin having the (a) ester bond constituting the binder is flexible, so that the chemical conversion film is destroyed when processed ().
  • the effect of making it difficult to peel off) can be achieved, and the epoxy resin having the bisphenol skeleton described in (b) can have the effect of improving the adhesion to the underlying zinc-based plated steel plate and the upper primer coating film.
  • the resin component is contained in the chemical conversion film in a total amount of 30 to 50% by mass. If the content of the resin component is less than 30% by mass, the binder effect of the chemical conversion film is lowered, and if it exceeds 50% by mass, the function of the inorganic component shown below, for example, the inhibitory action is lowered. From the same viewpoint, the content of the resin component in the chemical conversion film is preferably 35 to 45% by mass.
  • the content ratio ((a): (b)) of the anionic polyurethane resin having the (a) ester bond and the epoxy resin having the (b) bisphenol skeleton is 3:97 by mass ratio. It must be in the range of ⁇ 60: 40. This is because when the above (a): (b) is out of the above range, sufficient corrosion resistance cannot be obtained due to a decrease in flexibility and adhesion as a chemical conversion coating film. From the same viewpoint, the above (a): (b) is preferably 10:90 to 55:45.
  • the resin component includes a resin (other resin component) other than the above-mentioned (a) anionic polyurethane resin having an ester bond and (b) an epoxy resin having a bisphenol skeleton, depending on the required performance. be able to.
  • the other resin components are not particularly limited, and are, for example, at least one or two or more selected from acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin. Can be used in combination.
  • the total content of the (a) anionic polyurethane resin having an ester bond and the (b) epoxy resin having a bisphenol skeleton is preferably 50% by mass or more. It is more preferably 75% by mass or more. This is to ensure that the flexibility and adhesion of the film to be treated are reduced.
  • the chemical conversion film contains 2 to 10% by mass of vanadium compound, 40 to 60% by mass of zirconium compound and 0.5 to 5% by mass of fluorine compound as inorganic compounds. By including these compounds, the corrosion resistance of the chemical conversion film can be enhanced.
  • the vanadium compound is added to the chemical conversion treatment liquid and acts as a rust preventive (inhibitor).
  • the vanadium compound is contained in the chemical conversion film, the vanadium compound is appropriately eluted in a corrosive environment and combined with zinc ions or the like of a plating component that also elutes in a corrosive environment to form a dense protective film. ..
  • the formed protective film can further enhance the corrosion resistance not only to the flat surface portion of the steel sheet but also to the defective portion, the damaged portion of the plating film caused by processing, the corrosion progressing from the cut end face to the flat surface portion, and the like.
  • vanadium compound examples include vanadium pentoxide, metavanadic acid, ammonium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, magnesium vanadate, vanadyl acetylacetonate, and vanadium acetylacetonate.
  • vanadium pentoxide metavanadic acid
  • ammonium metavanadate vanadium oxytrichloride
  • vanadium trioxide vanadium dioxide
  • magnesium vanadate vanadyl acetylacetonate
  • vanadium acetylacetonate vanadium acetylacetonate
  • the content of the vanadium compound in the chemical conversion treatment film is 2 to 10% by mass. If the content of the vanadium compound in the chemical conversion coating is less than 2% by mass, the inhibitory effect is not sufficient, resulting in a decrease in corrosion resistance. On the other hand, if the content of the vanadium compound exceeds 10% by mass, the moisture resistance of the chemical conversion coating is reduced. This is because it causes a decrease in.
  • the zirconium compound is contained in the chemical conversion coating, and can be expected to improve the strength and corrosion resistance of the chemical conversion coating by reacting with the plating metal and coexisting with the resin component. Furthermore, the zirconium compound itself is a dense chemical conversion coating. It contributes to the formation of zirconium and is rich in coating properties, so a barrier effect can be expected. Examples of the zirconium compound include neutralizing salts such as zirconium sulfate, zirconium carbonate, zirconium nitrate, zirconium lactate, zirconium acetate, and zirconium chloride.
  • the content of the zirconium compound in the chemical conversion treatment film is 40 to 60% by mass. If the content of the zirconium compound in the chemical conversion coating is less than 40% by mass, the strength and corrosion resistance of the chemical conversion coating are deteriorated, and if the content of the zirconium compound exceeds 60% by mass, the chemical conversion coating is brittle. This is because the chemical conversion treatment film is destroyed or peeled off when it is subjected to severe processing.
  • the fluorine compound is contained in the chemical conversion film and acts as an adhesive-imparting agent with the plating film. As a result, it is possible to improve the corrosion resistance of the chemical conversion film.
  • a fluoride salt such as an ammonium salt, a sodium salt or a potassium salt, or a fluorine compound such as ferrous fluoride or ferric fluoride can be used. Among these, it is preferable to use ammonium fluoride or a fluoride salt such as sodium fluoride and potassium fluoride.
  • the content of the fluorine compound in the chemical conversion treatment film is 0.5 to 5% by mass. If the content of the fluorine compound in the chemical conversion treatment film is less than 0.5% by mass, sufficient adhesion at the processed portion cannot be obtained, and if the content of the fluorine compound exceeds 5% by mass, the moisture resistance of the chemical conversion treatment film becomes high. This is because it decreases.
  • the amount of the chemical conversion film adhered is not particularly limited.
  • the amount of the chemical conversion film adhered may be obtained by a method appropriately selected from existing methods such as a method of measuring the abundance of an element whose content in the film is known in advance by fluorescent X-ray analysis of the film. ..
  • the method for forming the chemical conversion film is not particularly limited, and can be appropriately selected according to the required performance, manufacturing equipment, and the like.
  • a chemical conversion treatment liquid is continuously applied onto the plating film with a roll coater or the like, and then, using hot air or induction heating, the plate temperature reaches about 60 to 200 ° C. (Peak Metal Temperature: PMT). It can be formed by drying.
  • PMT Peak Metal Temperature
  • a known method such as an airless spray, an electrostatic spray, a curtain flow coater or the like can be appropriately adopted in addition to the roll coater.
  • the chemical conversion film may be either a single-layer film or a multi-layer film as long as it contains the resin and the metal compound, and is not particularly limited.
  • the coated steel sheet of the present invention has a coating film formed on the plating film directly or via a chemical conversion film, and the coating film has at least a primer coating film.
  • the primer coating film contains a polyester resin having a urethane bond and an inorganic compound containing a vanadium compound, a phosphoric acid compound and magnesium oxide.
  • the primer coating film contains a polyester resin having a urethane bond as a main component. Since the polyester resin having a urethane bond has both flexibility and strength, it is possible to obtain an effect that cracks are less likely to occur in the primer coating film when it is processed, and a chemical conversion treatment film containing a urethane resin. Since it has a high affinity with, it can contribute to the improvement of corrosion resistance of the processed portion.
  • the term "main component" as used herein means that the component has the highest content among the components in the primer coating film.
  • polyester resin having a urethane bond a known resin such as a resin obtained by reacting a polyester polyol with a diisocyanate or a polyisocyanate having two or more isocyanate groups can be used. Further, a resin obtained by reacting the polyester polyol with the diisocyanate or the polyisocyanate in a state of excess hydroxylate (urethane-modified polyester resin) and cured with a blocked polyisocyanate can also be used.
  • the polyester polyol can be obtained by a known method using a dehydration condensation reaction between a polyhydric alcohol component and a polybasic acid component.
  • the polyhydric alcohol include glycols and trihydric or higher polyhydric alcohols.
  • the glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butanediol, 1,4.
  • a polyvalent carboxylic acid is usually used, but a monovalent fatty acid or the like can be used in combination if necessary.
  • the polyvalent carboxylic acid include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid, trimellitic acid, and the like.
  • polyisocyanate for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and xylylene diisocyanate (XDI), metaxylylene diisocyanate, tolylene diisocyanate (TDI), 4, 4 -Aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), cyclic aliphatic diisocyanates such as isophorone diisocyanate, hydride XDI, hydride TDI, hydride MDI, and adducts, biurets, isocyanurates and the like thereof. Will be. These polyisocyanates can be used alone or in combination of two or more.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and
  • the hydroxyl value of the polyester resin having a urethane bond is not particularly limited, but is preferably 5 to 120 mgKOH / g, more preferably 7 to 100 mgKOH / g from the viewpoint of solvent resistance, processability, and the like. It is g, more preferably 10 to 80 mgKOH / g. Further, the number average molecular weight of the polyester resin having a urethane bond is preferably 500 to 15,000, more preferably 700 to 12,000, still more preferably 800 to 10,000 from the viewpoint of solvent resistance, processability and the like. Is.
  • the content of the polyester resin having a urethane bond in the primer coating film is preferably 40 to 88% by mass. If the content of the polyester resin having a urethane bond is less than 40% by mass, the binder function as a primer coating film may be deteriorated, while if the content of the polyester resin having a urethane bond exceeds 88% by mass, the binder function may be deteriorated.
  • the functions of the following inorganic substances, such as inhibitory action, may be reduced.
  • the vanadium compound which is one of the inorganic compounds, acts as an inhibitor.
  • the vanadium compound include vanadium pentoxide, metavanadic acid, ammonium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, magnesium vanadate, vanadyl acetylacetonate, and vanadium acetylacetonate.
  • the vanadium compound added to the primer coating film may be the same as or different from the vanadium compound added to the chemical conversion treatment film.
  • vanazic acid compound vanadic acid ions that gradually elute to the moisture that invades from the outside react with the ions on the surface of the galvanized steel sheet to form a passivation film with good adhesion, which protects and prevents exposed metal parts. It is believed that rusting is manifested.
  • the content of the vanadium compound in the primer coating film is not particularly limited, but is preferably 4 to 20% by mass from the viewpoint of achieving both corrosion resistance and moisture resistance. If the content of the vanadium compound is less than 4% by mass, the inhibitory effect may be lowered and the corrosion resistance may be lowered, and if the content of the vanadium compound is more than 20% by mass, the moisture resistance of the primer coating film may be lowered. There is a risk.
  • the phosphoric acid compound which is one of the inorganic compounds, also acts as an inhibitor.
  • the phosphoric acid compound for example, phosphoric acid, an ammonium salt of phosphoric acid, an alkali metal salt of phosphoric acid, an alkaline earth metal salt of phosphoric acid and the like can be used.
  • an alkali metal salt of phosphoric acid such as calcium phosphate can be preferably used.
  • the content of the phosphoric acid compound in the primer coating film is not particularly limited, but is preferably 4 to 20% by mass from the viewpoint of achieving both corrosion resistance and moisture resistance. If the content of the phosphoric acid compound is less than 4% by mass, the inhibitory effect may be lowered and the corrosion resistance may be lowered, and if the content of the phosphoric acid compound is more than 20% by mass, the moisture resistance of the primer coating film may be lowered. May be invited.
  • Magnesium oxide which is one of the above-mentioned inorganic compounds, produces a product containing Mg by initial corrosion, and has the effect of stabilizing as a sparingly soluble magnesium salt and improving corrosion resistance.
  • the content of the magnesium oxide in the primer coating film is not particularly limited, but is preferably 4 to 20% by mass from the viewpoint of achieving both corrosion resistance and corrosion resistance of the processed portion. If the magnesium oxide content is less than 4% by mass, the effect may be lowered and the corrosion resistance may be lowered, and if the magnesium oxide content is more than 20% by mass, the flexibility of the primer coating film may be deteriorated. The corrosion resistance of the processed portion may decrease due to the decrease in the amount of
  • the primer coating film may contain components other than the polyester resin having a urethane bond and the inorganic compound described above.
  • a cross-linking agent used when forming a primer coating film can be mentioned.
  • the cross-linking agent reacts with the polyester resin having a urethane bond to form a cross-linked coating film, and is, for example, an oxazoline compound, an epoxy compound, a melamine compound, an isocyanate-based compound, a carbodiimide-based compound, a silane coupling compound, or the like. It is also possible to use two or more kinds of cross-linking agents in combination.
  • a blocked polyisocyanate compound or the like can be preferably used from the viewpoint of corrosion resistance of the processed portion of the obtained coated steel sheet.
  • the blocked polyisocyanate include alcohols such as butanol, oximes such as methylethylketooxime, lactams such as ⁇ -caprolactam, and diketones such as acetoacetic acid diester, using the isocyanate group of the polyisocyanate compound.
  • examples thereof include those blocked by imidazoles such as imidazole and 2-ethylimidazole, or phenols such as m-cresol.
  • the primer coating film may contain various known components usually used in the paint field, if necessary.
  • various surface conditioners such as leveling agents and defoamers, dispersants, anti-sedimentants, ultraviolet absorbers, light stabilizers, silane coupling agents, various additives such as titanate coupling agents, etc.
  • various pigments such as coloring pigments and extender pigments, bright materials, curing catalysts, and organic solvents.
  • the thickness of the primer coating film is preferably 1.5 ⁇ m or more. By setting the thickness of the primer coating film to 1.5 ⁇ m or more, it is possible to more reliably obtain the effect of improving corrosion resistance and the effect of improving the adhesion with the chemical conversion treatment film or the top coat film formed on the primer coating film. Because it can be done.
  • the method for forming the primer coating film is not particularly limited. Further, as for the coating method of the coating composition constituting the primer coating film, the coating composition can be preferably applied by a method such as roll coater coating or curtain flow coating. After the coating composition is coated, it can be baked by heating means such as hot air heating, infrared heating, and induction heating to obtain a primer coating film. The baking treatment is usually carried out at a maximum plate temperature of about 180 to 270 ° C., and can be performed in this temperature range for about 30 seconds to 3 minutes.
  • a topcoat coating film is further formed on the primer coating film.
  • the topcoat coating film can impart aesthetics such as color, luster, and surface condition to the coated steel sheet, and also has various performances such as workability, weather resistance, chemical resistance, stain resistance, water resistance, and corrosion resistance. Can be enhanced.
  • the composition of the topcoat coating film is not particularly limited, and the material, thickness, and the like can be appropriately selected according to the required performance.
  • the topcoat coating film can be formed by using a polyester resin-based paint, a silicon polyester resin-based paint, a polyurethane resin-based paint, an acrylic resin-based paint, a fluororesin-based paint, or the like.
  • the top coat is a titanium oxide, a valve handle, mica, carbon black or various other coloring pigments; metallic pigments such as aluminum powder and mica; extender pigments composed of carbonates and sulfates; silica fine particles and nylon resins.
  • Various fine particles such as beads and acrylic resin beads; a curing catalyst such as p-toluenesulfonic acid and dibutyltin dilaurate; wax; and other additives can be contained in an appropriate amount.
  • the thickness of the topcoat coating film is preferably 5 to 30 ⁇ m from the viewpoint of achieving both appearance and processability.
  • the thickness of the topcoat coating film is 5 ⁇ m or more, the color tone appearance can be more reliably stabilized, and when the thickness of the topcoat coating film is 30 ⁇ m or less, the workability is deteriorated (topcoat coating). The generation of cracks in the film) can be suppressed more reliably.
  • the coating method of the coating composition for forming the topcoat coating film is not particularly limited.
  • the coating composition can be applied by a method such as roll coater coating or curtain flow coating. After the coating composition is coated, it can be baked by heating means such as hot air heating, infrared heating, and induction heating to form a topcoat coating film.
  • the baking treatment is usually carried out with a maximum plate temperature of about 180 to 270 ° C. and about 30 seconds to 3 minutes in this temperature range.
  • Samples 1 to 44> A cold-rolled steel sheet with a thickness of 0.8 mm manufactured by a conventional method is used as a base steel sheet, and annealing and plating are performed with a hot-dip plating simulator manufactured by Resuka Co., Ltd. to obtain hot-dip plated steel sheets under the conditions shown in Table 1.
  • Samples 1-44 were prepared. Regarding the composition of the plating bath used for manufacturing the hot-dip plated steel sheet, the composition of the plating bath was Al: 30 to 75% by mass and Si: 0.5 to 4.5 so as to be the composition of the plating film of each sample shown in Table 1. It was varied in the range of% by mass, Mg: 0 to 10% by mass, and Sr: 0.00 to 0.15% by mass.
  • the bath temperature of the plating bath is 590 ° C when Al: 30 to 60% by mass and 630 ° C when Al: more than 60% by mass, and the plating penetration plate temperature of the base steel sheet is the same as the plating bath temperature. It was controlled to be. Furthermore, the plating treatment was carried out under the condition that the plate temperature was cooled to a temperature range of 520 to 500 ° C. in 3 seconds. The amount of the plating film adhered was controlled to be 85 ⁇ 5 g / m 2 per side for the samples 1 to 41 and 51 to 125 g / m 2 per side for the samples 42 to 44.
  • composition of plating film (adhesion amount, composition, X-ray diffraction intensity)
  • punch 100 mm ⁇ seal the non-measurement surface with tape, then dissolve and peel the plating with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H 0401: 2013, and the mass of the sample before and after peeling. From the difference, the amount of adhesion of the plating film was calculated. Table 1 shows the amount of adhesion of the plating film obtained as a result of the calculation. Then, the stripping solution was filtered, and the filtrate and solid content were analyzed respectively. Specifically, components other than insoluble Si were quantified by ICP emission spectroscopic analysis of the filtrate.
  • the solid content was dried and incinerated in a heating furnace at 650 ° C., and then melted by adding sodium carbonate and sodium tetraborate. Furthermore, insoluble Si was quantified by dissolving the melt with hydrochloric acid and ICP emission spectroscopic analysis of the solution.
  • the Si concentration in the plating film is the sum of the soluble Si concentration obtained by the filtrate analysis and the insoluble Si concentration obtained by the solid content analysis. Table 1 shows the composition of the plating film obtained as a result of the calculation.
  • the plating film on the evaluation symmetric plane is mechanically scraped until the underlying steel plate appears, the obtained powder is mixed well, and then 0.3 g is taken out and X is taken out.
  • the diffraction intensity of d 0.3135 nm) was measured. The measurement results are shown in Table 1.
  • Corrosion loss of 3 samples is 45 g / m 2 or less ⁇ : Corrosion loss of 3 samples is 70 g / m 2 or less ⁇ : Corrosion loss of 1 sample or more exceeds 70 g / m 2
  • each sample of the example of the present invention is superior to each sample of the comparative example in terms of corrosion resistance, surface appearance, processability, and bath stability in a well-balanced manner.
  • Example 2 Samples 1-112> (1) Plating shown in Tables 3 and 4 is performed by using a cold-rolled steel sheet with a thickness of 0.8 mm manufactured by a conventional method as a base steel sheet and performing an annealing treatment and a plating treatment with a hot-dip plating simulator manufactured by Resuka Co., Ltd. A sample of a hot-dip plated steel sheet with film conditions was prepared. Regarding the composition of the plating bath used for manufacturing the hot-dip plated steel sheet, the composition of the plating bath was Al: 30 to 75% by mass and Si: 0.5 to 4.5 so as to be the composition of the plating film of each sample shown in Table 2.
  • the bath temperature of the plating bath is 590 ° C when Al: 30 to 60% by mass and 630 ° C when Al: more than 60% by mass, and the plating penetration plate temperature of the base steel sheet is the same as the plating bath temperature. It was controlled to be. Furthermore, the plating treatment was carried out under the condition that the plate temperature was cooled to a temperature range of 520 to 500 ° C. in 3 seconds.
  • the amount of the plating film adhered was controlled to be 85 ⁇ 5 g / m 2 per side for samples 1 to 82 and 95 to 112, and 51 to 125 g / m 2 per side for samples 83 to 94.
  • a chemical conversion treatment liquid is applied on the plating film of each sample of the prepared hot-dip galvanized steel sheet with a bar coater, and dried in a hot air furnace (heating rate: 60 ° C / s, PMT: 120 ° C).
  • a chemical conversion film was formed in 1 and each sample of the surface-treated steel sheet shown in Tables 3 and 4 was prepared.
  • the chemical conversion treatment liquid surface treatment liquids A to F in which each component was dissolved in water as a solvent were prepared.
  • each component (resin, metal compound) contained in the surface treatment liquid are as follows.
  • Urethane resin Superflex 130, Superflex 126 (Daiichi Kogyo Seiyaku Co., Ltd.)
  • Acrylic resin Boncoat EC-740EF (DIC Corporation)
  • Metal compound P compound: aluminum dihydrogen dihydrogen tripolyphosphate Si compound: silica
  • V compound sodium metavanadate Mo compound: molybdic acid
  • Zr compound Zirconyl potassium carbonate
  • Table 2 shows the compositions of the prepared chemical conversion treatment liquids A to F and the amount of the formed chemical conversion film adhered.
  • the concentration of each component in Table 2 of the present specification is the concentration of solid content (mass%).
  • composition of plating film (adhesion amount, composition, X-ray diffraction intensity)
  • 100 mm ⁇ is punched out, the non-measurement surface is sealed with tape, and then the plating is melted and peeled off with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H 0401: 2013.
  • the amount of adhesion of the plating film was calculated from the mass difference.
  • the amount of adhesion of the obtained plating film is shown in Tables 3 and 4. Then, the stripping solution was filtered, and the filtrate and solid content were analyzed respectively.
  • components other than insoluble Si were quantified by ICP emission spectroscopic analysis of the filtrate.
  • the solid content was dried and incinerated in a heating furnace at 650 ° C., and then melted by adding sodium carbonate and sodium tetraborate.
  • insoluble Si was quantified by dissolving the melt with hydrochloric acid and ICP emission spectroscopic analysis of the solution.
  • the Si concentration in the plating film is the sum of the soluble Si concentration obtained by the filtrate analysis and the insoluble Si concentration obtained by the solid content analysis.
  • the composition of the plating film obtained as a result of the calculation is shown in Tables 3 and 4.
  • the plating film on the evaluation symmetric plane is mechanically scraped until the underlying steel plate appears, the obtained powder is mixed well, and then 0.3 g is taken out and X is taken out.
  • the diffraction intensity of d 0.3135 nm) was measured. The measurement results are shown in Tables 3 and 4.
  • Corrosion loss of 3 samples is 30 g / m 2 or less
  • Corrosion loss of 3 samples is 50 g / m 2 or less
  • Corrosion loss of 1 sample or more exceeds 50 g / m 2
  • each sample of the example of the present invention is superior in balance in corrosion resistance, white rust resistance, surface appearance, processability and bath stability as compared with each sample of the comparative example. You can see that there is. Further, from the results in Table 4, it can be seen that the white rust resistance of each sample subjected to the chemical conversion treatments A to D is excellent.
  • Example 3 Samples 1 to 44> (1)
  • the plating film conditions shown in Table 6 are obtained by using a cold-rolled steel sheet with a thickness of 0.8 mm manufactured by a conventional method as a base steel sheet and performing an annealing treatment and a plating treatment with a hot-dip plating simulator manufactured by Resuka Co., Ltd.
  • a sample of the hot-dip plated steel sheet was prepared.
  • the composition of the plating bath used for manufacturing the hot-dip plated steel sheet the composition of the plating bath was Al: 30 to 75% by mass and Si: 0.5 to 4.5 so as to be the composition of the plating film of each sample shown in Table 6.
  • the bath temperature of the plating bath is 590 ° C when Al: 30 to 60% by mass and 630 ° C when Al: more than 60% by mass, and the plating penetration plate temperature of the base steel sheet is the same as the plating bath temperature. It was controlled to be. Furthermore, the plating treatment was carried out under the condition that the plate temperature was cooled to a temperature range of 520 to 500 ° C. in 3 seconds. The amount of the plating film adhered was controlled to be 85 ⁇ 5 g / m 2 per side for the samples 1 to 41 and 42 to 125 g / m 2 per side for the samples 42 to 44.
  • the chemical conversion treatment liquid shown in Table 5 is applied on the plating film of each sample of the prepared hot-dip galvanized steel sheet with a bar coater, and dried in a hot air drying furnace (reached plate temperature: 90 ° C.). A chemical conversion-treated film having an adhesion of 0.1 g / m 2 was formed.
  • the chemical conversion treatment liquid used a chemical conversion treatment liquid having a pH of 8 to 10 prepared by dissolving each component in water as a solvent was used.
  • the types of each component (resin component, inorganic compound) contained in the chemical conversion treatment liquid are as follows.
  • a primer paint is applied on the chemical conversion film formed as described above with a bar coater, and the steel sheet is baked under the conditions of an ultimate temperature of 230 ° C. and a baking time of 35 seconds.
  • a primer coating film having the above was formed.
  • the topcoat coating composition is applied on the primer coating film formed as described above with a bar coater, and the steel sheet is baked under the conditions of reaching temperature of 230 ° C to 260 ° C and baking time of 40 seconds, as shown in Table 5.
  • a topcoat coating film having the resin conditions and film thickness shown was formed, and a coated steel sheet of each sample was produced.
  • the primer paint was obtained by mixing each component and then stirring with a ball mill for about 1 hour.
  • Resin component Urethane-modified polyester resin (a product obtained by reacting 455 parts by mass of polyester resin and 45 parts by mass of isophorone diisocyanate, having a resin acid value of 3, a number average molecular weight of 5,600, and a hydroxyl value of 36). , The one cured with blocked isocyanate was used. The urethane resin to be urethane-modified was produced under the following conditions.
  • a flask equipped with a stirrer, a rectification tower, a water separator, a cooling tube and a thermometer was charged with 320 parts by mass of isophthalic acid, 200 parts by mass of adipic acid, 60 parts by mass of trimethylolpropane and 420 parts by mass of cyclohexanedimethanenol.
  • Heat and stir, and while distilling the generated condensed water out of the system raise the temperature from 160 ° C to 230 ° C over 4 hours at a constant rate, and after reaching the temperature of 230 ° C, gradually add 20 parts by mass of xylene.
  • Resin I Melamine-cured polyester paint ("Precolor HD0030HR” manufactured by BASF Japan Ltd.)
  • Resin II Organosol-based baking-type fluororesin-based paint with a mass ratio of polyvinylidene fluoride and acrylic resin of 80:20 (“Precolor No. 8800HR” manufactured by BASF Japan Ltd.)
  • composition of plating film (adhesion amount, composition, X-ray diffraction intensity)
  • 100 mm ⁇ is punched out, the non-measurement surface is sealed with tape, and then the plating is melted and peeled off with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H 0401: 2013.
  • the amount of adhesion of the plating film was calculated from the mass difference.
  • Table 6 shows the amount of adhesion of the plating film obtained as a result of the calculation.
  • the stripping solution was filtered, and the filtrate and solid content were analyzed respectively. Specifically, components other than insoluble Si were quantified by ICP emission spectroscopic analysis of the filtrate.
  • the solid content was dried and incinerated in a heating furnace at 650 ° C., and then melted by adding sodium carbonate and sodium tetraborate. Furthermore, insoluble Si was quantified by dissolving the melt with hydrochloric acid and ICP emission spectroscopic analysis of the solution.
  • the Si concentration in the plating film is the sum of the soluble Si concentration obtained by the filtrate analysis and the insoluble Si concentration obtained by the solid content analysis. Table 6 shows the composition of the plating film obtained as a result of the calculation.
  • the plating film on the evaluation symmetric plane is mechanically scraped until the underlying steel plate appears, the obtained powder is mixed well, and then 0.3 g is taken out and X is taken out.
  • the diffraction intensity of d 0.3135 nm) was measured. The measurement results are shown in Table 6.
  • the corrosion acceleration test was started from wetting, samples were taken out every 20 cycles, washed with water and dried, and then visually observed to confirm the occurrence of red rust on the sheared end face on one side that was not tape-sealed. Then, the number of cycles when red rust was confirmed was evaluated according to the following criteria. The evaluation results are shown in Table 6. ⁇ : Number of red rust generation cycles of 3 samples ⁇ 600 cycles ⁇ : 600 cycles > Number of red rust generation cycles of 3 samples ⁇ 500 cycles ⁇ : Number of red rust generation cycles of at least 1 sample ⁇ 500 cycles
  • each sample of the example of the present invention is superior to each sample of the comparative example in terms of corrosion resistance, appearance after painting, processability after painting, and bath stability in a well-balanced manner. I understand.
  • the present invention it is possible to provide a molten Al-Zn-Si-Mg-Sr-based plated steel sheet having stably excellent corrosion resistance and good surface appearance. Further, according to the present invention, it is possible to stably provide a surface-treated steel sheet having excellent corrosion resistance and white rust resistance. Further, according to the present invention, it is possible to stably provide a coated steel sheet having excellent corrosion resistance and corrosion resistance of a processed portion.

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PCT/JP2021/038480 2020-10-30 2021-10-18 溶融Ａｌ－Ｚｎ－Ｓｉ－Ｍｇ－Ｓｒ系めっき鋼板、表面処理鋼板及び塗装鋼板 WO2022091851A1 (ja)

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KR1020237015482A KR20230082045A (ko) 2020-10-30 2021-10-18 용융 Al-Zn-Si-Mg-Sr계 도금 강판, 표면 처리 강판 및 도장 강판
CN202180073469.6A CN116507754A (zh) 2020-10-30 2021-10-18 热浸Al－Zn－Si－Mg－Sr系镀覆钢板、表面处理钢板和涂装钢板
AU2021368356A AU2021368356A1 (en) 2020-10-30 2021-10-18 HOT-DIP Al-Zn-Si-Mg-Sr COATED STEEL SHEET, SURFACE-TREATED STEEL SHEET, AND PRE-PAINTED STEEL SHEET

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WO2023166858A1 (ja) * 2022-03-04 2023-09-07 Ｊｆｅスチール株式会社 溶融Ａｌ－Ｚｎ系めっき鋼板、その製造方法、表面処理鋼板及び塗装鋼板

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