WO2020121431A1 - Plaque d'acier recouverte - Google Patents

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Publication number
WO2020121431A1
WO2020121431A1 PCT/JP2018/045652 JP2018045652W WO2020121431A1 WO 2020121431 A1 WO2020121431 A1 WO 2020121431A1 JP 2018045652 W JP2018045652 W JP 2018045652W WO 2020121431 A1 WO2020121431 A1 WO 2020121431A1
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WIPO (PCT)
Prior art keywords
inorganic pigment
coating film
inorganic
steel sheet
film
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PCT/JP2018/045652
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English (en)
Japanese (ja)
Inventor
邦彦 東新
史生 柴尾
靖洋 森
学 大谷
長瀬　孫則
Original Assignee
日本製鉄株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 日本製鉄株式会社 filed Critical 日本製鉄株式会社
Priority to PCT/JP2018/045652 priority Critical patent/WO2020121431A1/fr
Priority to JP2019532167A priority patent/JP6638867B1/ja
Publication of WO2020121431A1 publication Critical patent/WO2020121431A1/fr

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    • 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
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel

Definitions

  • the present invention relates to a coated steel sheet used for automobiles, home appliances, building materials, civil engineering, machinery, furniture, containers, etc.
  • coated products that have been processed into the desired shape and then painted, or precoated metal sheets with a coating on the steel sheet surface are used.
  • pre-coated steel sheets are coated with multiple coatings with different functions on the surface of the steel sheet, so it is required to have excellent adhesion to the coatings.
  • the precoated steel sheet is coated with a coating film composed of two layers, a primer layer having corrosion resistance and a top layer having designability, solvent resistance and the like.
  • Patent Document 1 discloses a coated steel sheet having a coating film containing a plurality of anticorrosion pigments on Zn plating.
  • Patent Document 2 discloses a chromate-free black coated metal plate having a thickness of 2 to 10 ⁇ m and having a resin-based black coating film formed thereon.
  • Patent Document 1 discloses a coated galvanized steel sheet in which a cured coating film is formed on a galvanized steel sheet that has been subjected to chemical conversion treatment.
  • a coating film is further formed on the coating film containing a plurality of anticorrosion pigments.
  • it is difficult to obtain the effect of improving the corrosion resistance with only one layer of the coating film containing a plurality of anticorrosion pigments, and a large amount of Zn is eluted from the coating film, which may result in poor corrosion resistance.
  • the chromate-free black painted metal plate described in Patent Document 2 has a metal portion because the metal plate is scratched when the coating film is scratched during the process until it is processed into a product shape or during processing. When exposed, scratches may be noticeable on the surface of the metal plate.
  • the inventors of the present invention solve the above problems by forming a hard inorganic film containing Zn and V or Zr on a steel sheet by cathodic electrolysis and further applying a single coating film thereon. planned. That is, by forming a hard inorganic film on a steel sheet, scratches are less likely to reach the steel sheet, and the coated steel sheet having excellent corrosion resistance due to V or Zr is manufactured at low cost to solve the above-mentioned problems. ..
  • Patent Document 3 discloses a surface-treated steel sheet having a plating layer containing Zn and V.
  • the inventors of the present invention generate a gas containing water when the plating layer described in Patent Document 3 and the inorganic film containing Zn and V or Zr formed by cathodic electrolysis treatment are heated. I found out that. Furthermore, when the present inventors further apply a coating material on the plating layer described in Patent Document 3 or the inorganic film and heat it to form a coating film, the plating layer or the inorganic film is used to form a gas. It was found that the gas penetrates the coating film and the design of the steel sheet on which the coating film is formed deteriorates. It is considered that the gas generated from the plating layer or the inorganic film is caused by water adsorbed on the surface of the plating layer or the inorganic film.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a coated steel sheet having excellent designability, flaw resistance, solvent resistance, corrosion resistance, workability, and adhesion.
  • the present inventors have studied a coating film to be applied on an inorganic film.
  • the coating film is subjected to a curing reaction to improve the solvent resistance of the coating film, the gas permeability of the coating film may decrease. Therefore, the present inventors have studied a method of maintaining a solvent resistance and a corrosion resistance of a coating film and not causing a defect in the coating film even when a gas is generated from an inorganic film as a lower layer of the coating film during heating.
  • the coating film at least two kinds of inorganic pigments having a predetermined average particle diameter and different average particle diameters are contained in the coating film in a predetermined content, a predetermined ratio and a predetermined number.
  • gas permeation through the interface between the binder resin and the inorganic pigment improves the gas permeability of the coating film and improves the design of the coated steel sheet.
  • the present inventors have found that when the gas permeability of the coating film is improved, the permeability of the corrosion factor at the interface between the binder resin and the inorganic pigment in the coating film is also improved, and the corrosion resistance of the coated steel sheet is poor. ..
  • a protective film made of a phosphorus compound is formed at the interface between the inorganic film and the coating film.
  • a protective film By forming a protective film at the interface between the inorganic film and the coating film, elution of Zn and Fe in the inorganic film into the coating film can be suppressed, so that the corrosion resistance of the coated steel sheet is improved.
  • the present invention was made based on the above findings, and the gist thereof is as follows.
  • a coated steel sheet includes a steel sheet, An inorganic film formed on at least one surface of the steel sheet and containing Zn and V or Zr; A binder resin, which is formed on the inorganic film and has a film thickness of more than 5 to 20 ⁇ m, and a particle diameter of 10 to 500 nm, and an inorganic pigment B having a particle diameter of 1000 to 10000 nm.
  • the ratio of (A) to the volume part (B) of the inorganic pigment B is 0.5 ⁇ (A)/(B) ⁇ 2.0,
  • the inorganic pigment is observed in a region of 20 ⁇ m in the direction parallel to the plate width direction and t ⁇ m in the plate thickness direction in a section perpendicular to the rolling direction of the coating film, where t is the film thickness of the coating film.
  • the number of A is 60 to 100,000, and the number of the inorganic pigment B is 2 to 50.
  • the inorganic pigment A or the inorganic pigment B containing P in the coating film may further contain Mg.
  • the binder resin may include a polyester resin and a melamine resin.
  • the melamine resin may be a butylated melamine resin.
  • the binder resin may include an epoxy resin.
  • V/Zn which is a mass ratio of V to Zn in the inorganic coating, or Zr to V.
  • Zr/Zn which is the mass ratio with respect to, may be 0.05 to 0.50 in terms of metal.
  • FIG. 1 is a diagram showing a coated steel sheet 10 according to the present embodiment.
  • the coated steel sheet 10 according to the present embodiment contains an inorganic coating 5 formed by cathodic electrolysis on at least one surface of the steel sheet 4, and a binder resin 3 and two or more kinds of inorganic pigments having different particle sizes thereon.
  • Coating film 6 formed by applying a coating material, heating and drying. Note that, in FIG. 1, the coating film 6 is illustrated in an enlarged manner in the plate thickness direction of the coated steel plate 10.
  • the coated steel sheet 10 according to the present embodiment has the inorganic coating 5 on at least one surface of the steel sheet 4 and the coating 6 on the inorganic coating 5, so that workability, adhesion, designability, and scratch resistance are provided. Excellent in resistance, solvent resistance and corrosion resistance.
  • excellent workability means that a coating film in a practically processed portion is difficult to be visually recognized as a defect such as a crack
  • excellent adhesion means that a coating film is practically used from a steel sheet.
  • excellent design means that there are few defects visually recognized on the surface of the coating film
  • excellent scratch resistance means that scratches are difficult to be visually recognized when scratched.
  • the solvent resistance is excellent, and the mark is hard to be visually recognized when the coating film is rubbed with the solvent
  • the excellent corrosion resistance means that the corrosion during the use in the practical environment. This means less generation of product.
  • the steel plate 4 according to the present embodiment is not particularly limited, and includes, for example, an extremely low C type (ferrite-based structure), an Al-k type, a two-phase structure type (for example, a structure containing martensite in ferrite, ferrite Any type of steel plate may be used, such as a structure containing bainite therein, a work-induced transformation type (structure containing retained austenite in ferrite), and a fine crystal type (structure mainly containing ferrite).
  • an extremely low C type ferrite-based structure
  • Al-k type for example, a structure containing martensite in ferrite, ferrite
  • a two-phase structure type for example, a structure containing martensite in ferrite, ferrite
  • Any type of steel plate may be used, such as a structure containing bainite therein, a work-induced transformation type (structure containing retained austenite in ferrite), and a fine crystal type (structure mainly containing ferrite).
  • the coated steel sheet 10 has an inorganic coating 5 containing Zn and V or Zr, which is formed by cathodic electrolysis on at least one surface of the steel sheet 4.
  • Zn in the inorganic coating 5 exists in the form of at least one of Zn metal, oxide, and hydroxide.
  • V or Zr in the inorganic coating 5 exists in the form of at least one of oxides and hydroxides of V or Zr.
  • the coated steel sheet 10 is excellent in corrosion resistance and scratch resistance.
  • the inorganic film 5 contains Zn and V or Zr
  • at least 1 g/m 2 of Zn and V or Zr are contained in the inorganic film 5. It means that it is contained at least 0.1 g/m 2 .
  • V/Zn which is the mass ratio of Zn and V in the inorganic coating 5, or Zr/Zn, which is the mass ratio of Zn and Zr in the inorganic coating 5, is 0.05 to 0.50 in terms of metal. preferable.
  • the metal conversion value of V/Zn can be obtained by dividing the content of V in the inorganic coating 5 by the content of Zn in the inorganic coating 5.
  • the Zr/Zn conversion value of metal can be obtained by dividing the content of Zr in the inorganic coating 5 by the content of Zn in the inorganic coating 5.
  • the components other than Zn and V or Zr in the inorganic film 5 are not particularly limited.
  • the inorganic film 5 may contain Fe, Ni, or the like in an amount of less than 5%.
  • the component of the inorganic film 5 is cut out from any position on the coated steel sheet, and the surface coating film is removed by rubbing with a film release agent, followed by ICP (Inductively Coupled Plasma) emission spectroscopy and fluorescent X-ray spectroscopy. It can be analyzed by a known method such as an analytical method.
  • ICP Inductively Coupled Plasma
  • fluorescent X-ray spectroscopy fluorescent X-ray spectroscopy. It can be analyzed by a known method such as an analytical method.
  • ICP emission spectroscopic analysis it is advisable to dissolve them in a solution prepared by adding an inhibitor to hydrochloric acid or the like so that the steel sheet does not dissolve.
  • the coated steel sheet 10 has, on the inorganic coating 5, an inorganic pigment A (inorganic pigment 1) having a particle diameter of 10 to 500 nm and an inorganic pigment B (inorganic pigment 2) having a particle diameter of 1000 to 10000 nm. ) And a coating film 6 containing at least two kinds thereof.
  • the coating film 6 contains the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in a predetermined content, a predetermined ratio, and a predetermined number.
  • the coated steel sheet 10 can have a good appearance.
  • At least one of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in the coating film 6 contains P. Therefore, when elemental mapping analysis is performed on the cross section of the coating film 6 according to the present embodiment by EDX (energy dispersive fluorescent X-ray analysis method), the inorganic pigment A (inorganic pigment 1) or the inorganic pigment B (inorganic pigment 2) is detected. P is detected in either one. P in the coating film 6 according to the present embodiment exists in the form of a phosphorus compound. When the coating film 6 is water-cooled immediately after curing, a part of the water vapor contained in the gas generated from the lower inorganic coating film 5 of the coating film 6 is cooled to become water.
  • EDX energy dispersive fluorescent X-ray analysis method
  • the binder resin 3 and the inorganic pigment A (inorganic pigment 1) and/or the inorganic pigment B (inorganic pigment B from the inorganic coating 5 to the surface of the coating film 6 are used. It is important to ensure the path of the interface with the pigment 2). Whatever pigment is used, the path is formed by adding many pigments to the coating film 6 so that almost all the pigments come into contact with each other.
  • the inorganic coating 5 contains the inorganic pigment A (inorganic pigment 1) having a particle diameter of 10 to 500 nm and the inorganic pigment B (inorganic pigment 2) having a particle diameter of 1000 to 10000 nm. Then, the total amount of the volume part (A) of the inorganic pigment A (inorganic pigment 1) and the volume part (B) of the inorganic pigment B (inorganic pigment 2) of the coating film 6 is 5 with respect to 100 parts by volume of the coating film.
  • the ratio of the volume part (A) of the inorganic pigment A (inorganic pigment 1) to the volume part (B) of the inorganic pigment B (inorganic pigment 2) is 0.5 ⁇ (A). /(B) ⁇ 2.0, and a region of 20 ⁇ m in the direction parallel to the plate width direction and t ⁇ m in the plate thickness direction in a cross section perpendicular to the rolling direction, where t is the film thickness of the coating film 6.
  • the number of the inorganic pigment A (inorganic pigment 1) is 60 to 100,000 and the number of the inorganic pigment B (inorganic pigment 2) is 2 to 50, which are observed in (region of 20 ⁇ m ⁇ t ⁇ m), the route is changed.
  • the maximum particle size of the inorganic pigment A (inorganic pigment 1) in this embodiment is equal to or smaller than the radius of the minimum particle size of the inorganic pigment B (inorganic pigment 2). Therefore, the gap between the adjacent inorganic pigments B (inorganic pigment 2) having a relatively large particle diameter and the inorganic pigment B (inorganic pigment 2) is likely to be filled with the inorganic pigment A (inorganic pigment 1).
  • not only the contact points between the inorganic pigments B (inorganic pigment 2) but also the contact points between the inorganic pigment B (inorganic pigment 2) and the inorganic pigment A (inorganic pigment 1) are routes.
  • the path from the inorganic coating 5 to the surface of the coating 6 is optimally formed. Therefore, the gas generated from the inorganic film 5 is likely to escape from the surface of the coating film 6, and the coating film 6 is less likely to have defects.
  • the coating film 6 contains only the inorganic pigment A (inorganic pigment 1), compared to the case where the inorganic pigment B (inorganic pigment 2) and the inorganic pigment A (inorganic pigment 1) are mixed in the coating film 6, gas The area of the interface between the pigment and the binder resin 3 which becomes the route of (2) becomes too large. Therefore, the gas permeability at the interface between the binder resin 3 in the coating film 6 and the inorganic pigment A (inorganic pigment 1) becomes too large, and the corrosion resistance of the coated steel sheet 10 deteriorates.
  • the coating film 6 contains only the inorganic pigment B (inorganic pigment 2), compared with the case where the inorganic pigment B (inorganic pigment 2) and the inorganic pigment A (inorganic pigment 1) are mixed in the coating film 6.
  • the area of the interface between the pigment and the binder resin 3, which serves as a gas path, is reduced.
  • the number of contacts between the inorganic pigments B (inorganic pigment 2) is also the number of contacts between the inorganic pigments B (inorganic pigment 2) and the inorganic pigment A (inorganic pigment 1) mixed in the coating film 6. Less than contacts. For this reason, the gas permeability of the coating film 6 becomes insufficient, and the design of the coated steel sheet 10 deteriorates.
  • inorganic pigments have a small particle size, so they tend to agglomerate during the process of dispersion in paint. Therefore, it is difficult to disperse the inorganic pigment having a small particle diameter in the coating film 6 while maintaining the primary particle diameter of each inorganic pigment.
  • Inorganic pigments having a small particle size are aggregated, and the aggregated inorganic pigments are present in the coating film 6 in the form of secondary particles having a particle size larger than the primary particle size. There are cases.
  • the particle size of the secondary particles is hereinafter referred to as “secondary particle size”.
  • the particle diameters of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in the coating film 6 in the present embodiment include not only the primary particle diameter but also the secondary particle diameter. That is, the inorganic pigment A (inorganic pigment 1) having a particle diameter of 10 to 500 nm indicates an inorganic pigment having a primary particle diameter and a secondary particle diameter of 10 to 500 nm, which are present in the coating film 6.
  • the inorganic pigment B (inorganic pigment 2) having a particle size of 1000 to 10000 nm is an inorganic pigment present in the coating film 6 having a primary particle size and a secondary particle size of 1000 to 10000 nm.
  • the total amount of the volume part (A) of the inorganic pigment A (inorganic pigment 1) and the volume part (B) of the inorganic pigment B (inorganic pigment 2) of the coating film 6 is 5 parts with respect to 100 parts by volume of the coating film 6. ⁇ 50 parts by volume.
  • the total amount of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in the coating film 6 is less than 5 parts by volume, the area of the interface between the pigment and the binder resin 3 that serves as a path for gas is Since it becomes smaller, the gas permeability of the coating film 6 becomes insufficient, and the design of the coated steel sheet 10 deteriorates.
  • the total amount of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in the coating film 6 exceeds 50 parts by volume, the area of the interface between the pigment and the binder resin 3 becomes too large. Therefore, the gas permeability of the coating film 6 becomes too high, and the corrosion resistance of the inorganic coating film 5 and the coated steel sheet 10 deteriorates. Furthermore, since the total amount of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) increases, the amount of the binder resin 3 becomes too small, and the durability of the coating film 6 decreases.
  • the total amount of the inorganic pigment A (inorganic pigment 1) volume part and the inorganic pigment B (inorganic pigment 2) volume part of the coating film 6 is 10 parts with respect to 100 parts by volume of the coating film 6. It is preferably from 30 to 30 parts by volume.
  • the ratio of the volume part (A) of the inorganic pigment A (inorganic pigment 1) and the volume part (B) of the inorganic pigment B (inorganic pigment 2) of the coating film 6 is 0.5 ⁇ (A)/(B) ⁇ It is 2.0.
  • the ratio of the volume part (A) of the inorganic pigment A (inorganic pigment 1) and the volume part (B) of the inorganic pigment B (inorganic pigment 2) of the coating film 6 is less than 0.5 or more than 2.0, Since the gas permeability of the coating film 6 deteriorates, the design of the coated steel sheet 10 deteriorates.
  • the ratio of the volume part (A) of the inorganic pigment A (inorganic pigment 1) and the volume part (B) of the inorganic pigment B (inorganic pigment 2) of the coating film 6 is 0.7 ⁇ (A)/(B) ⁇ 1.7 is preferred.
  • the film thickness of the coating film 6 is more than 5 to 20 ⁇ m (more than 5 ⁇ m, 20 ⁇ m or less).
  • the film thickness of the coating film 6 is preferably more than 7 ⁇ m or 16 ⁇ m or less.
  • the number of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in the coating film 6 is the cross section perpendicular to the rolling direction and the plate width direction when the thickness of the coating film 6 is t.
  • the number of inorganic pigments A (inorganic pigment 1) is 60 to 100,000 and the number of inorganic pigments B (inorganic pigment 2) is 20 ⁇ m in the parallel direction and t ⁇ m in the plate thickness direction (region of 20 ⁇ m ⁇ t ⁇ m). 2 to 50.
  • the pigment serving as a gas path and the binder resin 3 It is possible to secure a sufficient amount of the binder resin 3 while securing the area of the interface. For this reason, the gas permeability and durability of the coating film 6 can be maintained, and as a result, the design and corrosion resistance of the coated steel sheet 10 can be improved.
  • the coating film 6 may include an inorganic pigment C having a particle size (greater than 500 nm and less than 1000 nm) other than the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2).
  • the number of inorganic pigments having a particle size of more than 500 nm and less than 1000 nm contained in the coating film 6 is in the above-described 20 ⁇ m ⁇ t ⁇ m region (20 ⁇ m in the direction parallel to the plate width direction, and film thickness t ⁇ m in the plate thickness direction). In the area), 10 or less are preferable.
  • the inorganic pigment B and other inorganic pigments C are The number of contacting portions does not increase too much, the inorganic pigment B is pushed by the inorganic pigment C, and the inorganic pigments B (inorganic pigment 2) easily contact each other. Therefore, the gas permeability of the coating film 6 can be further improved, and the designability of the coated steel sheet 10 can be further improved.
  • the coating film 6 contains an inorganic pigment having a particle size of “less than 10 nm” or “more than 10000 nm”, the number of particles of “less than 10 nm” is 30 or less, and the particle size of “more than 10000 nm” is 4 or less. If the number is less than or equal to the number, the characteristics of the coated steel sheet according to this embodiment are not affected.
  • the particle size of the inorganic pigment in the coating film 6 of the coated steel sheet 10 is obtained by the following method.
  • FE-TEM field emission transmission electron microscope
  • the equivalent circle diameters of all the inorganic pigments in the observation region are calculated using the following formula 1, and the equivalent circle diameters are taken as the particle diameters of the respective inorganic pigments.
  • an inorganic pigment having a particle diameter of 10 to 500 nm is referred to as an inorganic pigment A (inorganic pigment 1)
  • an inorganic pigment having a particle diameter of more than 500 nm and less than 1000 nm is referred to as an inorganic pigment C
  • a particle diameter of 1000 to 10000 nm is referred to as an inorganic pigment A (inorganic pigment 1)
  • an inorganic pigment having a particle diameter of more than 500 nm and less than 1000 nm is referred to as an inorganic pigment C
  • a particle diameter of 1000 to 10000 nm is a particle diameter of 1000 to 10000 nm.
  • some inorganic pigment be the inorganic pigment B (inorganic pigment 2).
  • the numbers of the inorganic pigment A (inorganic pigment 1), the inorganic pigment C, and the inorganic pigment B (inorganic pigment 2) observed in the above observation area are obtained, and the number of the pigments in the plurality of observation areas (5 areas) is calculated
  • the numbers of the inorganic pigment A (inorganic pigment 1), the inorganic pigment C, and the inorganic pigment B (inorganic pigment 2) are obtained. Further, P element mapping analysis is performed on the above observation region by EDX to determine whether the inorganic pigment A (inorganic pigment 1) and/or the inorganic pigment B (inorganic pigment 2) is an inorganic pigment containing P (phosphorus compound). To do. In addition, it is determined whether or not the inorganic pigment A and/or the inorganic pigment B containing P (phosphorus compound) contains Mg by Mg element mapping analysis.
  • the inorganic pigment A inorganic pigment 1 having a particle size within the range of 10 to 500 nm
  • At least two kinds of the inorganic pigment B inorganic pigment 2 having a particle diameter in the range of 1,000 to 10,000 nm are included.
  • the relationship between the particle diameter and the number of inorganic pigments in the coating film 6 of the coated steel sheet 10 according to this embodiment is as shown in FIG.
  • the contents of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in the coating film 6 are calculated by observing the coating film cross section of the coating film 6.
  • an example of the calculation method will be described.
  • FE-TEM field emission transmission electron microscope
  • the average value and the average particle size of the number of each of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in each visual field are determined. From the average value and the average particle size of the number of each of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2), all of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) are obtained. The total area of view is obtained.
  • the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) in all fields of view the inorganic pigment A (inorganic pigment 1) and the inorganic material for the coating film 6
  • the area ratio of each of the pigments B (inorganic pigment 2) (area of coating film 6: area of inorganic pigment A (inorganic pigment 1), area of coating film 6: area of inorganic pigment B (inorganic pigment 2)) is obtained. Since the volume ratio can be calculated by multiplying the area ratio by the power of 3/2, the area ratio of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) to the area of the coating film 6 is 3 respectively.
  • the volume ratio of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2) to the coating film 6 (volume of coating film 6: volume of inorganic pigment A (inorganic pigment 1)
  • the volume of the coating film 6 the volume of the inorganic pigment B (inorganic pigment 2) is obtained. From these volume ratios, the volume part of the inorganic pigment A (inorganic pigment 1) and the volume part of the inorganic pigment B (inorganic pigment 2) with respect to 100 volume parts of the coating film 6 are calculated.
  • the total amount of the volume part of the inorganic pigment A (inorganic pigment 1) and the volume part of the inorganic pigment B (inorganic pigment 2) to 100 volume parts of the coating film 6 is obtained. Further, based on 100 parts by volume of the obtained coating film 6 and 100 parts by volume of the inorganic pigment A (inorganic pigment 1) and the inorganic pigment B (inorganic pigment 2), the inorganic pigment A (inorganic pigment 1) by volume is obtained. The ratio ((A)/(B)) of (A) and the volume part (B) of the inorganic pigment B (inorganic pigment 2) is obtained.
  • the inorganic pigment containing no P which can be used for the coating film 6 of the coated steel sheet 10 according to the present embodiment, it is possible to use a powder paint which is insoluble in water or oil, which is generally used as a paint. it can.
  • a powder paint which is insoluble in water or oil, which is generally used as a paint.
  • examples thereof include carbon black, iron oxide, titanium oxide, silica, aluminum, alumina, kaolin, calcium carbonate, barium sulfate, vanadate pigments, molybdate pigments and the like.
  • the corrosion resistance of the coated steel sheet 10 may be significantly reduced.
  • carbon black, titanium oxide, silica and aluminum are preferable.
  • the inorganic pigment A or the inorganic pigment B in the coating film 6 contains P (phosphorus compound).
  • P contained in the inorganic pigment in the coating film 6 is appropriately eluted into water in the gas generated from the inorganic coating film 5, penetrates into the inorganic coating film 5, and is an inorganic component (V or Zr) in the inorganic coating film 5.
  • a protective film made of a phosphorus compound is formed at the interface between the inorganic film 5 and the coating film 6.
  • the inorganic pigment containing P in the coating film 6 include phosphate pigments and phosphomolybdate pigments.
  • an inorganic pigment produced by baking a phosphoric acid compound and an organic acid is suitable as an inorganic pigment containing P in the coating film 6 because the P component is easily eluted.
  • the inorganic pigment containing P in the coating film 6 condensed aluminum phosphate, a pigment obtained by modifying a phosphate pigment with an alkaline earth metal ion, and the like can be given.
  • alkaline earth metal ions include Ca ions and Mg ions.
  • the inorganic pigment containing P in the coating film 6 is aluminum tripolyphosphate, zinc molybdenum orthophosphate, zinc polyphosphate, or the like because the corrosion resistance of the coated steel sheet 10 can be further improved.
  • the P-containing inorganic pigment in the coating film 6 further contains Mg
  • a protective coating is more likely to be formed at the interface between the inorganic coating 5 and the coating film 6, and the corrosion resistance of the coated steel sheet 10 is further improved.
  • the inorganic pigment containing P and Mg include magnesium phosphate, magnesium diphosphate, and magnesium tripolyphosphate treated with magnesium.
  • the coating film 6 of the coated steel sheet 10 according to the present embodiment contains one kind or two or more kinds of the binder resin 3.
  • the binder resin 3 has a hydroxyl group, a carboxylic acid group, an amino group or an epoxy group as a functional group at the terminal of the resin.
  • the binder resin 3 in the coating film 6 is not particularly limited, but examples thereof include acrylic resin, urethane resin, polyester resin, epoxy resin, and melamine resin.
  • a binder resin in which functional groups generally known as functional groups to be cured are combined may be used, and examples thereof include a hydroxyl group and an amino group, a carboxylic acid group and an amino group, and the like.
  • a combination of a hydroxyl group and an epoxy group may be used.
  • the binder resin 3 contains a polyester resin and a melamine resin, it becomes a cured coating film, so that the solvent resistance of the coating film 6 can be further improved.
  • the polyester resin is suitable because it improves the adhesion and workability between the inorganic coating 5 and the coating 6.
  • the polyester resin that can be used for the coating film 6 according to this embodiment can be formed by a polymerization reaction of a polyvalent carboxylic acid and a polyhydric alcohol.
  • the polyester resin that can be used for the coating film 6 according to the present embodiment may be modified.
  • the polyvalent carboxylic acid component is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, Azelaic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned.
  • the polyvalent carboxylic acid component one kind or two kinds or more of these can be optionally used.
  • the polyhydric alcohol is not particularly limited, but for example, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, triethylene glycol, 2-methyl-1,3-propanediol, 2, 2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl 1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 2-methyl-3-methyl -1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1 , 2-cyclohexanedimethanol, hydrogenated bisphenol-A, dimer diol, trimethylolethane, trimethylolpropane, gly
  • the melamine resin is not particularly limited, but examples thereof include methylated melamine and butylated melamine.
  • the binder resin 3 of the coating film 6 preferably contains a polyester resin and a butylated melamine resin.
  • Butylated melamine resin is excellent in self-condensation. In self-condensation, since the reaction proceeds after the temperature of the coating film 6 becomes higher, the time until the reaction (self-condensation) of the methylated melamine starts (the time until the binder resin 3 hardens) becomes longer. ..
  • the gas generated from the inorganic film 5 can escape from the surface of the coating film 6 for a longer time, and more gas permeates, so that the design of the coated steel sheet 10 is improved. Sex is improved. Since the butylated melamine resin is insoluble in water, it is preferable to use a solvent-based paint rather than an aqueous paint.
  • the binder resin 3 of the coating film 6 preferably contains an epoxy resin. Epoxy resins reduce the melt viscosity of the resin. Therefore, the gas permeability of the coating film 6 can be further improved in the time period until the coating film 6 is cured after the solvent is dried, and the design of the coated steel sheet 10 can be further improved.
  • the weight ratio of the polyester resin and the melamine resin in the binder resin 3 represented by [Pes]/[Me] is preferably 1 ⁇ [Pes]/[Me] ⁇ 10.
  • [Pes] indicates the weight of the polyester resin in the binder resin 3
  • [Me] indicates the weight of the melamine resin in the binder resin 3.
  • the coating film 6 further contains at least one of amine-neutralized dodecylbenzenesulfonic acid and amine-neutralized paratoluenesulfonic acid.
  • the crosslinking reaction between the polyester and melamine contained in the binder resin 3 is suppressed and the self-condensation reaction of melamine is promoted, so that the gas permeability of the coating film 6 is further improved.
  • the design of the coated steel sheet 10 is further improved.
  • the type and weight of the binder resin component in the coating film 6 can be analyzed by using an FT-IR (Fourier transform infrared spectrophotometer) or an NMR apparatus (nuclear magnetic resonance apparatus).
  • FT-IR Fullier transform infrared spectrophotometer
  • NMR apparatus nuclear magnetic resonance apparatus
  • the coated steel sheet 10 according to the present embodiment is manufactured by forming an inorganic coating 5 on at least one surface of the steel sheet 4 by cathodic electrolysis and applying a coating material on the inorganic coating 5 to form a coating film 6. It
  • a solution containing Zn ions and V ions or Zr ions can be used.
  • the solution containing Zn ions and V ions or Zr ions can be prepared by a known method. For example, it can be prepared by dissolving Zn sulfate and vanadyl oxide or zirconyl nitrate in sulfuric acid. ..
  • the pH of the solution for cathodic electrolysis be 1.0 to 4.0. If the pH of the solution for cathodic electrolysis is lower than 1.0, V ions or Zr ions may not be incorporated into the inorganic film 5. If the pH of the solution for cathodic electrolysis is higher than 4.0, V ions or Zr ions may precipitate in the solution as oxides, and V ions or Zr ions may not be incorporated into the inorganic coating 5.
  • V ions/Zn ions, or Zr ions/Zn ions are 0.2 to 0.9.
  • V ion/Zn ion or Zr ion/Zn ion in the solution for cathodic electrolysis is less than 0.2 or more than 0.9, V ion or Zr ion is not taken into the inorganic film 5.
  • the content of ions in the solution for cathodic electrolysis can be analyzed by a known method such as ICP (Inductively Coupled Plasma) emission spectroscopy or fluorescent X-ray spectroscopy. Further, the content of ions in the solution for cathodic electrolysis is determined by measuring the amount of components dissolved in the solution for cathodic electrolysis (amounts of Zn sulfate, vanadyl oxide, zirconyl nitrate, etc.) as V ions (g/L), Zn. It can also be obtained by converting into ions (g/L) and Zr ions (g/L).
  • a coating method of the coating material for forming the coating film 6 there are known methods such as a bar coater method, a roll coating method, a Ringer roll coating method, an air spray method, an airless spray method and a dipping method.
  • the method for drying the paint for forming the coating film 6 is not particularly limited, and examples thereof include a method of using hot air, induction heating, near infrared rays, open flame, or the like, alone or in combination.
  • steel plate As the steel plate, a SPCD steel plate described in JIS G 3141:2011, having a plate thickness of 0.8 mm and being a general cold-rolled steel plate for drawing was used.
  • Inorganic film A solution containing Zn ions and V ions and a solution containing Zn ions and Zr ions were prepared.
  • the solution was prepared by dissolving Zn sulfate and vanadyl oxide or zirconyl nitrate in sulfuric acid.
  • the components of the inorganic film were adjusted by adjusting the amounts of the components dissolved in the solution.
  • the pH of the solution was adjusted by the amount of sulfuric acid and the amount of Na hydroxide.
  • the prepared solution is shown in Table 1.
  • the mass (g/L) of each ion in Table 1 was obtained by converting the amount of components (Zn sulfate, vanadyl oxide, zirconyl nitrate) dissolved in the solution into the amount of each ion.
  • [Pes]/[Me] represents the weight ratio of the polyester resin and the melamine resin in the binder resin
  • [Pes]+[Me] represents the binder resin. Shows the total weight of the polyester resin and the melamine resin.
  • the coating materials shown in Table 5-1 and Table 5-2 were applied on the above inorganic film with a bar coater in an amount of 10 ⁇ m, and then heated in a hot air oven so that the ultimate plate temperature reached 230° C. in 30 seconds. Then, it was immersed in water and cooled to form a coating film. A coated steel sheet was obtained by the above method.
  • the components of the inorganic coating film and the coating film were analyzed by the following methods. The obtained results are shown in Table 6-1 and Table 6-2.
  • the components of the inorganic film were analyzed by the following methods. A sample was cut out from an arbitrary position on the coated steel sheet, and the coating film on the surface was removed by a coating film peeling agent. The components of the inorganic film were analyzed by performing ICP (Inductively Coupled Plasma) emission spectroscopy on the inorganic film exposed on the surface. In the ICP emission spectroscopic analysis method, the solution was measured by dissolving it in a solution of an inhibitor added to hydrochloric acid so as not to dissolve the steel sheet.
  • ICP Inductively Coupled Plasma
  • the inorganic coating contained 1 g/m 2 or more of Zn, it was described as “Yes” in Tables 6-1 and 6-2, and when Zn was less than 1 g/m 2 , it was described as “No”. Further, when the inorganic coating contains 0.1 g/m 2 or more of V or Zr, it is described as “Yes” in Table 6-1 and Table 6-2, and V or Zr is less than 0.1 g/m 2. In the case of, it described as "No.”
  • a thin film sample was prepared by the microtome method so that the cross section of the coated steel sheet 10 perpendicular to the rolling direction can be observed.
  • a 20 ⁇ m ⁇ t ⁇ m region (20 ⁇ m in the direction parallel to the plate width direction and film thickness t ⁇ m in the plate thickness direction of the steel sheet) of the coating film portion of the obtained thin film sample a 200 kV field emission transmission electron microscope (FE- 5 regions were observed using TEM) at a magnification of 100,000.
  • FE- 5 regions were observed using TEM at a magnification of 100,000.
  • the equivalent circle diameters of all the inorganic pigments in the observation visual field were calculated, and this equivalent circle diameter was defined as the particle diameter of each inorganic pigment.
  • the coating film contains the inorganic pigment B having a particle diameter in the range of 1000 to 10000 nm, and the number of the inorganic pigment B in the coating film is 2 to 50
  • Table 6-1 and Table 6- In the column of No. 2 inorganic pigment B, “Yes” was described, and when the coating film did not contain the inorganic pigment B, it was described as “No”.
  • the number of the inorganic pigments B in the coating film is less than 2, it is described as “less than” in the column of the inorganic pigment B in Table 6-1 and Table 6-2, and the inorganic pigments in the coating film are indicated.
  • the number of B was more than 50, it was described as "super.”
  • the inorganic pigment A and the inorganic pigment B in the coating film are an inorganic pigment containing P (phosphorus compound). “Yes” is indicated in the “P content” column in Tables 6-1 and 6-2. If the inorganic pigment A and the inorganic pigment B in the coating film were inorganic pigments containing no P (phosphorus compound), they were described as “No”.
  • the volume part of the inorganic pigment A and the volume part of the inorganic pigment B with respect to 100 volume parts of the coating film were obtained by the following method. Five-view observation of the cross section of the coating film (the coating film 6 part of the steel plate cut in the direction perpendicular to the rolling direction) at a magnification of 100,000 times using a 200 kV field emission transmission electron microscope (FE-TEM) did. The total area of the coating film observed in all visual fields was determined. Next, the average value and the average particle size of the number of each of the inorganic pigment A and the inorganic pigment B in each visual field were obtained.
  • FE-TEM field emission transmission electron microscope
  • the total area of the inorganic pigment A and the inorganic pigment B in the entire visual field was obtained. From the total area of the coating film and the total area of the inorganic pigment A and the inorganic pigment B in the entire field of view, the area ratio of each of the inorganic pigment A and the inorganic pigment B to the area of the coating film (coating area: inorganic pigment A Area, coating film area: inorganic pigment B area).
  • volume ratio of each of the inorganic pigment A and the inorganic pigment B to the coating film (volume of the coating film: volume of the inorganic pigment A is calculated by multiplying the area ratio of each of the inorganic pigment A and the inorganic pigment B to the area of the coating film by 3/2. , Volume of coating film: volume of inorganic pigment B). From these volume ratios, the volume part of the inorganic pigment A and the volume part of the inorganic pigment B with respect to 100 volume parts of the coating film were calculated. By calculating the total of these, the total ((A)+(B)) of the volume of the inorganic pigment A and the volume of the inorganic pigment B with respect to 100 parts by volume of the coating film was obtained.
  • the ratio of the volume part (A) of the inorganic pigment A and the volume part (B) of the inorganic pigment B ( (A)/(B)) was obtained.
  • Tables 6-1 and 6-2 show the ratio ((A)/(B)) to the volume part (B).
  • Binder resin in coating film The kinds of components of the binder resin in the coating film were analyzed using an NMR apparatus (nuclear magnetic resonance apparatus). In the case where the weight ratio [Pes]/[Me] of the polyester resin and the melamine resin in the binder resin was 1 to 10, in the case of “1 ⁇ Pes/Me ⁇ 10” in Table 6-1 and Table 6-2. “Yes” is described in the column, and “No” is described when [Pes]/[Me] is less than 1 or more than 10.
  • binder resin contains a butylated melamine resin
  • the binder resin contained an epoxy resin “Yes” was described in the “Ep-containing” column in Tables 6-1 and 6-2, and when the epoxy resin was not contained, “No” was described.
  • the following tests 1 to 6 were conducted on the coated steel sheets in Table 6-1 and Table 6-2. Out of the tests 1 to 6, when the evaluation in all the tests was 3 or more, the coated steel sheet according to the present invention was judged to be acceptable as the coated steel sheet having the desired characteristics. If at least one of the tests 1 to 6 was evaluated to be 2 or less, the coated steel sheet according to the present invention was determined to be unacceptable as a coated steel sheet having no desired characteristics.
  • the tests 1 to 6 will be described in detail below.
  • Test 1 Solvent resistance As for the solvent resistance of the coated steel sheet, a test piece of a predetermined size was sampled from the coated steel sheet of Table 6-1 and Table 6-2, the test piece was placed on a rubbing tester, and then impregnated with ethanol. The state of the coating film after the absorbent cotton was rubbed 10 times with a load of 49.03 kPa (0.5 kgf/cm 2 ) was evaluated according to the following evaluation criteria. 5: No mark is left on the rubbing surface. 4: An extremely slight mark is left on the rubbing surface (a level at which the rubbing mark can be discriminated by focusing on the eyes). 3: A slight mark is left on the rubbing surface (a level at which rubbing marks can be discerned when the eyes are closed). 2: A clear mark is attached to the rubbing surface (a level where the rubbing mark can be instantly identified). 1: The coating film is completely dissolved on the rubbed surface, and the inorganic coating film is exposed.
  • Test 2 Scratch resistance As for the scratch resistance of the coated steel sheet, a test piece of a predetermined size was sampled from the coated steel sheet of Table 6-1 and Table 6-2, and the test piece was placed on a rubbing tester and then the rubbing tester was tested. A cylindrical eraser manufactured by Ugawa Rubber Co., Ltd. was attached to the tip of the sliding jig, and the state of the coating film and the inorganic film after rubbing 100 times with a load of 16 N was evaluated according to the following evaluation criteria. 5: No exposed steel plate. 4: The exposed width of the steel sheet is less than 1 mm. 3: The exposed width of the steel sheet is 1 mm or more and less than 2 mm. 2: The exposed width of the steel sheet is 2 mm or more and less than 3 mm. 1: The exposed width of the steel plate is 3 mm or more.
  • Corrosion resistance of the coated steel sheet was measured in accordance with JIS Z 2371:2000 after collecting test pieces of a predetermined size from the coated steel sheets in Tables 6-1 and 6-2 and masking the end faces of the test pieces.
  • a salt spray test (SST) was performed for 48 hours, the rust generation state on the coating film surface was observed, and evaluated according to the following evaluation criteria. 5: No rust was generated. 4: Rust generation area is less than 1% of the entire surface of the test piece. 3: Rust generation area is 1% or more and less than 3% of the entire surface of the test piece. 2: Rust generation area is 3% or more and less than 5% of the entire surface of the test piece. 1: Rust generation area is 5% or more of the entire surface of the test piece.
  • Test 4 Appearance (design) The designability of the coated steel sheet was evaluated by taking 50 ⁇ 50 mm test pieces from the coated steel sheets shown in Tables 6-1 and 6-2, and measuring the number of sides (pinholes generated by foaming) in the test pieces. 5: There are 0 pinholes. 4: The number of pinholes is 1 or more and less than 5. 3: There are 5 or more pinholes and less than 10 pinholes. 2: The number of pinholes is 10 or more and less than 20. 1: 20 or more pinholes.
  • Test 5 Workability Test pieces obtained by cutting the coated steel sheets shown in Tables 6-1 and 6-2 to have a width of 5 cm and a predetermined length were subjected to JIS G 3312:2013 in an atmosphere of 20°C. A 2T bending test was performed. Specifically, two coated plates taken from the same steel plate as the test piece were sandwiched inside, and 180 degrees intimate bending was performed with the surface coated with the coating as the outside. The designability of the coated steel sheet was evaluated by observing the state of the coating film after the test and using the following evaluation criteria. 5: The coating film has no defects such as cracks and has a uniform colored appearance. No discoloration is observed.
  • Test 6 Adhesion The adhesion of the coated steel sheet (adhesion between the coating film and the inorganic film) was evaluated by the tape peeling test (used tape: Nichiban Cellotape (registered trademark)) after the workability evaluation of Test 5. The occurrence of film peeling was observed and evaluated according to the following evaluation criteria. 5: No peeling. 4: The peeled coating film was more than 0% and less than 5% of the area where the tape was attached. 3: The peeled coating film was 5% or more and less than 20% of the area where the tape was attached. 2: The peeled coating film is 20% or more and less than 50% of the area where the tape is attached. 1: The peeled coating film is 50% or more and less than 70% of the area of the tape.
  • Examples 1 to 56 of the present invention were all excellent in solvent resistance, scratch resistance, corrosion resistance, appearance (designability), workability, and adhesion.
  • Comparative Examples 1 to 5 since the inorganic coating did not contain V or Zr, the scratch resistance and the corrosion resistance were poor.
  • Comparative Example 6 since the coating film did not contain the inorganic pigment A and the inorganic pigment B, the corrosion resistance and the designability were poor.
  • Comparative Example 7 since the inorganic pigment A and the inorganic pigment B in the coating film did not contain P, the corrosion resistance was poor.
  • Comparative Examples 8 and 11 since the coating film did not contain the inorganic pigment A, the corrosion resistance and the designability were poor.
  • Comparative Example 9 since the coating film did not contain the inorganic pigment B, the designability was poor.
  • the coating film did not contain either the inorganic pigment A or the inorganic pigment B, and the inorganic pigment A or the inorganic pigment B did not contain P, so that the corrosion resistance and the designability were good. inferior.
  • the number of the inorganic pigments A and B contained in the coating film was small, and (A)/(B) was small, so that the designability was poor.
  • the number of the inorganic pigment A and the inorganic pigment B contained in the coating film was large, and (A)+(B) was more than 50 parts by volume, so that the corrosion resistance and the designability were poor.
  • Comparative Example 14 the number of the inorganic pigments B contained in the coating film is small and (A)/(B) is small, and in Comparative Example 15, the number of the inorganic pigments A contained in the coating film is large, and (A). Since /(B) was large and P was not included, the designability was poor. In Comparative Example 16, since the coating film did not contain the inorganic pigment B, the corrosion resistance and the designability were poor. In Comparative Example 18, the coating film did not contain the inorganic pigment B, so the corrosion resistance and the designability were poor. In Comparative Example 19, (A)+(B) was more than 50 parts by volume and (A)/(B) was small, so that the workability and the adhesion were poor. In Comparative Example 22, the film thickness of the coating film was 5 ⁇ m, and thus the scratch resistance was poor. In Comparative Example 23, the coating film thickness was more than 20 ⁇ m, so the designability was poor.

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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
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Abstract

Selon un mode de réalisation, la présente invention concerne une plaque d'acier recouverte comprenant une plaque d'acier, un revêtement inorganique contenant du Zn ainsi que du V ou du Zr, et un film de revêtement dont l'épaisseur est supérieure à 5 mais limitée au plus à 20 µm, contenant une résine liante, un pigment inorganique A dont la taille de particule est comprise entre 10 et 500 nm, et un pigment inorganique B dont la taille de particule est comprise entre 1 000 et 10 000 nm. Au moins l'un des pigment entre le pigment inorganique A et le pigment inorganique B contient du P. Par rapport à 100 parties en volume du film de revêtement, la quantité totale du pigment inorganique A et du pigment inorganique B dans le film de revêtement est comprise entre 5 et 50 parties en volume, et la proportion des parties en volume (A) pour le pigment inorganique A par rapport aux parties en volume (B) pour le pigment inorganique B est tel que 0,5 ≤ (A)/(B) ≤ 2,0. Dans une section transversale orthogonale à la direction de laminage du film de revêtement, lorsque t représente l'épaisseur de film du film de revêtement, le nombre de particules du pigment inorganique A est compris entre 60 et 100 000, et le nombre de particules du pigment inorganique B est compris entre 2 et 50, comme observé dans une région de t µm dans la direction d'épaisseur de la plaque de 20 µm dans une direction parallèle à la direction de largeur de la plaque.
PCT/JP2018/045652 2018-12-12 2018-12-12 Plaque d'acier recouverte WO2020121431A1 (fr)

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PCT/JP2018/045652 WO2020121431A1 (fr) 2018-12-12 2018-12-12 Plaque d'acier recouverte
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0324295A (ja) * 1989-06-22 1991-02-01 Nippon Steel Corp 黒色表面処理鋼板の製造方法
JP2010090409A (ja) * 2008-10-03 2010-04-22 Nippon Parkerizing Co Ltd 表面処理金属材料、金属表面処理用処理液、塗装金属材料、およびそれらの製造方法
JP2016194137A (ja) * 2015-03-31 2016-11-17 新日鐵住金株式会社 表面処理鋼板、及び塗装部材
WO2016199852A1 (fr) * 2015-06-09 2016-12-15 新日鐵住金株式会社 Tôle d'acier traitée en surface

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0324295A (ja) * 1989-06-22 1991-02-01 Nippon Steel Corp 黒色表面処理鋼板の製造方法
JP2010090409A (ja) * 2008-10-03 2010-04-22 Nippon Parkerizing Co Ltd 表面処理金属材料、金属表面処理用処理液、塗装金属材料、およびそれらの製造方法
JP2016194137A (ja) * 2015-03-31 2016-11-17 新日鐵住金株式会社 表面処理鋼板、及び塗装部材
WO2016199852A1 (fr) * 2015-06-09 2016-12-15 新日鐵住金株式会社 Tôle d'acier traitée en surface

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAKANO, HIROAKI ET AL.: "Electrodeposition of Zn-V Oxide Composite from Sulfate Solutions", TETSU-TO- HAGANE, vol. 93, no. 11, 1 November 2007 (2007-11-01), pages 703 - 708, XP055345526, DOI: 10.2355/tetsutohagane.93.703 *

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