WO2019124521A1 - プレコート鋼板 - Google Patents

プレコート鋼板 Download PDF

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Publication number
WO2019124521A1
WO2019124521A1 PCT/JP2018/047096 JP2018047096W WO2019124521A1 WO 2019124521 A1 WO2019124521 A1 WO 2019124521A1 JP 2018047096 W JP2018047096 W JP 2018047096W WO 2019124521 A1 WO2019124521 A1 WO 2019124521A1
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WIPO (PCT)
Prior art keywords
resin
coating film
steel sheet
steel plate
precoated steel
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PCT/JP2018/047096
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English (en)
French (fr)
Japanese (ja)
Inventor
邦彦 東新
史生 柴尾
浩雅 莊司
森下　敦司
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 CN201880081429.4A priority Critical patent/CN111479955B/zh
Priority to KR1020207019592A priority patent/KR102363571B1/ko
Priority to JP2019560576A priority patent/JP6915699B2/ja
Priority to MX2020006018A priority patent/MX2020006018A/es
Publication of WO2019124521A1 publication Critical patent/WO2019124521A1/ja

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • B32B15/09—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 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
    • 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
    • B32B15/098—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 condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a precoated steel sheet.
  • Priority is claimed on Japanese Patent Application No. 2017-243736, filed Dec. 20, 2017, the content of which is incorporated herein by reference.
  • coated products to be coated after processing and precoated steel plates coated with a coating are used.
  • Patent Document 1 discloses a coated steel plate having a coating film containing a plurality of rust preventive pigments on a Zn plating layer.
  • Patent Document 2 discloses a chromate-free black-coated metal sheet on which a black film based on a resin having a thickness of 2 to 10 ⁇ m is formed.
  • a black film based on a resin having a thickness of 2 to 10 ⁇ m is formed.
  • resistance to rubbing, resistance to sweat, corrosion resistance in processed parts, adhesion, and resistance to end face cohesive peeling are required.
  • the chromate-free black-coated metal sheet described in Patent Document 2 has a problem that wrinkles appear on the coating film until it is processed or during processing, and wrinkles are noticeable due to the wrinkles on the steel plate. Moreover, when a chemical conversion treatment was not performed between a coating film and a metal plate, it was a subject that adhesiveness was inferior remarkably.
  • Patent Document 3 discloses a steel plate provided with a plating layer containing Zn and V, and on which a coating film is applied.
  • the plated layer containing Zn and V is hard so that it is hard to get wrinkles, and since it is black, it is hard to be noticeable, so it is excellent in scratch resistance.
  • a steel plate having a coating film containing an organic resin on a plating layer containing Zn and V described in Patent Document 3 may be inferior in perspiration resistance and corrosion resistance of a processed portion.
  • perspiration resistance refers to a phenomenon in which, after perspiration adheres to a steel plate, permeating penetrates the coating film and the coating film is discolored, or perspiration dissolves the base of the coating film.
  • the coating film contains a water-dispersed resin containing a sulfonic acid group, a water-dispersed urethane resin, etc., it is known that the perspiration resistance is inferior.
  • the plated layer containing Zn and V was susceptible to cracking during processing and, at the same time, also cracking in the coating film, so that the corrosion resistance at the processed portion was inferior.
  • a coating film excellent in elongation is difficult to crack, but there is a problem that when the cut end face slides when the coated steel plate is pressed, the coating film is agglutinated and peeled (end film agglutinated peeling).
  • the “end-face coating film cohesive peeling” is a phenomenon in which the coating film at the cutting end peels off due to the cohesive failure of the coating film itself caused by the ironing process.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a precoated steel sheet which is excellent in scratch resistance, sweat resistance, corrosion resistance of a processed part, and end face cohesive peeling property.
  • the present inventors diligently studied to solve the above problems.
  • excellent scratch resistance, sweat resistance and the like can not be obtained unless the surface treatment and the primer layer are used between the steel plate and the coating film.
  • a binder resin having a butylated melamine resin and an OH group directly on a plating layer containing one or more of vanadium and zirconium and zinc without using an undercoating and a primer layer And curing reaction to form a coating film having a predetermined glass transition temperature, and it is found that excellent scratch resistance, perspiration resistance, end coating film cohesive peeling property, and corrosion resistance of a processed part can be obtained.
  • the Here, immediately above means that they are in contact without sandwiching the other layer therebetween.
  • the gist of the present invention is as follows. (1) The precoated steel sheet according to one aspect of the present invention is formed on a steel sheet, a plated layer containing at least one of vanadium and zirconium and zinc on at least one surface of the steel sheet, and directly on the plated layer. And a coating film comprising a cured product of a binder resin having an OH group and a butylated melamine resin, having a glass transition temperature of 25 ° C. to 80 ° C.
  • the zinc concentration is 5% of the maximum value starting from the depth position A at which the zinc concentration reaches the maximum value in the measurement range, and the depth position
  • the carbon concentration is always 1 atomic% or more in a range where the depth position B located closer to the steel plate side than A is the end point, and at the depth position A, the ratio of the carbon concentration to the zinc concentration is 8% or more It may be.
  • R1 to R6 of the structural units represented by the following formula (1) are —CH 2 OC 3 H You may have seven .
  • the binder resin is a polyester resin having an OH group, a polyol addition epoxy resin, a polyol addition polyurethane resin, a polyol addition olefin resin, a polyol It may be one or more selected from the group consisting of addition acrylic resin.
  • the binder resin may not contain a sulfonic acid group.
  • the glass transition temperature of the binder resin may be 7 ° C. or more and 71 ° C. or less.
  • the binder resin may have a hydroxyl value of 5 to 50 KOHmg / g.
  • the coating film may further contain a methylated melamine resin.
  • the precoated steel sheet according to any one of (1) to (8) may contain an adduct of a silane coupling agent in the coating.
  • the thickness of the coating film may be more than 5 ⁇ m and 20 ⁇ m or less.
  • the coating may further contain an epoxy resin.
  • FIG. 1 is a schematic cross-sectional view of a precoated steel plate 10 according to an embodiment of the present invention.
  • the precoated steel sheet 10 of the present invention contains zinc (Zn) and vanadium (V) or Zn and zirconium (Zr) by cathodic electrolytic treatment on at least one surface of the steel sheet 1 (that is, one surface or both surfaces of the steel sheet 1).
  • the resin may not sufficiently enter the plating layer and sufficient adhesion may not be obtained (Table 6) -2).
  • the steel plate 1 is not particularly limited.
  • extremely low C type, Al-k type, two phase structure type for example, structure including martensite in ferrite
  • processing induced transformation type structure including retained austenite in ferrite
  • microcrystalline type ferrite mainly A steel plate of any type such as a structure
  • the plating layer 2 contains, as elements, one or more of V and Zr and Zn ions. Specifically, the plating layer 2 contains any one or more of V and Zr metals, oxides, and hydroxides, and any one or more of Zn metals, oxides, and hydroxides.
  • the plating layer 2 is produced from an electrolytic treatment bath composed of a solution containing one or more of V and Zr and Zn ions.
  • the plating layer 2 can be produced by subjecting the steel plate 1 to cathodic electrolytic treatment using a solution containing one or more of V ions and Zr ions and Zn ions.
  • a solution containing one or more of V ions and Zr ions and Zn ions can be prepared by a conventionally known method. Specifically, it can be obtained, for example, by dissolving Zn sulfate, vanadyl oxide or zirconyl nitrate in an inorganic acid such as sulfuric acid.
  • the pH of the solution containing one or more of V ions and Zr ions and Zn ions is preferably 1.0 to 4.0.
  • the pH is lower than 1.0, one or more of V and Zr may not be taken into the plating layer 2.
  • the pH is greater than 4.0, V ions or Zr ions are precipitated as oxides in a solution containing one or more of V and Zr and Zn ions, and are not taken into the plating layer 2.
  • the ion) is preferably 0.20 to 0.90. If it is smaller than 0.20 or larger than 0.90, one or more of V ions and Zr ions may not be taken into the plating layer 2.
  • the component composition of the metal ion or plating layer 2 in a solution containing one or more of V ion and Zr ion and Zn ion can be obtained by a known method such as ICP (Inductively Coupled Plasma) emission spectroscopy or fluorescent X-ray spectroscopy. It can be analyzed.
  • ICP Inductively Coupled Plasma
  • the plating layer 2 is dissolved and measured with a solution in which an inhibitor is added to hydrochloric acid or the like so that the steel plate 1 does not dissolve.
  • the lower limit of the adhesion amount of Zn in the plating layer 2 is preferably 1.5 g / m 2 or more. When the adhesion amount of Zn is 1.5 g / m 2 or more, the scratch resistance is improved.
  • the upper limit of the adhesion amount of Zn is preferably 9 g / m 2 or less. It is because the adhesiveness of the plating layer 2 and the steel plate 1 improves that the adhesion amount of Zn is 9 g / m ⁇ 2 > or less, and an end-face coating film cohesion peeling property improves.
  • V ion and Zr ion When one or more kinds of V ion and Zr ion are present together with Zn ion in a solution containing one or more kinds of V ion and Zr ion and Zn ion, one or more kinds of V and Zr and Zn are like dendrite It precipitates on the outermost surface of the steel plate or the plating deposited previously, and a plating layer is formed. Therefore, many irregularities are formed on the surface of the plating layer 2 formed by performing the cathodic electrolytic treatment in the coexistence of Zn ions and one or more of V ions and Zr ions.
  • the total adhesion amount of one or more of V and Zr is preferably 0.35 g / m 2 or more and 1.00 g / m 2 or less in terms of V or Zr.
  • the total adhesion amount of one or more of V and Zr is 0.35 g / m 2 or more, one or more of Zn, V and Zr grow in a dendritic shape, so that the end face film cohesive peeling releasability is improved To be preferred.
  • V ion and Zr ion and Zn ion either V ion or Zr ion may be present alone, or both V ion and Zr ion are present. It may be
  • the mass ratio of one or more of V and Zr in the plating layer 2 to Zn is the mass ratio of the content of one or more of V and Zr to the content of Zn in terms of metal ((1 The species or more) / Zn) is preferably 0.05 to 0.50. If it is less than 0.05, it is not preferable because of the poor cling resistance. If it is more than 0.50, the adhesion between the plating layer 2 and the steel plate 1 is poor, and the end face film cohesive peeling property is poor, which is not preferable.
  • the glass transition temperature (Tg) of the coating 3 formed directly on the plating layer 2 is 25 ° C. or more and 80 ° C. or less. Tg is preferably 50 ° C. or more and 80 ° C. or less. If the Tg is less than 25 ° C., the cohesion of the coating film 3 is small, which is not preferable because it is inferior in perspiration resistance and edge coating cohesion releasability. If the temperature is higher than 80 ° C., the cohesion of the coating film 3 is large and the coating film 3 is hard, so that a large coating film crack is generated with the plating, which is not preferable because it is inferior in the corrosion resistance at the processed portion.
  • the Tg of the coating 3 can be measured using a rigid pendulum tester according to the method of measuring the thermal properties (Tg, hardness) of the coating according to ISO 12013-2.
  • the coating film 3 is excellent in perspiration resistance and end face coating film cohesiveness releasability by containing a butylated melamine resin and a binder resin having an OH group.
  • a butylated melamine resin and a binder resin having an OH group are mentioned as components of sweat.
  • sodium chloride, lactic acid, amino acids, urea and the like are mentioned.
  • resistance to sodium chloride and lactic acid artificial sweat.
  • a cured product of the binder resin having an OH group and the butylated melamine resin is formed in the coating film.
  • the OH group is necessary for the curing reaction for crosslinking the binder resin having an OH group and the butylated melamine resin.
  • a butylated melamine resin and a binder resin having an OH group to control the Tg of the coating film 3
  • a precoated steel plate 10 excellent in the corrosion resistance at the machined part and the end face coating film cohesive peeling property was obtained. .
  • polyester resin which has OH group which can be used for the coating film 3
  • polyester resin which has OH group epoxy resin (polyol addition epoxy resin) made to react using polyol, polyurethane resin (polyol addition polyurethane resin) And resins such as olefin resin (polyol added olefin resin) and acrylic resin (polyol added acrylic resin).
  • the OH group-containing binder resin may be only one type selected from the group of these resins, or two or more types.
  • the binder resin which has OH group does not contain a sulfonic acid group.
  • the binder resin having an OH group contains a sulfonic acid group, the sweat resistance of the coating film 3 is not preferable, which is not preferable.
  • the hydroxyl value of the binder resin having an OH group is preferably 50 or less. More preferably, it is 30 or less.
  • the lower limit of the hydroxyl value of the binder resin having an OH group is preferably 5 or more. More preferably, it is 7 or more. If the hydroxyl value is more than 50, the corrosion resistance at the machined part may be lowered, which is not preferable. Moreover, since Tg of the coating film 3 may exceed 80 degreeC, it is unpreferable. If the hydroxyl value is less than 5, it is not preferable because the reaction with butylated melamine does not proceed sufficiently. Moreover, since Tg may become less than 25 degreeC, it is unpreferable.
  • the unit of a hydroxyl value is KOHmg / g.
  • the epoxy resin As the epoxy resin, the polyurethane resin, the olefin resin and the acrylic resin, generally known resins can be used.
  • As the epoxy resin “jER (registered trademark)” manufactured by Japan Epoxy Resins Co., Ltd., “EPICLON (registered trademark) series” manufactured by DIC, and the like can be used.
  • As the urethane resin "Baihydrol (registered trademark) series” manufactured by Sumika Bayer Urethane Co., Ltd., “Cosmonate (registered trademark) series” manufactured by Mitsui Chemicals, "Hicell (registered trademark) series” manufactured by Toho Chemical Industry, DIC A company-made “bondic (registered trademark) series” etc. can be used.
  • olefin resin "Hitec (registered trademark) series” manufactured by Toho Chemical Industry Co., Ltd. can be used.
  • acrylic resin "Acrydic (registered trademark) series” manufactured by DIC, “Acryset (registered trademark) series” manufactured by Nippon Shokubai Co., Ltd., or the like can be used.
  • the binder resin having an OH group used for the coating film 3 is a polyester resin, it is preferable because the processed part corrosion resistance is more excellent.
  • the polyester resin is excellent in ductility and excellent in processability.
  • Alkyd resins, unsaturated polyester resins, modified alkyd resins and the like are used as polyester resins having an OH group.
  • the alkyd resin is a resin in which a condensation product of a polybasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin is used as a skeleton, and this is modified with a fatty acid oil.
  • Alkyd resins are classified into short oil-based alkyd resins, middle oil-based alkyd resins, long oil-based alkyd resins and ultralong oil-based alkyd resins according to the type and content of fats and oils used.
  • Unsaturated polyester resins are synthesized by esterifying unsaturated polybasic acids or saturated polybasic acids with glycols.
  • polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid and adipic acid, and glycols include propylene glycol.
  • glycols include propylene glycol.
  • the modified alkyd resin a natural resin, a phenol resin, or a resin modified with a polymerizable monomer such as styrene can be used.
  • polyester resin which has OH group a well-known polyester resin can be used.
  • polyester resin other than the above for example, "Byron TM” (Toyobo Co. R) manufactured by Toyobo Co., Ltd. and, Sumika Bayer Urethane Co., Ltd. "Desmophen TM” (Sumika Bayer Urethane Co. registered trademark) commercially available, such as Goods can be used.
  • Byron TM Toyobo Co. R
  • Desmophen TM Sudika Bayer Urethane Co. registered trademark
  • the resulting coating film 3 is more excellent in perspiration resistance, end coating film cohesion removability, and corrosion resistance of the processed portion It is suitable. If the temperature is less than 7 ° C., the cohesion of the obtained coating film 3 is insufficient and the perspiration resistance and the end face coating film cohesion releasability are unfavorably lowered. If the temperature is higher than 71 ° C., a large crack may be formed in the processed portion of the coating 3 and the corrosion resistance of the processed portion may be reduced, which is not preferable.
  • the Tg of the coating film 3 can be controlled by reacting a butylated melamine resin in the range of this Tg with a binder resin having an OH group at a predetermined temperature and a predetermined amount.
  • the resulting coating film 3 is more excellent in sweat resistance, end coating film cohesive peeling properties, and corrosion resistance of the processed portion. If it is less than 7 ° C., the cohesion of the obtained coating film 3 is insufficient, and the perspiration resistance and the end face coating film cohesive peeling property are inferior. If the temperature is higher than 71 ° C., a large crack is formed in the processed portion of the coating 3 and the corrosion resistance of the processed portion is inferior.
  • the Tg of the coating film 3 can be controlled by reacting a butylated melamine resin in this Tg range with a polyester resin at a predetermined temperature and a predetermined amount.
  • the proportion of the binder resin having an OH group in the coating 3 is preferably 50% by mass or more and 95% by mass or less with respect to the total resin constituting the coating 3.
  • the binder resin having an OH group is 50% by mass or more, the reaction between the binder resin having an OH group and the butylated melamine resin proceeds, and the coating film 3 becomes difficult to peel off, which is preferable.
  • Tg of the coating film 3 can be adjusted to 25 degreeC or more by the binder resin which has OH group being 50 mass% or more, it is preferable.
  • Tg of the coating film 3 can be adjusted to 80 degrees C or less by the ratio of the binder resin which has OH group being 95 mass% or less.
  • the proportion of the polyester resin having an OH group in the coating 3 is preferably 50% by mass or more and 95% by mass or less with respect to the entire resin constituting the coating 3.
  • R 1 to R 6 of the structural units represented by the following formula (1) are —CH 2 OC 3 H 7 .
  • R which is not —CH 2 OC 3 H 7 can be a group selected from H, CH 2 OH and CH 2 OCH 3 .
  • the butylated melamine resin commercially available butylated melamine resin can be used. Since a butylated melamine resin is usually insoluble in water, it is used as a paint using an organic solvent as a solvent.
  • the butylated melamine resin in the coating film 3 is 5 mass% or more and 50 mass% or less with respect to all the resin which comprises the coating film 3. If the content of the butylated melamine resin is 5% by mass or more, the reaction between the butylated melamine resin and the binder resin having an OH group proceeds, the coating film 3 becomes difficult to peel off, and the corrosion resistance at the processed portion is improved. By making the butylated melamine resin 50% by mass or less, it is preferable because the corrosion resistance at the processed part is improved.
  • the coating film 3 of the present invention may further contain a methylated melamine resin.
  • a methylated melamine resin and a butylated melamine resin is more preferable because the solvent resistance is excellent.
  • R 1 to R 6 of the structural units represented by the following formula (2) is —CH 2 OCH 3 .
  • R which is not —CH 2 OCH 3 can be a group selected from H and CH 2 OH.
  • the coating 3 may contain carbon black in an amount of 1% by mass to 20% by mass relative to the total solid content of the coating 3. Carbon black is preferable because it is more excellent in the design of the coating film when the carbon black is contained than when the carbon black is not contained.
  • the carbon black which can be used is not particularly limited, and for example, known carbon blacks such as furnace black, ketjen black, acetylene black and channel black can be used. Also, known ozone treated, plasma treated, liquid phase oxidized carbon black can be used.
  • a silane coupling agent may be contained in the paint used to produce the coating 3.
  • the addition of a silane coupling agent is preferable because the adhesion between the plating layer 2 and the coating film 3 is improved by the siloxane oligomer produced by the decomposition of the silane coupling agent.
  • the siloxane oligomer produced by the decomposition reacts with the hydroxyl group on the surface of the plating layer 2, the resin in the coating film 3 and the like. That is, an adduct of a silane coupling agent which is a reaction product of the siloxane oligomer and the hydroxyl group on the surface of the plating layer 2 or the resin in the coating 3 is formed.
  • the amount of silane coupling agent in the paint is preferably 1% to 20% by weight of the weight of the paint.
  • a common silane coupling agent can be used as a silane coupling agent.
  • a silane coupling agent for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxy
  • the film thickness of the coating film 3 is preferably more than 5 ⁇ m and 20 ⁇ m or less, and in this range, the sweat resistance of the coating film 3 and the end face coating film cohesive peeling property are excellent, so this range is preferable. If it is 5 ⁇ m or less, the barrier property is reduced and the sweat resistance is poor, which is not preferable. Further, if it exceeds 20 ⁇ m, the internal stress becomes large, the adhesion with the plating layer 2 is inferior, and the end face coating film cohesive peeling property is inferior, which is not preferable.
  • the film thickness of the coating film 3 can be determined by cross-sectional observation at 2000 times with an electron microscope and dividing the area of the coating film portion by the length in the longitudinal direction of the coating film. In addition, the area of a coating film part is obtained by analyzing the image obtained by cross-sectional observation with commercially available image analysis software.
  • the coating film 3 may further contain an epoxy resin separately from the binder resin having an OH group.
  • an epoxy resin By using an epoxy resin, the epoxy group is bonded to the surface of the plating layer 2 and thus it is preferable because sweat resistance and adhesion are more excellent.
  • a well-known epoxy resin can be used as an epoxy resin.
  • bisphenol A epoxy resin bisphenol F epoxy resin, novolac epoxy resin, etc. may be mentioned.
  • the coating 3 may contain an anticorrosive pigment.
  • an anticorrosive pigment known pigments generally applied to zinc-based plating can be used. For example, phosphorus-based, silica-based, vanadium-based and the like can be mentioned.
  • the depth at which the Zn concentration is 5% of the maximum value and located closer to the steel plate than the depth position A C concentration is always 1 atomic% or more (in elements which can be detected by GDS (C, Fe, H, N, Na, Ni, O, P, S, Si, Ti, V, Zn) in a range where the position B is an end point In the depth position A, the ratio of the C concentration to the Zn concentration is 8% or more.
  • FIG. 2 is a view showing the concentration distribution of V, Zn and C in the depth direction obtained by measuring the precoated steel plate 10 according to the embodiment of the present invention by the glow discharge light emission method.
  • the horizontal axis indicates the depth from the surface of the coating film 3, and the vertical axis indicates the change in concentration of each element.
  • C concentration is always 1 atomic% or more in a range starting from the depth position A and ending at the depth position B, and C at the depth position A with respect to Zn concentration
  • concentration ratio of 8% or more is satisfied. Satisfying this relationship indicates that the binder resin having an OH group and the melamine resin enter into the plating layer 2 without a void.
  • the binder resin having an OH group and the melamine resin enter into the plating layer 2
  • a sufficient anchor effect is obtained, and the adhesion between the coating 3 and the plating layer 2 is largely improved.
  • (Film forming method) As a method of applying the paint used for producing the coating film 3, for example, 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 an immersion method can be used. After the formation of the plating layer 2, washing and drying, the coating is applied. It is preferable to apply a paint within 120 seconds after drying of the plating layer 2. In general, when not applied immediately after drying of the plating layer 2, it is often coated with oil for rust prevention, then degreased and then painted. However, when degreasing, the surface activity is lower than immediately after the formation of the plating layer 2, and the resin of the coating 3 may not easily enter the plating layer 2.
  • the surface activity is low, and the resin of the coating 3 may not easily enter the plating layer 2.
  • the adhesion between the plating layer 2 and the coating film 3 is excellent if the time taken to apply the coating after forming and drying the plating layer 2 is 120 seconds or less, the coating film between the plating layer 2 and the coating film 3
  • the interfacial peeling of 3 can be suppressed.
  • interfacial peeling between the coating 3 and the plating layer 2 may occur instead of coating peeling due to cohesive failure, which can be suppressed.
  • the dynamic surface tension of the paint is adjusted to 15 mN / m or more and 30 mN / m or less. If the dynamic surface tension of the paint is less than 15 mN / m and more than 30 mN / m, the paint can not penetrate into the irregularities of the plating layer 2, which is not preferable.
  • a surfactant including an antifoaming agent and a leveling agent
  • a surfactant including an antifoaming agent and a leveling agent
  • known surfactants can be used, and commercially available surfactants such as BYK-333 and BYK-307 by BYK, Elmagen by Kao, and Surfynol by Nisshin Kagaku are known. However, there are many others, and they can be appropriately added according to the paint to be used. In addition, adjustment methods other than using a surfactant such as dilution or mixing of other solvents may be used.
  • a hot air, induction heating, near infrared rays, direct fire etc. can be used individually or in combination.
  • the paint is cured by heating, and those skilled in the art can adjust Tg by appropriately controlling the heating temperature and the holding time.
  • the paint is heated at a heating temperature (final plate temperature) of 150 ° C. or more and 250 ° C. or less. When the temperature is less than 150 ° C., the curing of the coating is insufficient and the solvent resistance is poor. When the temperature is more than 250 ° C., the coating is decomposed and the solvent resistance is poor.
  • the holding time is 8 seconds to 120 seconds. The holding time is the time for which the heating is held after reaching the set temperature. When the holding time is more than 120 seconds, the Tg of the coating 3 may be more than 80 ° C., which is not preferable. If the holding time is less than 8 seconds, the Tg of the coating 3 may be less than 25 ° C., which is not preferable.
  • Example 1 Steel Plate As a steel plate, a steel plate having a thickness of 0.8 mm was used as SPCD for drawing a general cold rolled steel plate described in JIS G 3141. 2. Plating layer A solution A containing Zn ions and V ions and a solution B containing Zn ions and Zr ions were prepared. Solution A was prepared by mixing Zn sulfate and vanadyl oxide in sulfuric acid, and solution B was prepared by mixing Zn sulfate and zirconyl nitrate in sulfuric acid. The composition of the plating layer was adjusted by the amount of these solution components. The pH was adjusted with the amount of sulfuric acid and the amount of Na hydroxide.
  • a plated layer was formed on the above steel plate by cathodic electrolytic treatment (current density: 20 to 150 A / dm 2 ). Each component in the formed plating layer was identified and confirmed by ICP emission spectrometry.
  • the components of the prepared solution are listed in Table 1, and the components of the plating layer are listed in Table 2.
  • Table 1 the mass (g / L) of each ion was converted from the mass of Zn sulfate used, vanadyl oxide, and zirconyl nitrate used.
  • the paint was prepared by mixing and stirring the resins described in Table 3-1, Table 3-2, and Table 3-3, and optionally the inorganic pigments described in Table 4, using Solvesso 150 as a solvent (solid content) 30%).
  • the Saimel 327 and the Saimel 325 in Table 3-2 are methylated melamine resins, and the Mycoat 506 is a butylated melamine resin.
  • the paints produced are described in Table 5. Paints 32 and 33 are water-based paints in which 95% or more of the solvent is water (solid content: 30%).
  • the paint described in Table 5 is coated with a bar coater to a thickness of 10 ⁇ m Then, the coating was heated with a hot air furnace and held for 8 to 120 seconds so that the heating temperature (final plate temperature) was 200 ° C. in 30 seconds. Thereafter, it was immersed in water and cooled to form a coating film.
  • the surfactant "Surfynol 104 (manufactured by Nisshin Chemical Co., Ltd.)" was used to adjust the dynamic surface tension of the paint.
  • the coating film of the produced precoated steel plate is described in Table 6.
  • the Tg of the coating was measured using a rigid pendulum tester according to the method of measuring the thermal properties (Tg, hardness) of the coating according to ISO 12013-2.
  • the evaluation results are described in Table 6.
  • the dynamic surface tension of the paint was measured by Kyowa Interface Science BP-D5 (maximum bubble pressure method), and the time from the minimum bubble pressure to the maximum bubble pressure was 100 ms.
  • the evaluation results are described in Table 6.
  • the GDS of the coating was measured using GD-PROFILER2 manufactured by Horiba, Ltd. under the conditions of a discharge power of 35 W and an argon pressure of 600 Pa, with the surface of the coating as the starting point and the steel plate as the end point to measure the spectral intensity in the depth direction.
  • the depth position B where the Zn concentration is 5% of the maximum value and located closer to the steel plate than the depth position A is the end point.
  • C concentration is always 1 atomic% or more, and a case where the ratio of C concentration to Zn concentration at depth position A is 8% or more is Good, and a case of less than 8% is Bad.
  • the evaluation results are described in Tables 6-1 and 6-2.
  • Test 1 Sweat Resistance 0.05 ml of artificial sweat fluid (Method D) (JIS L 0848) was dropped on a test piece prepared by cutting a precoated steel plate prepared under the conditions described in Tables 6-1 and 6-2 to 50 ⁇ 100 mm, After leaving for 24 hours under the conditions of 40 degrees relative humidity and 98%, the state of the dripping mark was evaluated by the following evaluation criteria. Pass was made 3 or more by the following evaluation criteria. 5: There is no trace left. 4: There is a very slight mark (a level at which the mark can be discerned from an angle) 3: There is a slight mark (a level at which the mark can be determined from the front) 2: Clearly mark. (Level that trace can be judged instantly) 1: The steel plate is exposed.
  • Test 2 Wrinkling resistance After installing test specimens prepared by cutting pre-coated steel plates manufactured under the conditions described in Tables 6-1 and 6-2 into 50 ⁇ 100 mm in a rubbing tester, at the tip of the sliding jig of the rubbing tester, Ms. A cylindrical eraser manufactured by Toray Industries, Ltd. was attached, and the film state after 100 cycles of rubbing with a load of 16 N was evaluated according to the following evaluation criteria. Pass was made 3 or more by the following evaluation criteria. 5: There is no exposure of the steel plate. 4: The exposed width of the steel plate is less than 1 mm. 3: The exposed width of the steel plate is 1 mm or more and less than 2 mm. 2: The exposed width of the steel plate is 2 mm or more and less than 3 mm. 1: The exposed width of the steel plate is 4 mm or more.
  • Test 3 Corrosion resistance of processed parts A test plate obtained by cutting a precoated steel plate prepared under the conditions described in Tables 6-1 and 6-2 to 50 ⁇ 50 mm is extruded by 7 mm using an Erichsen tester, and the edge and back surface of the test plate are tape sealed A salt spray test (SST) (JIS-Z-2371) was performed. The occurrence of white rust after 24 hours was observed and evaluated according to the following criteria. Pass was made 3 or more by the following evaluation criteria. 5: There is no rust. 4: Rust generation area is less than 1%. 3: The rust generation area is 1% or more and less than 5%. 2: The rust generation area is 5% or more and less than 10%. 1: The rust generation area is 10% or more.
  • Test 4 End coating film cohesive peeling releasability
  • the pre-coated steel plate prepared under the conditions described in Tables 6-1 and 6-2 is cut, and the lower burr portion formed on the lower side of the cut steel plate is further subjected to a burr direction using a mold After processing into (the direction of burrs produced when cut), the tape was firmly attached to the coating on the end face, and after peeling off the tape was visually observed to check for the peeling of the coating. Pass was made 3 or more by the following evaluation criteria. 5: The coating does not peel at all. 4: Peeling of the coating is less than 10% of the area where the tape is applied. 3: Peeling of the coating film is 10% or more and less than 30% of the area where the tape is attached. 2: Peeling of the coating film is 30% or more and less than 50% of the area where the tape is attached. 1: Peeling of a coating film is 50% or more of the area which stuck the tape.
  • Test 5 Solvent resistance 49.03 kPa (0.5 kgf) of cotton-impregnated cotton impregnated with ethanol after installing a test plate prepared by cutting the pre-coated steel plate prepared under the conditions described in Tables 6-1 and 6-2 into 50 ⁇ 50 mm in a rubbing tester. The state of the coating after 10 cycles of rubbing with a load of 1 / cm 2 ) was evaluated according to the following evaluation criteria. Pass was made 3 or more by the following evaluation criteria. 5: There is no mark on the rubbing surface at all. 4: There is a very slight mark on the rubbing surface (a level at which you can distinguish the rubbing trace by focusing your eyes).
  • a slight mark is formed on the rubbed surface (a level at which rubbing marks can be easily identified if the eyes are tightened).
  • a clear mark is formed on the rubbing surface (a level at which rubbing marks can be instantly determined). 1: The coating film is dissolved on the rubbing surface, and the substrate is exposed.
  • Adhesion Test pieces of the precoated steel sheet prepared under the conditions described in Tables 6-1 and 6-2 were cut into a width of 5 cm in accordance with JIS. 2 T bending was performed in an atmosphere at 20 ° C. according to a test method according to G3312. The processed part was subjected to a tape peeling test (tape used: tape manufactured by Nichiban Co., Ltd.) to observe the occurrence of peeling of the coating film. Pass was made 3 or more by the following evaluation criteria. 5: No peeling 4: The peeled coating is less than 5% of the area on which the tape is applied. 3: 5% or more and less than 20% of the area where the peeled coating film is attached to the tape. 2: The peeled coating film is 20% or more and less than 50% of the area on which the tape is attached. 1: 50% or more and less than 70% of the area where the peeled coating film is attached to the tape.
  • Tables 7-1 and 7-2 The evaluation results of the above tests are summarized in Tables 7-1 and 7-2. As can be seen from Tables 7-1 and 7-2, all of the examples (invention examples) of the present invention were excellent in sweat resistance, scratch resistance, corrosion resistance of a processed part, solvent resistance, and adhesion.
  • Comparative Examples 1 to 5 since the plating layer did not contain V and Zr, the result was that the resistance to cracking and corrosion resistance at the processed portion were inferior.
  • Comparative Example 6 did not contain a binder resin having an OH group in the coating film, and therefore, the result was inferior in perspiration resistance, end coating film aggregation releasability, and the like.
  • Comparative Examples 7 and 9 since the Tg of the coating film was low, the result was inferior in perspiration resistance, end coating film cohesive removability, and the like.
  • the paint 2 used in Comparative Example 7 has the same composition as the paint 3 used in Example 15.
  • the Tg of Comparative Example 7 is lower than the Tg of Example 15 by adjusting the heating conditions.
  • Comparative Examples 8 and 10 since the Tg of the coating film was high, the corrosion resistance at the processed portion was poor. Since the comparative example 11 does not contain a butylated melamine resin in a coating film, it became a result to which a process part corrosion resistance, an end surface coating film cohesive peeling property, etc. are inferior. In Comparative Examples 12 and 13, since the Tg of the coating film was low, the end-face coating film cohesive peelability was poor. Since comparative examples 14 and 15 do not contain butylated melamine resin in a coating film, it became a result to which processing part corrosion resistance, end surface coating film cohesive peeling property, and adhesiveness are inferior. Since the comparative example 16 does not contain a melamine resin, it became a result to which the process part corrosion resistance, the end face coating film cohesive peeling property, and adhesiveness are inferior.
  • the precoated steel sheet of the present invention is excellent in scratch resistance, sweat resistance, corrosion resistance of the processed portion, and cohesive end removability on end faces, and therefore, for automobiles, home appliances, construction materials, civil engineering, machines, furniture, containers It is extremely useful for

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