WO2020213690A1 - Zinc-based plated steel sheet - Google Patents
Zinc-based plated steel sheet Download PDFInfo
- Publication number
- WO2020213690A1 WO2020213690A1 PCT/JP2020/016765 JP2020016765W WO2020213690A1 WO 2020213690 A1 WO2020213690 A1 WO 2020213690A1 JP 2020016765 W JP2020016765 W JP 2020016765W WO 2020213690 A1 WO2020213690 A1 WO 2020213690A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- layer
- steel sheet
- hairline
- oxide layer
- Prior art date
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- 239000011701 zinc Substances 0.000 title claims abstract description 460
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 402
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 399
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 244
- 239000010959 steel Substances 0.000 title claims abstract description 244
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- 238000009499 grossing Methods 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- 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
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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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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- 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
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Definitions
- the present invention relates to a galvanized steel sheet.
- the present application claims priority based on Japanese Patent Application No. 2019-078556 filed in Japan on April 17, 2019 and Japanese Patent Application No. 2019-18265 filed in Japan on October 3, 2019. These contents are incorporated here.
- design is required for articles that people can see, such as electrical equipment, building materials, and automobiles.
- a method of enhancing the design a method of painting or attaching a film to the surface of an article is common, but in recent years, mainly in nature-oriented Europe and the United States, materials that make use of the texture of metal have been used.
- the application is increasing. From the viewpoint of utilizing the texture of metal, painting and resin coating impair the texture of metal, so stainless steel and aluminum, which have excellent corrosion resistance even when unpainted, are used as the material of the article. Further, in order to improve the design of the stainless steel material or the aluminum material, fine arcuate irregularities called vibrations are added, or embossing is performed.
- the appearance with fine linear irregularities called hairlines is preferred and is often used.
- they may be colored.
- the coloring method a method of coating the surface of the stainless steel material or the aluminum material with a colored coating film, a method of changing the thickness of the oxide layer existing on the surface of the stainless steel material or the aluminum material, and the like are used.
- a high degree of blackness it is not preferable to color with only the coating film because the hairline is hidden and invisible.
- a method of blackening with an oxide layer is used.
- Hairline finish is defined in JIS G4305: 2012 as one of the surface finishes of stainless steel materials, "polished with an abrasive of an appropriate particle size so as to have a continuous polish”. ing.
- a technique for imparting appropriate corrosion resistance to a steel material a technique for imparting zinc plating or zinc alloy plating having excellent sacrificial corrosion resistance to the steel material is widely used.
- a technique for steel materials in which a hairline design is added to such zinc plating or zinc alloy plating hereinafter, zinc plating and zinc alloy plating are collectively referred to as "zinc-based plating"
- a hairline orthogonal to the hairline direction is used.
- a translucent adhesive layer and a translucent film layer plating layer are provided on the surface of a plating layer having a surface roughness Ra (arithmetic average roughness) of 0.1 to 1.0 ⁇ m in the orthogonal direction.
- Patent Document 1 The roughness parameters (Ra and PPI) in the hairline direction and the hairline orthogonal direction formed on the surface layer of the Zn—Al—Mg hot-dip galvanized layer are set to a specific range, and on the surface of the Zn—Al—Mg hot-dip galvanized layer.
- Technique for forming a transparent resin film layer see Patent Document 2 below
- Patent Document 3 A technique for coating a steel sheet whose texture has been transferred to Zn and Zn-based alloy plating by rolling with a resin so that the surface roughness is within a certain range.
- Patent Document 6 discloses a technique for forming a hairline on the surface of an oxide layer.
- a steel sheet rolling method in which a plated steel sheet for which a hairline is to be formed is rolled by a rolling roll or the like having a predetermined roughness, and a plating grinding method for grinding the surface of a plated steel sheet for which a hairline is to be formed are used.
- the lack of metallic feeling (metal glossiness) as described above is particularly caused by forming a hairline on the original plating plate in the above-mentioned steel sheet rolling method, then electroplating, and then depositing an oxide layer on the surface of the plating layer. This was remarkable in the plated steel sheet on which the hairline was formed.
- the stainless steel material itself has good corrosion resistance due to the oxide film existing on the surface of the stainless steel material, painting for improving the corrosion resistance is not necessary. That is, since the metal base itself can be used for the surface, basically no resin coating is required. On the other hand, when a resin coating is applied to a stainless steel material, the purpose is to impart coloring or another texture. Therefore, in stainless steel materials, the loss of metallic feeling as found by the present inventors did not pose a problem. The same applies to aluminum materials.
- Patent Document 6 discloses a technique for forming a hairline on the surface of an oxide layer.
- an oxide layer is formed by steam-oxidizing a zinc-based plating layer.
- Such steam oxidation needs to be carried out over time in a complicated and large-scale facility. Therefore, it cannot be performed in-line (that is, on the same line as other processes such as plating). Therefore, the formation of the oxide layer is costly.
- the hairline obtained by partially grinding the formed oxide layer discolors with time in the atmosphere. That is, it is necessary to control and shorten the time required for grinding to coat the upper layer with the film.
- Patent Document 6 since the oxide layer formed by steam oxidation is thick, it is necessary to form the hairline deeply in order to form the hairline to a visible level. That is, in order for the hairline to be visible, it is necessary to form the hairline at least to a depth up to the zinc-based plating layer below the oxide layer. In Patent Document 6, since the oxide layer is thick, it is necessary to form a hairline deeper by that amount. For this reason, not only is it time-consuming to form the hairline, but also a large amount of waste such as shavings is generated. Therefore, Patent Document 6 cannot fundamentally solve the problem of metallic feeling.
- the present invention has been made in view of the above problems, and an object of the present invention is to have good corrosion resistance, good blackness and hairline even when an inexpensive steel material is used. It is an object of the present invention to provide a galvanized steel sheet having an appearance and excellent metallic feeling and processing adhesion.
- the zinc-based plated steel sheet according to the embodiment of the present invention is a zinc-based plated steel sheet located on the surface of at least one of the steel sheet and the steel sheet, and has a hairline formed as a recess extending in a predetermined direction. It includes a layer and an oxide layer located on the surface of the zinc-based plating layer and having an average thickness of 0.05 ⁇ m or more and 3.0 ⁇ m or less.
- the oxide layer may be located at least on the surface of the zinc-based plated layer other than the recess.
- the zinc-based plated steel sheet according to ⁇ 1> or ⁇ 2> may further include a translucent organic resin coating layer on the surface of the oxide layer.
- the blackness of the surface of the zinc-based plated steel sheet may be 40 or less in L * value.
- the oxide layer comprises a rough portion and a smooth portion, and the rough portion has a surface roughness Ra A.
- the smooth portion includes a region having a surface roughness Ra B of more than 5 nm and 500 nm or less, and the boundary between the rough portion and the smooth portion is orthogonal to the predetermined direction.
- 1 of the maximum height Ry obtained by subtracting the lowest point H 0 from the highest point H 1 of the oxide layer within an observation width of 1 cm along the hair line orthogonal direction in the cross section in the direction orthogonal to the hairline and in the direction of the plate thickness. Assuming that the height is 3/4 and it is on a virtual straight line parallel to the hairline orthogonal direction, the oxide layer in which the boundary between the rough portion and the smooth portion is defined is viewed in a plan view and has the same area.
- an area of the coarse portion and S a, the area of the smooth portion is taken as S B, the area ratio S B / S a is from 0.6 to 10.0, and the rough portion
- the average height difference between the rough portion and the smooth portion adjacent to the rough portion may be 0.3 ⁇ m or more and 5.0 ⁇ m or less.
- Galvanized steel sheet according to ⁇ 6> above ⁇ 5> is the total area of the region the surface roughness Ra A of the rough portion is less than 500nm ultra 5000nm is, relative to the area S A of the rough portion 85 % or more, and the total area of regions the surface roughness Ra B in the smooth portion is less than 5nm super 500nm is good I is 65% or more with respect to the area S B of the smoothing section.
- the rough portion is formed in the hairline, and the average length along the stretching direction of the hairline may be 1 cm or more.
- the smooth portion is formed in the hairline, and the average length along the stretching direction of the hairline may be 1 cm or more.
- the hairline has an average of three hairlines in an arbitrary 1 cm width range along the direction orthogonal to the hairline. It may be present at a frequency of cm or more and 80 lines / cm or less.
- recesses are formed on the surface of the steel sheet at positions corresponding to the hairlines in the zinc-based plated layer. Good.
- the zinc-based plating layer is a zinc-based electroplating layer, and the average adhesion amount of the zinc-based electroplating layer is May be 5 g / m 2 or more and 40 g / m 2 or less.
- the zinc-based electroplating layer contains a total of 5 masses of any one or more additive elements selected from the group consisting of Fe, Ni, and Co. It may contain% or more and 20% by mass or less, and a balance composed of Zn and impurities.
- the zinc-based plating layer is a zinc-based hot-dip plating layer, and the average adhesion amount of the zinc-based hot-dip plating layer is May be more than 40 g / m 2 and 150 g / m 2 or less.
- the zinc-based hot-dip galvanized layer contains 1% by mass or more in total of any one or more additive elements selected from the group consisting of Al and Mg. It may contain 60% by mass or less and a balance composed of Zn and impurities.
- the organic resin coating layer may have a coloring pigment.
- the concave portion and the flat portion which is a region other than the concave portion are formed on the surface of the oxide layer, and the concave portion is formed.
- the average depth is 0.1 ⁇ m or more and less than 3.0 ⁇ m, the bottom of the recess reaches the zinc-based plating layer below the oxide layer, and the oxide layer existing in the recess is viewed in a plan view.
- the ratio AR1 / AR2 of the area ratio AR1 to the area ratio AR2 of the oxide layer existing in the flat portion in a plan view may be 0 or more and 0.5 or less.
- the zinc-based plated steel sheet according to ⁇ 17> may have an average depth of the recesses of 0.1 ⁇ m or more and less than 2.0 ⁇ m.
- the zinc-based plating layer may be a zinc-based electroplating layer.
- the oxide layer is selected from the group consisting of zinc hydroxide and zinc oxide. The above may be included.
- the zinc-based plated steel sheet according to any one of ⁇ 16> to ⁇ 18> may have an average thickness of the oxide layer of 0.05 ⁇ m or more and less than 3.0 ⁇ m.
- the recess includes a region where the surface roughness RaA'is more than 5 nm and 500 nm or less, and the flat portion has a surface roughness. It may include a region where RaB'is more than 500 nm and less than 5000 nm.
- the zinc-based plated steel sheet according to any one of ⁇ 16> to ⁇ 21> may have an average length of 1 cm or more along the length direction of the recess.
- the recesses In the zinc-based plated steel sheet according to any one of ⁇ 16> to ⁇ 22>, the recesses have an arbitrary width of 1 cm along a direction orthogonal to the length direction of the recesses. On average, it may be present at a frequency of 3 lines / cm or more and 80 lines / cm or less.
- the average adhesion amount of the zinc-based plated layer may be 5 g / m 2 or more and 40 g / m 2 or less. .. ⁇ 25>
- the zinc-based plated steel sheet according to any one of ⁇ 16> to ⁇ 24> is selected from the group in which the oxide layer is composed of Fe, Ni, and Co as the second component. It may contain more than a species of additive element.
- the zinc-based plated layer is one or more selected from the group consisting of Fe, Ni, and Co.
- the organic resin coating layer may contain a black pigment.
- the zinc-based plated steel sheet according to ⁇ 27> has two or more organic resin coating layers, and the black pigment may be contained in any one or more layers other than the bottom layer.
- the organic resin coating layer may further contain any one or more additive elements selected from Si, P, and Zr.
- the "%" indication of the content of each element in the chemical composition means “mass%”.
- the numerical range represented by using “-” means a range including the numerical values before and after "-” as the lower limit value and the upper limit value.
- the numerical range when "greater than” or “less than” is added to the numerical values before and after “to” means a range in which these numerical values are not included as the lower limit value or the upper limit value.
- the term “process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
- the galvanized steel sheet according to the embodiment of the present invention is Steel plate and A zinc-based plating layer located on at least one surface of the steel sheet and having a hairline formed as a recess extending in a predetermined direction.
- the galvanized steel sheet according to the present embodiment has good corrosion resistance, good blackness and hairline appearance, metallic feeling and processing even when an inexpensive steel material is used.
- the galvanized steel sheet according to this embodiment was found based on the following findings.
- a black pigment is added to an organic resin coating layer provided on a zinc-based plating layer on which a hairline is formed, and the film thickness of the organic resin coating layer and the concentration of the black pigment are adjusted to obtain a zinc-based plated steel plate. It is black and has a hairline appearance, and gives a metallic feel. In this case, there is a trade-off relationship between the blackness and the appearance of the hairline and the addition of a metallic feeling. When the blackness is increased, the hiding property of the organic resin coating layer is increased, so that the hairline formed on the surface of the plating layer becomes invisible and the metallic feeling is also lowered.
- the present inventors have diligently studied a method for improving the blackness, hairline appearance and metallic feeling of a galvanized steel sheet having a predetermined corrosion resistance while using an inexpensive steel material.
- an oxide layer is formed on the surface layer of the zinc-based plating layer with an average thickness of 0.05 ⁇ m or more that exhibits black color, the blackness is improved and the hairline formed on the zinc-based plating layer is not concealed.
- the appearance of hairline and metallic feeling can be improved.
- the oxide layer has an average thickness of 3 ⁇ m or less, cracks are suppressed in the oxide layer and the processing adhesion between the zinc-based plating layer and the organic resin coating layer is improved.
- the galvanized steel sheet according to the embodiment of the present invention has good corrosion resistance, good blackness and hairline appearance even when an inexpensive steel material is used due to the above configuration.
- a galvanized steel sheet having excellent metallic feeling and processing adhesion was obtained.
- the present inventors diligently studied a method for improving the metallic feeling, and if the particle size of the oxide in the oxide layer formed on the surface layer of the zinc-based plating layer can be controlled, the plating layer It was considered that even when the upper layer was coated with resin, it was possible to improve the metallic feeling with black color. As a result of further studies based on this idea, the present inventors have obtained the following findings. In order to suppress diffused reflection that occurs on the surface of the oxide layer, it has been found that diffused reflection can be suppressed by providing a smooth portion that reduces the unevenness of the crystal particles of the plating layer before forming the oxide layer. It was.
- the portion where the unevenness of the crystal particles of the plating layer remains becomes a rough portion, and the particle size of the oxide formed on the surface also increases.
- the presence of oxide particles having a large particle size improves processing adhesion.
- processing adhesion with the resin coating layer can be obtained. Therefore, it has been found that by appropriately adjusting the ratio of the rough portion and the smooth portion, both the metallic feeling and the processing adhesion can be obtained. It was also confirmed that when the oxide layer is thin, it is affected by the surface roughness of the plating layer.
- the present inventors have diligently studied the ratio of the rough portion and the smooth portion, and even when the organic resin coating layer is present in the upper layer of the oxide layer, the blackness We have come up with suitable conditions for achieving both a metallic feeling, processing adhesion between the organic resin coating layer and the zinc-based plating layer, and a hairline appearance.
- the oxide layer is composed of a rough portion (A) and a smooth portion (B).
- the rough portion (A) includes a region having a surface roughness Ra A of more than 500 nm and 5000 nm or less.
- the smooth portion (B) includes a region having a surface roughness Ra B of more than 5 nm and 500 nm or less.
- the boundary between the rough portion (A) and the smooth portion (B) is within a range of 1 cm in observation width along the hairline orthogonal direction in a cross section in the hairline orthogonal direction orthogonal to the predetermined direction and in the plate thickness direction.
- the height is 1/3 of the maximum height Ry obtained by subtracting the minimum point H 0 from the highest point H 1 of the oxide layer in the above and is on a virtual straight line parallel to the hairline orthogonal direction, the coarse the smoothing section and the section (a) and the oxide layer plan view in which the boundary is defined in (B), and the same unit of area from each other, the rough portions of the area of (a) and S a, the smoothing unit ( the area of B) when the S B, the area ratio S B / S a is in the range from 0.6 to 10.0,
- the average height difference between the rough portion (A) and the smooth portion (B) adjacent to the rough portion (A) is preferably 0.3 ⁇ m to 5.0 ⁇ m.
- FIGS. 1A and 1B are explanatory views schematically showing an example of the structure of the galvanized steel sheet according to the present embodiment.
- the zinc-based plated steel sheet 1 according to the present embodiment includes a steel sheet 11 as a base material, a zinc-based plating layer 13 located on one surface of the steel sheet 11, and zinc-based plating. It has at least an oxide layer 14 located on the surface of the layer 13.
- the zinc-based plated steel sheet 1 according to the present embodiment further has a translucent organic resin coating layer 15 on the surface side of the zinc-based plated layer 13. preferable. In particular, having the organic resin coating layer 15 is preferable from the viewpoint of ensuring fingerprint resistance, processability, and corrosion resistance.
- the steel sheet 11 which is the base material of the galvanized steel sheet according to the present embodiment is not particularly limited, and is known depending on the mechanical strength (for example, tensile strength, etc.) required for the galvanized steel sheet. It is possible to appropriately use various steel materials (mild steel, ordinary steel, high-strength steel, etc.).
- a zinc-based plating layer 13 is formed on at least one surface of the steel plate 11. As schematically shown in FIG. 1A, the zinc-based plating layer 13 has a recess 101 forming a hairline extending in a predetermined direction (in the case of FIG. 1A, the direction perpendicular to the paper surface), and a non-hairline portion 103. are doing. In the zinc-based plating layer 13, a rough portion as described in detail below is formed in the recess 101 forming the hairline, and a smooth portion as described in detail below is formed in the non-hairline portion 103. You may.
- a smooth portion of the oxide layer 14 as described in detail below is formed in the recess 101 forming the hairline, and the non-hairline portion 103 is described in detail below.
- Such a rough portion of the oxide layer 14 may be formed.
- the average length along the stretching direction of the hairline is preferably 1 cm or more.
- the hairline depth (hairline depth after the oxide layer 14 is formed on the surface of the zinc-based plating layer 13) is exemplified in the range of 0.2 ⁇ m or more and 2.5 ⁇ m or less. Further, the cross-sectional shape of the hairline in the cross section orthogonal to the extending direction of the hairline is mainly V-shaped, but may include a U-shape.
- hairline direction the "direction in which the hairline is extended”
- hairline orthogonal direction the "direction orthogonal to the extension direction of the hairline”
- zinc-based plating layer 13 for example, a zinc-based electroplating layer (electrozinc plating layer, electrozinc alloy plating layer) and a zinc-based hot-dip galvanizing layer (hot-dip galvanizing layer, hot-dip zinc alloy plating layer) are used.
- the zinc-based electroplating layer and the zinc-based hot-dip galvanizing layer may be described with reference to reference numeral 13.
- the zinc alloy plating preferably contains 35% by mass or more of zinc with respect to the total mass of the plating layer.
- the Zn content in the zinc-based plating layer 13 is preferably 35% by mass or more, more preferably 70% by mass or more, and particularly preferably 70% by mass or more, based on the total mass of the plating layer. Is 80% by mass or more. On the other hand, the upper limit of the Zn content in the zinc-based plating layer is 100% by mass.
- a plating method there are an electroplating method, a hot-dip plating method, a thermal spraying method, a vapor deposition plating method, and the like.
- the thermal spraying method may not be suitable because the uniformity of appearance cannot be ensured due to the voids inside the plating layer.
- the vapor deposition method may be unsuitable because the film formation rate is slow and the productivity is poor. Therefore, in the galvanized steel sheet 1 according to the present embodiment, it is preferable to use an electroplating method or a hot-dip plating method in order to apply zinc-based plating to the surface of the steel sheet.
- the electrozinc alloy plating layer contains at least one additive element selected from the element group consisting of Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr, and Zn. And, preferably.
- the electrozinc alloy plating layer preferably contains at least one additive element selected from the element group consisting of Fe, Ni, and Co in a total of 5% by mass or more and 20% by mass or less. That is, the zinc-based electroplating layer contains a total of 5% by mass to 20% by mass of any one or more additive elements selected from the group consisting of Fe, Ni, and Co, and a balance composed of Zn and impurities. Is preferably contained.
- the electrozinc alloy plating layer contains at least one of Fe, Ni, and Co as an additive element within the above total content range, more excellent corrosion resistance (white rust resistance / barrier property) is realized. It becomes possible.
- the electrogalvanized layer and the electrogalvanized alloy plated layer may contain impurities as a balance.
- the impurities are not intentionally added as a component of the zinc-based electroplating layer, but are mixed in the raw material or are mixed in the manufacturing process, and are Al, Mg, Si, Ti. , B, S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr, Ag, W, H and the like.
- electrogalvanizing although it depends on the type of electroplated steel sheet manufactured in the same manufacturing facility, Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, Zr, etc.
- the intentionally added Fe, Ni, and Co and the Fe, Ni, and Co mixed as impurities can be distinguished from each other by the concentration in the zinc-based electroplating layer 13. That is, for example, since the lower limit of the total content of Fe, Ni, and Co when added intentionally is 5% by mass, if the total content is less than 5% by mass, it can be discriminated as an impurity.
- the composition of the zinc-based electroplating layer as described above can be analyzed by, for example, the following method. That is, the average composition of the plating layer is obtained by analyzing with an electron probe microanalyzer (EPMA) from the cross-sectional direction along the plate thickness direction. At this time, the oxide layer formed on the surface of the plating layer is excluded. Whether or not it is an oxide layer is judged by the oxygen concentration. If the oxygen concentration is 20% by mass or more, it is judged to be an oxide layer.
- EPMA electron probe microanalyzer
- the average adhesion amount of the zinc-based electroplating layer 13 is preferably 5 g / m 2 or more and 40 g / m 2 or less. If the average adhesion amount of the zinc-based electroplating layer 13 is less than 5 g / m 2 , the base iron (that is, the steel plate 11) may be exposed when the hairline is applied. On the other hand, when the average adhesion amount of the zinc-based electroplating layer 13 exceeds 40 g / m 2 , the hairline formed by grinding or rolling on the steel plate 11 may be less noticeable by the zinc-based electroplating layer 13. , Not preferable.
- the lower limit of the average adhesion amount of the zinc-based electroplating layer 13 is more preferably 7 g / m 2 and even more preferably 10 g / m 2 .
- the upper limit of the average adhesion amount of the zinc-based electroplating layer 13 is more preferably 35 g / m 2 or less, and further preferably 30 g / m 2 .
- the zinc-based hot-dip galvanizing layer includes a "hot-dip galvanizing layer” or a "hot-dip galvanizing alloy plating layer".
- the hot-dip galvanized layer is composed of, for example, zinc and elements such as Al, Sb, and Pb having a total balance of less than 5% by mass.
- the hot-dip zinc alloy plating layer is composed of, for example, zinc and an alloy element having a total of 1% by mass or more in the balance.
- the alloy element group at least one element selected from Fe, Al, Mg, Si and the like is selected.
- the hot-dip zinc alloy plating layer preferably contains at least one selected from the group consisting of Al and Mg in a total amount of 1% by mass or more and 60% by mass or less.
- the zinc-based hot-dip galvanized layer contains 1% by mass to 60% by mass in total of any one or more additive elements selected from the group consisting of Al and Mg, and a balance composed of Zn and impurities. It is preferable to do so.
- the hot-dip galvanized alloy plating layer is contained within the range of the above total content, it is possible to realize more excellent corrosion resistance (white rust resistance / barrier property).
- the hot-dip galvanized layer and the hot-dip zinc alloy plated layer may contain impurities as a balance.
- the impurities are not intentionally added as zinc-based hot-dip galvanizing components, but are mixed in the raw material or mixed in the manufacturing process, and are mixed in Al, Mg, Si, Ni, Ti. , Pb, Sb and the like.
- the intentionally added alloying element and the element mixed as an impurity can be distinguished from each other by the concentration in the zinc-based hot-dip galvanizing layer 13. That is, for example, since the lower limit of the total content of Al and Mg when intentionally added is 1% by mass, if the total content is less than 1% by mass, it can be discriminated as an impurity.
- composition of the zinc-based hot-dip plating layer as described above can be analyzed by, for example, the same method as the method for analyzing the composition of the zinc-based electroplating layer described above.
- the average adhesion amount of the zinc-based hot-dip plating layer 13 is preferably more than 40 g / m 2 and 150 g / m 2 or less.
- the average adhesion amount of the zinc-based hot-dip galvanizing layer 13 is 40 g / m 2 or less, it is necessary to increase the gas pressure during gas wiping to control the adhesion amount after hot-dip galvanizing, and a uniform plating adhesion amount can be obtained. It may not be.
- the average adhesion amount of the zinc-based hot-dip plating layer 13 exceeds 150 g / m 2 , it is necessary to reduce the plate passing speed, which is not preferable because the productivity is lowered.
- the lower limit of the average adhesion amount of the zinc-based hot-dip plating layer 13 is more preferably 45 g / m 2 or more, and further preferably 50 g / m 2 or more.
- the upper limit of the average adhesion amount of the zinc-based hot-dip plating layer 13 is more preferably 120 g / m 2 or less, and further preferably 90 g / m 2 or less.
- the surface of the zinc-based plating layer 13 to which the hairline is provided is covered with the oxide layer 14 as schematically shown in FIG. 1A. That is, the oxide layer 14 is provided along the surface texture of the zinc-based plating layer 13, and the oxide layer 14 is also provided with a hairline.
- the galvanized steel sheet has a high degree of blackness due to having such an oxide layer 14.
- the oxide layer 14 is located at least on the surface of the zinc-based plating layer 13 other than the recesses.
- the average thickness of the oxide layer 14 is 0.05 ⁇ m or more and 3.0 ⁇ m or less. When the average thickness of the oxide layer 14 is less than 0.05 ⁇ m, sufficient blackness cannot be obtained, and the hairline and metallic feeling are deteriorated. On the other hand, when the average thickness of the oxide layer 14 exceeds 3.0 ⁇ m, the oxide layer 14 is cracked by the processing, and the processing adhesion is lowered.
- the lower limit of the average thickness of the oxide layer 14 is more preferably 0.07 ⁇ m, and even more preferably 1.0 ⁇ m.
- the upper limit of the average thickness of the oxide layer 14 is preferably 2.7 ⁇ m, more preferably 2.5 ⁇ m.
- the average thickness of the oxide layer is measured as follows. A sample cut along the thickness direction is collected from the galvanized steel sheet. Then, the cross section (cross section along the plate thickness direction) of the plating layer and the oxide layer is observed with a transmission electron microscope (TEM-EDS) equipped with an energy dispersive X-ray analyzer (EDS) to remove oxygen elements. Map. Next, a region having an oxygen concentration of 20% by mass or more existing from the surface toward the plating layer is defined as an oxide layer, and the thickness of the oxide layer is measured at a plurality of locations. Then, the average value of the thicknesses of the oxide layers measured at a plurality of locations is calculated.
- TEM-EDS transmission electron microscope
- EDS energy dispersive X-ray analyzer
- the oxide layer 14 is composed of, for example, a Zn-based oxide or a hydroxide.
- oxides or hydroxides derived from alloying elements other than Zn may be contained.
- Specific examples of Zn-based oxides or hydroxides include ZnO, ZnO 1-x , Zn (OH) 2, and the like.
- As a method for forming the oxide layer 14 well-known methods such as acid immersion treatment and Zn oxide treatment are exemplified.
- the surface of the oxide layer 14 to which the hairline is provided is provided with a translucent organic resin coating layer 15.
- the fact that the organic resin coating layer 15 has translucency (transparency) means that the oxide layer 14 can be visually observed through the organic resin coating layer 15 formed on the surface.
- translucency and “transparency” are used in the same meaning.
- the resin used for forming the organic resin coating layer 15 is preferably one having sufficient transparency, chemical resistance, corrosion resistance, processability, scratch resistance and the like.
- resins include polyester resins, epoxy resins, urethane resins, polyester resins, phenol resins, polyether sulfone resins, melamine alkyd resins, acrylic resins, polyamide resins, and polyimides.
- Based resins, silicone resins, polyvinyl acetate resins, polyolefin resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins and the like can be used.
- various additives are contained in the organic resin coating layer 15 within a range that does not impair transparency and appearance and does not deviate from the range specified in the present invention. You may let me.
- Examples of the performance added to the organic resin coating layer 15 include corrosion resistance, slidability, scratch resistance, conductivity, and color tone.
- corrosion resistant it may contain a rust preventive or an inhibitor
- if it is slidable or scratch resistant it may contain wax or beads
- a known colorant such as a pigment or a dye may be contained.
- the organic resin coating layer 15 according to the present embodiment contains a known colorant such as a pigment or a dye, it is preferable to contain the colorant to such an extent that the hairline can be visually recognized.
- the colorant include Bengara, aluminum, mica, carbon black, titanium oxide, cobalt blue and the like.
- the content of the colorant is preferably 1 to 10% by mass, more preferably 2 to 5% by mass, based on the organic resin coating layer 15.
- the average thickness of the organic resin coating layer 15 is preferably 10 ⁇ m or less.
- the average thickness of the organic resin coating layer 15 exceeds 10 ⁇ m, the distance through which the light passes through the organic resin coating layer 15 becomes long, so that the reflected light is reduced and the glossiness is likely to be lowered. Further, due to the deformation of the resin due to the processing, the texture of the surface of the zinc-based plating layer 13 and the shape of the surface of the organic resin coating layer 15 are likely to be misaligned.
- the average thickness of the organic resin coating layer 15 is preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less.
- the thickness of the thinnest portion of the organic resin coating layer 15 when viewed from the cross section is 0.1 ⁇ m or more and is coated with the organic resin.
- the average thickness of the layer 15 is preferably 1.0 ⁇ m or more.
- the "thinnest part” means the minimum value of the film thickness measured at 20 points at 100 ⁇ m intervals by cutting out a length of 5 mm at an arbitrary position in the direction orthogonal to the hairline to prepare a cross-sectional sample.
- the "average thickness” means the average of 20 points. It is more preferable that the thickness of the thinnest portion of the organic resin coating layer 15 is 0.5 ⁇ m or more, and the average thickness of the organic resin coating layer 15 is 3.0 ⁇ m or more.
- FIGS. 1A and 1B show a case where the zinc-based plating layer 13, the oxide layer 14, and the organic resin coating layer 15 are formed on one surface of the steel sheet 11, the front and back sides of the steel sheet 11 are shown.
- a zinc-based plating layer 13 and an organic resin coating layer 15 may be formed on the two surfaces.
- FIG. 2 is an explanatory diagram for explaining an example of a zinc-based plating layer and an oxide layer according to the present embodiment.
- 3 to 5 are graphs for explaining an example of the zinc-based plating layer and the oxide layer according to the present embodiment.
- FIG. 6 is an explanatory diagram for explaining another example of the zinc-based plating layer and the oxide layer 14 according to the present embodiment.
- the zinc-based plating layer 13 has a recess 101 forming a hairline and a non-hairline portion 103 on the surface layer portion.
- the oxide layer 14 also has a recess 101 for forming a hairline and a non-hairline portion 103 along the surface texture of the zinc-based plating layer 13. That is, the oxide layer 14 has a hairline corresponding to the hairline of the zinc-based plating layer 13. Focusing on the surface shape of the micro-oxide layer 14 that is different from the hairline, the oxide layer 14 has a rough portion 111 including a region having a surface roughness Ra A of more than 500 nm and 5000 nm or less, and a surface roughness Ra. It has a smoothing portion 113 including a region where B is more than 5 nm and 500 nm or less.
- the rough portion 111 as described above may be formed in the hairline, or the smooth portion 113 as described above may be formed in the hairline. That is, the rough portion 111 as described above may be formed in the recess 101 forming the hairline, and the smooth portion 113 as described above may be formed in the non-hairline portion 103. .. Alternatively, the smooth portion 113 as described above may be formed in the recess 101 forming the hairline, and the rough portion 111 as described above may be formed in the non-hairline portion 103. ..
- the area ratio of the rough portion and the smooth portion in the oxide layer 14 is determined by observing the actual surface state with a scanning electron microscope (SEM) or the like and measuring each area ratio. It is also possible, but as will be described later, the roughness profile is measured with a laser microscope, the rough portion corresponding portion and the smooth portion corresponding portion are set by the boundary line by the virtual straight line based on the measurement, and the area ratio thereof is used.
- the boundary line between the rough portion 111 and the smooth portion 113 in the oxide layer 14 is defined as follows. First, as shown in FIGS. 2 and 9A, in the oxide layer 14, the rough portion 111 is formed in the recess 101 forming the hairline, and the smooth portion 113 is mainly formed in the non-hairline portion 103.
- a laser microscope having a display resolution in the height direction of 1 nm or more and a display resolution in the width direction of 1 nm or more that is, a laser microscope having a display resolution in the height direction and the width direction better than 1 nm.
- the observation field of view of the laser microscope is less than 1 cm, a plurality of fields of view may be observed and these may be connected to measure the surface height.
- the “smoothing portion 113” is a region defined by a set of points whose height from the lowest point (H 0 ) is (H 1 ⁇ H 0 ) ⁇ 1/3 or more.
- the "coarse portion 111” is a region defined by a set of points whose height from the lowest point (H 0 ) is less than (H 1- H 0 ) x 1/3.
- the boundary between the rough portion 111 and the smooth portion 113 is an oxide layer within an observation width of 1 cm along the hairline orthogonal direction in each of the cross sections in the hairline orthogonal direction and the plate thickness direction (FIG. 9A). It exists on a virtual straight line BL which is 1/3 of the maximum height Ry obtained by subtracting the lowest point H 0 from the highest point H 1 of 14 and is parallel to the hairline orthogonal direction.
- the rough portion 111 corresponds to a portion that has not been affected by processing such as grinding or rolling after the oxide layer 14 is formed. Therefore, when the surface of the oxide layer 14 is observed under a microscope, oxide particles having a height can be confirmed in the rough portion 111 of the oxide layer 14.
- the average particle size Dave which indicates the size of the oxide particles in the oxide layer 14, can be obtained by the following method. First, the surface of the oxide layer 14 is observed by SEM. The visual field magnification at that time is in the range of 1000 to 10000 times, but if the oxide particles cannot be confirmed even at the maximum magnification of 10000 times, the number is counted as zero. Subsequently, the flat area S per oxide particle is obtained from the contour of the oxide particles. Then, assuming a circle having the same flat area as the flat area, the diameter is obtained as the representative diameter D by the following formula (1). Then, the average particle size Dave can be obtained by arbitrarily selecting 10 oxide particles in the observation field of view and obtaining the average value of the representative diameters D of the 10 oxide particles.
- D 2 ⁇ (S / ⁇ ) 0.5 ... Equation (1)
- D is a representative diameter of the oxide particles in a plan view, and the unit thereof is ⁇ m.
- S is a circular equivalent area of the oxide particles in a plan view, and the unit thereof is ⁇ m 2 .
- the density of oxide particles is determined by the following method. First, as described above, the surface of the oxide layer 14 is observed by SEM, and the density of the oxide particles is obtained by counting how many oxide particles above the particle size threshold are within the range of 100 ⁇ m ⁇ 100 ⁇ m. Be done.
- the particle size threshold differs depending on the plating type and alloy of the lower zinc-based plating layer 13. For example, when the lower zinc-based plating layer 13 is a Zn—Ni electroplating layer, the particle size threshold is 0.1 ⁇ m to 3.0 ⁇ m.
- the average particle size Dave of the oxide particles in the rough portion 111 is in the range of 0.5 ⁇ m to 2.7 ⁇ m. Further, the density of the oxide particles in the rough portion 111 is in the range of 2 ⁇ 10 10 particles / m 2 to 5 ⁇ 10 14 particles / m 2 . As an example of the measured values, when the zinc-based plating layer 13 is a Zn—Fe electroplating layer, the oxide particles in the rough portion 111 have an average particle size Dave of 2.1 ⁇ m and a density of 5 ⁇ 10 13. It was 2 pieces / m 2 .
- the average particle size Dave of the oxide particles in the rough portion 111 is in the range of 0.6 ⁇ m to 7.2 ⁇ m.
- the density of the oxide particles in the rough portion 111 is in the range of 0.5 ⁇ 10 10 particles / m 2 to 3.6 ⁇ 10 14 particles / m 2 .
- the oxide particles in the rough portion 111 have an average particle size Dave of 6.2 ⁇ m and a density of 2.0 ⁇ . It was 10 12 pieces / m 2 .
- the average particle size Dave of the oxide particles in the rough portion 111 is in the range of 0.3 ⁇ m to 2.4 ⁇ m.
- the density of the oxide particles in the rough portion 111 is in the range of 5 ⁇ 10 10 particles / m 2 to 8.4 ⁇ 10 14 particles / m 2 .
- the oxide particles in the rough portion 111 have an average particle size Dave of 0.7 ⁇ m and a density of 4.0 ⁇ . It was 10 12 pieces / m 2 .
- the zinc-based plating layer 13 is a zinc-based electroplating layer and contains any one or more elements selected from the group consisting of Fe, Ni, and Co as additive elements, it is coarse.
- the density of the oxide particles having a particle size of 0.3 ⁇ m or more in the part 111 is 10 10 particles / m 2 or more.
- the smooth portion 113 is formed in the recess 101 forming the hairline, and the rough portion 111 is mainly formed in the non-hairline portion 103.
- a laser microscope having a display resolution in the height direction of 1 nm or more and a display resolution in the width direction of 1 nm or more that is, a laser microscope having a display resolution in the height direction and the width direction better than 1 nm.
- the observation field of view of the laser microscope is less than 1 cm, a plurality of fields of view may be observed and these may be connected to measure the surface height.
- the “coarse portion 111” is a region defined by a set of points whose height from the lowest point (H 0 ) is (H 1 ⁇ H 0 ) ⁇ 1/3 or more.
- the “smoothing portion 113” is a region defined by a set of points whose height from the lowest point (H 0 ) is less than (H 1 ⁇ H 0 ) ⁇ 1/3.
- the boundary between the rough portion 111 and the smooth portion 113 is the highest point H 1 of the oxide layer 14 within the range of the observation width of 1 cm along the hairline orthogonal direction in each cross section in the hairline orthogonal direction and the plate thickness direction. It exists on a virtual straight line BL which is 1/3 of the maximum height Ry obtained by subtracting the lowest point H 0 from the height and is parallel to the hairline orthogonal direction.
- the rough portion 111 as described above corresponds to the portion where the unevenness of the crystal particles of the lower layer plating layer exists, and the smooth portion 113 as described above is lower than the rough portion 111. Corresponds to the part where the unevenness of the crystal particles in the plating layer is small.
- the rough portion 111 in which the irregularities of the oxide particles are present and the smooth portion 113 in which the irregularities of the oxide particles are smaller than the rough portion 111 are present in an appropriate ratio.
- the smooth portion 113 realizes an improvement in metallic feeling
- the rough portion 111 realizes processing adhesion with the organic resin coating layer 15 which is preferably provided on the upper layer of the oxide layer 14.
- the oxide layer 14 has both the rough portion 111 and the smooth portion 113 as described above, as is schematically shown in FIG. 2, the rough portion 111 and the smooth portion 113 adjacent to each other For each, the average surface height of the rough portion 111 and the average surface height of the smooth portion 113 can be considered.
- the average height difference between the rough portion 111 and the smooth portion 113 adjacent to the rough portion 111 is in the range of 0.3 ⁇ m to 5.0 ⁇ m.
- the average height between the recesses 101 and the non-hairline portions 103 is high and low.
- the difference is also in the range of 0.3 ⁇ m to 5.0 ⁇ m.
- a rough portion A 2 formed in the recess 101 to form a hairline, the smoothing unit B 3 formed in the non hairline unit 103, are adjacent to each other, crude
- the average height difference between the portion A 2 and the smooth portion B 3 can be specified by a known measuring method.
- the height difference ( ⁇ h in FIG. 2) between the average surface height of the smooth portion B 3 and the average surface height of the rough portion A 2 is within the range of 0.3 ⁇ m to 5.0 ⁇ m.
- the same relationship is established between the rough portion A 2 and the smooth portion B 2 , between the rough portion A 1 and the smooth portion B 2, and between the rough portion A 1 and the smooth portion B 1. are doing.
- the hairline becomes inconspicuous, and it is useless to perform hairline processing on the zinc-based plating layer 13 and the oxide layer 14. .
- the average height difference between the smooth portion 113 and the rough portion 111 adjacent to each other exceeds 5.0 ⁇ m, the hairline becomes too coarse to obtain a beautiful hairline, and the design as a hairline is impaired.
- the lower limit of the average height difference between the smooth portion 113 and the coarse portion 111 adjacent to each other is preferably 0.8 ⁇ m, more preferably 1.0 ⁇ m.
- the upper limit of the average height difference between the smooth portion 113 and the rough portion 111 adjacent to each other is preferably 2.6 ⁇ m, more preferably 2.2 ⁇ m.
- the average height difference between the rough portion 111 and the smooth portion 113 can be measured, for example, by measuring the surface of the oxide layer 14 with a laser microscope. At this time, at each of the plurality of locations of the oxide layer 14, the difference ⁇ h between the average surface height h1 of a certain rough portion 111 and the average surface height h2 of the smooth portion 113 adjacent to the rough portion 111 is set. Ask. Then, 20 or more sets of difference ⁇ h of the combination of the rough portion 111 and the smooth portion 113 are obtained, and the average value thereof is set as “the average height difference between the rough portion 111 and the smooth portion 113”.
- the average surface height h1 of the rough portion 111 is an average value of the maximum height and the minimum height of the rough portion 111 between the boundaries with the smooth portion 113.
- the average surface height h2 of the smooth portion 113 is the average value of the maximum height and the minimum height of the smooth portion 113 between the boundary with the rough portion 111.
- the total plane area of the area and the coarse portion A 2 of the coarse portion A 1 is the area S A becomes coarse portion 111 within the range shown in FIG. 2
- total area of the smooth portion B 1 of the area and the smooth portion B 2 of the area and the smooth portion B 3 becomes the area S B of the smooth portion 113 within the range shown in FIG.
- the flat area is the area when the oxide layer 14 is viewed in a plan view as shown in FIG. 8 (specifically, when the surface of the oxide layer 14 is viewed as an image when observed with an electron microscope. Area).
- the surface roughness Ra B of the smooth portion 113 (arithmetic mean roughness Ra specified in JIS B 0601 (2001)) is determined. It shows the result of measuring the 60 degree gloss (G60) using a commercially available gloss meter when it was changed. 3, the horizontal axis is the surface roughness R B of the smoothing unit 113, the vertical axis is the measurement result of the 60 degree gloss. Further, FIG. 3 shows measurement results in each of the hairline stretching direction (hereinafter, hairline direction) and the direction orthogonal to the hairline (hereinafter, hairline orthogonal direction).
- hairline direction hereinafter, hairline direction
- hairline orthogonal direction the direction orthogonal to the hairline
- FIG. 4 by adjusting the surface roughness Ra B of the smoothing part 113 to 20 ⁇ 5 nm, in the case of changing the area ratio S B / S A, with a commercially available gloss meter, 60 degrees
- the result of measuring the gloss (G60) is shown. 4
- the horizontal axis is the area ratio S B / S A
- the vertical axis is the measurement result of the 60 degree gloss.
- FIG. 5 shows the result of providing the organic resin coating layer 15 on the surface of the sample similar to that used for the measurement of FIG. 4 and evaluating the processing adhesion thereof.
- the evaluation of the processing adhesion is carried out in the same manner as the method described in the following examples, and is performed in five stages from a score 5 meaning excellent processing adhesion to a score 1 meaning inferior processing adhesion. evaluated.
- the sample in the sample area ratio S B / S A is 10 or less, processability adhesion whereas evaluates to score 5, the area ratio S B / S A exceeds 10 Then, the processing adhesion was lowered.
- the area ratio S B / S A that is preferably in the range of 0.6 to 10.0, revealed.
- the lower limit of the area ratio S B / S A is preferably 1.5, more preferably 2.5.
- the upper limit of the area ratio S B / S A is preferably 8.0, more preferably 6.5.
- the height data measured by a laser microscope having a display resolution in the direction of 1 nm or more and a display resolution in the width direction of 1 nm or more is binarized, and known image processing is performed on the obtained binarized data. It can be measured by applying.
- the average height difference between the coarse portion 111 and the smoothing unit 113, and the condition of the area ratio S B / S A of the coarse portion 111 and the smoothing unit 113 is as follows. That is, not only when the rough portion 111 is formed in the recess 101 forming the hairline and the smooth portion 113 is formed in the non-hairline portion 103 as shown in FIG. 2, but also in FIG. It has been confirmed that the same applies to the case where the smooth portion 113 is formed in the recess 101 forming the hairline and the rough portion 111 is formed in the non-hairline portion 103 as shown in the above.
- h1 is the average surface height of the smooth portion 113
- h2 is the average surface height of the rough portion 111.
- the coarse portion 111 is present in an appropriate ratio, so that the processing adhesion when the organic resin coating layer 15 is provided on the upper layer of the oxide layer 14 is ensured.
- the rough portion 111 has an appropriately wide region having an appropriate surface roughness, so that the contact area with the organic resin coating layer 15 is increased. It is preferable to increase.
- the surface roughness of the rough portion 111 is measured when the rough portion 111 is measured using a laser microscope having a display resolution in the height direction of 1 nm or more and a display resolution in the width direction of 1 nm or more.
- Ra a is considered a region is 500nm ultra 5000nm or less, the total area of such regions, with respect to the area S a of the coarse portion 111 is preferably made 85% or more.
- the galvanized steel sheet 1 By having the rough portion 111 having a region having a surface roughness Ra A of more than 500 nm and 5000 nm or less, it is possible to more reliably realize a contact state with the organic resin coating layer 15, which can realize excellent processing adhesion. Can be done. Total area of such regions, with respect to the area S A of the coarse portion 111, if less than 85%, the galvanized steel sheet 1 according to this embodiment, to realize excellent processability adhesion May be difficult. Therefore, the galvanized steel sheet 1 according to this embodiment, the ratio of the total area to the area S A of the coarse portion 111 preferably be 85% or more.
- the ratio of the total area of the region where the surface roughness Ra A is equal to or less than 500nm ultra 5000nm is higher well, preferably 90% or more, more preferably 95% That is all.
- the upper limit of the ratio of the total area to the area S A of the coarse portion 111 is not particularly specified, and may be 100%.
- the smooth portion 113 is present in an appropriate ratio, so that the metallic feeling of the galvanized steel sheet 1 according to the present embodiment is realized.
- the smooth portion 113 may have an appropriately wide region having an appropriate surface roughness. preferable.
- Ra B is considered an area is 5nm super 500nm or less, the total area of such regions, to the area S B of the smoothing unit 113 is preferably made 65% or more.
- the smooth portion 113 has a region having a surface roughness Ra B of more than 5 nm and 500 nm or less, excellent glossiness can be more reliably realized.
- the ratio of the total area to the area S B of the smoothing portion 113, the higher the better, is preferably 70% or more, more preferably 75% or more.
- the surface roughness Ra B of the smooth portion 113 or The surface roughness Ra A of the rough portion 111 can be measured along the same direction as the hairline at 1 ⁇ m intervals, and can be obtained by the following equations (2) and (3).
- the measurement length of Ra is set to 50 ⁇ m or more.
- Ra may be obtained by observing a plurality of fields of view and connecting the plurality of fields of view. The number of measurements is 20 or more.
- the rough portion 111 includes a region having a surface roughness Ra A of more than 500 nm and 5000 nm or less
- the surface roughness Ra A of the rough portion 111 is set at 1 ⁇ m intervals along the same direction as the hairline. Measure with a measurement length of 50 ⁇ m or more.
- the average surface roughness Ra A measured 20 times or more is more than 500 nm and 5000 nm or less
- the rough portion 111 includes a region where the surface roughness Ra A is more than 500 nm and 5000 nm or less
- the average surface roughness Ra B of the smooth portion 113 measured 20 times or more is more than 5 nm and 500 nm or less
- the smooth portion 113 has a region where the surface roughness Ra B is more than 5 nm and 500 nm or less.
- surface roughness Ra A and Ra B mean arithmetic mean roughness Ra defined in JIS B 0601 (2001).
- the recess 101 (that is, the hairline) including the rough portion 111 or the smooth portion 113 as described above has an arbitrary 1 cm width range along the hairline orthogonal direction. It is preferably present at a frequency of 3 lines / cm or more and 80 lines / cm or less.
- the frequency of hairline formation in the direction orthogonal to the hairline within the range of 3 lines / cm to 80 lines / cm, more excellent design can be realized. If the frequency of hairline formation in the direction orthogonal to the hairline is less than 3 lines / cm, the density of the hairline becomes too low, and there is a high possibility that the hairline cannot be recognized. On the other hand, when the frequency of hairline formation in the direction orthogonal to the hairline exceeds 80 lines / cm, the density of the hairline becomes too high to obtain a beautiful hairline, and the design of the hairline may be impaired. ..
- the lower limit of the frequency of existence of the recess 101 (that is, the hairline) in an arbitrary 1 cm width range along the direction orthogonal to the hairline is more preferably 10 lines / cm, and further preferably 15 lines / cm.
- the upper limit of the frequency of existence of the recesses 101 (that is, hairlines) in an arbitrary 1 cm width range along the direction orthogonal to the hairline is more preferably 70 lines / cm, and further preferably 65 lines / cm.
- the frequency of existence of the recess 101 is arbitrary by observing the surface of the oxide layer 14 with a laser microscope having a display resolution in the height direction of 1 nm or more and a display resolution in the width direction of 1 nm or more.
- the range of 1 mm width can be specified by counting the number of recesses 101. That is, the average frequency of the recesses 101 is obtained by measuring 20 or more points in an arbitrary 1 mm width range on the surface of the oxide layer 14 and dividing the total number of recesses 101 in each range by the number of measurement points. Can be done.
- FIGS. 1A and 1B the case where the recess 101 is provided only in the zinc-based plating layer 13 and the oxide layer 14 is shown.
- a recess 105 forming a hairline extending in a predetermined direction may be provided on the surface of the steel sheet 11. Good.
- the zinc-based hot-dip galvanizing fills the recesses forming the hairline with its own thickness. Therefore, the plating is zinc-based electroplating.
- the recess 105 is provided on the surface of the steel sheet 11 at a position corresponding to the hairline (that is, the recess 101) in the zinc-based plating layer 13 and the oxide layer 14. You may.
- the blackness of the surface of the galvanized steel sheet 1 according to the present embodiment is preferably 40 or less in terms of L * value, and more preferably 35 or less.
- L * value means the L * value in CIE1976L * a * b * color system.
- the L * value can be measured with a reflection spectrophotometer.
- the L * value is measured according to JIS Z8781-4 (2013).
- a confirmation method for example, a method of observing the zinc-based plated steel sheet 1 from the cross-sectional direction, a photograph of the oxide layer 14 taken from the surface, and only the oxide layer 14 and the zinc-based plated layer 13 with hydrochloric acid to which an inhibitor is added. Examples thereof include a method of comparing the oxide layer 14 and the photograph taken from the surface after the removal.
- a method for manufacturing a zinc-based electroplated steel sheet 1 having a structure as shown in FIGS. 1A and 1B will be briefly described.
- the steel sheet 11 whose surface roughness has been adjusted is degreased with an alkaline solution and pickled with an acid using hydrochloric acid, sulfuric acid or the like.
- the zinc-based electroplating layer 13 is formed on the surface of the steel plate 11.
- the surface roughness of the steel sheet 11 can be adjusted by using a known method.
- the surface roughness of the steel sheet 11 is rolled by rolling with a roll adjusted so that the surface roughness is within a desired range.
- a method such as a method of transferring the roughness can be used.
- a known electroplating method can be used.
- the electroplating bath for example, a sulfuric acid bath, a chloride bath, a zincate bath, a cyanide bath, a pyrophosphate bath, a boric acid bath, a citric acid bath, another complex bath, or a combination thereof can be used.
- an electrozinc alloy plating layer 13 containing a desired amount of Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W and Zr can be formed. Further, it is more preferable to add an additive to the plating bath in order to stabilize the ions in the plating bath and control the plating characteristics.
- compositions, temperature, flow velocity, current density at the time of plating, energization pattern, etc. of the electroplating bath may be appropriately selected so as to obtain a desired plating composition, and are not particularly limited. Further, the thickness can be controlled by adjusting the current value and the time within the range of the current density having a desired composition.
- a hairline is formed on the plated steel sheet provided with the zinc-based electroplating layer 13 obtained as described above.
- the method for imparting a hairline is not particularly limited, and various known methods can be used. Examples of such known methods include a method of polishing with a polishing belt, a method of polishing with an abrasive grain brush, a method of transferring with a textured roll, and a predetermined grinding apparatus, as in the case of imparting a hairline to a stainless steel material. Examples of the method of grinding with.
- the depth and frequency of the hairline can be controlled to a desired state by adjusting the particle size of the polishing belt or the abrasive grain brush, the depth of the texture of the roll, the reducing force, the relative speed, and the number of times.
- the surface of the zinc-based electroplating layer 13 on which the hairline is formed as described above has irregularities due to the crystal particles of the plating. Therefore, in the method for producing a zinc-based electroplated steel plate according to the present embodiment, after the hairline is formed, the surface shape of the zinc-based electroplated layer 13 satisfies various conditions of the oxide layer 14 as described above.
- the surface of the zinc-based electroplating layer 13 is ground, polished, or rolled with a roll having a surface roughness adjusted by a known method until the shape is obtained.
- the oxide layer 14 is formed on the surface of the zinc-based electroplating layer 13 to which the hairline is provided.
- the portion where the unevenness of the crystal particles of the plating layer remains corresponds to the hairline portion in the above-mentioned grinding treatment, polishing treatment, or rolling treatment.
- the non-hairline portion 103 around the remaining portion is appropriately ground, polished, or rolled.
- the treated portion becomes a smooth portion in which the unevenness of the crystal particles in the plating layer is suppressed.
- the oxide layer 14 is formed on the flat portion of the plating layer, it becomes the smooth portion 113.
- the recess 101 that has not been treated and forms a hairline becomes a rough portion in which the unevenness of the crystal particles of the plating layer remains. Then, when the oxide layer 14 is formed on the rough portion of the plating layer, it becomes the rough portion 111.
- the flat portion (non-hairline portion 103) that was not scraped by the abrasive grain brush is in a state where the unevenness of the crystal particles of the plating layer remains as before.
- the smooth portion 113 of the oxide layer 14 formed in the smooth portion is predominantly present, and the recess 101 having a high glossiness coexists.
- a known method can be used as the method for forming the oxide layer 14, and examples thereof include a method in which an acidic aqueous solution in which nitrate and phosphoric acid are mixed is brought into contact with the zinc-based electroplating layer. In this way, the oxide layer 14 is formed on the surface of the zinc-based electroplating layer 13. At this time, oxides having a small particle size are deposited on the surface of the smooth zinc-based electroplating layer 13, and oxides having a large particle size are deposited on the surface of the coarse zinc-based electroplating layer 13. Therefore, the oxide layer 14 can be provided with the above-mentioned suitable surface properties.
- the surface of the oxide layer 14 to which the hairline is provided is coated with the organic resin coating layer 15 as needed.
- the paint used for forming the organic resin coating layer 15 follows the surface shape of the oxide layer 14 at the moment when it is applied to the oxide layer 14, and once reflects the surface shape of the oxide layer 14. It is preferable that the leveling of is slow. That is, it is desirable that the paint has a low viscosity at a high shear rate and a high viscosity at a low shear rate.
- the shear rate is 0.1 [1 / sec]
- the viscosity is 10 [Pa ⁇ s] or more
- the shear rate is 1000 [1 / sec]
- the viscosity is 0.01 [Pa ⁇ s] or less. It is desirable to have a shear viscosity.
- the shear viscosity in order to adjust the shear viscosity within the above range, for example, in the case of a paint using an aqueous emulsion resin, it can be adjusted by adding a hydrogen-bonding viscosity adjusting agent.
- a hydrogen-bonding viscosity modifiers can increase the viscosity of the paint because they are bound to each other by hydrogen bonds at a low shear rate, but at high shear rates, the hydrogen bonds are broken and the viscosity decreases. To do. This makes it possible to adjust the shear viscosity according to the desired coating conditions.
- the method for coating the organic resin coating layer 15 is not particularly limited, and a known method can be used.
- a paint adjusted to the viscosity as described above apply it by a spraying method, a roll coater method, a curtain coater method, a die coater method, or a dipping pulling method, and then naturally dry or bake it to form it. it can.
- the drying temperature and drying time, and the baking temperature and baking time may be appropriately determined so that the organic resin coating layer 15 to be formed has desired performance. At this time, if the temperature rising rate is slow, the time from the softening point of the resin component to the completion of baking becomes long and the leveling progresses, so that the temperature rising rate is preferably high.
- a method for manufacturing a zinc-based electroplated steel sheet (plated steel sheet having a zinc-based electroplated layer 13) having the structures as shown in FIGS. 7A and 7B will be briefly described.
- a steel sheet having been adjusted in surface roughness in the same manner as in the above "Manufacturing method-Part 1" is used.
- the steel sheet 11 is obtained by forming a hairline on the steel sheet before plating.
- the method of imparting a hairline to the steel sheet is not particularly limited, but is a method of polishing with a polishing belt, a method of polishing with an abrasive grain brush, a method of transferring with a textured roll, and a method of grinding with a predetermined grinding device. It is preferable to use a method or the like. As a result, the recess 105 as shown in FIGS. 7A and 7B is formed on the surface of the steel plate 11.
- the zinc-based electroplating layer 13 is formed on the steel plate 11 on which the hairline is formed. Since the method for forming the zinc-based electroplating layer 13 can be carried out in the same manner as in the above-mentioned "Manufacturing method-No. 1", detailed description thereof will be omitted below.
- the zinc-based electroplating layer 13 is formed while maintaining the surface shape of the steel sheet 11 on which the hairline is formed. That is, the zinc-based electroplating layer 13 having a hairline at a position and shape corresponding to the hairline of the steel plate 11 in a plan view is formed.
- Crystal particles of the plating layer are present on the surface of the zinc-based electroplating layer 13 formed as described above, as in the above "Manufacturing method-No. 1". That is, the surface of the zinc-based electroplating layer 13 at this point is in a state where both the recess 101 and the non-hairline portion 103 are covered with the unevenness of the crystal particles of the plating. Therefore, in the present production method, after the zinc-based electroplating layer 13 is formed, the zinc-based electroplating layer 13 is zinc-based by a known method until the surface shape of the zinc-based electroplating layer 13 satisfies various conditions as described above. The surface of the electroplating layer 13 is ground, polished, or rolled with a roll having an adjusted surface roughness.
- the rough portion and the smooth portion corresponding to the rough portion 111 and the smooth portion 113 of the oxide layer 14 are formed on the surface of the zinc-based electroplating layer 13 as in the above-mentioned "Manufacturing method-No. 1".
- the non-hairline portion 103 of the surface of the zinc-based electroplating layer 13 is polished.
- the convex portion of the crystal particles is scraped, so that the surface roughness becomes lower than the original state and becomes smooth, and the smooth portion is predominantly present.
- the oxide layer 14 is formed on the smooth portion of the plating layer, it becomes the smooth portion 113.
- the recess 101 which forms a recess that is difficult for the abrasive grain brush to reach, is a rough portion in a state in which the unevenness of the crystal particles of the plating layer remains almost as before. Then, when the oxide layer 14 is formed on the rough portion of the plating layer, it becomes the rough portion 111. As described above, the non-hairline portion 103 in which the rough portion 111 of the oxide layer 14 formed in the rough portion of the plating layer is predominantly present to ensure the processing adhesion, and the oxide layer formed in the smooth portion of the plating layer. The smooth portion 113 of 14 is predominantly present, and the recess 101 having a high glossiness coexists.
- the surface of the oxide layer 14 to which the hairline is provided is coated with the organic resin coating layer 15 as needed. Since the formation of the organic resin coating layer 15 can be carried out in the same manner as in the above-mentioned "Manufacturing method-No. 1", detailed description thereof will be omitted below.
- the surface of the zinc-based electroplating layer 13 to which the hairline is provided is coated with an organic resin, if necessary. Since the formation of the organic resin coating layer 15 can be carried out in the same manner as in the above-mentioned "Manufacturing method-No. 1", detailed description thereof will be omitted below.
- the method for manufacturing the galvanized steel sheet according to the present embodiment has been described above.
- the form shown in FIG. 7A is smoother not only in the plane but also in the depth direction. Since the portion is formed and the hairline is deepened, a high glossiness (texture) can be easily obtained.
- the form shown in FIG. 7B and the form shown in FIG. 7B are compared, the form shown in FIG. 7B is more likely to obtain a higher glossiness (texture).
- a known hot-dip galvanizing method can be used as a method for forming the zinc-based hot-dip galvanizing layer 13.
- a type of hot-dip galvanizing bath one having a total of elements other than Zn of less than 5% by mass can be used.
- a plating bath containing Zn and 2% by mass of Al is used as a type of zinc alloy hot-dip galvanizing bath.
- those having a total alloy element content of 5% by mass or more can be used, for example, those containing 55% by mass of Al, 13% by mass of Al and 3% by mass.
- Those containing Mg and the like can be used.
- composition, temperature, gas wiping flow rate, plating adhesion amount, etc. of the hot-dip galvanizing bath may be appropriately selected so as to obtain a desired plating composition, and are not particularly limited.
- the hairline according to the present embodiment is formed on the plated steel sheet 11 provided with the zinc-based hot-dip galvanized layer 13 obtained as described above.
- the method for imparting a hairline is not particularly limited, and various known methods can be used. Examples of such known methods include a method of polishing with a polishing belt, a method of polishing with an abrasive grain brush, a method of transferring with a textured roll, and a predetermined grinding apparatus, as in the case of imparting a hairline to a stainless steel material. Examples of the method of grinding with.
- the depth and frequency of the hairline can be controlled to a desired state by adjusting the particle size of the polishing belt or the abrasive grain brush, the depth of the texture of the roll, the reducing force, the relative speed, and the number of times.
- the surface of the zinc-based hot-dip plating layer 13 on which the hairline is formed as described above there is no unevenness due to plating crystal particles as in the zinc-based electroplating layer 13 described above. Unevenness is formed on the surface of the zinc-based hot-dip plating layer 13.
- the surface shape of the zinc-based hot-dip galvanized layer 13 satisfies various conditions of the surface texture of the oxide layer 14 as described above.
- the surface of the zinc-based hot-dip galvanized layer 13 is ground, polished, or rolled with a roll having an adjusted surface roughness by a known method until the surface shape is obtained.
- the oxide layer 14 is formed on the surface of the zinc-based hot-dip plating layer 13 to which the hairline is provided.
- the untreated portion becomes a smooth portion in which the unevenness of the crystal particles of the plating is suppressed.
- the oxide layer 14 is formed on the flat portion of the plating layer, it becomes the smooth portion 113.
- the treated recess 101 becomes a rough portion in which the unevenness of the crystal particles of the plating remains.
- the oxide layer 14 is formed on the rough portion of the plating layer, it becomes the rough portion 111.
- a case where such a form shown in FIG. 6 is formed by polishing with an abrasive grain brush will be described.
- the surface of the zinc-based hot-dip galvanized layer 13 before forming the hairline is flat. It is covered with the unevenness of the crystal particles of the plating.
- the scraped portion becomes a hairline (recessed portion 101).
- the surface roughness becomes higher than in the original state. That is, the formation of the hairline and the adjustment of the surface roughness in the hairline are performed at the same time.
- the flat portion (non-hairline portion 103) that was not scraped by the abrasive grain brush is in a smooth plating state as before.
- the smooth portion 113 of the oxide layer 14 formed on the flat portion is predominantly present, and the recess 101 having a high glossiness coexists.
- a known method can be used as the method for forming the oxide layer 14, and examples thereof include a method in which an acidic aqueous solution in which nitrate and phosphoric acid are mixed is brought into contact with the zinc-based electroplating layer.
- This oxide layer forms oxide particles according to the metal particle diameter on the surface of the zinc-based hot-dip plating layer as a base. Therefore, oxides having a small particle size are deposited on the surface of the smooth zinc-based hot-dip galvanized layer, and oxides having a large particle size are deposited on the surface of the coarse zinc-based hot-dip galvanized layer. Therefore, the oxide layer 14 can be provided with the above-mentioned suitable surface properties.
- the surface of the oxide layer 14 to which the hairline is provided is coated with the organic resin coating layer 15 as needed.
- the paint used for forming the organic resin coating layer 15 is the same as the paint used for the above-mentioned galvanized steel sheet.
- the method for coating the organic resin coating layer is not particularly limited, and a known method can be used.
- a paint adjusted to the viscosity as described above apply it by a spraying method, a roll coater method, a curtain coater method, a die coater method, or a dipping pulling method, and then naturally dry or bake it to form it. it can.
- the drying temperature and drying time, and the baking temperature and baking time may be appropriately determined so that the organic resin coating layer 15 to be formed has desired performance. At this time, if the temperature rising rate is slow, the time from the softening point of the resin component to the completion of baking becomes long and the leveling progresses, so that the temperature rising rate is preferably high.
- the galvanized steel sheet 1' includes a steel sheet 11', a zinc-based plated layer 13', and an oxide layer 14'. On the surface of the oxide layer 14', a linearly formed recess 101'and a flat portion 103' that is a region other than the recess 101'are formed.
- the recess 101' corresponds to the hairline portion and the flat portion 103'corresponds to the non-hairline portion.
- the galvanized steel sheet 1' covers the recess 101'and the flat portion 103' and has a translucent organic resin coating layer 15'. It is preferable to further provide'.
- the zinc-based plating layer 13', the oxide layer 14', and the organic resin coating layer 15' may be provided on both sides of the steel sheet 11', or may be provided on only one side.
- the steel sheet 11' which is the base material of the galvanized steel sheet 1'is not particularly limited, and is known depending on the mechanical strength (for example, tensile strength, etc.) required for the galvanized steel sheet 1'.
- Various steel materials can be appropriately used as the steel sheet 11'.
- Zinc-based plating layer The zinc-based plating layer 13'is formed on at least one surface of the steel plate 11'.
- the reason why zinc-based plating was selected as the metal type for plating in the modified example of this embodiment is that zinc-based plating has excellent sacrificial anticorrosion properties.
- the zinc-based plating layer 13' is, for example, a zinc-based electroplating layer or a zinc-based hot-dip galvanizing layer.
- the zinc-based electroplating layer is formed on the surface of the steel sheet 11'by electrogalvanizing the steel sheet 11'.
- the zinc-based hot-dip galvanized layer is formed on the surface of the steel sheet 11'by hot-dip galvanizing the steel sheet 11'.
- the zinc-based plating layer 13' may be formed by another plating method such as a thermal spraying method or a thin-film deposition plating method. However, in the thermal spraying method, since voids are formed inside the zinc-based plating layer 13', there is a possibility that the uniformity of appearance cannot be guaranteed.
- the zinc-based plating layer 13' preferably is a zinc-based electroplating layer or a zinc-based hot-dip galvanizing layer. Further, the zinc-based plating layer 13'is more preferably a zinc-based electroplating layer. By forming the zinc-based plating layer 13'by electrogalvanization, the zinc-based plating layer 13'can be easily thinned. Therefore, the raw material cost and the like can be reduced. Although the details will be described later, even if the zinc-based plating layer 13'is a thin film, the characteristics (corrosion resistance, hairline appearance, etc.) of the zinc-based plated steel sheet 1'can be sufficiently enhanced.
- the zinc-based electroplating layer is classified into an electrogalvanizing layer and an electrogalvanizing alloy plating layer.
- the electrogalvanized layer is composed of Zn and impurities.
- the electrozinc alloy plating layer contains additive elements described later, and the balance is composed of Zn and impurities.
- the Zn content is 35% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass of the zinc-based plating layer 13'. ..
- the upper limit of the Zn content is 100% by mass at the maximum, but it is less than 100% by mass considering that impurities are almost certainly present.
- the electrozinc alloy plating layer is one or more selected from the group consisting of Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr as the above-mentioned additive elements. It is preferable that the additive elements are contained in an amount of 5 to 20% by mass in total of these additive elements with respect to the total mass of the zinc-based plating layer 13'. In particular, in the electrozinc alloy plating layer, as the above-mentioned additive element, any one or more additive elements selected from the group consisting of Fe, Ni, and Co are added to the total mass of the zinc-based plating layer 13'. It is more preferable that the total content of these additive elements is 5 to 20% by mass. In this case, the corrosion resistance (white rust resistance, barrier property, etc.) of the galvanized steel sheet 1'is further improved.
- the impurities contained in the electrogalvanized layer and the electrogalvanized alloy plating layer are not intentionally added as components of the zinc-based electroplating layer, but are mixed in the raw material or mixed in the manufacturing process.
- impurities include Al, Mg, Si, Ti, B, S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr. , Ag, W, H and the like.
- Other types of impurities include Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, and Zr.
- Elements other than the above-mentioned additive elements may be added to the electrogalvanized layer and the electrogalvanized alloy plated layer as long as the effects of the modifications of the present embodiment are not impaired.
- Such additive elements are also classified as impurities.
- the total mass% of the elements serving as impurities is preferably less than 1% by mass at the maximum with respect to the total mass of the zinc-based electroplating layer. In this case, these elements have almost no effect on the zinc-based plating layer 13'.
- the intentionally added Fe, Ni, and Co and the Fe, Ni, and Co mixed as impurities can be distinguished from each other by the concentration in the zinc-based plating layer 13'.
- the composition of the zinc-based plating layer 13' (that is, the zinc-based electroplating layer described above and the zinc-based hot-dip plating layer described later) is, for example, the same as the method for analyzing the composition of the zinc-based electroplating layer described above. It is possible to analyze.
- the plated steel sheet is immersed in 10% by mass hydrochloric acid containing an inhibitor (for example, NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.) to dissolve and peel off, and the dissolved solution is inductively coupled plasma emission spectrometer (Inductively Coupled Plasma). : ICP) can also be used for analysis.
- the zinc-based hot-dip galvanizing layer is classified into a hot-dip galvanizing layer and a hot-dip zinc alloy plating layer.
- the hot-dip galvanized layer is composed of Zn and impurities.
- the hot-dip zinc alloy plating layer contains additive elements described later, and the balance is composed of Zn and impurities.
- the Zn content is 35% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass of the zinc-based plating layer 13'. ..
- the upper limit of the Zn content is 100% by mass at the maximum, but it is less than 100% by mass considering that impurities are almost certainly present.
- any one or more additive elements selected from the group consisting of Al, Sb, and Pb may be added to the hot-dip galvanized layer.
- the total amount of these elements added is preferably 1% by mass or more and less than 5% by mass.
- any one or more additive elements selected from the group consisting of Fe, Al, Mg, and Si are added to the total mass of the zinc-based plating layer 13. It is preferable that the total amount of the added elements of the above is 1 to 60% by mass.
- any one or more additive elements selected from the group consisting of Al and Mg are added to the total mass of the zinc-based plating layer 13'. It is more preferable that the total amount of the added elements is 1 to 60% by mass. In this case, the corrosion resistance (white rust resistance, barrier property, etc.) of the galvanized steel sheet 1'is further improved.
- the impurities contained in the hot-dip galvanizing layer and the hot-dip zinc alloy plating layer are not intentionally added as components of the zinc-based hot-dip galvanizing layer, but are mixed in the raw material or mixed in the manufacturing process. , So-called impurities. Examples of such impurities include Al, Mg, Si, Ni, Ti, Pb, Sb and the like. Elements other than the above-mentioned additive elements may be added to the hot-dip galvanizing layer and the hot-dip zinc alloy plating layer as long as the effects of the modifications of the present embodiment are not impaired. Such additive elements are also classified as impurities.
- the total mass% of the elements serving as impurities is preferably less than 1% by mass at the maximum with respect to the total mass of the zinc-based hot-dip galvanized layer. In this case, these elements have almost no effect on the zinc-based plating layer 13'.
- the intentionally added additive element and the impurity can be distinguished from each other by the concentration in the zinc-based plating layer 13'. That is, for example, since the lower limit of the total content of the added elements intentionally added is 1% by mass, if the total content of each element is less than 1% by mass, these elements can be discriminated as impurities.
- the average adhesion amount of the zinc-based plating layer 13' is preferably 5 to 40 g / m 2 .
- the average amount of adhesion is a value obtained by dividing the total mass of the zinc-based plating layer 13'attached to the steel sheet 11'by the area of the surface to which the zinc-based plating layer 13'attached.
- the amount of plating adhesion can be measured, for example, by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.) to dissolve and peel it off, and measuring the mass change of the steel sheet before and after immersion.
- the average adhesion amount of the zinc-based plating layer 13' is less than 5 g / m 2 , the base iron (that is, the steel plate 11') is exposed when the recess 101'(that is, the hairline) is formed in the oxide layer 14. there is a possibility. Therefore, the appearance of the hairline and the corrosion resistance may be deteriorated.
- the manufacturing cost may increase.
- the lower limit of the average adhesion amount of the zinc-based plating layer 13' is more preferably 7 g / m 2 or more, and more preferably 10 g / m 2 or more.
- the upper limit of the average adhesion amount of the zinc-based plating layer 13' is more preferably 35 g / m 2 or less, and more preferably 30 g / m 2 or less.
- Oxide layer > The oxide layer 14'is formed on the surface of the zinc-based plating layer 13'.
- the oxide layer 14' is formed on the surface of the zinc-based plating layer 13'by oxidizing the zinc-based plating layer 13'. The specific contents of the oxidation treatment will be described later.
- the zinc-based plated steel sheet 1' has a high degree of blackness by having such an oxide layer 14'.
- the blackness of the surface of the galvanized steel sheet 1' can be set to 50 or less in L * value by the oxide layer 14'.
- L * is preferably 40 or less, more preferably 35 or less.
- the organic resin coating layer 15'containing the black pigment is formed on the surface of the oxide layer 14'(the surface of the recess 101'and the flat portion 103' described later)
- the L * value is 40 or less due to the synergistic effect of these.
- the L * value means the L * value in CIE1976L * a * b * color system, measured in reflection spectrodensitometer.
- the oxide layer 14 preferably further contains any one or more additive elements selected from the group consisting of Fe, Ni, and Co as the second component. These elements are derived from the zinc-based plating layer 13', especially the electrozinc alloy plating layer. When the oxide layer 14'contains these second components, the blackness of the galvanized steel sheet 1 becomes higher.
- the average thickness of the oxide layer 14' is preferably 0.05 ⁇ m or more and less than 3.0 ⁇ m. If the average thickness of the oxide layer 14'is less than 0.05 ⁇ m, sufficient blackness may not be obtained. When the average thickness of the oxide layer 14'is 3.0 ⁇ m or more, cracks may occur in the oxide layer 14'during the processing of the galvanized steel sheet 1'. If such a crack is formed in the oxide layer 14', the processing adhesion, particularly the adhesion to the organic resin coating layer 15, may be deteriorated.
- the lower limit of the average thickness of the oxide layer 14' is more preferably 0.07 ⁇ m, and more preferably 1.0 ⁇ m.
- the upper limit of the average thickness of the oxide layer 14' is preferably 2.7 ⁇ m, more preferably 2.5 ⁇ m.
- the average thickness of the oxide layer 14' is specified by, for example, the following method. That is, any region of the cross section of the galvanized steel sheet 1'in the plate thickness direction is set as the cross section observation region.
- the cross-section observation region includes at least a region from the surface of the oxide layer 14'to a depth of 0.3 ⁇ m or more.
- this cross-section observation region is observed with a transmission electron microscope (TEM-EDS) equipped with an EDS (Energy Dispersive X-ray Analyzer). In this way, the element distribution in the cross-section observation region is specified.
- the oxygen concentration (the oxygen concentration here is the oxygen concentration in each micro region in the cross-sectional observation region, that is, the mass% of the oxygen in the micro region with respect to the total mass of all the elements existing in the micro region).
- the region where is 20% by mass or more is specified as the oxide layer 14'.
- the composition of the oxide layer 14' can also be specified by specifying the element distribution in the oxide layer 14'by TEM-EDS.
- the thickness of the oxide layer 14' may be measured at a plurality of places, and the arithmetic mean value thereof may be used as the average thickness of the oxide layer 14'.
- the recess 101' is formed by polishing the surface of the oxide layer 14', that is, removing a part of the oxide layer 14'.
- the bottom portion 101a'of the recess 101'(the portion existing at the deepest position of each recess 101) reaches the zinc-based plating layer 13'under the oxide layer 14'.
- the appearance of the hairline is improved. That is, the appearance (visibility) of the hairline is improved by the contrast between the metal color of the zinc-based plating layer 13'in the recess 101'and the black color of the oxide layer 14'.
- the average depth of the recess 101' is 0.1 ⁇ m or more and less than 3.0 ⁇ m. As described above, in the modified example of the present embodiment, the average depth of the recess 101'is very shallow. However, as shown in the examples described later, a good hairline appearance is obtained. Further, since the average depth of the recess 101'is very shallow, the recess 101'can be easily formed and the generation of shavings can be suppressed. When the average depth of the recess 101 is less than 0.1 ⁇ m, the bottom of the recess 101'does not reach the zinc-based plating layer 13', and a good hairline appearance cannot be obtained. In addition, the metallic feeling is also reduced.
- the average depth of the recess 101' is 3.0 ⁇ m or more, not only is it time-consuming to form the recess 101', but also a large amount of shavings are generated. In addition, corrosion resistance and processing adhesion are reduced.
- the average depth of the recess 101' is preferably 0.1 ⁇ m or more and less than 2.0 ⁇ m.
- the average depth of the recess 101' is measured by, for example, the following method. That is, a laser microscope having a display resolution in the depth direction of 1 nm or more and a display resolution in the direction perpendicular to the depth direction (plane direction) of 1 nm or more is prepared. Then, an arbitrary 1 cm ⁇ 1 cm region on the surface of the oxide layer 14'is set as a plan view observation region. This plan view observation region is scanned with a laser microscope along the direction orthogonal to the hairline. The scanning interval is, for example, 100 ⁇ m. As a result, a plurality of line profiles of the surface shape are acquired. An example of the line profile is shown in FIG. The horizontal axis of FIG.
- the distance in the depth direction (that is, the bottom 101a'of the recess 101') from the straight line connecting the adjacent boundary points in the same recess to the point at the deepest position between the boundary points (the boundary points from the bottom 101a').
- the length of the straight line in the depth direction drawn along the straight line connecting the two) is defined as the depth of the recess 101'.
- the average depth of the recesses is calculated by arithmetically averaging the depths of all the recesses 101'measured in each line profile.
- the position of the recess 101'in the plan view observation region is also specified by this method. Further, in the modified example, the method of defining the boundary point is different from that of the present embodiment due to the difference in the manufacturing method.
- the boundary point between the recess 101'and the flat portion 103' is located closer to the bottom than in the above embodiment. Since the zinc-based plating layer 13'is exposed in the recess 101', the appearance of the hairline is good. In order to realize excellent visibility, it is preferable that the zinc-based plating layer is scraped to a certain depth. That is, [(H 1 ⁇ H 0 ) ⁇ (average thickness of the oxide layer)] is preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more.
- the average length of the recess 101'along the length direction is 1 cm or more.
- the recesses 101' preferably exist in an arbitrary 1 cm width range along the direction orthogonal to the length direction of the recesses 101' at a frequency of 3 to 80 lines / cm on average.
- the number of recesses 101'existing within an arbitrary 1 cm width range is also referred to as "the number of recesses 101'per unit width".
- the length of each recess 101'existing in the plan view observation region along the length direction may be measured, and it may be determined whether or not the arithmetic mean value thereof is 1 cm. Further, a number of 1 cm wide regions are arbitrarily selected in the plan view observation region, and the number of recesses 101'existing in each selected region is measured. Then, the number of recesses 101'existing in each region is arithmetically averaged. Then, it may be determined whether or not the arithmetic mean value is 3 to 80 lines / cm.
- AR1 / AR2 is 0 or more and 0.5 or less. When this condition is satisfied, the blackness, hairline appearance and metallic feeling are improved.
- the area ratio AR1 is a value obtained by dividing the area of the oxide layer 14'existing in the recess 101'in the plan view by the area of the recess 101'in the plan view. Since the recess 101'is formed by polishing the oxide layer 14', ideally, the oxide layer 14'is not present on the surface of the recess 101'. Therefore, the area ratio AR1 becomes 0, and the area ratio AR1 / AR2 becomes 0. However, the oxide layer 14'in the recess 101' may not be sufficiently removed due to wear of the abrasive material or the like. In this case, since the oxide layer 14'slightly remains in the recess 101', AR1 becomes larger than 0. However, if AR1 becomes excessively large, most of the surface of the recess 101'will be covered with the oxide layer 14', and the hairline appearance and metallic feeling will be impaired.
- the area ratio AR2 is a value obtained by dividing the area of the oxide layer 14'existing in the flat portion 103'in the plan view by the area of the flat portion 103'in the plan view. Since the flat portion 103'is a portion where the oxide layer 14 remains, the AR2 is ideally 100. However, there is a possibility that the flat portion 103'is also slightly polished by the abrasive in the process of forming the recess 101'. As a result, AR2 can be less than 100. When AR2 becomes excessively small, the oxide layer 14'existing in the flat portion 103'is reduced, and the blackness is lowered. Therefore, the present inventor paid attention to the balance between the two, and found that when the area ratio ratio AR1 / AR2 is 0 to 0.5, the blackness, the hairline appearance, and the metallic feeling are good.
- the area ratio AR1, the area ratio AR2, and the area ratio ratio AR1 / AR2 are measured by the following methods. That is, the above-mentioned plan view observation region is observed with a field emission electron probe microanalyzer (FE-EPMA). In this way, the element distribution in the plan view observation region is specified. Then, in each region in the recess 101', the oxygen concentration (the oxygen concentration here is the oxygen concentration in each minute region in the plan view observation region, that is, the total mass of all the elements existing in the minute region). (% By mass of oxygen in the microregion) is measured. FE-EPMA detects elemental information at a depth of about 1 ⁇ m.
- FE-EPMA detects elemental information at a depth of about 1 ⁇ m.
- the oxide layer 14 when the average thickness of the oxide layer exceeds 1 ⁇ m, the region where the oxygen detected by the FE-EPMA is 20% by mass or more is specified as the oxide layer 14.
- the oxide layer 14' When the average thickness of the oxide layer is 1 ⁇ m or less, the region where the obtained oxygen concentration satisfies the following relationship is specified as the oxide layer 14'. Detected oxygen concentration> Average thickness of oxide layer [ ⁇ m] / 1 [ ⁇ m] x 20% by mass
- the region other than the oxide layer 14' is the zinc-based plating layer 13'exposed in the recess 101'.
- the area of the oxide layer 14'existing in the recess 101'in the plan view observation region in the plan view can be obtained, and this is divided by the area of the recess 101'in the plan view observation region in the plan view.
- the area ratio AR1 is obtained.
- the region to be the oxide layer 14' is specified by the same method as described above.
- the region other than the oxide layer 14' is the zinc-based plating layer 13'exposed in the flat portion 103'.
- the area of the oxide layer 14'existing in the flat portion 103'in the plan view observation region in the plan view can be obtained. Therefore, this is calculated by the area of the flat portion 103'in the plan view observation region in the plan view.
- the area ratio AR2 is obtained by dividing.
- the area ratio AR1 / AR2 is obtained by dividing the area ratio AR1 by the area ratio AR2.
- the recess 101' includes a region having a surface roughness RaA' of more than 5 nm and 500 nm or less, and the flat portion 103' includes a region having a surface roughness RaB' of more than 500 nm and 5000 nm or less.
- the surface roughness RaA'and RaB' are both centerline average roughness (arithmetic mean roughness). That is, the surface roughness RaA'and RaB'mean the arithmetic mean roughness Ra defined in JIS B 0601 (2001), and the measuring method thereof is the surface roughness Ra A of the rough portion 111 or the surface of the smooth portion 113. It is the same as the roughness Ra B.
- the recess 101' By polishing the surface of such an oxide layer 14', a recess 101'is formed on the surface of the oxide layer 14'. Therefore, since the surface of the recess 101'is polished, the surface roughness RaA' becomes small. Then, when the surface roughness RaA'is more than 5 nm and 500 nm or less, the metallic feeling becomes particularly good. Therefore, it is preferable that the recess 101'includes a region having a surface roughness RaA' of more than 5 nm and 500 nm or less.
- the flat portion 103' since the flat portion 103'is not polished as much as the concave portion 101', the above-mentioned rough unevenness often remains almost as it is. Due to the anchor effect due to such rough irregularities, the adhesion between the oxide layer 14'and the organic resin coating layer 15', that is, the processing adhesion is improved. Therefore, it is preferable that the flat portion 103'includes a region having a surface roughness RaB' of more than 500 nm and 5000 nm or less.
- the surface roughness RaA'and RaB' are measured by the line profile of the surface shape described above.
- the surface roughness RaA'and RaB'measured by a plurality of line profiles may be arithmetically averaged, or the surface roughness RaA'and RaB' measured from any of the line profiles may be selected as representative values. Good.
- the surface of the oxide layer 14' is formed with the above-mentioned rough irregularities due to the dense distribution of oxide particles having a relatively large particle size. Therefore, the average particle size and density of such oxide particles will be briefly described.
- the average particle size of the oxide particles is measured by, for example, the following method. First, the surface of the oxide layer 14'is observed by SEM. The visual field magnification at that time may be in the range of 1000 to 10000 times. However, if the oxide particles cannot be confirmed even at the maximum magnification of 10000 times, the number of oxide particles is counted as zero in the observation field of view. The observation field of view is changed until at least 10 oxide particles can be observed in the observation field of view.
- the flat area S ( ⁇ m 2 ) per oxide particle is obtained based on the contour of the oxide particles.
- the representative diameter D ( ⁇ m) of the oxide particles is obtained based on the flat area S and the following formula (1).
- the representative diameter D is the equivalent circle diameter of the oxide particles.
- 10 oxide particles in the observation field of view are arbitrarily selected, and the average value of the representative diameters D of the 10 oxide particles is taken as the average particle size.
- D 2 ⁇ (S / ⁇ ) 0.5 ... Equation (1)
- the density of oxide particles can be determined by, for example, the following method. First, the surface of the oxide layer 14'is observed by SEM as described above. Then, the number of oxide particles whose average particle size is equal to or larger than the particle size threshold is counted within the range of 100 ⁇ m ⁇ 100 ⁇ m. As a result, the density of oxide particles is determined.
- the particle size threshold differs depending on the plating type and alloy of the lower zinc-based plating layer 13'. For example, when the lower zinc-based plating layer 13'is a Zn—Ni electrozinc alloy plating layer, the particle size threshold is 0.1 to 3.0 ⁇ m.
- the particle size threshold is 0.3 to 3.6 ⁇ m.
- the particle size threshold is 0.4 to 9.6 ⁇ m. If the oxide particles cannot be confirmed even when the SEM magnification is set to the maximum magnification (10000 times), the number is counted as zero. In this case, the observation field of view is changed until the oxide particles are observed.
- the average particle size of the oxide particles is 0.5 to 2.7 ⁇ m in the region where the surface roughness RaB' is more than 500 nm and 5000 nm or less.
- the value is within the range, and the density is often within the range of 2 ⁇ 10 10 to 5 ⁇ 10 14 pieces / m 2 .
- the average particle size of the oxide particles is 0.6 to 7.
- the value is in the range of 2 ⁇ m, and the density is often in the range of 0.5 ⁇ 10 10 to 3.6 ⁇ 10 14 pieces / m 2 .
- the average particle size of the oxide particles is 0.3 to 2 in the region where the surface roughness RaB'is more than 500 nm and 5000 nm or less. It is within the range of 4 ⁇ m, and the density is often within the range of 5 ⁇ 10 10 to 8.4 ⁇ 10 14 pieces / m 2 .
- the zinc-based plating layer 13' is a zinc-based electroplating layer and contains any one or more elements selected from the group consisting of Fe, Ni, and Co as additive elements, the surface roughness RaB In the region where'is more than 500 nm and 5000 nm or less, the average particle size of the oxide particles is 0.3 ⁇ m or more, and the density is often 10 10 particles / m 2 or more.
- the average particle size and density of the oxide particles are not limited to the above-mentioned values.
- the flat portion 103' includes a region having a surface roughness RaB' of more than 500 nm and 5000 nm or less, good work adhesion is good even if the average particle size and density of the oxide particles are outside the above ranges. Is obtained.
- the galvanized steel sheet 1' According to the galvanized steel sheet 1'according to the modified example of the present embodiment, good blackness, hairline appearance, and metallic feeling even when an inexpensive galvanized steel sheet is used. Can be realized. Further, since the average depth of the recess 101'is as shallow as 0.1 ⁇ m or more and less than 3.0 ⁇ m, the recess 101'can be easily formed and the generation of shavings can be suppressed. Even if the average depth of the recesses is very shallow, the appearance of the hairline is excellent in visibility. In the modified example, the bottom of the recesses reaches the zinc-based plating layer, and the metallic color and oxide of the zinc-based plating layer. This is due to the large contrast with the black color of the layer.
- the galvanized steel sheet 1' preferably further has an organic resin coating layer 15'that covers the recess 101'and the flat portion 103'.
- the organic resin coating layer 15' has translucency (transparency).
- translucency translucency
- the fact that the organic resin coating layer 15'has translucency (transparency) means that the recess 101'and the flat portion 103' can be visually observed through the organic resin coating layer 15'. ..
- the resin used for forming the organic resin coating layer 15' preferably having sufficient transparency, chemical resistance, corrosion resistance, processability, scratch resistance and the like.
- resins include polyester resins, epoxy resins, urethane resins, polyester resins, phenol resins, polyether sulfone resins, melamine alkyd resins, acrylic resins, polyamide resins, and polyimides.
- examples thereof include based resins, silicone resins, polyvinyl acetate resins, polyolefin resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins and the like.
- additives may be added to the organic resin coating layer 15'as long as the effects of the modifications of the present embodiment are not impaired. These additives can impart corrosion resistance, slidability, scratch resistance, conductivity, color tone, etc. to the galvanized steel sheet 1'.
- a rust preventive or an inhibitor may be added to the organic resin coating layer 15'.
- These rust preventives or inhibitors preferably contain any one or more elements selected from Si, P, and Zr as their components. In this case, the corrosion resistance of the galvanized steel sheet 1 is further improved.
- wax, beads or the like may be added to the organic resin coating layer 15'.
- a conductive agent or the like may be added to the organic resin coating layer 15'.
- a known colorant such as a pigment or a dye may be added to the organic resin coating layer 15'.
- a black pigment to the organic resin coating layer 15', the blackness of the galvanized steel sheet 1 can be further enhanced.
- a colorant such as a black pigment
- the colorant include Bengara, aluminum, mica, carbon black, titanium oxide, cobalt blue and the like.
- the content of the colorant is preferably 1 to 10% by mass, more preferably 2 to 5% by mass, based on the total mass of the organic resin coating layer 15'.
- the organic resin coating layer 15' may have a multilayer structure.
- the colorant is added to any one or more layers other than the bottom layer (the layer covering the recess 101'and the flat portion 103').
- the addition amount is preferably mass% as described above with respect to the total mass of the layer to be added.
- the visibility of the appearance of the hairline is enhanced by the contrast between the metallic color of the zinc-based plating layer and the black color of the oxide layer.
- the bottom layer coating film has a relatively thick coating film at the recesses forming the hairline. Therefore, when the colorant is added to the lowermost layer of the organic resin coating layer 15', the hairline may be hidden by the black coating film.
- the average thickness of the organic resin coating layer 15' is preferably 10 ⁇ m or less.
- the average thickness of the entire layer including all the layers is preferably 10 ⁇ m or less.
- the average thickness of the organic resin coating layer 15'exceeds 10 ⁇ m the distance through which light passes through the organic resin coating layer 15'is long, so that the glossiness may decrease. Further, there is a possibility that a gap may occur between the texture of the surface of the oxide layer 14'and the texture of the surface of the organic resin coating layer 15'. Therefore, the average thickness of the organic resin coating layer 15'is preferably 10 ⁇ m or less.
- the average thickness of the organic resin coating layer 15' is more preferably 8 ⁇ m or less.
- the lower limit of the average thickness of the organic resin coating layer 15' is more preferably 1.0 ⁇ m. If the average thickness of the organic resin coating layer 15'is less than 1.0 ⁇ m, the function of the organic resin coating layer 15'may not be fully exhibited.
- the average thickness of the organic resin coating layer 15' is measured by observing the cross section of the zinc-based plated steel sheet 1'including the organic resin coating layer 15'in the thickness direction. That is, the position of the organic resin coating layer 15'is specified from the cross section, and the thickness thereof is measured at a plurality of places. Then, the arithmetic mean value of the measured values is taken as the average thickness of the organic resin coating layer 15'.
- the minimum value of the thickness measured at each measurement point is preferably 0.1 ⁇ m or more. This is because if the minimum thickness is less than 0.1 ⁇ m, the corrosion resistance at that location may be lower than at other locations.
- a zinc-based plating layer 13' is formed on the surface of the steel sheet 11'.
- the electrogalvanizing method or the hot-dip galvanizing method is preferable as described above. Therefore, these plating methods will be described here.
- a known electrogalvanizing method can be used.
- the electroplating bath used in the electrogalvanizing method include a sulfuric acid bath, a chloride bath, a zincate bath, a cyanide bath, a pyrophosphate bath, a boric acid bath, a citric acid bath, other complex baths, and combinations thereof.
- the electrozinc alloy plating bath in addition to Zn ions, one or more monatomic ions or complex ions selected from Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr.
- a zinc-based electroplating layer containing a desired amount By adding Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr, a zinc-based electroplating layer containing a desired amount can be formed.
- additive elements it is preferable to add any one or more elements selected from the group consisting of Fe, Co, and Ni. Further, it is more preferable to add an additive to the plating bath in order to stabilize the ions in the plating bath and control the plating characteristics.
- the composition, temperature, flow velocity, current density at the time of plating, energization pattern, etc. of the electroplating bath may be appropriately selected so as to obtain a desired plating composition, and are not particularly limited. Further, the amount of adhesion of the zinc-based electroplating layer can be controlled by adjusting the current value and the time within the range of the current density at which the zinc-based electroplating layer has a desired composition.
- a known hot-dip galvanizing method can be used. First, the steel sheet 11'with the adjusted surface roughness is annealed. Then, the steel plate 11'is immersed in a hot-dip galvanizing bath with the steel plate temperature set to, for example, 450 ° C., and the temperature is raised. As a result, a zinc-based hot-dip galvanized layer is formed on the surface of the steel sheet 11'. The amount of plating adhered is adjusted by gas wiping with nitrogen gas or the like when the steel sheet 11'is lifted. When the steel sheet 11'and the zinc-based hot-dip galvanized layer are alloyed, the zinc-based hot-dip galvanized layer is heated by, for example, IH so that the ultimate temperature after plating is, for example, 500 ° C.
- one or more of the above-mentioned additive elements selected from the group consisting of Fe, Al, Mg, and Si may be added to the hot-dip galvanizing bath.
- the composition, temperature, gas wiping flow rate, plating adhesion amount, etc. of the hot-dip plating bath may be appropriately selected so as to obtain a desired plating composition, and are not particularly limited.
- a method in which an acidic aqueous solution in which nitrate and phosphoric acid are mixed is brought into contact with the zinc-based plating layer 13'
- a method in which an acidic aqueous solution in which tartaric acid and a fluoride are mixed is brought into contact with the zinc-based plating layer 13', and electrolytic treatment is performed, nickel and antimony.
- a method of bringing an acidic aqueous solution containing a fluorine compound into contact with the zinc-based plating layer 13' since the oxide layer 14'composed of coarse oxide particles can be formed, rough irregularities can be formed on the surface of the oxide layer 14', and thus the oxide layer 14'.
- the surface roughness Ra of ‘’ can be more than 500 nm and 5000 nm or less. Moreover, this method is very simple and can be implemented in-line.
- the average thickness of the oxide layer 14' can be adjusted by appropriately adjusting the concentration of the acidic aqueous solution, the immersion time, and the like. On the other hand, the steam oxidation described in Patent Document 6 cannot be carried out in-line. Further, the unevenness of the surface of the oxide layer 14'is also very small.
- the specific hairline forming method is not particularly limited, and a method similar to the conventionally used hairline forming method can be used.
- Specific hairline forming methods include, for example, a method of polishing the surface of the oxide layer 14'with an abrasive (for example, a polishing belt and an abrasive grain brush), and pressing a roll having a texture on the surface of the oxide layer 14'. Examples thereof include a method of transferring the texture to the surface of the oxide layer 14', a method of grinding the surface of the oxide layer 14'with a grinding device, and the like.
- the surface structure of the oxide layer 14' (for example, the depth, length, frequency, area ratio AR1, AR2, surface roughness RaA', RaB', etc. of the recess 101') is determined by, for example, the particle size of the abrasive and the abrasive. It is adjusted by adjusting the pressing force of the roll, the polishing time, the texture depth of the roll, the compressing force of the roll, the relative speed of the roll, the number of times the roll is pressed, and the like.
- the average depth of the recess 101' is 0.1 ⁇ m or more and less than 3.0 ⁇ m, so that the generation of shavings can be suppressed. Further, by suppressing the amount of grinding of the formed plating layer and oxide layer, it is possible to reduce the cost required for the portion that is not a product.
- the organic resin coating layer 15' is formed on the surfaces of the recess 101'and the flat portion 103'.
- the organic resin coating layer 15' may be omitted, it is preferable to form the organic resin coating layer 15'from the viewpoint of enhancing characteristics such as corrosion resistance and blackness.
- the method for forming the organic resin coating layer 15' is not particularly limited, and examples thereof include a method using a paint. Specifically, a paint having the same composition as the organic resin coating layer 15'is applied to the surfaces of the recess 101'and the flat portion 103' and dried. As a result, the organic resin coating layer 15'is formed on the surfaces of the recess 101'and the flat portion 103'.
- the organic resin coating layer 15' By further applying a paint to the surface of the organic resin coating layer 15'and drying it, the organic resin coating layer 15'can have a multilayer structure.
- a colorant for example, a black pigment to any layer other than the bottom layer.
- the paint used for forming the organic resin coating layer 15' follows the surface shape of the recess 101'and the flat portion 103'at the moment when the paint is applied to the recess 101'and the flat portion 103', and the oxide It is preferable that the leveling after following the surface shape of the layer 14'is slow. That is, it is preferable that the viscosity of the paint is low at a high shear rate and the viscosity of the paint is high at a low shear rate. For example, when the shear rate is 0.1 [1 / sec], the shear viscosity is 10 [Pa ⁇ s] or more, and when the shear rate is 1000 [1 / sec], the shear viscosity is 0.01. It is preferably [Pa ⁇ s] or less.
- the shear viscosity can be adjusted by adding a hydrogen-bonding viscosity modifier to the paint.
- a hydrogen-bonding viscosity modifier bind each other by hydrogen bonds at low shear rates, so that the viscosity of the coating material can be increased.
- the hydrogen bond of the viscosity modifier is broken, so that the viscosity of the paint decreases. Thereby, the shear viscosity of the paint can be adjusted to a value according to the coating conditions.
- the method of applying the paint to the recess 101'and the flat portion 103' is not particularly limited, and a known method can be appropriately used.
- Specific examples of the coating method include a spraying method, a roll coater method, a curtain coater method, a die coater method, and a dipping pulling method.
- the paint is naturally dried or baked to form the organic resin coating layer 15'.
- the drying time, drying temperature, etc. may be adjusted as appropriate, but if the rate of temperature rise is slow, the time from the softening point of the resin component to the completion of baking may become long, and leveling may proceed. Therefore, it is preferable that the rate of temperature rise is high.
- Table 1A among the column “Ra A is 500nm ultra 5000nm or less of the total area” in Table 3A and Table 5B, the ratio of roughness satisfying area among the left column area S A (maximum 1.0 ), And the right column is the actual area that satisfies the roughness condition.
- the area S A ⁇ [left column] become [right column.
- the average height difference in Tables 1B, 3B, and 5B is the average value of ⁇ h shown in FIG. 2 or FIG.
- the difference ⁇ h between the average surface height of a certain rough portion 111 and the average surface height of the smooth portion 113 adjacent to the rough portion 111 is obtained, and this is calculated for each combination of the rough portion 111 and the smooth portion 113.
- the contents of the present invention are not limited by the contents described in the examples shown below.
- Example 1 Electroplating; an example in which the rough part forms a hairline
- a steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) is treated with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L at a treatment liquid of 60 ° C. and a current. It was electrolytically degreased and washed with water under the conditions of a density of 20 A / dm 2 and a treatment time of 10 seconds. Next, the electrolytically degreased steel sheet was immersed in an aqueous solution of H 2 SO 4 at a concentration of 50 g / L at 60 ° C. for 10 seconds and further washed with water to perform pre-plating treatment.
- the rolling method was a method in which a rolling roll having a pattern on the surface was pressed down on the design surface.
- the rolling speed was 200 mpm and the rolling roll diameter was 500 mm.
- the additive element described in the column of "plating composition” is an element added to the electroplating solution containing zinc as a main component, and when such a column is blank. Means electrogalvanized.
- the Zn—Ni plating layer (Tables 1A to 1C: Nos. 1 to 18, 23 to 29) was formed as follows. When plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , Zn sulphate sulphate and Ni sulphate hexahydrate were adjusted to the ratios shown in Table 1 below. Using a plating bath with a pH of 2.0 containing a total of 1.2 M of Japanese product and Ni-sulfate hexahydrate and 50 g / L of anhydrous sodium sulfate, the amount of adhesion was the value shown in Tables 1A to 1C. The plating time was adjusted so as to be.
- the Zn—Fe plating layer (Tables 1A to 1C: No. 19) was formed as follows. When plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the Zn heptahydrate sulfate and Fe (II) sulphate heptahydrate are adjusted in a ratio that gives the compositions shown in Tables 1A to 1C below. Using a plating bath of pH 2.0 containing a total of 1.2 M of Zn heptahydrate sulfate and Fe (II) sulphate heptahydrate and 50 g / L of anhydrous sodium sulfate, the amount of adhesion is shown. The plating time was adjusted so as to have the values shown in Table 1C from 1A.
- the Zn—Co plating layer (Tables 1A to 1C: No. 20) was formed as follows. Sulfuric acid, which was prepared by adjusting Zn heptahydrate sulfate and Co heptahydrate sulfate in a ratio such that the compositions shown in Tables 1A to 1C below were obtained when plating was performed at a bath temperature of 50 ° C. and a current density of 50 A / dm 2. Using a plating bath having a pH of 2.0 containing a total of 1.2 M of Zn heptahydrate and Co sulphate heptahydrate and 50 g / L of anhydrous sodium sulfate, the amount of adhesion is shown in Tables 1A to 1C. The plating time was adjusted so that the value would be the same.
- the Zn—Ni—Fe—Co plating layer (Tables 1A to 1C: No. 21) was formed as follows. When plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the composition of Table 1A to Table 1C below is obtained with Zn sulphate hydrate, Ni hexahydrate sulphate and Co sulphate sulphate. The sum of Zn sulphate heptahydrate, Ni sulphate hexahydrate, Fe (II) sulphate heptahydrate, and Co sulphate heptahydrate prepared by adjusting Japanese product and Fe (II) sulfate heptahydrate. The plating time was adjusted so that the adhesion amount was the value shown in Tables 1A to 1C using a plating bath having a pH of 2.0 containing 1.2 M and 50 g / L of anhydrous sodium sulfate.
- the Zn plating layer (Tables 1A to 1C: No. 22) was formed as follows. Adhesion amount when plating with a pH 2.0 plating bath containing 1.2 M of Zn sulphate heptahydrate and 50 g / L of anhydrous sodium sulfate at a bath temperature of 50 ° C. and a current density of 50 A / dm 2. The plating time was adjusted so that the values shown in Tables 1A to 1C were obtained.
- the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
- the composition of the obtained plating layer is obtained by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.), dissolving and peeling, and analyzing the dissolved solution by ICP. confirmed.
- the steel plate sample of 29 was adjusted as follows. After forming the zinc-based electroplating layer 13, the surface of the zinc-based electroplating layer 13 is brush-polished so that the surface shapes of the recesses 101 and the non-hairline portion 103 shown in Tables 1A to 1C are obtained. The grain size of the polishing paper, the rolling force, the number of times of polishing, etc.) were adjusted as appropriate. As a result, the surface shape of the zinc-based electroplating layer 13 was formed such that the recess 101 was composed of the rough portion 111 and the non-hairline portion 103 was composed of the smooth portion 113.
- No. 2-No. An acidic aqueous solution (sodium nitrate 120 g / L, phosphoric acid 45 g / L: pH 0.6, 30 ° C.) was spray-sprayed on the steel plate samples 26, 28, and 29, and the oxide layer 14 was sprayed on the surface of the zinc-based electroplating layer 13. (Specifically, an oxide layer mainly composed of Zn) was formed. The thickness of the oxide layer was adjusted by the temperature of the acidic aqueous solution and the spray spray time. The thickness of the oxide layer was determined by observing the cross section with TEM-EDS, and was measured by changing the measurement magnification of TEM-EDS according to the thickness. The underline in the table indicates that it is outside the specified range of the present invention.
- the various surface roughness, surface height, number of hairlines, area ratio, etc. of the rough portion (A) and the smooth portion (B) in the oxide layer 14 shown in Tables 1A to 1C are in the height direction.
- the measurement was performed according to the above method using a laser microscope / VK-9710 manufactured by KEYENCE Corporation having a display resolution of 1 nm or more and a display resolution in the width direction of 1 nm or more.
- the amount of plating adhered was analyzed by FE-EPMA from the direction perpendicular to the surface. Then, the amount of plating adhesion was calculated from the thickness of the Zn-based plating layer excluding the oxide layer formed on the outermost layer, the average composition of the plating layer, and the specific gravity of each metal.
- Ra A or Ra B is the left column in the column of the following total area 500nm ultra 5000nm indicates the value of the area S A or area S B ⁇ total area.
- a transparent organic resin coating layer was formed on the above-mentioned plated steel sheet having a hairline (steel sheet excluding No. 26).
- the transparent organic resin coating layer was formed by the following method. That is, a urethane resin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex 170) and a melamine resin (manufactured by Ornex Japan Co., Ltd., Cymel 327) were mixed so as to have a solid content mass ratio of 85:15.
- black pigment manufactured by Toyo Color Co., Ltd., EMF Black HK-3
- blue pigment manufactured by Dainichiseika Co., Ltd., AF Blue E-2B
- the mass concentration in the coating film was 2 mass%.
- Polyethylene wax Mitsubishi Chemicals, Inc., Chemipearl W500
- the concentration in the dry film was 2% by mass, and the mixture was stirred. Further, the obtained mixture was diluted with water to prepare treatment solutions having various concentrations and viscosities. These treatment liquids were applied to the surface of the steel sheet with a roll coater.
- the dry film thickness was adjusted to be the thickness shown in Table 1C below.
- the painted steel sheet was held in a hot air furnace kept at 280 ° C. for 30 seconds.
- the ultimate temperature of the steel sheet was 210 ° C., and after heating, it was cooled by spraying water.
- the blackness (L * value) of the prepared steel sheet sample was measured according to the method described above.
- the conspicuity of the hairline permeability (appearance of the hairline)
- the hairlines formed on the steel sheet sample were installed vertically so as to be up and down, observed at different distances, and the conspicuity was evaluated from the distance at which the hairlines could be visually confirmed according to the following criteria. The results obtained are summarized in Table 2 below.
- Hairline can be seen from a distance of 5: 1 m 4:70 cm or more and less than 1 m can be seen from a distance of 3:50 cm or more and less than 70 cm Hairline can be seen from a distance of 2:30 cm or more and less than 50 cm Visible Hairline is not visible from a distance of 1:30 cm
- a clear coating film was applied to the hairline stainless steel specified in JIS G4305: 2012.
- the clear coating film is coated with a commercially available polyester / melamine paint (NSC200HQ manufactured by Nippon Paint Industrial Coatings Co., Ltd.) and baked and cured in a hot air furnace for 30 seconds to change the coating film thickness.
- NSC200HQ commercially available polyester / melamine paint
- Table 2 The results obtained are summarized in Table 2 below.
- the corrosion resistance of the obtained zinc-based electroplated steel sheet was evaluated by the following method. That is, a test piece having a width of 70 mm and a length of 150 mm was prepared from each of the obtained galvanized steel sheets. The edge and the back surface were tape-sealed, and a salt spray test (JIS Z 2371) was performed. Then, the white rust generation area ratio of the unsealed portion after 24 hours was visually observed and evaluated according to the following evaluation criteria. The white rust generation area ratio is a percentage of the area of the white rust generation site with respect to the area of the observation site. The results obtained are summarized in Table 2 below.
- the processing adhesion (adhesion with the organic resin coating layer) of the obtained zinc-based electroplated steel sheet was evaluated by the following method. That is, a test piece having a width of 50 mm and a length of 50 mm was prepared from each of the obtained galvanized steel sheets. After bending the obtained test piece at 180 °, a tape peeling test was performed on the outside of the bent portion. The appearance of the tape peeled portion was observed with a magnifying glass having a magnification of 10 times, and evaluated according to the following evaluation criteria. The bending process was carried out in an atmosphere of 20 ° C. with a 0.5 mm spacer in between. The results obtained are summarized in Table 2 below.
- the galvanized steel sheet according to the embodiment of the present invention has good corrosion resistance, high blackness and hairline appearance even when an inexpensive steel material is used. Moreover, it can be seen that it is excellent in metallic feeling and processing adhesion. No. using a blue pigment as a coloring pigment. It can be seen that 28 also has good corrosion resistance, has a high blackness and a hairline appearance, and is excellent in metallic feeling and processing adhesion.
- Example 2 Electroplating, an example in which a smooth part forms a hairline
- a steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) is treated with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L at a treatment liquid of 60 ° C. and a current density. It was electrolytically degreased and washed with water under the conditions of 20 A / dm 2 and a treatment time of 10 seconds. Next, the electrolytically degreased steel material was immersed in an H 2 SO 4 aqueous solution having a concentration of 50 g / L at 60 ° C. for 10 seconds and further washed with water to perform a plating pretreatment.
- the Zn—Ni plating layer (Tables 3A to 3C: Nos. 41 to 57 and 62 to 68) was formed as follows. When plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , Zn sulphate sulphate and Ni sulphate hexahydrate were adjusted to the ratios shown in Table 3 below.
- Table 3B shows the amount of plating adhered after hairline formation using a plating bath with a pH of 2.0 containing a total of 1.2 M of Japanese product and Ni hexahydrate sulfate and 50 g / L of anhydrous sodium sulfate. The plating time was adjusted so as to be a value.
- the Zn—Fe plating layer (Tables 3A to 3C: No. 58) was formed as follows. Sulfuric acid, which was prepared by adjusting Zn heptahydrate sulfate and Fe (II) sulfuric acid heptahydrate in a ratio such that the composition shown in Table 3 below was obtained when plating was performed at a bath temperature of 50 ° C. and a current density of 50 A / dm 2. Using a pH 2.0 plating bath containing a total of 1.2 M of Zn heptahydrate and Fe (II) sulfate heptahydrate and 50 g / L of anhydrous sodium sulfate, the amount of plating adhered after hairline formation.
- the plating time was adjusted so that was the value shown in Table 3.
- the Zn—Co plating layer (Tables 3A to 3C: No. 59) was formed as follows. Sulfuric acid, which was prepared by adjusting Zn heptahydrate sulfate and Co heptahydrate sulfate at a ratio of the compositions shown in Tables 3A to 3C below when plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2.
- Table 3 shows the amount of plating adhered after hairline formation using a pH 2.0 plating bath containing a total of 1.2 M of Zn heptahydrate and Co sulphate heptahydrate and 50 g / L of anhydrous sodium sulfate. The plating time was adjusted so as to have the value shown in.
- the Zn—N—Fe—Co plating layer (Tables 3A to 3C: No. 60) was formed as follows. When plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the compositions shown in Tables 3A to 3C below are such that Zn sulphate hydrate, Ni hexahydrate sulphate and Co sulphate sulphate.
- the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
- the composition of the obtained plating layer is obtained by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.), dissolving and peeling, and analyzing the dissolved solution by ICP. confirmed.
- a hairline was formed on the surface of the steel sheet by grinding after forming the zinc-based electroplating layer 13.
- the grinding method was a method in which a roll having a pattern on the surface was rotated and pressed down onto a design surface having a zinc-based electroplating layer 13 (that is, the surface of the zinc-based electroplating layer 13).
- the grinding brush was rotated in the direction opposite to the plate passing direction of the steel plate sample.
- the hairline depth was adjusted by the brush material, the rotation speed, and the load between the brush and the steel plate.
- the hairline density was adjusted by the thread diameter and density of the brush.
- the rolling method was a method in which a rolling roll having a pattern on the surface was pressed onto the design surface of the zinc-based electroplated steel sheet 1 (that is, the surface of the zinc-based electroplated layer 13).
- the rolling speed was 50 mpm.
- the surface shape of the oxide layer 14 is formed such that the concave portion 101 is composed of the smooth portion 113 and the non-hairline portion 103 is composed of the rough portion 111.
- the boundary between the coarse portion 111 and the smoothing portion 113, the hairline orthogonal direction a and the thickness direction of the cross section, from the highest point H 1 of the oxide layer 14 within the range of the observation width 1cm along the hairline orthogonal direction It is assumed that the height is 1/3 of the maximum height Ry minus the lowest point H 0 and is on a virtual straight line parallel to the hairline orthogonal direction.
- a transparent organic resin coating layer was formed on the above-mentioned plated steel sheet having a hairline (steel sheet excluding No. 65).
- the transparent organic resin was formed by the following method. That is, a urethane resin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex 170) and a melamine resin (manufactured by Ornex Japan Co., Ltd., Cymel 327) were mixed so as to have a solid content mass ratio of 85:15.
- black pigment manufactured by Toyo Color Co., Ltd., EMF Black HK-3
- blue pigment manufactured by Dainichi Seika Co., Ltd., AF Blue E-2B
- Polyethylene wax Mitsubishi Chemicals, Inc., Chemipearl W500
- the concentration in the dry film was 2% by mass, and the mixture was stirred. Further, the obtained mixture was diluted with water to prepare treatment solutions having various concentrations and viscosities. These treatment liquids were applied to the surface of the steel sheet with a roll coater.
- the dry film thickness was adjusted to be the thickness shown in Table 3C below.
- the painted steel sheet was held in a hot air furnace kept at 280 ° C. for 30 seconds.
- the ultimate temperature of the steel sheet was 210 ° C., and after heating, it was cooled by spraying water.
- the galvanized steel sheet according to the embodiment of the present invention has good corrosion resistance, high blackness and hairline appearance even when an inexpensive steel material is used. Moreover, it can be seen that it is excellent in metallic feeling and processing adhesion.
- Example 3 Hot dip galvanizing, an example in which the rough part forms a hairline
- a steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) is treated with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L at a treatment liquid of 60 ° C. and a current. It was electrolytically degreased and washed with water under the conditions of a density of 20 A / dm 2 and a treatment time of 10 seconds. Then, it was heated to 800 ° C. in a 5% hydrogen gas atmosphere and held for 5 minutes. Then, it was air-cooled to 450 ° C. to remove the oxide layer formed on the surface of the steel sheet.
- the Zn—Al—Mg plating layer (Tables 5A to 5D: No. 81 to 97, 101 to 107) has the composition shown in Tables 5A to 5D below when plated at a plating bath temperature of 450 ° C. The plating bath composition was adjusted accordingly. Further, the amount of plating adhesion was adjusted according to the gas wiping conditions after plating so that the amount of plating adhesion after hairline formation was the value shown in Table 5.
- the Zn—Al plating layer (Tables 5A to 5D: No. 98) was adjusted in plating bath composition so as to have the composition shown in Table 5 below when plated at a plating bath temperature of 650 ° C. Further, the amount of plating adhesion was adjusted according to the gas wiping conditions after plating so that the amount of plating adhesion after hairline formation would be the value shown in Table 5C.
- the Zn—Fe plating layer (Tables 5A to 5D: No. 99) is plated at a plating bath temperature of 500 ° C. so that the amount of plating adhered after hairline formation is the value shown in Table 5C, and the gas after plating. Adjusted the wiping conditions. Further, Fe contained in the steel sheet and Zn contained in the zinc hot-dip galvanized layer were alloyed, and the plated steel sheet was heated at 500 ° C. so as to have the compositions shown in Tables 5A to 5D below.
- Example No. in which hot dip galvanizing is performed 100 was plated at a plating bath temperature of 500 ° C. Further, the amount of plating adhesion was adjusted according to the gas wiping conditions after plating so that the amount of plating adhesion after hairline formation would be the value shown in Table 5C.
- the composition of the obtained plating layer was obtained by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.) to dissolve and peel it off.
- the solution was confirmed by analysis by ICP.
- a hairline was formed on the surface of the zinc-based hot-dip galvanized steel sheet 1 by grinding.
- the grinding method was a method in which a roll having a pattern on the surface was rotated and pressed down onto a design surface having a zinc-based hot-dip galvanized layer 13 (that is, the surface of the zinc-based hot-dip galvanized layer 13).
- the grinding brush was rotated in the direction opposite to the plate passing direction of the steel plate sample.
- the hairline depth was adjusted by the brush material, the rotation speed, and the load between the brush and the steel plate.
- the hairline density was adjusted by the thread diameter and density of the brush.
- the surface shape of the oxide layer 14 is formed such that the concave portion 101 is composed of the smooth portion 113 and the non-hairline portion 103 is composed of the rough portion 111.
- the boundary between the coarse portion 111 and the smoothing portion 113, the hairline orthogonal direction a and the thickness direction of the cross section, from the highest point H 1 of the oxide layer 14 within the range of the observation width 1cm along the hairline orthogonal direction It is assumed that the height is 1/3 of the maximum height Ry minus the lowest point H 0 and is on a virtual straight line parallel to the hairline orthogonal direction.
- a transparent organic resin coating layer was formed on the above-mentioned plated steel sheet having a hairline (steel sheet excluding No. 105).
- the transparent organic resin coating layer was formed by the following method. That is, a urethane resin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex 170) and a melamine resin (manufactured by Ornex Japan Co., Ltd., Cymel 327) were mixed so as to have a solid content mass ratio of 85:15.
- black pigment manufactured by Toyo Color Co., Ltd., EMF Black HK-3
- blue pigment manufactured by Dainichi Seika Co., Ltd., AF Blue E-2B
- Polyethylene wax Mitsubishi Chemicals, Inc., Chemipearl W500
- the concentration in the dry film was 2% by mass, and the mixture was stirred. Further, the obtained mixture was diluted with water to prepare treatment solutions having various concentrations and viscosities. These treatment liquids were applied to the surface of the steel sheet with a roll coater.
- the dry film thickness was adjusted to be the thickness shown in Table 5D below.
- the painted steel sheet was held in a hot air furnace kept at 280 ° C. for 30 seconds.
- the ultimate temperature of the steel sheet was 210 ° C., and after heating, it was cooled by spraying water.
- the galvanized steel sheet according to the present invention has good corrosion resistance, good blackness and hairline appearance, even when an inexpensive steel material is used. It can be seen that it is excellent in metallic feeling and processing adhesion.
- test sample of a galvanized steel sheet was prepared by the following steps.
- the outline of the manufacturing process is shown in Table 7A.
- the underline in the table indicates that it is outside the specified range of the present invention.
- the electrolytically degreased steel sheet was immersed in an aqueous solution of H 2 SO 4 having a concentration of 50 g / L kept at 60 ° C. for 10 seconds, and further washed with water.
- the steel sheet was heated to 800 ° C. in a 5% hydrogen gas atmosphere and held for 5 minutes. Then, it was air-cooled to 450 ° C.
- the composition of the obtained plating layer is obtained by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.), dissolving and peeling, and analyzing the dissolved solution by ICP. confirmed.
- an inhibitor NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.
- electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 .
- the plating time was adjusted so that the amount of plating adhered was the value shown in Table 7C.
- the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
- electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 .
- the plating time was adjusted so that the amount of plating adhered was the value shown in Table 2-1.
- the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
- Electrogalvanization layer forming step No. 20'
- a plating bath having a pH of 2.0 containing 1.2 M of Zn heptahydrate sulfate and 50 g / L of anhydrous sodium sulfate was prepared. Then, electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 .
- the plating time was adjusted so that the amount of plating adhered was the value shown in Table 7C. Further, the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
- oxide layer forming step an oxide layer was formed on the surface of the zinc-based plating layer by a method different for each steel sheet. No. In 1'to 31'and 34' to 37', an oxide layer was formed by the following blackening treatment 1, and No. In 32', an oxide layer was formed by the following blackening treatment 3, and No. In 33', an oxide layer was formed by the following blackening treatment 4. The average thickness and composition of the obtained oxide layer were measured by the method described above.
- Blackening treatment 1 Add an acidic aqueous solution (sodium nitrate (manufactured by Kanto Chemical Co., Inc.) 120 g / L, phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) 45 g / L, pH 0.6, 30 ° C.) to the surface of the zinc-based plating layer 3 Sprayed for seconds.
- an acidic aqueous solution sodium nitrate (manufactured by Kanto Chemical Co., Inc.) 120 g / L, phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) 45 g / L, pH 0.6, 30 ° C.
- Blackening treatment 3 Acidic aqueous solution (nickel sulfate hexahydrate (manufactured by Kanto Chemical Holding Co., Ltd.) 45 g / L, antimony chloride (III) (manufactured by Kanto Chemical Holding Co., Ltd.) 2 g / L, borohydride (Kanto Chemical Holding Co., Ltd.) Each test material was immersed in 7 g / L, pH 1.0, temperature 70 ° C.) for 3 seconds.
- Blackening treatment 4 With reference to Example 2 of Patent Document 6 (Japanese Unexamined Patent Publication No. 2017-218647), steam treatment (temperature: 120 ° C., relative humidity: 95%, oxygen concentration: 1.0%, treatment time 20h).
- the surface of the oxide layer was polished with an abrasive grain brush to form the above-mentioned recesses and flat portions on the surface of the oxide layer.
- the average depth of the recess 101', the average length along the length direction, the number of lines per unit width, the area ratios AR1 and AR2, the area ratio ratio AR1 / AR2, and the surface roughness RaA' are more than 5 nm and 500 nm or less.
- Table 7B describes the presence or absence of the average roughness RaA of the recesses) and the region where the surface roughness RaB'of the flat portion 103'is more than 500 nm and 5000 nm or less (Table 7B shows the average roughness of the flat portion).
- the grain size, reducing force, and polishing time of the abrasive grain brush were adjusted so that the presence or absence of degree RaB') was the value or category shown in Table 7A and Table 7B. “-” Indicates that evaluation is not possible with respect to the presence or absence of smooth regions and coarse regions.
- the surface structure obtained was specified by the method described above.
- black pigments EMF Black HK-3 manufactured by Toyo Color Co., Ltd.
- blue pigments AF Blue E-2B manufactured by Dainichiseika Co., Ltd.
- a blue pigment containing 2% by mass of the black pigment 2 and the blue pigment contained in the above was prepared.
- a Si-based additive containing Si as an active ingredient (manufactured by Nissan Chemical Co., Ltd./Snowtex N), a P-based additive containing P as an active ingredient (manufactured by Kanto Chemical Co., Ltd./ammonium phosphate), and Zr are contained as active ingredients.
- a Zr-based additive (manufactured by Kishida Chemical Co., Ltd./ammonium zirconium carbonate) was prepared. No. In 36', the organic resin coating layer was two layers, and the upper layer and the lower layer contained a black pigment.
- an upper layer containing a black pigment was formed on the lower layer.
- the amount of each paint applied was adjusted so that the overall average thickness of the upper layer and the lower layer had the values shown in Table 7C.
- the amount of each paint applied was set to be substantially the same so that the upper layer and the lower layer had the same thickness.
- an organic resin coating layer was further formed on the surfaces of the recess and the flat portion. The average thickness was measured by the method described above.
- the paint for the upper layer was black paint 2
- the additives for the paints for the upper layer and the lower layer were Si-based additives.
- the paint for the upper layer was a blue paint
- the additives for the paints for the upper layer and the lower layer were Si-based additives.
- an organic resin coating layer was further formed on the surfaces of the concave portion and the flat portion.
- the paint for the upper layer was black paint 1
- the additives for the paints for the upper layer and the lower layer were P-based additives.
- an organic resin coating layer was further formed on the surfaces of the concave portion and the flat portion.
- the paint for the upper layer was black paint 1
- the additives for the paints for the upper layer and the lower layer were Zr-based additives.
- an organic resin coating layer was further formed on the surfaces of the concave portion and the flat portion.
- the L * value in the CIE1976L * a * b * color system was measured with a colorimeter (CR-400 manufactured by Konica Minolta). If the L * value is 50 or less, it can be said that a high degree of blackness is achieved.
- the L * value is preferably 40 or less.
- the hairlines (recesses) formed in the prepared test sample were vertically placed so as to be up and down, and the hairlines were visually observed by changing the distance between the observer and the test sample. Then, the appearance of the hairline was evaluated based on the distance at which the hairline could be visually confirmed and the following evaluation criteria.
- the hairline can be seen from a distance of 5: 1 m.
- the hairline can be visually recognized from a distance of 4: 70 cm or more and less than 1 m.
- the hairline can be visually recognized from a distance of 3: 50 cm or more and less than 70 cm.
- the hairline can be visually recognized from a distance of 2:30 cm or more and less than 50 cm.
- the hairline is not visible from a distance of 1:30 cm.
- a clear paint was applied to the hairline stainless steel sheet specified in JIS G4305: 2012.
- a commercially available polyester / melamine paint (Nippon Paint Industrial Coatings Co., Ltd., NSC200HQ) was used as the clear paint, and the coating was performed with a bar coater. Then, the stainless steel sheet coated with the paint was baked and hardened in a hot air furnace for 30 seconds. By such a step, a plurality of types of comparative samples having different coating film thicknesses were prepared. Then, the metallic feeling of the test sample and these comparative samples was compared, and the metallic feeling of the test sample was evaluated based on the following evaluation criteria.
- a test piece having a width of 50 mm and a length of 50 mm was cut out from the test sample. Then, the test piece was bent at 180 °. The bending process was carried out by sandwiching a 0.5 mm spacer between the test piece and the bending machine in an atmosphere of 20 ° C. Then, a tape peeling test was performed on the outside of the bent portion. That is, a commercially available adhesive tape (cellotape manufactured by Nichiban Co., Ltd. (registered trademark)) was attached to the outside of the bent portion, and then peeled off.
- a commercially available adhesive tape (cellotape manufactured by Nichiban Co., Ltd. (registered trademark)) was attached to the outside of the bent portion, and then peeled off.
- the peeled adhesive tape was observed with a loupe having a magnification of 10 times, and the area% of the organic resin coating layer adhered to the adhesive tape (the area% of the peeled portion with respect to the total area of the organic resin coating layer of the bent portion) was measured. .. Then, the processing adhesion was evaluated according to the following evaluation criteria. No. 1 having no organic resin coating layer. At 25, this test was not performed. Therefore, No. in Table 8 The processing adhesion of 25'is indicated by "-".
- the average thickness of the oxide layer is 3.0 ⁇ m or more.
- the metallic feeling and the processing adhesion tended to be slightly lowered. Therefore, it can be seen that the average thickness of the oxide layer is preferably less than 3.0 ⁇ m.
- the average length along the length direction of the recess is less than 1 cm.
- the average length along the length direction of the recess is preferably 1 cm or more.
- the number of recesses per unit width exceeds 80 lines / cm. At 13', the processing adhesion tended to be slightly lowered. Therefore, it can be seen that the number of recesses per unit width is preferably 80 / cm or less.
- the average adhesion amount of the zinc-based plating layer is less than 5 g / m 2 .
- the hairline appearance and corrosion resistance tended to be slightly deteriorated. Therefore, it can be seen that the average adhesion amount of the zinc-based plating layer is preferably 5 g / m 2 or more.
- the amount of Ni added to the electrozinc alloy plating layer is less than 5% by mass.
- corrosion resistance was slightly reduced. Therefore, it can be seen that the addition amount when the additive element is added is preferably 5% by mass or more.
- the amount of the black pigment added to the organic resin coating layer exceeds 5% by mass.
- the appearance of the hairline tended to be slightly deteriorated. Therefore, it can be seen that it is preferable that the amount of the black pigment added is 5% by mass or less and that the lower coating film does not contain the black pigment.
- No. 26', No. The evaluation of the appearance of the hairline of 36'is 2, but it is a level that is not a problem in practical use.
- the lower layer that is, the organic resin coating layer containing the black pigment directly covers the surface of the concave portion and the flat portion.
- the lower layer does not have a colorant such as a black pigment.
- zinc-based plating has good corrosion resistance, a good hairline appearance, and excellent blackness, metallic feeling, and processing adhesion. It becomes possible to provide a steel plate.
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Abstract
Description
特にヘアラインと呼ばれる細かい線状の凹凸を付与した外観が好まれて多用されている。さらにステンレス鋼材やアルミ材の意匠性を高めるため、着色する場合がある。
着色方法としては、ステンレス鋼材やアルミ材の表面に着色塗膜を被覆する方法、ステンレス鋼材やアルミ材の表面に存在する酸化物層の厚みを変えて着色する方法等が用いられる。特に高い黒色度が要求される場合、塗膜のみで着色するとヘアラインが隠蔽されて見えなくなるため好ましくない。高い黒色度が要求される場合には酸化物層により黒色化する方法が用いられる。 Generally, design is required for articles that people can see, such as electrical equipment, building materials, and automobiles. As a method of enhancing the design, a method of painting or attaching a film to the surface of an article is common, but in recent years, mainly in nature-oriented Europe and the United States, materials that make use of the texture of metal have been used. The application is increasing. From the viewpoint of utilizing the texture of metal, painting and resin coating impair the texture of metal, so stainless steel and aluminum, which have excellent corrosion resistance even when unpainted, are used as the material of the article. Further, in order to improve the design of the stainless steel material or the aluminum material, fine arcuate irregularities called vibrations are added, or embossing is performed.
In particular, the appearance with fine linear irregularities called hairlines is preferred and is often used. Furthermore, in order to enhance the design of stainless steel and aluminum, they may be colored.
As the coloring method, a method of coating the surface of the stainless steel material or the aluminum material with a colored coating film, a method of changing the thickness of the oxide layer existing on the surface of the stainless steel material or the aluminum material, and the like are used. Especially when a high degree of blackness is required, it is not preferable to color with only the coating film because the hairline is hidden and invisible. When a high degree of blackness is required, a method of blackening with an oxide layer is used.
このような亜鉛めっき又は亜鉛合金めっき(以下、亜鉛めっきと亜鉛合金めっきとを総称して、「亜鉛系めっき」とも言う。)にヘアライン意匠を付与した鋼材に関する技術として、ヘアライン方向に直交するヘアライン直交方向の表面粗さRa(算術平均粗さ)が0.1~1.0μmであるめっき層の表面に対し、透光性を有する接着剤層と透光性を有するフィルム層めっき層とを形成する技術(以下の特許文献1を参照。)、
Zn-Al-Mg系溶融めっき層の表層に形成されたヘアライン方向及びヘアライン直交方向の粗さパラメータ(Ra及びPPI)を特定の範囲とし、かつ、Zn-Al-Mg系溶融めっき層の表面に透明樹脂皮膜層を形成する技術(以下の特許文献2を参照。)、
Zn及びZn系合金めっきに圧延でテクスチャを転写した鋼板に対し、表面粗度が一定範囲内となるような樹脂を被覆する技術(以下の特許文献3を参照。)、
が提案されている。
特許文献6には、酸化物層の表面にヘアラインを形成する技術が開示されている。 As a technique for imparting appropriate corrosion resistance to a steel material, a technique for imparting zinc plating or zinc alloy plating having excellent sacrificial corrosion resistance to the steel material is widely used.
As a technique for steel materials in which a hairline design is added to such zinc plating or zinc alloy plating (hereinafter, zinc plating and zinc alloy plating are collectively referred to as "zinc-based plating"), a hairline orthogonal to the hairline direction is used. A translucent adhesive layer and a translucent film layer plating layer are provided on the surface of a plating layer having a surface roughness Ra (arithmetic average roughness) of 0.1 to 1.0 μm in the orthogonal direction. Technique for forming (see
The roughness parameters (Ra and PPI) in the hairline direction and the hairline orthogonal direction formed on the surface layer of the Zn—Al—Mg hot-dip galvanized layer are set to a specific range, and on the surface of the Zn—Al—Mg hot-dip galvanized layer. Technique for forming a transparent resin film layer (see
A technique for coating a steel sheet whose texture has been transferred to Zn and Zn-based alloy plating by rolling with a resin so that the surface roughness is within a certain range (see
Has been proposed.
メタリック感の不足が顕著である理由は定かではないが、ヘアラインを鋼板圧延法でめっき原板に付与することで作製しためっき鋼板では、めっき層の最表面にめっきの結晶粒子の凹凸が存在し、この凹凸が酸化されることで粗大な粒子をめっき層表面に形成することで、入射してきた光が酸化物層表面で乱反射するためであると考えられる。 Here, as a method for forming a hairline, a steel sheet rolling method in which a plated steel sheet for which a hairline is to be formed is rolled by a rolling roll or the like having a predetermined roughness, and a plating grinding method for grinding the surface of a plated steel sheet for which a hairline is to be formed are used. , There is. The lack of metallic feeling (metal glossiness) as described above is particularly caused by forming a hairline on the original plating plate in the above-mentioned steel sheet rolling method, then electroplating, and then depositing an oxide layer on the surface of the plating layer. This was remarkable in the plated steel sheet on which the hairline was formed.
The reason why the lack of metallic feeling is remarkable is not clear, but in the plated steel sheet produced by applying the hairline to the original plating plate by the steel sheet rolling method, the unevenness of the crystal particles of plating exists on the outermost surface of the plating layer. It is considered that this is because the incident light is diffusely reflected on the surface of the oxide layer by forming coarse particles on the surface of the plating layer by oxidizing the unevenness.
<1>本発明の一実施形態に係る亜鉛系めっき鋼板は、鋼板と、前記鋼板の少なくとも一方の表面に位置しており、所定の方向に延伸する凹部であるヘアラインが形成された亜鉛系めっき層と、前記亜鉛系めっき層の表面に位置しており、平均厚みが0.05μm以上3.0μm以下である酸化物層と、を備える。
<2>上記<1>に記載の亜鉛系めっき鋼板は、少なくとも前記凹部以外の前記亜鉛系めっき層の表面に前記酸化物層が位置してよい。
<3>上記<1>又は<2>に記載の亜鉛系めっき鋼板は、前記酸化物層の表面に、透光性を有する有機樹脂被覆層を更に備えてよい。
<4>上記<1>から<3>のいずれか1項に記載の亜鉛系めっき鋼板は、前記亜鉛系めっき鋼板の表面の黒色度は、L*値で40以下であってよい。
<5>上記<1>から<4>のいずれか1項に記載の亜鉛系めっき鋼板は、前記酸化物層は、粗部と平滑部とからなり、前記粗部は、表面粗さRaAが500nm超5000nm以下である領域を含み、前記平滑部は、表面粗さRaBが5nm超500nm以下である領域を含み、前記粗部と前記平滑部との境界を、前記所定の方向に直交するヘアライン直交方向でかつ板厚方向の断面において、前記ヘアライン直交方向に沿った観察幅1cmの範囲内における前記酸化物層の最高点H1から最低点H0を差し引いた最大高さRyの1/3の高さでかつ前記ヘアライン直交方向に平行をなす仮想直線上にあるとした場合、前記粗部と前記平滑部との境界が規定された前記酸化物層を平面視し、互いに同一面積単位で、前記粗部の面積をSAとし、前記平滑部の面積をSBとしたときに、面積比SB/SAが、0.6以上10.0以下であり、前記粗部と当該粗部に隣り合う前記平滑部との間の平均高低差は、0.3μm以上5.0μm以下であってよい。
<6>上記<5>に記載の亜鉛系めっき鋼板は、前記粗部における前記表面粗さRaAが500nm超5000nm以下である領域の合計面積が、前記粗部の面積SAに対して85%以上であり、前記平滑部における前記表面粗さRaBが5nm超500nm以下である領域の合計面積が、前記平滑部の面積SBに対して65%以上であるってよい。
<7>上記<5>又は<6>に記載の亜鉛系めっき鋼板は、前記粗部が前記ヘアラインに形成され、前記ヘアラインの延伸方向に沿った平均長さが、1cm以上であってよい。
<8>上記<5>又は<6>に記載の亜鉛系めっき鋼板は、前記平滑部が前記ヘアラインに形成され、前記ヘアラインの延伸方向に沿った平均長さが、1cm以上であってよい。
<9>上記<1>から<8>のいずれか1項に記載の亜鉛系めっき鋼板は、前記ヘアラインは、前記ヘアライン直交方向に沿った任意の1cm幅の範囲に、平均して3本/cm以上80本/cm以下の頻度で存在してよい。
<10>上記<1>から<9>のいずれか1項に記載の亜鉛系めっき鋼板は、前記鋼板の表面において、前記亜鉛系めっき層における前記ヘアラインに対応する位置に、凹部が形成されてよい。
<11>上記<1>から<10>のいずれか1項に記載の亜鉛系めっき鋼板は、前記亜鉛系めっき層は、亜鉛系電気めっき層であり、前記亜鉛系電気めっき層の平均付着量は、5g/m2以上40g/m2以下であってよい。
<12>上記<11>に記載の亜鉛系めっき鋼板は、前記亜鉛系電気めっき層は、Fe、Ni、およびCoからなる群より選択されるいずれか1つ以上の添加元素を合計で5質量%以上20質量%以下と、Zn及び不純物からなる残部と、を含有してよい。
<13>上記<1>から<10>のいずれか1項に記載の亜鉛系めっき鋼板は、前記亜鉛系めっき層は、亜鉛系溶融めっき層であり、前記亜鉛系溶融めっき層の平均付着量は、40g/m2超150g/m2以下であってよい。
<14>上記<13>に記載の亜鉛系めっき鋼板は、前記亜鉛系溶融めっき層は、Al、およびMgからなる群より選択される何れか1つ以上の添加元素を合計で1質量%以上60質量%以下と、Zn及び不純物から成る残部と、を含有してよい。
<15>上記<3>に記載の亜鉛系めっき鋼板は、前記有機樹脂被覆層が着色顔料を有してよい。
<16>上記<1>又は<2>に記載の亜鉛系めっき鋼板は、前記酸化物層の表面には、前記凹部と、前記凹部以外の領域である平坦部とが形成され、前記凹部の平均深さは0.1μm以上3.0μm未満であり、前記凹部の底部は前記酸化物層の下層の前記亜鉛系めっき層に到達し、前記凹部に存在する前記酸化物層の平面視での面積率AR1と、前記平坦部に存在する前記酸化物層の平面視での面積率AR2との比AR1/AR2が0以上0.5以下であってよい。
<17>上記<17>に記載の亜鉛系めっき鋼板は、前記凹部の平均深さが0.1μm以上2.0μm未満であってよい。
<18>上記<17>に記載の亜鉛系めっき鋼板は、前記亜鉛系めっき層が亜鉛系電気めっき層であってよい。
<19>上記<16>から<18>のいずれか1項に記載の亜鉛系めっき鋼板は、前記酸化物層が、亜鉛水酸化物及び亜鉛酸化物からなる群より選択される何れか1種以上を含んでよい。
<20>上記<16>から<18>のいずれか1項に記載の亜鉛系めっき鋼板は、前記酸化物層の平均厚みが0.05μm以上3.0μm未満であってよい。
<21>上記<16>から<20>のいずれか1項に記載の亜鉛系めっき鋼板は、前記凹部は表面粗さRaA’が5nm超500nm以下である領域を含み、前記平坦部は表面粗さRaB’が500nm超5000nm以下である領域を含んでよい。
<22>上記<16>から<21>のいずれか1項に記載の亜鉛系めっき鋼板は、前記凹部の長さ方向に沿った平均長さが1cm以上であってよい。
<23>上記<16>から<22>のいずれか1項に記載の亜鉛系めっき鋼板は、前記凹部は、前記凹部の長さ方向に直交する方向に沿った任意の1cm幅の範囲に、平均して3本/cm以上80本/cm以下の頻度で存在してよい。
<24>上記<16>から<23>のいずれか1項に記載の亜鉛系めっき鋼板は、前記亜鉛系めっき層の平均付着量は、5g/m2以上40g/m2以下であってよい。
<25>上記<16>から<24>のいずれか1項に記載の亜鉛系めっき鋼板は、前記酸化物層が第二成分としてFe、Ni、及びCoからなる群より選択される何れか1種以上の添加元素を含有してよい。
<26>上記<16>から<25>のいずれか1項に記載の亜鉛系めっき鋼板は、前記亜鉛系めっき層は、Fe、Ni、及びCoからなる群より選択される何れか1種以上の添加元素を、これらの添加元素の合計で5質量%以上20質量%以下含有し、前記亜鉛系めっき層の残部はZn及び不純物であってよい。
<27>上記<3>に記載の亜鉛系めっき鋼板は、前記有機樹脂被覆層が黒色顔料を含有してよい。
<28>上記<27>に記載の亜鉛系めっき鋼板は、前記有機樹脂被覆層が2層以上であり、最下層以外のいずれか1以上の層に前記黒色顔料が含有されてよい。
<29>上記<28>に記載の亜鉛系めっき鋼板は、前記有機樹脂被覆層が更にSi、P、及びZrから選択される何れか1種以上の添加元素を含有してよい。 Means for solving the problem include the following aspects.
<1> The zinc-based plated steel sheet according to the embodiment of the present invention is a zinc-based plated steel sheet located on the surface of at least one of the steel sheet and the steel sheet, and has a hairline formed as a recess extending in a predetermined direction. It includes a layer and an oxide layer located on the surface of the zinc-based plating layer and having an average thickness of 0.05 μm or more and 3.0 μm or less.
<2> In the zinc-based plated steel sheet according to <1>, the oxide layer may be located at least on the surface of the zinc-based plated layer other than the recess.
<3> The zinc-based plated steel sheet according to <1> or <2> may further include a translucent organic resin coating layer on the surface of the oxide layer.
<4> In the zinc-based plated steel sheet according to any one of <1> to <3>, the blackness of the surface of the zinc-based plated steel sheet may be 40 or less in L * value.
<5> In the zinc-based plated steel sheet according to any one of <1> to <4>, the oxide layer comprises a rough portion and a smooth portion, and the rough portion has a surface roughness Ra A. The smooth portion includes a region having a surface roughness Ra B of more than 5 nm and 500 nm or less, and the boundary between the rough portion and the smooth portion is orthogonal to the predetermined direction. 1 of the maximum height Ry obtained by subtracting the lowest point H 0 from the highest point H 1 of the oxide layer within an observation width of 1 cm along the hair line orthogonal direction in the cross section in the direction orthogonal to the hairline and in the direction of the plate thickness. Assuming that the height is 3/4 and it is on a virtual straight line parallel to the hairline orthogonal direction, the oxide layer in which the boundary between the rough portion and the smooth portion is defined is viewed in a plan view and has the same area. a unit, an area of the coarse portion and S a, the area of the smooth portion is taken as S B, the area ratio S B / S a is from 0.6 to 10.0, and the rough portion The average height difference between the rough portion and the smooth portion adjacent to the rough portion may be 0.3 μm or more and 5.0 μm or less.
Galvanized steel sheet according to <6> above <5> is the total area of the region the surface roughness Ra A of the rough portion is less than 500nm ultra 5000nm is, relative to the area S A of the rough portion 85 % or more, and the total area of regions the surface roughness Ra B in the smooth portion is less than 5nm super 500nm is good I is 65% or more with respect to the area S B of the smoothing section.
<7> In the galvanized steel sheet according to <5> or <6>, the rough portion is formed in the hairline, and the average length along the stretching direction of the hairline may be 1 cm or more.
<8> In the galvanized steel sheet according to <5> or <6>, the smooth portion is formed in the hairline, and the average length along the stretching direction of the hairline may be 1 cm or more.
<9> In the zinc-based plated steel sheet according to any one of <1> to <8>, the hairline has an average of three hairlines in an arbitrary 1 cm width range along the direction orthogonal to the hairline. It may be present at a frequency of cm or more and 80 lines / cm or less.
<10> In the zinc-based plated steel sheet according to any one of <1> to <9>, recesses are formed on the surface of the steel sheet at positions corresponding to the hairlines in the zinc-based plated layer. Good.
<11> In the zinc-based plated steel sheet according to any one of <1> to <10>, the zinc-based plating layer is a zinc-based electroplating layer, and the average adhesion amount of the zinc-based electroplating layer is May be 5 g / m 2 or more and 40 g / m 2 or less.
<12> In the zinc-based plated steel sheet according to <11>, the zinc-based electroplating layer contains a total of 5 masses of any one or more additive elements selected from the group consisting of Fe, Ni, and Co. It may contain% or more and 20% by mass or less, and a balance composed of Zn and impurities.
<13> In the zinc-based plated steel sheet according to any one of <1> to <10>, the zinc-based plating layer is a zinc-based hot-dip plating layer, and the average adhesion amount of the zinc-based hot-dip plating layer is May be more than 40 g / m 2 and 150 g / m 2 or less.
<14> In the zinc-based plated steel sheet according to <13>, the zinc-based hot-dip galvanized layer contains 1% by mass or more in total of any one or more additive elements selected from the group consisting of Al and Mg. It may contain 60% by mass or less and a balance composed of Zn and impurities.
<15> In the zinc-based plated steel sheet according to <3> above, the organic resin coating layer may have a coloring pigment.
<16> In the zinc-based plated steel sheet according to <1> or <2>, the concave portion and the flat portion which is a region other than the concave portion are formed on the surface of the oxide layer, and the concave portion is formed. The average depth is 0.1 μm or more and less than 3.0 μm, the bottom of the recess reaches the zinc-based plating layer below the oxide layer, and the oxide layer existing in the recess is viewed in a plan view. The ratio AR1 / AR2 of the area ratio AR1 to the area ratio AR2 of the oxide layer existing in the flat portion in a plan view may be 0 or more and 0.5 or less.
<17> The zinc-based plated steel sheet according to <17> may have an average depth of the recesses of 0.1 μm or more and less than 2.0 μm.
<18> In the zinc-based plated steel sheet according to <17>, the zinc-based plating layer may be a zinc-based electroplating layer.
<19> In the zinc-based plated steel sheet according to any one of <16> to <18>, the oxide layer is selected from the group consisting of zinc hydroxide and zinc oxide. The above may be included.
<20> The zinc-based plated steel sheet according to any one of <16> to <18> may have an average thickness of the oxide layer of 0.05 μm or more and less than 3.0 μm.
<21> In the zinc-based plated steel sheet according to any one of <16> to <20>, the recess includes a region where the surface roughness RaA'is more than 5 nm and 500 nm or less, and the flat portion has a surface roughness. It may include a region where RaB'is more than 500 nm and less than 5000 nm.
<22> The zinc-based plated steel sheet according to any one of <16> to <21> may have an average length of 1 cm or more along the length direction of the recess.
<23> In the zinc-based plated steel sheet according to any one of <16> to <22>, the recesses have an arbitrary width of 1 cm along a direction orthogonal to the length direction of the recesses. On average, it may be present at a frequency of 3 lines / cm or more and 80 lines / cm or less.
<24> In the zinc-based plated steel sheet according to any one of <16> to <23>, the average adhesion amount of the zinc-based plated layer may be 5 g / m 2 or more and 40 g / m 2 or less. ..
<25> The zinc-based plated steel sheet according to any one of <16> to <24> is selected from the group in which the oxide layer is composed of Fe, Ni, and Co as the second component. It may contain more than a species of additive element.
<26> In the zinc-based plated steel sheet according to any one of <16> to <25>, the zinc-based plated layer is one or more selected from the group consisting of Fe, Ni, and Co. The total of these additive elements may be 5% by mass or more and 20% by mass or less, and the balance of the zinc-based plating layer may be Zn and impurities.
<27> In the zinc-based plated steel sheet according to <3> above, the organic resin coating layer may contain a black pigment.
<28> The zinc-based plated steel sheet according to <27> has two or more organic resin coating layers, and the black pigment may be contained in any one or more layers other than the bottom layer.
<29> In the zinc-based plated steel sheet according to <28>, the organic resin coating layer may further contain any one or more additive elements selected from Si, P, and Zr.
なお、本明細書及び図面において、実質的に同一の機能構成を有する構成要素については、同一の符号を付することにより重複説明を省略する。
化学組成の各元素の含有量の「%」表示は、「質量%」を意味する。
「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
「~」の前後に記載される数値に「超」または「未満」が付されている場合の数値範囲は、これら数値を下限値または上限値として含まない範囲を意味する。
「工程」との用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
In the present specification and the drawings, components having substantially the same functional configuration are designated by the same reference numerals to omit duplicate description.
The "%" indication of the content of each element in the chemical composition means "mass%".
The numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
The numerical range when "greater than" or "less than" is added to the numerical values before and after "to" means a range in which these numerical values are not included as the lower limit value or the upper limit value.
The term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
鋼板と、
前記鋼板の少なくとも一方の表面に位置しており、所定の方向に延伸する凹部であるヘアラインが形成された亜鉛系めっき層と、
前記亜鉛系めっき層の表面に位置しており、平均厚みが0.05μm以上3.0μm以下である酸化物層と、
を備える。 The galvanized steel sheet according to the embodiment of the present invention is
Steel plate and
A zinc-based plating layer located on at least one surface of the steel sheet and having a hairline formed as a recess extending in a predetermined direction.
An oxide layer located on the surface of the zinc-based plating layer and having an average thickness of 0.05 μm or more and 3.0 μm or less.
To be equipped.
本実施形態に係る亜鉛系めっき鋼板は、次の知見により、見出された。 Due to the above configuration, the galvanized steel sheet according to the present embodiment has good corrosion resistance, good blackness and hairline appearance, metallic feeling and processing even when an inexpensive steel material is used. A galvanized steel sheet with excellent adhesion.
The galvanized steel sheet according to this embodiment was found based on the following findings.
ただし、酸化物層を3μm以下の平均厚さとすると、酸化物層に亀裂が抑制され、亜鉛系めっき層と有機樹脂被覆層との加工密着性が向上することも知見した。 Therefore, the present inventors have diligently studied a method for improving the blackness, hairline appearance and metallic feeling of a galvanized steel sheet having a predetermined corrosion resistance while using an inexpensive steel material. As a result, if an oxide layer is formed on the surface layer of the zinc-based plating layer with an average thickness of 0.05 μm or more that exhibits black color, the blackness is improved and the hairline formed on the zinc-based plating layer is not concealed. , It was found that the appearance of hairline and metallic feeling can be improved.
However, it was also found that when the oxide layer has an average thickness of 3 μm or less, cracks are suppressed in the oxide layer and the processing adhesion between the zinc-based plating layer and the organic resin coating layer is improved.
酸化物層表面で起こる乱反射を抑制するために、酸化物層を形成する前にめっき層の結晶粒子の凹凸を減らした平滑部を設けることで乱反射を抑制可能であるとの知見を得るに至った。一方、めっき層の表面においてめっき層の結晶粒子の凹凸が残存している部分は粗部となり、その表面に形成される酸化物の粒子径も大きくなる。この粒径が大きな酸化物粒子の存在により、加工密着性が向上する。それにより樹脂被覆層との加工密着性を得ることが出来る。
そこで、かかる粗部及び平滑部の割合を適切に調整することで、メタリック感及び加工密着性を両立できるとの知見を得ることができた。また、酸化物層の厚みが薄い場合はめっき層の表面粗度の影響を受けることを確認した。 Further, the present inventors diligently studied a method for improving the metallic feeling, and if the particle size of the oxide in the oxide layer formed on the surface layer of the zinc-based plating layer can be controlled, the plating layer It was considered that even when the upper layer was coated with resin, it was possible to improve the metallic feeling with black color. As a result of further studies based on this idea, the present inventors have obtained the following findings.
In order to suppress diffused reflection that occurs on the surface of the oxide layer, it has been found that diffused reflection can be suppressed by providing a smooth portion that reduces the unevenness of the crystal particles of the plating layer before forming the oxide layer. It was. On the other hand, on the surface of the plating layer, the portion where the unevenness of the crystal particles of the plating layer remains becomes a rough portion, and the particle size of the oxide formed on the surface also increases. The presence of oxide particles having a large particle size improves processing adhesion. As a result, processing adhesion with the resin coating layer can be obtained.
Therefore, it has been found that by appropriately adjusting the ratio of the rough portion and the smooth portion, both the metallic feeling and the processing adhesion can be obtained. It was also confirmed that when the oxide layer is thin, it is affected by the surface roughness of the plating layer.
前記酸化物層は、粗部(A)と平滑部(B)とからなり、
前記粗部(A)は、表面粗さRaAが500nm超5000nm以下である領域を含み、
前記平滑部(B)は、表面粗さRaBが5nm超500nm以下である領域を含み、
前記粗部(A)と前記平滑部(B)との境界を、前記所定の方向に直交するヘアライン直交方向でかつ板厚方向の断面において、前記ヘアライン直交方向に沿った観察幅1cmの範囲内における前記酸化物層の最高点H1から最低点H0を差し引いた最大高さRyの1/3の高さでかつ前記ヘアライン直交方向に平行をなす仮想直線上にあるとした場合、前記粗部(A)と前記平滑部(B)との境界が規定された前記酸化物層を平面視し、互いに同一面積単位で、前記粗部(A)の面積をSAとし、前記平滑部(B)の面積をSBとしたときに、面積比SB/SAが、0.6~10.0の範囲内であり、
前記粗部(A)と当該粗部(A)に隣り合う前記平滑部(B)との間の平均高低差は、0.3μm~5.0μmである、ことが好ましい。 Based on this finding, in the galvanized steel sheet according to the embodiment of the present invention,
The oxide layer is composed of a rough portion (A) and a smooth portion (B).
The rough portion (A) includes a region having a surface roughness Ra A of more than 500 nm and 5000 nm or less.
The smooth portion (B) includes a region having a surface roughness Ra B of more than 5 nm and 500 nm or less.
The boundary between the rough portion (A) and the smooth portion (B) is within a range of 1 cm in observation width along the hairline orthogonal direction in a cross section in the hairline orthogonal direction orthogonal to the predetermined direction and in the plate thickness direction. When it is assumed that the height is 1/3 of the maximum height Ry obtained by subtracting the minimum point H 0 from the highest point H 1 of the oxide layer in the above and is on a virtual straight line parallel to the hairline orthogonal direction, the coarse the smoothing section and the section (a) and the oxide layer plan view in which the boundary is defined in (B), and the same unit of area from each other, the rough portions of the area of (a) and S a, the smoothing unit ( the area of B) when the S B, the area ratio S B / S a is in the range from 0.6 to 10.0,
The average height difference between the rough portion (A) and the smooth portion (B) adjacent to the rough portion (A) is preferably 0.3 μm to 5.0 μm.
以下では、まず、図1A及び図1Bを参照しながら、本発明の一実施形態に係る亜鉛系電気めっき鋼板の全体構成について詳細に説明する。図1A及び図1Bは、本実施形態に係る亜鉛系めっき鋼板の構造の一例を模式的に示した説明図である。 (About the overall composition of galvanized steel sheet)
In the following, first, the overall configuration of the galvanized steel sheet according to the embodiment of the present invention will be described in detail with reference to FIGS. 1A and 1B. 1A and 1B are explanatory views schematically showing an example of the structure of the galvanized steel sheet according to the present embodiment.
また、図1Bに示したように、本実施形態に係る亜鉛系めっき鋼板1は、亜鉛系めっき層13の表面側に、透光性を有する有機樹脂被覆層15を更に有していることが好ましい。特に、有機樹脂被覆層15を有すると、耐指紋性、加工性、及び、耐食性が確保できる観点で好ましい。 As is schematically shown in FIG. 1A, the zinc-based plated
Further, as shown in FIG. 1B, the zinc-based plated
本実施形態に係る亜鉛系めっき鋼板の基材である鋼板11は、特に限定されるものではなく、亜鉛系めっき鋼板に求められる機械的強度(例えば、引張強度等)等に応じて、公知の各種の鋼材(軟鋼、普通鋼、高張力鋼など)を適宜利用することが可能である。 <About the base material>
The
鋼板11の少なくとも一方の表面には、亜鉛系めっき層13が形成されている。
亜鉛系めっき層13は、図1Aに模式的に示したように、所定の方向(図1Aの場合、紙面垂直方向)に延伸するヘアラインを形成する凹部101と、非ヘアライン部103と、を有している。
亜鉛系めっき層13において、ヘアラインを形成する凹部101内に、以下で詳述するような粗部が形成され、かつ、非ヘアライン部103内に、以下で詳述するような平滑部が形成されてもよい。または、亜鉛系めっき層13において、ヘアラインを形成する凹部101内に、以下で詳述するような、酸化物層14の平滑部が形成され、かつ、非ヘアライン部103に、以下で詳述するような、酸化物層14の粗部が形成されてもよい。何れの場合においても、ヘアラインの延伸方向に沿った平均長さは、1cm以上であることが好ましい。 <About zinc-based plating layer>
A zinc-based
As schematically shown in FIG. 1A, the zinc-based
In the zinc-based
亜鉛系めっき層13としては、例えば、亜鉛系電気めっき層(電気亜鉛めっき層、電気亜鉛合金めっき層)、亜鉛系溶融めっき層(溶融亜鉛めっき層、溶融亜鉛合金めっき層を使用する。なお、以下、亜鉛系電気めっき層および亜鉛系溶融めっき層は、符号13を付して説明する場合がある。 [Type and composition of zinc-based plating layer]
As the zinc-based
特に、電気亜鉛合金めっき層は、Fe、Ni、及び、Coからなる元素群から選択される少なくとも何れかの添加元素を、合計で5質量%以上20質量%以下含有することが好ましい。つまり、亜鉛系電気めっき層は、Fe、Ni、およびCoからなる群より選択されるいずれか1つ以上の添加元素を合計で5質量%~20質量%と、Zn及び不純物からなる残部と、を含有することが好ましい。電気亜鉛合金めっき層が、Fe、Ni、Coの少なくとも何れかの添加元素を上記の合計含有量の範囲内で含有することで、より優れた耐食性(耐白錆性/バリア性)を実現することが可能となる。 Here, the electrozinc alloy plating layer contains at least one additive element selected from the element group consisting of Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr, and Zn. And, preferably.
In particular, the electrozinc alloy plating layer preferably contains at least one additive element selected from the element group consisting of Fe, Ni, and Co in a total of 5% by mass or more and 20% by mass or less. That is, the zinc-based electroplating layer contains a total of 5% by mass to 20% by mass of any one or more additive elements selected from the group consisting of Fe, Ni, and Co, and a balance composed of Zn and impurities. Is preferably contained. When the electrozinc alloy plating layer contains at least one of Fe, Ni, and Co as an additive element within the above total content range, more excellent corrosion resistance (white rust resistance / barrier property) is realized. It becomes possible.
なお、意図的に添加したFe、Ni、Coと、不純物として混入したFe、Ni、Coとは、亜鉛系電気めっき層13中の濃度により判別できる。すなわち、例えば、意図的に添加した場合におけるFe、Ni、Coの合計含有量の下限値が5質量%であるため、合計含有量が5質量%未満であれば不純物として判別できる。 Further, the electrogalvanized layer and the electrogalvanized alloy plated layer may contain impurities as a balance. Here, the impurities are not intentionally added as a component of the zinc-based electroplating layer, but are mixed in the raw material or are mixed in the manufacturing process, and are Al, Mg, Si, Ti. , B, S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr, Ag, W, H and the like. Further, when performing electrogalvanizing, although it depends on the type of electroplated steel sheet manufactured in the same manufacturing facility, Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, Zr, etc. may be mixed as impurities. However, even if impurities are present in a total amount of about 1% by mass with respect to the total mass of the plating, the effect obtained by the plating is not impaired.
The intentionally added Fe, Ni, and Co and the Fe, Ni, and Co mixed as impurities can be distinguished from each other by the concentration in the zinc-based
亜鉛系電気めっき層13の平均付着量は、5g/m2以上40g/m2以下であることが好ましい。亜鉛系電気めっき層13の平均付着量が5g/m2未満の場合、ヘアラインの付与時に、地鉄(すなわち、鋼板11)が露出してしまう可能性がある。一方、亜鉛系電気めっき層13の平均付着量が40g/m2を超える場合には、鋼板11に研削又は圧延で形成したヘアラインが、亜鉛系電気めっき層13により目立ち難くなる可能性があるため、好ましくない。亜鉛系電気めっき層13の平均付着量の下限値は、より好ましくは7g/m2であり、更に好ましくは10g/m2である。また、亜鉛系電気めっき層13の平均付着量の上限値は、より好ましくは35g/m2以下であり、更に好ましくは30g/m2である。 [About the average amount of zinc-based electroplating layer]
The average adhesion amount of the zinc-based
溶融亜鉛めっき層は、例えば、亜鉛と、残部が合計で5質量%未満のAl、Sb、Pbなどの元素で構成される。
溶融亜鉛合金めっき層は、例えば、亜鉛と、残部を合計1質量%以上の合金元素で構成される。合金元素群としては、Fe、Al、Mg、Si等から選択される少なくともいずれかの元素が選択される。特に、溶融亜鉛合金めっき層は、Al、およびMgからなる群より選択される何れか1つ以上を合計で1質量%以上60質量%以下含有することが好ましい。つまり、亜鉛系溶融めっき層は、Al、およびMgからなる群より選択される何れか1つ以上の添加元素を合計で1質量%~60質量%と、Zn及び不純物からなる残部と、を含有することが好ましい。溶融亜鉛合金めっき層が、上記の合計含有量の範囲内で含有することで、より優れた耐食性(耐白錆性/バリア性)を実現することが可能となる。 The zinc-based hot-dip galvanizing layer includes a "hot-dip galvanizing layer" or a "hot-dip galvanizing alloy plating layer".
The hot-dip galvanized layer is composed of, for example, zinc and elements such as Al, Sb, and Pb having a total balance of less than 5% by mass.
The hot-dip zinc alloy plating layer is composed of, for example, zinc and an alloy element having a total of 1% by mass or more in the balance. As the alloy element group, at least one element selected from Fe, Al, Mg, Si and the like is selected. In particular, the hot-dip zinc alloy plating layer preferably contains at least one selected from the group consisting of Al and Mg in a total amount of 1% by mass or more and 60% by mass or less. That is, the zinc-based hot-dip galvanized layer contains 1% by mass to 60% by mass in total of any one or more additive elements selected from the group consisting of Al and Mg, and a balance composed of Zn and impurities. It is preferable to do so. When the hot-dip galvanized alloy plating layer is contained within the range of the above total content, it is possible to realize more excellent corrosion resistance (white rust resistance / barrier property).
なお、意図的に添加した合金元素と、不純物として混入した元素とは、亜鉛系溶融めっき層13中の濃度により判別できる。すなわち、例えば、意図的に添加した場合におけるAl、Mgの合計含有量の下限値が1質量%であるため、合計含有量が1質量%未満であれば不純物として判別できる。 Further, the hot-dip galvanized layer and the hot-dip zinc alloy plated layer may contain impurities as a balance. Here, the impurities are not intentionally added as zinc-based hot-dip galvanizing components, but are mixed in the raw material or mixed in the manufacturing process, and are mixed in Al, Mg, Si, Ni, Ti. , Pb, Sb and the like. However, even if impurities are present in a total amount of about 1% by mass with respect to the total mass of the plating, the effect obtained by the plating is not impaired.
The intentionally added alloying element and the element mixed as an impurity can be distinguished from each other by the concentration in the zinc-based hot-
亜鉛系溶融めっき層13の平均付着量は、40g/m2超150g/m2以下であることが好ましい。亜鉛系溶融めっき層13の平均付着量が40g/m2以下の場合、溶融めっき後の付着量制御のためのガスワイピング時のガス圧力を大きくする必要があり、均一なめっき付着量が得られない場合がある。一方、亜鉛系溶融めっき層13の平均付着量が150g/m2を超える場合には、通板速度を下げる必要があり、生産性が低下するため、好ましくない。
亜鉛系溶融めっき層13の平均付着量の下限値は、より好ましくは45g/m2以上であり、更に好ましくは50g/m2以上である。また、亜鉛系溶融めっき層13の平均付着量の上限値は、より好ましくは120g/m2以下であり、更に好ましくは90g/m2以下である。 [About the average adhesion amount of the zinc-based hot-dip plating layer 13]
The average adhesion amount of the zinc-based hot-
The lower limit of the average adhesion amount of the zinc-based hot-
ヘアラインを付与された亜鉛系めっき層13の表面は、図1Aに模式的に示したように、酸化物層14で覆われている。つまり、酸化物層14は亜鉛系めっき層13の表面性状に沿って設けられて、酸化物層14にもヘアラインが付与されている。亜鉛系めっき鋼板は、このような酸化物層14を有することにより高い黒色度を有する。本願において、酸化物層14は、少なくとも凹部以外の亜鉛系めっき層13の表面に位置する。 <About the oxide layer>
The surface of the zinc-based
酸化物層14の平均厚みの下限値は、0.07μmであることがより好ましく、1.0μmであることが更に好ましい。酸化物層14の平均厚みの上限値は2.7μmであることが好ましく、更に好ましくは2.5μmである。 The average thickness of the
The lower limit of the average thickness of the
亜鉛系めっき鋼板から、板厚方向に沿って切断した試料を採取する。そして、エネルギー分散型X線分析装置(EDS)を搭載した透過型電子顕微鏡(TEM-EDS)により、めっき層及び酸化物層の断面(板厚方向に沿った断面)を観察し、酸素元素をマッピングする。次に、表面からめっき層方向に存在する酸素濃度が20質量%以上の領域を酸化物層として定義し、酸化物層の厚みを複数個所測定する。そして、複数個所測定した酸化物層の厚みの平均値を算出する。 The average thickness of the oxide layer is measured as follows.
A sample cut along the thickness direction is collected from the galvanized steel sheet. Then, the cross section (cross section along the plate thickness direction) of the plating layer and the oxide layer is observed with a transmission electron microscope (TEM-EDS) equipped with an energy dispersive X-ray analyzer (EDS) to remove oxygen elements. Map. Next, a region having an oxygen concentration of 20% by mass or more existing from the surface toward the plating layer is defined as an oxide layer, and the thickness of the oxide layer is measured at a plurality of locations. Then, the average value of the thicknesses of the oxide layers measured at a plurality of locations is calculated.
具体的な、Znを主体とする酸化物または水酸化物としては、例えば、ZnO、ZnO1-×、Zn(OH)2等が例示される。
酸化物層14の形成方法としては、酸浸漬処理、酸化Zn処理、等の周知の方法が例示される。 The
Specific examples of Zn-based oxides or hydroxides include ZnO, ZnO 1-x , Zn (OH) 2, and the like.
As a method for forming the
ヘアラインを付与された酸化物層14の表面には、図1Bに模式的に示したように、透光性を有する有機樹脂被覆層15を備えることが好ましい。
ここで、有機樹脂被覆層15が透光性(透過性)を有するとは、表面に形成した有機樹脂被覆層15を通して、酸化物層14が目視で観察できることを意味する。なお、本明細書において、「透光性」及び「透過性」は同様の意味で用いられる。 [About organic resin coating layer]
As schematically shown in FIG. 1B, it is preferable that the surface of the
Here, the fact that the organic
着色剤としては、べんがら、アルミ、マイカ、カーボンブラック、酸化チタン、コバルトブルー等が例示できる。着色剤の含有量は、有機樹脂被覆層15に対して1~10質量%が好ましく、2~5質量%がより好ましい。 When the organic
Examples of the colorant include Bengara, aluminum, mica, carbon black, titanium oxide, cobalt blue and the like. The content of the colorant is preferably 1 to 10% by mass, more preferably 2 to 5% by mass, based on the organic
有機樹脂被覆層15の平均厚みは、10μm以下であることが好ましい。有機樹脂被覆層15の平均厚みが10μmを超えると、光が有機樹脂被覆層15内を通る距離が長くなることによって反射光が減少し、光沢度が低下する可能性が高くなる。また、加工に伴う樹脂の変形によって、亜鉛系めっき層13の表面のテクスチャと、有機樹脂被覆層15の表面の形状とのずれが、発生しやすくなる。以上の理由により、有機樹脂被覆層15の平均厚みは、10μm以下であることが好ましく、8μm以下であることがより好ましい。 [Thickness of organic resin coating layer]
The average thickness of the organic
次に、図2から図6を参照しながら、本実施形態に係る亜鉛系めっき層13および酸化物層14の表面形状について、詳細に説明する。図2は、本実施形態に係る亜鉛系めっき層および酸化物層一例を説明するための説明図である。図3から図5は、本実施形態に係る亜鉛系めっき層および酸化物層の一例を説明するためのグラフである。図6は、本実施形態に係る亜鉛系めっき層および酸化物層14の他の一例を説明するための説明図である。 (About the surface shapes of the zinc-based
Next, the surface shapes of the zinc-based
また、ヘアラインとは異なるミクロ的な酸化物層14の表面形状に着目すると、酸化物層14は、表面粗さRaAが500nm超5000nm以下である領域を含む粗部111と、表面粗さRaBが5nm超500nm以下である領域を含む平滑部113と、を有している。 As mentioned earlier, the zinc-based
Focusing on the surface shape of the
酸化物層14における粗部111及び平滑部113間の境界線については、以下のとおりに定義した。
まず、図2及び図9Aに示すように、酸化物層14において、粗部111がヘアラインを形成する凹部101内に形成され、かつ、平滑部113が主に非ヘアライン部103内に形成される場合に着目する。この場合、高さ方向の表示分解能が1nm以上であり、かつ、幅方向の表示分解能が1nm以上であるレーザー顕微鏡(すなわち、高さ方向及び幅方向の表示分解能が1nmよりも優れたレーザー顕微鏡)を用いて、倍率500倍で平面視1cm×1cmの範囲における酸化物層14の表面高さを測定する。レーザー顕微鏡の観察視野が1cmに満たない場合は、複数視野を観察し、これらを連結して表面高さを測定しても良い。 Here, the area ratio of the rough portion and the smooth portion in the
The boundary line between the
First, as shown in FIGS. 2 and 9A, in the
まず、酸化物層14の表面をSEMで観察する。その際の視野倍率は、1000~10000倍の範囲内とするが、最大倍率である10000倍でも酸化物粒子が確認出来ない場合には、個数がゼロであるとカウントする。続いて、酸化物粒子の輪郭より、酸化物粒子1つあたりの平面積Sを求める。そして、その平面積と同じ平面積を持つ円を想定し、その直径を、下記の式(1)により前記代表径Dとして求める。そして、観察視野内における10個の酸化物粒子を任意に選び、それら10個の酸化物粒子の代表径Dの平均値を得ることで、平均粒径Daveが求められる。 The average particle size Dave , which indicates the size of the oxide particles in the
First, the surface of the
ここで、Dは、酸化物粒子の平面視における代表径であってその単位はμmである。また、Sは、酸化物粒子の平面視における円形相当面積であってその単位はμm2である。 D = 2 × (S / π) 0.5 ... Equation (1)
Here, D is a representative diameter of the oxide particles in a plan view, and the unit thereof is μm. Further, S is a circular equivalent area of the oxide particles in a plan view, and the unit thereof is μm 2 .
まず、上述のように酸化物層14の表面をSEMで観察し、粒径閾値以上の酸化物粒子が100μm×100μmの範囲内にいくつあるかをカウントすることで、酸化物粒子の密度が求められる。前記粒径閾値は、下層の亜鉛系めっき層13のめっき種や合金毎に異なり、例えば、下層の亜鉛系めっき層13が、Zn-Ni電気めっき層である場合0.1μm~3.0μmの範囲内の値、Zn-Fe電気めっき層である場合0.3μm~3.6μmの範囲内の値、Zn-Co電気めっき層である場合0.4μm~9.6μmの範囲内の値となることが多い。
なお、SEMの倍率を最大倍率(10000倍)にしても酸化物粒子が確認出来ない場合には、個数がゼロであるとカウントする。 The density of oxide particles is determined by the following method.
First, as described above, the surface of the
If the oxide particles cannot be confirmed even when the SEM magnification is set to the maximum magnification (10000 times), the number is counted as zero.
酸化物層14では、酸化物粒子の凹凸が存在している粗部111と、粗部111よりも酸化物粒子の凹凸が小さい平滑部113と、を適切な割合で存在させている。これにより、平滑部113ではメタリック感の向上を実現するとともに、粗部111では、酸化物層14の上層に設けられることが好ましい有機樹脂被覆層15との加工密着性を実現する。 In the
In the
酸化物層14は、上記のように、粗部111及び平滑部113の双方を有していることから、図2に模式的に示したように、互いに隣り合う粗部111及び平滑部113のそれぞれについて、粗部111の平均表面高さ、及び、平滑部113の平均表面高さを考えることができる。この際、酸化物層14では、粗部111と、かかる粗部111に隣り合う平滑部113と、の平均高低差(粗部111とかかる粗部111に隣り合う平滑部113との平均表面高さの差)は0.3μm~5.0μmの範囲となっている。すなわち、酸化物層14では、ヘアラインを形成する凹部101の略全てが粗部111で、非ヘアライン部103の略全てが平滑部113である場合、これら凹部101及び非ヘアライン部103間の平均高低差も、0.3μm~5.0μmの範囲となる。 [Difference between the average surface height of the rough part and the average surface height of the smooth part]
Since the
ここで、粗部111の平均表面高さh1は、粗部111における平滑部113との境界間での最大高さと最小高さとの平均値とする。同様に、平滑部113の平均表面高さh2は、平滑部113における粗部111との境界間での最大高さと最小高さとの平均値とする。 The average height difference between the
Here, the average surface height h1 of the
粗部111と平滑部113との境界が規定された酸化物層を平面視(板厚方向から観察)した場合、酸化物層14において、粗部111の面積(粗部111に該当する領域の合計平面積)をSAとし、平滑部113の面積(平滑部113に該当する領域の合計平面積)をSBとしたときに、互いに同一面積単位における面積比SB/SAが、0.6以上10.0以下の範囲内となっている。この際、例えば図2に示した範囲内においては、粗部A1の平面積と粗部A2の面積の合計が、図2に示した範囲内での粗部111の面積SAとなり、平滑部B1の面積と平滑部B2の面積と平滑部B3の面積の合計が、図2に示した範囲内での平滑部113の面積SBとなる。なお、平面積とは、図8のように、酸化物層14を平面視した場合の面積(具体的には、酸化物層14の表面を電子顕微鏡で観察した際の画像として見た場合の面積)である。 [Area ratio of rough area to smooth area]
When the oxide layer in which the boundary between the
ただし、図6中、h1は、平滑部113の平均表面高さであり、h2は、粗部111の平均表面高さを示す。 Incidentally, as described above, the average height difference between the
However, in FIG. 6, h1 is the average surface height of the
酸化物層14では、粗部111が適切な割合で存在していることで、酸化物層14の上層に有機樹脂被覆層15が設けられた際の加工密着性を担保している。ここで、粗部111によって加工密着性を担保するためには、粗部111が、適切な表面粗さを有する適切な広さの領域を有することで、有機樹脂被覆層15との接触面積が増加することが好ましい。 [About surface roughness in rough areas]
In the
また、酸化物層14では、平滑部113が適切な割合で存在していることで、本実施形態に係る亜鉛系めっき鋼板1のメタリック感を実現している。ここで、平滑部113によるメタリック感の向上効果を実現するためには、図4にも例示したように、平滑部113が、適切な表面粗さを有する適切な広さの領域を有することが好ましい。 [About surface roughness in smooth parts]
Further, in the
平滑部合計面積:SB×(RaBが5nm超500nm以下となった回数/全測定回数)・・・式(3) Crude unit total area: S A × (number / total number of measurements Ra A is equal to or less than 500nm ultra 5000 nm) · · · Equation (2)
Smoothing unit total area: S B × (number / total number of measurements Ra B becomes 5nm ultra 500nm or less) Equation (3)
同様に、平滑部113について、20回以上測定した平均の、表面粗さRaBが5nm超500nm以下となる場合、「平滑部113が、表面粗さRaBが5nm超500nm以下である領域を含む」と定義する。
なお、本明細書において、表面粗さRaA及びRaBは、JIS B 0601(2001)に規定された算術平均粗さRaを意味する。 Here, "the
Similarly, when the average surface roughness Ra B of the
In addition, in this specification, surface roughness Ra A and Ra B mean arithmetic mean roughness Ra defined in JIS B 0601 (2001).
また、亜鉛系めっき層13及び酸化物層14において、上記のような粗部111又は平滑部113を含む凹部101(つまり、ヘアライン)は、ヘアライン直交方向に沿った任意の1cm幅の範囲に、3本/cm以上80本/cm以下の頻度で存在することが好ましい。ヘアライン直交方向におけるヘアラインの形成頻度を、3本/cm~80本/cmの範囲内とすることで、より優れた意匠性を実現することができる。ヘアライン直交方向におけるヘアラインの形成頻度が3本/cm未満である場合には、ヘアラインの密度が低くなりすぎて、ヘアラインを認識できない可能性が高くなる。一方、ヘアライン直交方向におけるヘアラインの形成頻度が80本/cmを超える場合には、ヘアラインの密度が高くなりすぎて美麗なヘアラインとならず、ヘアラインとしての意匠性が損なわれてしまう可能性がある。 [About hairline formation frequency]
Further, in the zinc-based
ここで、図1A及び図1Bでは、亜鉛系めっき層13及び酸化物層14のみに凹部101が設けられている場合について図示していた。しかしながら、本実施形態に係る亜鉛系めっき鋼板1では、図7A及び図7Bに示したように、鋼板11の表面に対しても、所定の方向に延伸するヘアラインを形成する凹部105を設けてもよい。この場合、亜鉛系溶融めっきは自身の厚みで、ヘアラインを形成する凹部を埋めてしまう。そのため、めっきは亜鉛系電気めっきとする。 (About other configuration examples of galvanized steel sheets)
Here, in FIGS. 1A and 1B, the case where the
本実施形態に係る亜鉛系めっき鋼板1の表面の黒色度は、L*値で40以下であることが好ましく、35以下がより好ましい。
ここで、L*値は、CIE1976L*a*b*表色系におけるL*値を意味する。そして、L*値は、反射分光濃度計で測定できる。
L*値の測定は、JIS Z8781-4(2013)に準じて行う。L*値の測定装置には正反射光を含むSCI方式と正反射光を含まないSCE方式がある。いずれも黒色度を表すが、本発明においてはSCI方式で測定した。 (About the blackness of the surface of galvanized steel sheet)
The blackness of the surface of the galvanized
Here, L * value means the L * value in CIE1976L * a * b * color system. The L * value can be measured with a reflection spectrophotometer.
The L * value is measured according to JIS Z8781-4 (2013). There are two types of L * value measuring devices: the SCI method, which includes specularly reflected light, and the SCE method, which does not include specularly reflected light. Both represent blackness, but in the present invention, the measurement was performed by the SCI method.
続いて、以上説明したような本実施形態に係る亜鉛系電気めっき鋼板(亜鉛系電気めっき層13を有するめっき鋼板)の製造方法について、簡単に説明する。 (About the manufacturing method of galvanized steel sheet)
Subsequently, a method for manufacturing a zinc-based electroplated steel sheet (plated steel sheet having a zinc-based electroplated layer 13) according to the present embodiment as described above will be briefly described.
以下では、まず、図1A及び図1Bに示したような構造を有する亜鉛系電気めっき鋼板1の製造方法について、簡単に説明する。
かかる場合には、まず、表面粗さの調整された鋼板11に対し、アルカリ溶液による脱脂と塩酸や硫酸等を用いた酸による酸洗とを施す。そして、鋼板11の表面に亜鉛系電気めっき層13を形成する。ここで、鋼板11の表面粗さの調整は、公知の方法を利用することが可能であり、例えば、表面粗さが所望の範囲となるように調整されたロールで鋼板11を圧延して表面粗さを転写する方法、などの方法を用いることができる。 <Manufacturing method-
In the following, first, a method for manufacturing a zinc-based
In such a case, first, the
一方、処理を受けておらずヘアラインを形成する凹部101が、めっき層の結晶粒子の凹凸が残存している粗部となる。そして、めっき層の粗部に酸化物層14を形成すると、粗部111となる。 Here, in the hairline formation on the zinc-based
On the other hand, the
一方、処理を受けていない非ヘアライン部103が、めっき層の粗部となる。そして、めっき層の粗部に酸化物層14を形成すると、粗部111となる。 On the contrary, in the above-mentioned grinding treatment, polishing treatment, or rolling treatment, when only the portion to be the hairline portion is selectively ground, polished, and rolled, it is schematically shown in FIG. The
On the other hand, the untreated
一方、亜鉛系電気めっき層13の表面のうち、砥粒ブラシで削られなかった平坦部分(非ヘアライン部103)は元の通り、めっき層の結晶粒子の凹凸が残った状態になっている。
以上により、図6に示したように、めっき層の粗部に形成した酸化物層14の粗部111が支配的に存在して加工密着性が担保された非ヘアライン部103と、めっき層の平滑部に形成した酸化物層14の平滑部113が支配的に存在して光沢度の高い凹部101とが併存することになる。 A case where such a form shown in FIG. 6 is formed by polishing with an abrasive grain brush will be described. Although the surface of the zinc-based
On the other hand, on the surface of the zinc-based
As described above, as shown in FIG. 6, the
次に、図7A及び図7Bに示したような構造を有する亜鉛系電気めっき鋼板(亜鉛系電気めっき層13を有するめっき鋼板)の製造方法について、簡単に説明する。
かかる場合、上記「製造方法-その1」と同様にして表面粗さの調整まで終了した鋼板を用いる。そして、この鋼板に対して、めっき処理を施す前にヘアラインを形成することで、鋼板11が得られる。鋼板にヘアラインを付与する方法については、特に限定されるものではないが、研磨ベルトで研磨する方法、砥粒ブラシで研磨する方法、テクスチャを付与したロールで転写する方法、所定の研削機器で研削する方法等を利用することが好ましい。これにより、鋼板11の表面に、図7A及び図7Bに示したような凹部105が形成される。 <Manufacturing method-
Next, a method for manufacturing a zinc-based electroplated steel sheet (plated steel sheet having a zinc-based electroplated layer 13) having the structures as shown in FIGS. 7A and 7B will be briefly described.
In such a case, a steel sheet having been adjusted in surface roughness in the same manner as in the above "Manufacturing method-
そこで、本製造方法では、亜鉛系電気めっき層13の形成後に、亜鉛系電気めっき層13の表面形状が先だって説明したような各種の条件を満足する表面形状となるまで、公知の方法により亜鉛系電気めっき層13の表面を研削したり、研磨したり、表面粗度を調整したロールで圧延したりする。これにより、上記「製造方法-その1」と同様に、亜鉛系電気めっき層13の表面に、酸化物層14の粗部111及び平滑部113に対応する粗部及び平滑部が形成される。 Crystal particles of the plating layer are present on the surface of the zinc-based
Therefore, in the present production method, after the zinc-based
一方、砥粒ブラシが届きにくい凹部をなす凹部101では、ほぼ元の通り、めっき層の結晶粒子の凹凸が残った状態の粗部になっている。そして、めっき層の粗部に酸化物層14を形成すると、粗部111となる。
以上により、めっき層の粗部に形成した酸化物層14の粗部111が支配的に存在して加工密着性が担保された非ヘアライン部103と、めっき層の平滑部に形成した酸化物層14の平滑部113が支配的に存在して光沢度の高い凹部101とが併存することになる。 More specifically, for example, when polishing with an abrasive grain brush, only the
On the other hand, the
As described above, the
なお、亜鉛系電気めっき鋼板1としては、図1Aに示した形態と図7Aに示した形態とを見比べた場合、図7Aに示した形態の方が、平面だけでなく深さ方向にも平滑部が形成され、ヘアラインに深みが生じるため、高い光沢感(質感)が得られやすい。同様の理由により、図1Bに示した形態と図7Bに示した形態とを見比べた場合も、図7Bに示した形態の方が高い光沢感(質感)が得られやすい。 The method for manufacturing the galvanized steel sheet according to the present embodiment has been described above.
As for the zinc-based
続いて、以上説明したような本実施形態に係る亜鉛系溶融めっき鋼板(亜鉛系溶融めっき層13を有するめっき鋼板)の製造方法について、簡単に説明する。 (About the manufacturing method of galvanized steel sheet)
Subsequently, a method for manufacturing a zinc-based hot-dip galvanized steel sheet (plated steel sheet having a zinc-based hot-dip galvanized layer 13) according to the present embodiment as described above will be briefly described.
以下では、まず、図1A及び図1Bに示したような構造を有する亜鉛系溶融めっき鋼板1の製造方法について、簡単に説明する。
かかる場合には、まず、表面粗さの調整された鋼板11を焼鈍し、鋼板温度を450℃とした状態で溶融めっきの中に浸漬し、引き上げる。めっき付着量は引き揚げ時に窒素ガスでワイピングし調整する。鋼板11とめっき層を合金化する場合は、めっき後に到達温度が500℃となる様に誘導加熱(以下、単にIHという場合がある。)で加熱する。 <Manufacturing method-
Hereinafter, first, a method for producing the zinc-based hot-dip galvanized
In such a case, first, the
一方、処理を行った凹部101が、めっきの結晶粒子の凹凸が残存している粗部となる。そして、めっき層の粗部に酸化物層14を形成すると、粗部111となる。 Here, in the hairline formation on the zinc-based hot-
On the other hand, the treated
一方、処理を受けていない非ヘアライン部103が、粗部となる。そして、めっき層の粗部に酸化物層14を形成すると、粗部111となる。 On the contrary, in the above-mentioned grinding treatment, polishing treatment, or rolling treatment, when only the portion to be the hairline portion is selectively ground, polished, and rolled, it is schematically shown in FIG. Such a
On the other hand, the untreated
上記の実施形態では、ヘアラインを付与された亜鉛系めっき層の表面に、酸化物層で覆われている場合を説明した。以下では、酸化物層の表面にヘアラインを付与する場合を、図10から図12を参照して説明する。変形例では、酸化物層の一部を除去し、凹部の底部は亜鉛系めっき層に到達しているため、亜鉛系めっき層の金属色と酸化物層の黒色とのコントラストにより、凹部の平均深さが非常に浅くても、ヘアライン外観の視認性に優れる。 (Modification example)
In the above embodiment, the case where the surface of the zinc-based plating layer provided with the hairline is covered with the oxide layer has been described. In the following, the case of imparting a hairline to the surface of the oxide layer will be described with reference to FIGS. 10 to 12. In the modified example, a part of the oxide layer is removed and the bottom of the recess reaches the zinc-based plating layer. Therefore, the contrast between the metallic color of the zinc-based plating layer and the black color of the oxide layer causes the average of the recesses. Even if the depth is very shallow, the visibility of the hairline appearance is excellent.
まず、図10及び図11に基づいて本実施形態の変形例に係る亜鉛系めっき鋼板1’の全体構成について説明する。亜鉛系めっき鋼板1’は、鋼板11’と、亜鉛系めっき層13’と、酸化物層14’とを備える。酸化物層14’の表面には、線状に形成された凹部101’と、凹部101’以外の領域である平坦部103’とが形成される。凹部101’はヘアライン部に相当し、平坦部103’は非ヘアライン部に相当する。亜鉛系めっき鋼板1’の特性(特に耐食性等)をさらに向上させるために、亜鉛系めっき鋼板1’は、凹部101’及び平坦部103’を覆い、かつ透光性を有する有機樹脂被覆層15’を更に備えることが好ましい。亜鉛系めっき層13’、酸化物層14’、及び有機樹脂被覆層15’は鋼板11’の両面に設けられてもよく、片面のみに設けられてもよい。以下、各構成要素について説明する。 <1. Overall composition of galvanized steel sheet>
First, the overall configuration of the galvanized steel sheet 1'according to the modified example of the present embodiment will be described with reference to FIGS. 10 and 11. The galvanized steel sheet 1'includes a steel sheet 11', a zinc-based plated layer 13', and an oxide layer 14'. On the surface of the oxide layer 14', a linearly formed recess 101'and a flat portion 103' that is a region other than the recess 101'are formed. The recess 101'corresponds to the hairline portion and the flat portion 103'corresponds to the non-hairline portion. In order to further improve the characteristics (particularly corrosion resistance, etc.) of the galvanized steel sheet 1', the galvanized steel sheet 1'covers the recess 101'and the flat portion 103' and has a translucent organic resin coating layer 15'. It is preferable to further provide'. The zinc-based plating layer 13', the oxide layer 14', and the organic resin coating layer 15'may be provided on both sides of the steel sheet 11', or may be provided on only one side. Hereinafter, each component will be described.
亜鉛系めっき鋼板1’の基材である鋼板11’は、特に限定されるものではなく、亜鉛系めっき鋼板1’に求められる機械的強度(例えば、引張強度等)等に応じて、公知の各種の鋼材(軟鋼、普通鋼、高張力鋼など)を鋼板11’として適宜利用することが可能である。 <2. Steel plate >
The steel sheet 11'which is the base material of the galvanized steel sheet 1'is not particularly limited, and is known depending on the mechanical strength (for example, tensile strength, etc.) required for the galvanized steel sheet 1'. Various steel materials (mild steel, ordinary steel, high-strength steel, etc.) can be appropriately used as the steel sheet 11'.
亜鉛系めっき層13’は、鋼板11’の少なくとも一方の表面に形成される。なお、本実施形態の変形例においてめっきの金属種として亜鉛系めっきを選択したのは、亜鉛系めっきが優れた犠牲防食性を有するからである。 <3. Zinc-based plating layer>
The zinc-based plating layer 13'is formed on at least one surface of the steel plate 11'. The reason why zinc-based plating was selected as the metal type for plating in the modified example of this embodiment is that zinc-based plating has excellent sacrificial anticorrosion properties.
亜鉛系電気めっき層は、電気亜鉛めっき層及び電気亜鉛合金めっき層に区分される。電気亜鉛めっき層は、Zn及び不純物で構成される。電気亜鉛合金めっき層は、後述する添加元素を含み、残部がZn及び不純物で構成される。いずれのめっき層においても、Znの含有量は亜鉛系めっき層13’の総質量に対して35質量%以上であり、より好ましくは70質量%以上であり、より好ましくは80質量%以上である。Znの含有量の上限値は最大で100質量%であるが、不純物がほぼ確実に存在することを考慮すると、100質量%未満である。 (3-1. Composition of zinc-based electroplating layer)
The zinc-based electroplating layer is classified into an electrogalvanizing layer and an electrogalvanizing alloy plating layer. The electrogalvanized layer is composed of Zn and impurities. The electrozinc alloy plating layer contains additive elements described later, and the balance is composed of Zn and impurities. In any of the plating layers, the Zn content is 35% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass of the zinc-based plating layer 13'. .. The upper limit of the Zn content is 100% by mass at the maximum, but it is less than 100% by mass considering that impurities are almost certainly present.
亜鉛系溶融めっき層は、溶融亜鉛めっき層及び溶融亜鉛合金めっき層に区分される。溶融亜鉛めっき層は、Zn及び不純物で構成される。溶融亜鉛合金めっき層は、後述する添加元素を含み、残部がZn及び不純物で構成される。いずれのめっき層においても、Znの含有量は亜鉛系めっき層13’の総質量に対して35質量%以上であり、より好ましくは70質量%以上であり、より好ましくは80質量%以上である。Znの含有量の上限値は最大で100質量%であるが、不純物がほぼ確実に存在することを考慮すると、100質量%未満である。なお、溶融亜鉛めっき層には、Al、Sb、及びPbからなる群から選択されるいずれか1種以上の添加元素を添加してもよい。この場合、これらの元素の添加量は合計で1質量%以上、5質量%未満であることが好ましい。 (3-2. Composition of zinc-based hot-dip plating layer)
The zinc-based hot-dip galvanizing layer is classified into a hot-dip galvanizing layer and a hot-dip zinc alloy plating layer. The hot-dip galvanized layer is composed of Zn and impurities. The hot-dip zinc alloy plating layer contains additive elements described later, and the balance is composed of Zn and impurities. In any of the plating layers, the Zn content is 35% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass of the zinc-based plating layer 13'. .. The upper limit of the Zn content is 100% by mass at the maximum, but it is less than 100% by mass considering that impurities are almost certainly present. In addition, any one or more additive elements selected from the group consisting of Al, Sb, and Pb may be added to the hot-dip galvanized layer. In this case, the total amount of these elements added is preferably 1% by mass or more and less than 5% by mass.
亜鉛系めっき層13’の平均付着量は、5~40g/m2であることが好ましい。なお、平均付着量は、鋼板11’に付着した亜鉛系めっき層13’の総質量を亜鉛系めっき層13’が付着した表面の面積で除算することで得られる値である。めっき付着量は例えば、めっきした鋼板をインヒビター(朝日化学工業社製 NO.700AS)入りの10質量%塩酸に浸漬して溶解剥離し、浸漬前後の鋼板の質量変化によって測定可能である。亜鉛系めっき層13’の平均付着量が5g/m2未満の場合、酸化物層14に凹部101’(すなわちヘアライン)を形成する際に、地鉄(すなわち鋼板11’)が露出してしまう可能性がある。このため、ヘアライン外観及び耐食性が低下する可能性がある。一方、亜鉛系めっき層13’の平均付着量が40g/m2を超える場合には、製造コストが増大する可能性がある。亜鉛系めっき層13’の平均付着量の下限値は、より好ましくは7g/m2以上であり、より好ましくは10g/m2以上である。また、亜鉛系めっき層13’の平均付着量の上限値は、より好ましくは35g/m2以下であり、より好ましくは30g/m2以下である。 (3-3. Average amount of zinc-based plating layer adhered)
The average adhesion amount of the zinc-based plating layer 13'is preferably 5 to 40 g / m 2 . The average amount of adhesion is a value obtained by dividing the total mass of the zinc-based plating layer 13'attached to the steel sheet 11'by the area of the surface to which the zinc-based plating layer 13'attached. The amount of plating adhesion can be measured, for example, by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.) to dissolve and peel it off, and measuring the mass change of the steel sheet before and after immersion. When the average adhesion amount of the zinc-based plating layer 13'is less than 5 g / m 2 , the base iron (that is, the steel plate 11') is exposed when the recess 101'(that is, the hairline) is formed in the
酸化物層14’は、亜鉛系めっき層13’の表面に形成される。酸化物層14’は、亜鉛系めっき層13’を酸化することで亜鉛系めっき層13’の表面に形成される。酸化処理の具体的な内容は後述する。 <4. Oxide layer>
The oxide layer 14'is formed on the surface of the zinc-based plating layer 13'. The oxide layer 14'is formed on the surface of the zinc-based plating layer 13'by oxidizing the zinc-based plating layer 13'. The specific contents of the oxidation treatment will be described later.
酸化物層14’の表面には、線状に形成された凹部101’と、凹部101’以外の領域である平坦部103’とが形成される。凹部101’はいわゆるヘアラインである。 <5. Surface structure of oxide layer>
On the surface of the oxide layer 14', a linearly formed recess 101'and a flat portion 103' that is a region other than the recess 101'are formed. The recess 101'is a so-called hairline.
凹部101’では亜鉛系めっき層13’が露出しているので、ヘアライン外観が良好となる。優れた視認性を実現するためには、亜鉛系めっき層がある程度の深さで削られていることが好ましい。すなわち、[(H1-H0)-(酸化物層の平均厚み)]が0.1μm以上であることが好ましく、0.3μm以上であることがさらに好ましい。 The average depth of the recess 101'is measured by, for example, the following method. That is, a laser microscope having a display resolution in the depth direction of 1 nm or more and a display resolution in the direction perpendicular to the depth direction (plane direction) of 1 nm or more is prepared. Then, an arbitrary 1 cm × 1 cm region on the surface of the oxide layer 14'is set as a plan view observation region. This plan view observation region is scanned with a laser microscope along the direction orthogonal to the hairline. The scanning interval is, for example, 100 μm. As a result, a plurality of line profiles of the surface shape are acquired. An example of the line profile is shown in FIG. The horizontal axis of FIG. 12 indicates the measurement length (μm), and the vertical axis indicates the surface height (μm) from a preset reference position. Then, the line profile, H 1 to the highest point within the range of the observation width 1cm along the hairline orthogonal directions, if the lowest point was H 0 (these highest point H 1, the lowest point H 0 is hairline perpendicular direction A point existing at a height of H 0 + 2/3 × (H 1- H 0 ) and on a line intersecting the hairline at right angles is a recess 101'and a flat portion 103'. The boundary point with. Then, the distance in the depth direction (that is, the bottom 101a'of the recess 101') from the straight line connecting the adjacent boundary points in the same recess to the point at the deepest position between the boundary points (the boundary points from the bottom 101a'). The length of the straight line in the depth direction drawn along the straight line connecting the two) is defined as the depth of the recess 101'. Then, the average depth of the recesses is calculated by arithmetically averaging the depths of all the recesses 101'measured in each line profile. The position of the recess 101'in the plan view observation region is also specified by this method. Further, in the modified example, the method of defining the boundary point is different from that of the present embodiment due to the difference in the manufacturing method. In the modified example, the boundary point between the recess 101'and the flat portion 103'is located closer to the bottom than in the above embodiment.
Since the zinc-based plating layer 13'is exposed in the recess 101', the appearance of the hairline is good. In order to realize excellent visibility, it is preferable that the zinc-based plating layer is scraped to a certain depth. That is, [(H 1 − H 0 ) − (average thickness of the oxide layer)] is preferably 0.1 μm or more, and more preferably 0.3 μm or more.
検出された酸素濃度>酸化物層平均厚さ[μm]/1[μm]×20質量%
酸化物層14’以外の領域は凹部101’内で露出した亜鉛系めっき層13’である。これにより、平面視観察領域内の凹部101’に存在する酸化物層14’の平面視での面積が求まるので、これを平面視観察領域内の凹部101’の平面視での面積で除算することで面積率AR1を求める。 Here, the area ratio AR1, the area ratio AR2, and the area ratio ratio AR1 / AR2 are measured by the following methods. That is, the above-mentioned plan view observation region is observed with a field emission electron probe microanalyzer (FE-EPMA). In this way, the element distribution in the plan view observation region is specified. Then, in each region in the recess 101', the oxygen concentration (the oxygen concentration here is the oxygen concentration in each minute region in the plan view observation region, that is, the total mass of all the elements existing in the minute region). (% By mass of oxygen in the microregion) is measured. FE-EPMA detects elemental information at a depth of about 1 μm. Therefore, when the average thickness of the oxide layer exceeds 1 μm, the region where the oxygen detected by the FE-EPMA is 20% by mass or more is specified as the
Detected oxygen concentration> Average thickness of oxide layer [μm] / 1 [μm] x 20% by mass
The region other than the oxide layer 14'is the zinc-based plating layer 13'exposed in the recess 101'. As a result, the area of the oxide layer 14'existing in the recess 101'in the plan view observation region in the plan view can be obtained, and this is divided by the area of the recess 101'in the plan view observation region in the plan view. By doing so, the area ratio AR1 is obtained.
D=2×(S/π)0.5・・・式(1) When 10 or more oxide particles can be confirmed in the observation field of view, the flat area S (μm 2 ) per oxide particle is obtained based on the contour of the oxide particles. Then, the representative diameter D (μm) of the oxide particles is obtained based on the flat area S and the following formula (1). As is clear from the formula (1), the representative diameter D is the equivalent circle diameter of the oxide particles. Then, 10 oxide particles in the observation field of view are arbitrarily selected, and the average value of the representative diameters D of the 10 oxide particles is taken as the average particle size.
D = 2 × (S / π) 0.5 ... Equation (1)
図11に示すように、亜鉛系めっき鋼板1’は、凹部101’及び平坦部103’を覆う有機樹脂被覆層15’をさらに有することが好ましい。有機樹脂被覆層15’は、透光性(透過性)を有する。ここで、有機樹脂被覆層15’が透光性(透過性)を有するとは、有機樹脂被覆層15’を介して凹部101’及び平坦部103’を目視で観察可能であることを意味する。 <6. Organic resin coating layer>
As shown in FIG. 11, the galvanized steel sheet 1'preferably further has an organic resin coating layer 15'that covers the recess 101'and the flat portion 103'. The organic resin coating layer 15'has translucency (transparency). Here, the fact that the organic resin coating layer 15'has translucency (transparency) means that the recess 101'and the flat portion 103' can be visually observed through the organic resin coating layer 15'. ..
変形例では、亜鉛系めっき層の金属色と酸化物層の黒色とのコントラストにより、ヘアライン外観の視認性を高めている。また、最下層塗膜はヘアラインを形成する凹部で相対的に塗膜厚が厚くなる。そのため、着色剤を有機樹脂被覆層15’の最下層に添加すると、黒色塗膜によりヘアラインが隠ぺいされる恐れがある。 The organic resin coating layer 15'may have a multilayer structure. In this case, among the above-mentioned additives, it is particularly preferable that the colorant is added to any one or more layers other than the bottom layer (the layer covering the recess 101'and the flat portion 103'). By adding the colorant to a layer other than the bottom layer, the appearance of the hairline can be improved. In this case, the addition amount is preferably mass% as described above with respect to the total mass of the layer to be added.
In the modified example, the visibility of the appearance of the hairline is enhanced by the contrast between the metallic color of the zinc-based plating layer and the black color of the oxide layer. Further, the bottom layer coating film has a relatively thick coating film at the recesses forming the hairline. Therefore, when the colorant is added to the lowermost layer of the organic resin coating layer 15', the hairline may be hidden by the black coating film.
(7-1.準備工程)
つぎに、本実施形態の変形例に係る亜鉛系めっき鋼板1’の製造方法について説明する。まず、表面粗さの調整された鋼板11’に対してアルカリ溶液による脱脂を行う。ついで、鋼板11’の表面を覆う酸化物層を除去する。酸化物層を除去する方法としては、酸洗、水素ガス雰囲気中での焼鈍等が挙げられる。例えば、亜鉛系電気めっきを行う場合、酸洗を行ってもよい。亜鉛系溶融めっき層を行う場合、焼鈍を行ってもよい。 <7. Manufacturing method of galvanized steel sheet>
(7-1. Preparation process)
Next, a method for manufacturing the galvanized steel sheet 1'according to the modified example of the present embodiment will be described. First, the steel sheet 11'with the adjusted surface roughness is degreased with an alkaline solution. Then, the oxide layer covering the surface of the steel sheet 11'is removed. Examples of the method for removing the oxide layer include pickling and annealing in a hydrogen gas atmosphere. For example, when zinc-based electroplating is performed, pickling may be performed. When the zinc-based hot-dip plating layer is formed, annealing may be performed.
ついで、鋼板11’の表面に亜鉛系めっき層13’を形成する。ここで、亜鉛系めっき層13’を形成する方法は、上述したように電気亜鉛めっき方法または溶融亜鉛めっき方法が好ましい。そこで、ここではこれらのめっき方法について説明する。 (7-2. Zinc-based plating layer forming process)
Then, a zinc-based plating layer 13'is formed on the surface of the steel sheet 11'. Here, as the method for forming the zinc-based plating layer 13', the electrogalvanizing method or the hot-dip galvanizing method is preferable as described above. Therefore, these plating methods will be described here.
本実施形態の変形例では、公知の電気亜鉛めっき方法を使用することができる。電気亜鉛めっき方法で使用する電気めっき浴としては、例えば、硫酸浴、塩化物浴、ジンケート浴、シアン化物浴、ピロリン酸浴、ホウ酸浴、クエン酸浴、その他錯体浴及びこれらの組合せ等が挙げられる。電気亜鉛合金めっき浴には、Znイオンの他に、Co、Cr、Cu、Fe、Ni、P、Sn、Mn、Mo、V、W、及びZrから選ばれる1つ以上の単イオン又は錯イオンを添加することで、Co、Cr、Cu、Fe、Ni、P、Sn、Mn、Mo、V、W、Zrを所望量含有する亜鉛系電気めっき層を形成することができる。これらの添加元素のうち、Fe、Co、及びNiからなる群から選択される何れか1種以上の元素を添加することが好ましい。また、めっき浴中のイオンを安定化させ、かつめっきの特性を制御するために、上記めっき浴に対して添加剤を加えることが、さらに好ましい。 (7-2-1. Zinc-based electroplating layer forming process)
In the modified example of this embodiment, a known electrogalvanizing method can be used. Examples of the electroplating bath used in the electrogalvanizing method include a sulfuric acid bath, a chloride bath, a zincate bath, a cyanide bath, a pyrophosphate bath, a boric acid bath, a citric acid bath, other complex baths, and combinations thereof. Can be mentioned. In the electrozinc alloy plating bath, in addition to Zn ions, one or more monatomic ions or complex ions selected from Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr. By adding Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr, a zinc-based electroplating layer containing a desired amount can be formed. Among these additive elements, it is preferable to add any one or more elements selected from the group consisting of Fe, Co, and Ni. Further, it is more preferable to add an additive to the plating bath in order to stabilize the ions in the plating bath and control the plating characteristics.
本実施形態の変形例では、公知の溶融亜鉛めっき方法を使用することができる。まず、表面粗さの調整された鋼板11’を焼鈍する。ついで、鋼板温度を例えば450℃とした状態で鋼板11’を溶融めっき浴に浸漬し、引き上げる。これにより、鋼板11’の表面に亜鉛系溶融めっき層が形成される。めっき付着量は鋼板11’の引き揚げ時に窒素ガス等によるガスワイピングにより調整される。鋼板11’と亜鉛系溶融めっき層とを合金化する場合は、めっき後に到達温度が例えば500℃となる様に亜鉛系溶融めっき層を例えばIHで加熱する。 (7-2-2. Zinc-based hot-dip galvanizing layer forming process)
In the modified example of this embodiment, a known hot-dip galvanizing method can be used. First, the steel sheet 11'with the adjusted surface roughness is annealed. Then, the steel plate 11'is immersed in a hot-dip galvanizing bath with the steel plate temperature set to, for example, 450 ° C., and the temperature is raised. As a result, a zinc-based hot-dip galvanized layer is formed on the surface of the steel sheet 11'. The amount of plating adhered is adjusted by gas wiping with nitrogen gas or the like when the steel sheet 11'is lifted. When the steel sheet 11'and the zinc-based hot-dip galvanized layer are alloyed, the zinc-based hot-dip galvanized layer is heated by, for example, IH so that the ultimate temperature after plating is, for example, 500 ° C.
以上の工程により、鋼板11の表面に亜鉛系めっき層13’を形成する。ついで、亜鉛系めっき層13’の表面に酸化物層14’を形成する。すなわち、亜鉛系めっき層13’の表面を黒化処理する。亜鉛系めっき層13’の表面を黒化処理する方法としては、次の方法が挙げられる。例えば硝酸塩とりん酸を混合した酸性水溶液を亜鉛系めっき層13’に接触させる方法、酒石酸とフッ素化物を混合した酸性水溶液を亜鉛系めっき層13’に接触させて電解処理する方法、ニッケル、アンチモンおよびフッ素化合物を含む酸性水溶液を亜鉛系めっき層13’に接触させる方法等である。これらの方法によれば、粗大な酸化物粒子からなる酸化物層14’を形成することができるので、酸化物層14’の表面に粗い凹凸を形成することができ、ひいては、酸化物層14’の表面粗さRaを500nm超5000nm以下とすることができる。さらにこの方法は非常に簡易であり、インラインで実施することができる。なお、酸化物層14’の平均厚みは酸性水溶液の濃度及び浸漬時間等を適宜調整することで調整可能である。一方、特許文献6に記載された水蒸気酸化はインラインで実施することができない。さらに、酸化物層14’の表面の凹凸も非常に小さくなる。 (7-3. Oxide layer forming step)
By the above steps, the zinc-based plating layer 13'is formed on the surface of the
ついで、酸化物層14’の表面に上述した凹部101’及び平坦部103’を形成する。すなわち、酸化物層14’の表面にヘアラインを形成する。具体的なヘアライン形成方法は特に制限されず、従来用いられていたヘアライン形成方法と同様の方法を使用することができる。具体的なヘアライン形成方法としては、例えば、酸化物層14’の表面を研磨材(例えば研磨ベルト及び砥粒ブラシ)で研磨する方法、酸化物層14’の表面にテクスチャを付与したロールを押圧することでテクスチャを酸化物層14’の表面に転写する方法、酸化物層14’の表面を研削機器で研削する方法等が挙げられる。 (7-4. Hairline forming process)
Then, the recess 101'and the flat portion 103' described above are formed on the surface of the oxide layer 14'. That is, a hairline is formed on the surface of the oxide layer 14'. The specific hairline forming method is not particularly limited, and a method similar to the conventionally used hairline forming method can be used. Specific hairline forming methods include, for example, a method of polishing the surface of the oxide layer 14'with an abrasive (for example, a polishing belt and an abrasive grain brush), and pressing a roll having a texture on the surface of the oxide layer 14'. Examples thereof include a method of transferring the texture to the surface of the oxide layer 14', a method of grinding the surface of the oxide layer 14'with a grinding device, and the like.
ついで、凹部101’及び平坦部103’の表面に有機樹脂被覆層15’を形成する。なお、有機樹脂被覆層15’は省略されてもよいが、耐食性、黒色度等の特性を高めるという観点からは有機樹脂被覆層15’を形成することが好ましい。有機樹脂被覆層15’の形成方法は特に問われないが、例えば塗料を用いる方法が挙げられる。具体的には、有機樹脂被覆層15’と同様の組成を有する塗料を凹部101’及び平坦部103’の表面に塗布し、乾燥させる。これにより、凹部101’及び平坦部103’の表面に有機樹脂被覆層15’を形成する。有機樹脂被覆層15’の表面にさらに塗料を塗布し、乾燥させることで、有機樹脂被覆層15’を多層構造とすることができる。有機樹脂被覆層15’を多層構造とする場合、最下層以外の何れかの層に着色剤、例えば黒色顔料を添加することが好ましい。以上の工程により、本実施形態の変形例に係る亜鉛系めっき鋼板1’を作製する。 (7-5. Organic resin coating layer forming step)
Then, the organic resin coating layer 15'is formed on the surfaces of the recess 101'and the flat portion 103'. Although the organic resin coating layer 15'may be omitted, it is preferable to form the organic resin coating layer 15'from the viewpoint of enhancing characteristics such as corrosion resistance and blackness. The method for forming the organic resin coating layer 15'is not particularly limited, and examples thereof include a method using a paint. Specifically, a paint having the same composition as the organic resin coating layer 15'is applied to the surfaces of the recess 101'and the flat portion 103' and dried. As a result, the organic resin coating layer 15'is formed on the surfaces of the recess 101'and the flat portion 103'. By further applying a paint to the surface of the organic resin coating layer 15'and drying it, the organic resin coating layer 15'can have a multilayer structure. When the organic resin coating layer 15'has a multilayer structure, it is preferable to add a colorant, for example, a black pigment to any layer other than the bottom layer. Through the above steps, the galvanized steel sheet 1'according to the modified example of this embodiment is produced.
なお、後述する表1A、表1B、表3A、表3B及び表5Bにおける面積SA及び面積SBは、それぞれ、観察視野の全面積を1.0とした場合におけるそれぞれの面積(ただし無次元値)であり、面積SA+面積SB=1.0になる。
また、表1A、表3A及び表5Bにおける「RaAが500nm超5000nm以下の合計面積」の欄のうち、左欄は面積SAのうちで粗度条件を満たす面積の割合(最大1.0)であり、右欄は粗度条件を満たす実面積である。よって、面積SA×[左欄]=[右欄]になる。
同様に、表1B、表3B及び表5Bにおける「RaBが5nm超500nm以下の合計面積」の欄のうち、左欄は面積SBのうちで粗度条件を満たす面積の割合(最大1.0)であり、右欄は粗度条件を満たす実面積である。よって、面積SB×[左欄]=[右欄]になる。
また、表1B、表3B及び表5Bにおける平均高低差は、図2又は図6に示す△hの平均値である。すなわち、ある粗部111の平均表面高さと、この粗部111に隣り合う平滑部113の平均表面高さとの差分△hを求め、これを、粗部111及び平滑部113の各組み合わせのそれぞれについて求める。そして、求めた各△hの平均値を求め、これを表1及び表3の平均高低差とした。
なお、以下に示す実施例に記載の内容により、本発明の内容が制限されるものではない。 Hereinafter, the effects of the present invention will be specifically described with reference to examples of the invention.
Incidentally, Table 1A, which will be described later, Table 1B, Table 3A, the area S A and the area S B in Table 3B and Table 5B, respectively, the respective areas (although dimensionless in the case where the entire area of the observation field and 1.0 a value), the area S a + area S B = 1.0.
Further, Table 1A, among the column "Ra A is 500nm ultra 5000nm or less of the total area" in Table 3A and Table 5B, the ratio of roughness satisfying area among the left column area S A (maximum 1.0 ), And the right column is the actual area that satisfies the roughness condition. Therefore, the area S A × [left column] = become [right column.
Similarly, Table 1B, among the column "Ra B is 5nm super 500nm or less of the total area" in Table 3B and Table 5B, left column the proportion of roughness satisfying area among the area S B (up to 1. 0), and the right column is the actual area satisfying the roughness condition. Therefore, the area S B × [left column] = [the right column.
The average height difference in Tables 1B, 3B, and 5B is the average value of Δh shown in FIG. 2 or FIG. That is, the difference Δh between the average surface height of a certain
The contents of the present invention are not limited by the contents described in the examples shown below.
厚さが0.6mmである鋼板(JIS G 3141で規定された冷延鋼板のうちで絞り用のSPCD)を、濃度30g/LのNa4SiO4処理液を用い、処理液60℃、電流密度20A/dm2、処理時間10秒の条件で電解脱脂し、水洗した。次いで、電解脱脂した鋼板を、60℃の濃度50g/LであるH2SO4水溶液に10秒間浸漬し、更に水洗することで、めっき前処理を行った。 (Experimental example 1: Electroplating; an example in which the rough part forms a hairline)
A steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) is treated with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L at a treatment liquid of 60 ° C. and a current. It was electrolytically degreased and washed with water under the conditions of a density of 20 A / dm 2 and a treatment time of 10 seconds. Next, the electrolytically degreased steel sheet was immersed in an aqueous solution of H 2 SO 4 at a concentration of 50 g / L at 60 ° C. for 10 seconds and further washed with water to perform pre-plating treatment.
なお、表中の下線は、本発明の規定範囲外であることを示す。 After that, No. 2-No. An acidic aqueous solution (sodium nitrate 120 g / L, phosphoric acid 45 g / L: pH 0.6, 30 ° C.) was spray-sprayed on the steel plate samples 26, 28, and 29, and the
The underline in the table indicates that it is outside the specified range of the present invention.
表1A及び表1B中、RaA又はRaBが500nm超5000nm以下の合計面積の欄における左欄は、面積SA又は面積SB×合計面積の値を示す。 The various surface roughness, surface height, number of hairlines, area ratio, etc. of the rough portion (A) and the smooth portion (B) in the
In Table 1A and Table 1B, Ra A or Ra B is the left column in the column of the following total area 500nm ultra 5000nm indicates the value of the area S A or area S B × total area.
次に、作製した鋼板サンプルについてヘアラインの目立ちやすさ(透過性(ヘアラインの見え方))を評価した。鋼板サンプルに形成したヘアラインが上下になるように垂直に設置し、距離を変えて観察し、目視でヘアラインが確認できる距離から目立ちやすさを以下の基準で評価した。得られた結果を、以下の表2にまとめて示した。 The blackness (L * value) of the prepared steel sheet sample was measured according to the method described above.
Next, the conspicuity of the hairline (permeability (appearance of the hairline)) was evaluated for the prepared steel sheet sample. The hairlines formed on the steel sheet sample were installed vertically so as to be up and down, observed at different distances, and the conspicuity was evaluated from the distance at which the hairlines could be visually confirmed according to the following criteria. The results obtained are summarized in Table 2 below.
5:1mの距離からヘアラインが視認できる
4:70cm以上、1m未満の距離からヘアラインが視認できる
3:50cm以上、70cm未満の距離からヘアラインが視認できる
2:30cm以上、50cm未満の距離からヘアラインが視認できる
1:30cmの距離からヘアラインが視認できない (Evaluation criteria)
Hairline can be seen from a distance of 5: 1 m 4:70 cm or more and less than 1 m can be seen from a distance of 3:50 cm or more and less than 70 cm Hairline can be seen from a distance of 2:30 cm or more and less than 50 cm Visible Hairline is not visible from a distance of 1:30 cm
5:ステンレス(塗装なし)同等以上のメタリック感
4:ステンレス(塗膜厚5μm)同等
3:ステンレス(塗膜厚10μm)同等
2:ステンレス(塗膜厚30μm)同等
1:メタリック感が感じられない (Evaluation criteria)
5: Stainless steel (no coating) equivalent or better metallic feeling 4: Stainless steel (
すなわち、得られたそれぞれの亜鉛系電気めっき鋼板から、幅70mm×長さ150mmの試験片を作製した。エッジ及び裏面をテープシールして、塩水噴霧試験(JIS Z 2371)を行った。そして、24時間後の非シール部分の白錆発生面積率を目視で観察し、以下の評価基準で評価した。白錆発生面積率とは、観察部位の面積に対する白錆発生部位の面積の百分率である。得られた結果を、以下の表2にまとめて示した。 The corrosion resistance of the obtained zinc-based electroplated steel sheet was evaluated by the following method.
That is, a test piece having a width of 70 mm and a length of 150 mm was prepared from each of the obtained galvanized steel sheets. The edge and the back surface were tape-sealed, and a salt spray test (JIS Z 2371) was performed. Then, the white rust generation area ratio of the unsealed portion after 24 hours was visually observed and evaluated according to the following evaluation criteria. The white rust generation area ratio is a percentage of the area of the white rust generation site with respect to the area of the observation site. The results obtained are summarized in Table 2 below.
5:白錆発生率10%未満
4:白錆発生率10%以上25%未満
3:白錆発生率25%以上50%未満
2:白錆発生率50%以上75%未満
1:白錆発生率75%以上 (Evaluation criteria)
5: White rust occurrence rate less than 10% 4: White
すなわち、得られたそれぞれの亜鉛系電気めっき鋼板から、幅50mm×長さ50mmの試験片を作製した。得られた試験片に対して180°の折り曲げ加工を施した後、折り曲げ部の外側に対してテープ剥離試験を実施した。テープ剥離部の外観を拡大率10倍のルーペで観察し、下記の評価基準で評価した。折り曲げ加工は、20℃の雰囲気中において、0.5mmのスペーサーを間に挟んで実施した。得られた結果を、以下の表2にまとめて示した。 The processing adhesion (adhesion with the organic resin coating layer) of the obtained zinc-based electroplated steel sheet was evaluated by the following method.
That is, a test piece having a width of 50 mm and a length of 50 mm was prepared from each of the obtained galvanized steel sheets. After bending the obtained test piece at 180 °, a tape peeling test was performed on the outside of the bent portion. The appearance of the tape peeled portion was observed with a magnifying glass having a magnification of 10 times, and evaluated according to the following evaluation criteria. The bending process was carried out in an atmosphere of 20 ° C. with a 0.5 mm spacer in between. The results obtained are summarized in Table 2 below.
5:有機樹脂被覆層に剥離が認められない
4:極一部の有機樹脂被覆層に剥離が認められる(剥離面積≦2%)
3:一部の有機樹脂被覆層に剥離が認められる(2%<剥離面積≦10%)
2:有機樹脂被覆層に剥離が認められる(10%<剥離面積≦20%)
1:有機樹脂被覆層に剥離が認められる(剥離面積>20%) (Evaluation criteria)
5: No peeling is observed in the organic resin coating layer 4: Peeling is observed in a very small part of the organic resin coating layer (peeling area ≤ 2%)
3: Peeling is observed on some organic resin coating layers (2% <peeling area ≤ 10%)
2: Peeling is observed in the organic resin coating layer (10% <peeling area ≤ 20%)
1: Peeling is observed on the organic resin coating layer (peeling area> 20%)
また、No.7の比較材においては酸化物層の厚みが規定よりも大きく、加工密着性が劣位であった。
また、No.27の比較材においては、有機樹脂被覆層中の着色顔料濃度が高いため、酸化物層が存在しなくてもL*値が40以下となった。しかし、有機樹脂被覆層の隠ぺい性が高くヘアラインが隠ぺいされて見えなかった。 No. 1 to No. Of the 29 steel plate samples, No. 1 and No. In the comparative material of No. 2, the oxide layer was not formed, the thickness of the oxide layer did not meet the regulation, and the blackness was inferior.
In addition, No. In the comparative material of No. 7, the thickness of the oxide layer was larger than specified, and the processing adhesion was inferior.
In addition, No. In the comparative material of No. 27, since the concentration of the colored pigment in the organic resin coating layer was high, the L * value was 40 or less even in the absence of the oxide layer. However, the organic resin coating layer was highly concealed and the hairline was concealed and could not be seen.
着色顔料に青色の顔料を使用したNo.28についても、良好な耐食性を備え、高い黒色度とヘアライン外観を有し、かつ、メタリック感及び加工密着性に優れていることがわかる。 As is clear from Table 2 above, the galvanized steel sheet according to the embodiment of the present invention has good corrosion resistance, high blackness and hairline appearance even when an inexpensive steel material is used. Moreover, it can be seen that it is excellent in metallic feeling and processing adhesion.
No. using a blue pigment as a coloring pigment. It can be seen that 28 also has good corrosion resistance, has a high blackness and a hairline appearance, and is excellent in metallic feeling and processing adhesion.
厚さが0.6mmである鋼板(JIS G 3141で規定された冷延鋼板のうち絞り用のSPCD)を、濃度30g/LのNa4SiO4処理液を用い、処理液60℃、電流密度20A/dm2、処理時間10秒の条件で電解脱脂し、水洗した。次いで、電解脱脂した鋼材を、60℃の濃度50g/LであるH2SO4水溶液に10秒間浸漬し、更に水洗することで、めっき前処理を行った。 (Experimental example 2: Electroplating, an example in which a smooth part forms a hairline)
A steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) is treated with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L at a treatment liquid of 60 ° C. and a current density. It was electrolytically degreased and washed with water under the conditions of 20 A / dm 2 and a treatment time of 10 seconds. Next, the electrolytically degreased steel material was immersed in an H 2 SO 4 aqueous solution having a concentration of 50 g / L at 60 ° C. for 10 seconds and further washed with water to perform a plating pretreatment.
Zn-Coめっき層(表3Aから表3C:No.59)は、以下のようにして形成した。浴温50℃、電流密度50A/dm2でめっきしたときに、以下の表3Aから表3Cの組成となるような比で硫酸Zn七水和物と硫酸Co七水和物を調整した、硫酸Zn七水和物と硫酸Co七水和物とを合計で1.2Mと、無水硫酸ナトリウム50g/Lと、を含むpH2.0のめっき浴を用い、ヘアライン形成後のめっき付着量が表3に示した値となるように、めっき時間を調整した。 The Zn—Fe plating layer (Tables 3A to 3C: No. 58) was formed as follows. Sulfuric acid, which was prepared by adjusting Zn heptahydrate sulfate and Fe (II) sulfuric acid heptahydrate in a ratio such that the composition shown in Table 3 below was obtained when plating was performed at a bath temperature of 50 ° C. and a current density of 50 A / dm 2. Using a pH 2.0 plating bath containing a total of 1.2 M of Zn heptahydrate and Fe (II) sulfate heptahydrate and 50 g / L of anhydrous sodium sulfate, the amount of plating adhered after hairline formation. The plating time was adjusted so that was the value shown in Table 3.
The Zn—Co plating layer (Tables 3A to 3C: No. 59) was formed as follows. Sulfuric acid, which was prepared by adjusting Zn heptahydrate sulfate and Co heptahydrate sulfate at a ratio of the compositions shown in Tables 3A to 3C below when plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2. Table 3 shows the amount of plating adhered after hairline formation using a pH 2.0 plating bath containing a total of 1.2 M of Zn heptahydrate and Co sulphate heptahydrate and 50 g / L of anhydrous sodium sulfate. The plating time was adjusted so as to have the value shown in.
なお、粗部111と平滑部113との境界は、ヘアライン直交方向でかつ板厚方向の断面において、前記ヘアライン直交方向に沿った観察幅1cmの範囲内における酸化物層14の最高点H1から最低点H0を差し引いた最大高さRyの1/3の高さでかつ前記ヘアライン直交方向に平行をなす仮想直線上にあるとした。 By the above procedure, the surface shape of the
Incidentally, the boundary between the
表3A及び表3B中、RaA又はRaBが500nm超5000nm以下の合計面積の欄における左欄は、面積SA又は面積SB×合計面積の値を示す。 Here, various surface roughness, surface height, number of hairlines, area ratio, etc. of the rough portion (A) and the smooth portion (B) in the
In Table 3A and Table 3B, Ra A or Ra B is the left column in the column of the following total area 500nm ultra 5000nm indicates the value of the area S A or area S B × total area.
また、No.47の比較材においては酸化物層の厚みが規定よりも大きく、加工密着性が劣位であった。 No. 41-No. Of the 68 steel samples, No. In the comparative examples of 41 and 42, the oxide layer was not formed, the thickness of the oxide layer did not meet the regulation, and the blackness was inferior.
In addition, No. In the comparative material of 47, the thickness of the oxide layer was larger than specified, and the processing adhesion was inferior.
厚さが0.6mmである鋼板(JIS G 3141で規定された冷延鋼板のうちで絞り用のSPCD)を、濃度30g/LのNa4SiO4処理液を用い、処理液60℃、電流密度20A/dm2、処理時間10秒の条件で電解脱脂し、水洗した。次いで、5%水素ガス雰囲気で800℃に加熱し5分間保持した。その後、450℃まで空冷し、鋼板表面に形成した酸化物層を除去した。 (Experimental example 3: Hot dip galvanizing, an example in which the rough part forms a hairline)
A steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) is treated with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L at a treatment liquid of 60 ° C. and a current. It was electrolytically degreased and washed with water under the conditions of a density of 20 A / dm 2 and a treatment time of 10 seconds. Then, it was heated to 800 ° C. in a 5% hydrogen gas atmosphere and held for 5 minutes. Then, it was air-cooled to 450 ° C. to remove the oxide layer formed on the surface of the steel sheet.
なお、粗部111と平滑部113との境界は、ヘアライン直交方向でかつ板厚方向の断面において、前記ヘアライン直交方向に沿った観察幅1cmの範囲内における酸化物層14の最高点H1から最低点H0を差し引いた最大高さRyの1/3の高さでかつ前記ヘアライン直交方向に平行をなす仮想直線上にあるとした。 By the above procedure, the surface shape of the
Incidentally, the boundary between the
表5B中、RaA又はRaBが500nm超5000nm以下の合計面積の欄における左欄は、面積SA又は面積SB×合計面積の値を示す。 Here, various surface roughness, surface height, number of hairlines, area ratio, etc. of the rough portion (A) and the smooth portion (B) in the
In Table 5B, Ra A or Ra B is the left column in the column of the total area of less than 500nm ultra 5000nm indicates the value of the area S A or area S B × total area.
また、No.87の比較材においては酸化物層の厚みが規定よりも大きく、加工密着性が劣位であった。 No. 81-No. Of the 107 steel samples, No. In the comparative examples of 81 and 82, the oxide layer was not formed, the thickness of the oxide layer did not meet the regulation, and the blackness was inferior.
In addition, No. In the comparative material of 87, the thickness of the oxide layer was larger than specified, and the processing adhesion was inferior.
つぎに、本実施形態の変形例の実施例を説明する。本実施例では、まず、以下の工程により亜鉛系めっき鋼板の試験サンプルを準備した。製造工程の概要を表7Aに示す。なお、表中の下線は、本発明の規定範囲外であることを示す。 <1. Preparation of test sample>
Next, an embodiment of a modified example of the present embodiment will be described. In this example, first, a test sample of a galvanized steel sheet was prepared by the following steps. The outline of the manufacturing process is shown in Table 7A. The underline in the table indicates that it is outside the specified range of the present invention.
厚さが0.6mmである鋼板(JIS G 3141で規定された冷延鋼板のうちで絞り用のSPCD)を、濃度30g/LのNa4SiO4処理液を用いて電離脱脂し、水洗した。ここで、脱脂条件は、処理液60℃、電流密度20A/dm2、処理時間10秒とした。ついで、鋼板の表面を覆う酸化物層を除去した。具体的には、亜鉛系電気めっきを行う場合、電解脱脂した鋼板を、60℃に保温した濃度50g/LのH2SO4水溶液に10秒間浸漬し、更に水洗した。亜鉛系溶融めっきを行う場合、鋼板を5%水素ガス雰囲気で800℃に加熱し5分間保持した。その後、450℃まで空冷した。 (1-1. Preparation process)
A steel sheet having a thickness of 0.6 mm (SPCD for drawing among cold-rolled steel sheets specified in JIS G 3141) was ionized and greased with a Na 4 SiO 4 treatment liquid having a concentration of 30 g / L and washed with water. .. Here, the degreasing conditions were a treatment liquid of 60 ° C., a current density of 20 A / dm 2 , and a treatment time of 10 seconds. Then, the oxide layer covering the surface of the steel sheet was removed. Specifically, in the case of zinc-based electroplating, the electrolytically degreased steel sheet was immersed in an aqueous solution of H 2 SO 4 having a concentration of 50 g / L kept at 60 ° C. for 10 seconds, and further washed with water. When performing zinc-based hot-dip galvanizing, the steel sheet was heated to 800 ° C. in a 5% hydrogen gas atmosphere and held for 5 minutes. Then, it was air-cooled to 450 ° C.
ついで、亜鉛系めっき層形成工程を行った。具体的な工程は以下の通りである。なお、得られためっき層の組成は、めっきした鋼板をインヒビター(朝日化学工業社製 NO.700AS)入りの10質量%塩酸に浸漬して溶解剥離し、溶解した溶液をICPで分析することで確認した。 (1-2. Zinc-based plating layer forming process)
Then, a zinc-based plating layer forming step was performed. The specific process is as follows. The composition of the obtained plating layer is obtained by immersing the plated steel sheet in 10% by mass hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.), dissolving and peeling, and analyzing the dissolved solution by ICP. confirmed.
鋼板を浴温50℃、電流密度50A/dm2でめっきしたときに、電気亜鉛合金めっき層が以下の表2-1に示す組成となるように、硫酸Zn七水和物と硫酸Ni六水和物を混合した。ついで、硫酸Zn七水和物と硫酸Ni六水和物とを合計で1.2Mと、無水硫酸ナトリウム50g/Lとを含むpH2.0のめっき浴を用意した。ついで、このめっき浴を用いて浴温50℃、電流密度50A/dm2で電気亜鉛めっきを行った。ここで、めっき付着量が表7Cに示した値となるように、めっき時間を調整した。また、鋼板に対する相対流速が1m/secとなるように、めっき液を流動させた。 (1-2-1. Zn-Ni electrozinc alloy plating layer forming step: No. 1'to 17', 21' to 31', 34' to 37')
When the steel sheet is plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , Zn heptahydrate sulfate and Ni hexahydrate sulfate are obtained so that the electrolytic zinc alloy plating layer has the composition shown in Table 2-1 below. Japanese products were mixed. Then, a plating bath having a pH of 2.0 containing a total of 1.2 M of Zn sulphate heptahydrate and Ni sulphate hexahydrate and 50 g / L of anhydrous sodium sulfate was prepared. Then, electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 . Here, the plating time was adjusted so that the amount of plating adhered was the value shown in Table 7C. Further, the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
鋼板を浴温50℃、電流密度50A/dm2でめっきしたときに、電気亜鉛合金めっき層が以下の表2-1に示す組成となるように、硫酸Zn七水和物と硫酸Fe(II)七水和物を混合した。ついで、硫酸Zn七水和物と硫酸Fe(II)七水和物とを合計で1.2Mと、無水硫酸ナトリウム50g/Lとを含むpH2.0のめっき浴を用意した。ついで、このめっき浴を用いて浴温50℃、電流密度50A/dm2で電気亜鉛めっきを行った。ここで、めっき付着量が表2-1に示した値となるように、めっき時間を調整した。また、鋼板に対する相対流速が1m/secとなるように、めっき液を流動させた。 (1-2-2. Zn-Fe electrozinc alloy plating layer forming step: No. 18')
When the steel plate is plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the composition of the electrozinc alloy plating layer is shown in Table 2-1 below, so that Zn heptahydrate sulfate and Fe (II) sulfuric acid are used. ) The heptahydrate was mixed. Then, a plating bath having a pH of 2.0 containing a total of 1.2 M of Zn sulfate heptahydrate and Fe (II) sulfate heptahydrate and 50 g / L of anhydrous sodium sulfate was prepared. Then, electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 . Here, the plating time was adjusted so that the amount of plating adhered was the value shown in Table 2-1. Further, the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
鋼板を浴温50℃、電流密度50A/dm2でめっきしたときに、電気亜鉛合金めっき層が以下の表2-1に示す組成となるように、硫酸Zn七水和物と硫酸Co七水和物を混合した。ついで、硫酸Zn七水和物と硫酸Co七水和物とを合計で1.2Mと、無水硫酸ナトリウム50g/Lとを含むpH2.0のめっき浴を用意した。ついで、このめっき浴を用いて浴温50℃、電流密度50A/dm2で電気亜鉛めっきを行った。ここで、めっき付着量が表7Cに示した値となるように、めっき時間を調整した。また、鋼板に対する相対流速が1m/secとなるように、めっき液を流動させた。 (1-2-3. Zn-Co electrozinc alloy plating layer forming step: No. 19')
When the steel sheet is plated at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the composition of the electrozinc alloy plating layer is shown in Table 2-1 below. Japanese products were mixed. Then, a plating bath having a pH of 2.0 containing a total of 1.2 M of Zn heptahydrate sulfate and Co heptahydrate sulfate and 50 g / L of anhydrous sodium sulfate was prepared. Then, electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 . Here, the plating time was adjusted so that the amount of plating adhered was the value shown in Table 7C. Further, the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
硫酸Zn七水和物1.2Mと、無水硫酸ナトリウム50g/Lとを含むpH2.0のめっき浴を用意した。ついで、このめっき浴を用いて浴温50℃、電流密度50A/dm2で電気亜鉛めっきを行った。ここで、めっき付着量が表7Cに示した値となるように、めっき時間を調整した。また、鋼板に対する相対流速が1m/secとなるように、めっき液を流動させた。 (1-2-5. Electrogalvanization layer forming step: No. 20')
A plating bath having a pH of 2.0 containing 1.2 M of Zn heptahydrate sulfate and 50 g / L of anhydrous sodium sulfate was prepared. Then, electrogalvanization was performed using this plating bath at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 . Here, the plating time was adjusted so that the amount of plating adhered was the value shown in Table 7C. Further, the plating solution was flowed so that the relative flow velocity with respect to the steel sheet was 1 m / sec.
鋼板をめっき浴温450℃でめっきしたときに、溶融亜鉛合金めっき層が以下の表2-1に示す組成となるように、めっき浴の組成を調整した。ついで、鋼板温度を450℃に保持した鋼板を450℃のめっき浴に浸漬し、その後鋼板を引き上げることで鋼板の表面に溶融亜鉛合金めっき層を形成した。ついで、めっき付着量が表7Cに示した値となるように、ガスワイピングを行った。 (1-2-7. Zn-Al-Mg hot-dip zinc alloy plating layer forming step: No. 32', 33')
The composition of the plating bath was adjusted so that the hot-dip zinc alloy plating layer had the composition shown in Table 2-1 below when the steel sheet was plated at a plating bath temperature of 450 ° C. Then, the steel sheet whose temperature was maintained at 450 ° C. was immersed in a plating bath at 450 ° C., and then the steel sheet was pulled up to form a hot-dip galvanized alloy plating layer on the surface of the steel sheet. Then, gas wiping was performed so that the amount of plating adhered was the value shown in Table 7C.
酸化物層形成工程では、鋼板毎に異なる方法で亜鉛系めっき層の表面に酸化物層を形成した。No.1’~31’、34’~37’では以下の黒化処理1により酸化物層を形成し、No.32’では以下の黒化処理3により酸化物層を形成し、No.33’では以下の黒化処理4により酸化物層を形成した。得られた酸化物層の平均厚み、組成は上述した方法により測定した。 (1-3. Oxide layer forming step)
In the oxide layer forming step, an oxide layer was formed on the surface of the zinc-based plating layer by a method different for each steel sheet. No. In 1'to 31'and 34' to 37', an oxide layer was formed by the following
黒化処理3:酸性水溶液(硫酸ニッケル六水和物(関東化学ホールディング社製)45g/L、塩化アンチモン(III)(関東化学ホールディング社製)を2g/L、ホウフッ化水素酸(関東化学ホールディング社製)を7g/L、pH1.0、温度70℃)に各供試材を3秒間浸漬させた。
黒化処理4:特許文献6(特開2017-218647号公報)の実施例2を参考に、水蒸気処理(温度:120℃、相対湿度:95%、酸素濃度:1.0%、処理時間20h)を行った。
いずれの供試材も、黒化処理を施した後、水洗、乾燥を行った。また黒化処理1~3の酸性水溶液のpHは硫酸(関東化学ホールディング社製)により調整した。 Blackening treatment 1: Add an acidic aqueous solution (sodium nitrate (manufactured by Kanto Chemical Co., Inc.) 120 g / L, phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) 45 g / L, pH 0.6, 30 ° C.) to the surface of the zinc-based
Blackening treatment 3: Acidic aqueous solution (nickel sulfate hexahydrate (manufactured by Kanto Chemical Holding Co., Ltd.) 45 g / L, antimony chloride (III) (manufactured by Kanto Chemical Holding Co., Ltd.) 2 g / L, borohydride (Kanto Chemical Holding Co., Ltd.) Each test material was immersed in 7 g / L, pH 1.0, temperature 70 ° C.) for 3 seconds.
Blackening treatment 4: With reference to Example 2 of Patent Document 6 (Japanese Unexamined Patent Publication No. 2017-218647), steam treatment (temperature: 120 ° C., relative humidity: 95%, oxygen concentration: 1.0%, treatment time 20h). ) Was performed.
All of the test materials were blackened, washed with water, and dried. The pH of the acidic aqueous solution of the blackening
ついで、酸化物層の表面を砥粒ブラシで研磨することで、酸化物層の表面に上述した凹部及び平坦部を形成した。ここで、凹部101’の平均深さ、長さ方向に沿った平均長さ、単位幅当たりの本数、面積率AR1、AR2、面積率比AR1/AR2、表面粗さRaA’が5nm超500nm以下である領域(表7Bに凹部の平均粗度RaA’の有無と記載)の有無、及び平坦部103’の表面粗さRaB’が500nm超5000nm以下である領域(表7Bに平坦部の平均粗度RaB’の有無と記載)の有無が、表7Aおよび表7Bに示す値または区分となるように、砥粒ブラシの粒度、圧下力、及び研磨時間を調整した。平滑領域及び粗領域の有無に関し、「-」は評価不能であることを示す。なお、得られた表面構造の特定は上述した方法により行った。 (1-4. Hairline forming process)
Then, the surface of the oxide layer was polished with an abrasive grain brush to form the above-mentioned recesses and flat portions on the surface of the oxide layer. Here, the average depth of the recess 101', the average length along the length direction, the number of lines per unit width, the area ratios AR1 and AR2, the area ratio ratio AR1 / AR2, and the surface roughness RaA'are more than 5 nm and 500 nm or less. (Table 7B describes the presence or absence of the average roughness RaA of the recesses) and the region where the surface roughness RaB'of the flat portion 103'is more than 500 nm and 5000 nm or less (Table 7B shows the average roughness of the flat portion). The grain size, reducing force, and polishing time of the abrasive grain brush were adjusted so that the presence or absence of degree RaB') was the value or category shown in Table 7A and Table 7B. “-” Indicates that evaluation is not possible with respect to the presence or absence of smooth regions and coarse regions. The surface structure obtained was specified by the method described above.
一部の鋼板(No.1’~24’、26’~37’)では、凹部及び平坦部の表面にさらに有機樹脂被覆層を形成した。これらのうち、No.31以外の鋼板では有機樹脂被覆層は2層(上層、下層)とした。まず、ウレタン系樹脂(第一工業製薬社製、スーパーフレックス170)と、メラミン樹脂(オルネクスジャパン社製、サイメル327)とを、固形分質量比が85:15となるように混合した。一方、着色顔料として黒色顔料(トーヨーカラー社製、EMF Black HK-3)及び青色顔料(大日精化社製、AFブルーE-2B)を準備した。ついで、これらの材料と水を混合することで、顔料を含まない無色塗料、黒色顔料を固形分(顔料含む)の総質量に対して2質量%で含む黒色塗料1、黒色顔料を15質量%で含む黒色顔料2、青色顔料を2質量%で含む青色塗料を準備した。ついで、Siを有効成分として含むSi系添加剤(日産化学社製/スノーテックスN)、Pを有効成分として含むP系添加剤(関東化学社製/リン酸アンモニウム)、Zrを有効成分として含むZr系添加剤(キシダ化学社製/炭酸ジルコニウムアンモニウム)を準備した。No.36’は、有機樹脂被覆層が2層で、上層および下層に黒色顔料を含有させた。 (1-5. Organic resin film forming step)
In some steel sheets (No. 1'to 24', 26' to 37'), an organic resin coating layer was further formed on the surfaces of the concave portion and the flat portion. Of these, No. For steel sheets other than 31, the organic resin coating layer was two layers (upper layer and lower layer). First, a urethane resin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex 170) and a melamine resin (manufactured by Ornex Japan Co., Ltd., Cymel 327) were mixed so that the solid content mass ratio was 85:15. On the other hand, black pigments (EMF Black HK-3 manufactured by Toyo Color Co., Ltd.) and blue pigments (AF Blue E-2B manufactured by Dainichiseika Co., Ltd.) were prepared as coloring pigments. Then, by mixing these materials with water, a colorless paint containing no pigment, a black paint containing 2% by mass of a black pigment with respect to the total mass of solids (including pigment) 1, and 15% by mass of a black pigment. A blue pigment containing 2% by mass of the
以上の工程により作製された亜鉛系めっき鋼板のサンプルを以下の方法で評価した。結果を表8にまとめて示す。 <2. Evaluation of test sample>
A sample of the galvanized steel sheet produced by the above steps was evaluated by the following method. The results are summarized in Table 8.
CIE1976L*a*b*表色系におけるL*値を測色計(コニカミノルタ社製CR-400)で測定した。L*値が50以下であれば高い黒色度が実現できていると言える。L*値は40以下が好ましい。 (2-1. Blackness (L * value))
The L * value in the CIE1976L * a * b * color system was measured with a colorimeter (CR-400 manufactured by Konica Minolta). If the L * value is 50 or less, it can be said that a high degree of blackness is achieved. The L * value is preferably 40 or less.
作製した試験サンプルに形成したヘアライン(凹部)が上下になるように垂直に設置し、観察者と試験サンプルとの距離を変えて目視でヘアラインを観察した。ついで、目視でヘアラインが確認できた距離と、以下の評価基準とに基づいて、ヘアライン外観を評価した。 (2-2. Appearance of hairline (easiness to see hairline))
The hairlines (recesses) formed in the prepared test sample were vertically placed so as to be up and down, and the hairlines were visually observed by changing the distance between the observer and the test sample. Then, the appearance of the hairline was evaluated based on the distance at which the hairline could be visually confirmed and the following evaluation criteria.
5:1mの距離からヘアラインが視認できる。
4:70cm以上、1m未満の距離からヘアラインが視認できる。
3:50cm以上、70cm未満の距離からヘアラインが視認できる。
2:30cm以上、50cm未満の距離からヘアラインが視認できる。
1:30cmの距離からヘアラインが視認できない。 (Evaluation criteria)
The hairline can be seen from a distance of 5: 1 m.
The hairline can be visually recognized from a distance of 4: 70 cm or more and less than 1 m.
The hairline can be visually recognized from a distance of 3: 50 cm or more and less than 70 cm.
The hairline can be visually recognized from a distance of 2:30 cm or more and less than 50 cm.
The hairline is not visible from a distance of 1:30 cm.
JIS G4305:2012で規定されるヘアラインステンレス鋼板にクリア塗料を塗布した。クリア塗料には市販のポリエステル/メラミン塗料(日本ペイント・インダストリアルコーティングス社製、NSC200HQ)を使用し、塗布はバーコーターで行った。その後、塗料を塗布したステンレス鋼板を熱風炉で30秒間焼付け硬化した。このような工程により塗膜の厚みが異なる複数種類の比較用サンプルを準備した。ついで、試験サンプルとこれらの比較用サンプルとのメタリック感を比較し、以下の評価基準に基づいて試験サンプルのメタリック感を評価した。 (2-3. Metallic feeling)
A clear paint was applied to the hairline stainless steel sheet specified in JIS G4305: 2012. A commercially available polyester / melamine paint (Nippon Paint Industrial Coatings Co., Ltd., NSC200HQ) was used as the clear paint, and the coating was performed with a bar coater. Then, the stainless steel sheet coated with the paint was baked and hardened in a hot air furnace for 30 seconds. By such a step, a plurality of types of comparative samples having different coating film thicknesses were prepared. Then, the metallic feeling of the test sample and these comparative samples was compared, and the metallic feeling of the test sample was evaluated based on the following evaluation criteria.
5:ステンレス(塗装なし)同等以上のメタリック感
4:ステンレス(塗膜厚5μm)同等
3:ステンレス(塗膜厚10μm)同等
2:ステンレス(塗膜厚30μm)同等
1:メタリック感が感じられない (Evaluation criteria)
5: Stainless steel (no coating) equivalent or better metallic feeling 4: Stainless steel (
試験サンプルから幅70mm×長さ150mmの試験片を切り出した。ついで、試験片のエッジ及び裏面をテープシールして、塩水噴霧試験(JIS Z 2371)を行った。そして、24時間後の非シール部分の白錆発生率を目視で測定し、白錆発生率と以下の評価基準で耐食性を評価した。白錆発生率とは、観察部位の面積に対する白錆発生部位の面積%である。 (2-4. Corrosion resistance)
A test piece having a width of 70 mm and a length of 150 mm was cut out from the test sample. Then, the edge and the back surface of the test piece were tape-sealed, and a salt spray test (JIS Z 2371) was performed. Then, the white rust occurrence rate of the unsealed portion after 24 hours was visually measured, and the corrosion resistance was evaluated based on the white rust occurrence rate and the following evaluation criteria. The white rust occurrence rate is the area% of the white rust occurrence part with respect to the area of the observation part.
5:白錆発生率10%未満
4:白錆発生率10%以上25%未満
3:白錆発生率25%以上50%未満
2:白錆発生率50%以上75%未満
1:白錆発生率75%以上 (Evaluation criteria)
5: White rust occurrence rate less than 10% 4: White
試験サンプルから幅50mm×長さ50mmの試験片を切り出した。ついで、試験片に180°の折り曲げ加工を施した。折り曲げ加工は、20℃の雰囲気中において、0.5mmのスペーサーを試験片と折り曲げ機との間に挟んで実施した。ついで、折り曲げ部の外側に対してテープ剥離試験を実施した。すなわち、市販の接着テープ(ニチバン社製セロテープ(登録商標))を折り曲げ部の外側に貼りつけ、その後剥離する処理を行った。ついで、剥離した接着テープを拡大率10倍のルーペで観察し、接着テープに付着した有機樹脂被覆層の面積%(折り曲げ部分の有機樹脂被覆層の総面積に対する剥離部分の面積%)を測定した。ついで、下記の評価基準で加工密着性を評価した。なお、有機樹脂被覆層を有さないNo.25では本試験を行わなかった。このため、表8におけるNo.25’の加工密着性は「-」で示した。 (2-5. Processing adhesion)
A test piece having a width of 50 mm and a length of 50 mm was cut out from the test sample. Then, the test piece was bent at 180 °. The bending process was carried out by sandwiching a 0.5 mm spacer between the test piece and the bending machine in an atmosphere of 20 ° C. Then, a tape peeling test was performed on the outside of the bent portion. That is, a commercially available adhesive tape (cellotape manufactured by Nichiban Co., Ltd. (registered trademark)) was attached to the outside of the bent portion, and then peeled off. Then, the peeled adhesive tape was observed with a loupe having a magnification of 10 times, and the area% of the organic resin coating layer adhered to the adhesive tape (the area% of the peeled portion with respect to the total area of the organic resin coating layer of the bent portion) was measured. .. Then, the processing adhesion was evaluated according to the following evaluation criteria. No. 1 having no organic resin coating layer. At 25, this test was not performed. Therefore, No. in Table 8 The processing adhesion of 25'is indicated by "-".
5:有機樹脂被覆層に剥離が認められない
4:極一部の有機樹脂被覆層に剥離が認められる(剥離部分の面積%≦2%)
3:一部の有機樹脂被覆層に剥離が認められる(2%<剥離部分の面積%≦10%)
2:有機樹脂被覆層に剥離が認められる(10%<剥離部分の面積%≦20%)
1:有機樹脂被覆層に大きな剥離が認められる(剥離部分の面積%>20%) (Evaluation criteria)
5: No peeling is observed in the organic resin coating layer 4: Peeling is observed in a very small part of the organic resin coating layer (area% of peeled portion ≤ 2%)
3: Peeling is observed on some organic resin coating layers (2% <area% of peeled part ≤ 10%)
2: Peeling is observed in the organic resin coating layer (10% <area% of peeled part ≤ 20%)
1: Large peeling is observed in the organic resin coating layer (area% of peeled part> 20%)
実施例となるNo.2’~6’、8’~32’では、良好な黒色度、ヘアライン外観、メタリック感、耐食性、及び加工密着性が得られた。具体的には、L*値が50以下、あるいは40以下となり、ヘアライン外観、メタリック感、耐食性、及び加工密着性の評価がほぼすべて3以上となった。なお、黒色顔料を含有する有機樹脂被覆層を有するNo.2’~24’、26’、28’~33’において、L*値が40以下となった。 (2-6. Consideration)
No. which is an example. In 2'to 6'and 8'to 32', good blackness, hairline appearance, metallic feeling, corrosion resistance, and processing adhesion were obtained. Specifically, the L * value was 50 or less, or 40 or less, and the evaluations of hairline appearance, metallic feeling, corrosion resistance, and processing adhesion were almost all 3 or more. No. 1 having an organic resin coating layer containing a black pigment. In 2'to 24', 26', and 28' to 33', the L * value was 40 or less.
11、11’ 鋼板
13、13’ 亜鉛系めっき層
14、14’ 酸化物層
15、15’ 有機樹脂被覆層
101、101’105 凹部
103 非ヘアライン部
103’ 平坦部
111 粗部
113 平滑部 1,
Claims (29)
- 鋼板と、
前記鋼板の少なくとも一方の表面に位置しており、所定の方向に延伸する凹部であるヘアラインが形成された亜鉛系めっき層と、
前記亜鉛系めっき層の表面に位置しており、平均厚みが0.05μm以上3.0μm以下である酸化物層と、
を備える亜鉛系めっき鋼板。 Steel plate and
A zinc-based plating layer located on at least one surface of the steel sheet and having a hairline formed as a recess extending in a predetermined direction.
An oxide layer located on the surface of the zinc-based plating layer and having an average thickness of 0.05 μm or more and 3.0 μm or less.
A galvanized steel sheet with. - 少なくとも前記凹部以外の前記亜鉛系めっき層の表面に前記酸化物層が位置する、請求項1に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to claim 1, wherein the oxide layer is located on the surface of the zinc-based plated layer other than at least the recess.
- 前記酸化物層の表面に、透光性を有する有機樹脂被覆層を更に備える、
請求項1または請求項2に記載の亜鉛系めっき鋼板。 A translucent organic resin coating layer is further provided on the surface of the oxide layer.
The galvanized steel sheet according to claim 1 or 2. - 前記亜鉛系めっき鋼板の表面の黒色度は、L*値で40以下である、請求項1から請求項3のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to any one of claims 1 to 3, wherein the blackness of the surface of the zinc-based plated steel sheet is 40 or less in L * value.
- 前記酸化物層は、粗部と平滑部とからなり、
前記粗部は、表面粗さRaAが500nm超5000nm以下である領域を含み、
前記平滑部は、表面粗さRaBが5nm超500nm以下である領域を含み、
前記粗部と前記平滑部との境界を、前記所定の方向に直交するヘアライン直交方向でかつ板厚方向の断面において、前記ヘアライン直交方向に沿った観察幅1cmの範囲内における前記酸化物層の最高点H1から最低点H0を差し引いた最大高さRyの1/3の高さでかつ前記ヘアライン直交方向に平行をなす仮想直線上にあるとした場合、
前記粗部と前記平滑部との境界が規定された前記酸化物層を平面視し、互いに同一面積単位で、前記粗部の面積をSAとし、前記平滑部の面積をSBとしたときに、面積比SB/SAが、0.6以上10.0以下であり、
前記粗部と当該粗部に隣り合う前記平滑部との間の平均高低差は、0.3μm以上5.0μm以下である、
請求項1から請求項4のいずれか1項に記載の亜鉛系めっき鋼板。 The oxide layer is composed of a rough portion and a smooth portion.
The rough portion includes a region where the surface roughness Ra A is more than 500 nm and 5000 nm or less.
The smooth portion includes a region having a surface roughness Ra B of more than 5 nm and 500 nm or less.
The boundary between the rough portion and the smooth portion is defined as a cross section in the direction orthogonal to the hairline orthogonal to the predetermined direction and in the plate thickness direction, and the oxide layer of the oxide layer within an observation width of 1 cm along the direction orthogonal to the hairline. Assuming that the height is 1/3 of the maximum height Ry obtained by subtracting the minimum point H 0 from the highest point H 1 and is on a virtual straight line parallel to the hairline orthogonal direction.
Said oxide layer boundary is defined between the smooth portion and the coarse portion in plan view, in the same area unit together, the area of the coarse portion and S A, when the area of the smooth portion and the S B In addition, the area ratio S B / S A is 0.6 or more and 10.0 or less.
The average height difference between the rough portion and the smooth portion adjacent to the rough portion is 0.3 μm or more and 5.0 μm or less.
The galvanized steel sheet according to any one of claims 1 to 4. - 前記粗部における前記表面粗さRaAが500nm超5000nm以下である領域の合計面積が、前記粗部の面積SAに対して85%以上であり、
前記平滑部における前記表面粗さRaBが5nm超500nm以下である領域の合計面積が、前記平滑部の面積SBに対して65%以上である、
請求項5に記載の亜鉛系めっき鋼板。 The total area of the region the surface roughness Ra A of the rough portion is less than 500nm ultra 5000nm is 85% or more with respect to the area S A of the coarse portion,
The total area of the surface roughness Ra B is less than 5nm ultra 500nm region of the smooth portion is 65% or more with respect to the area S B of the smoothing part,
The galvanized steel sheet according to claim 5. - 前記粗部が前記ヘアラインに形成され、
前記ヘアラインの延伸方向に沿った平均長さが、1cm以上である、
請求項5または請求項6に記載の亜鉛系めっき鋼板。 The rough portion is formed on the hairline,
The average length of the hairline along the stretching direction is 1 cm or more.
The galvanized steel sheet according to claim 5 or 6. - 前記平滑部が前記ヘアラインに形成され、
前記ヘアラインの延伸方向に沿った平均長さが、1cm以上である、
請求項5または請求項6に記載の亜鉛系めっき鋼板。 The smooth portion is formed on the hairline,
The average length of the hairline along the stretching direction is 1 cm or more.
The galvanized steel sheet according to claim 5 or 6. - 前記ヘアラインは、前記ヘアライン直交方向に沿った任意の1cm幅の範囲に、平均して3本/cm以上80本/cm以下の頻度で存在する、
請求項1から請求項8のいずれか1項に記載の亜鉛系めっき鋼板。 The hairlines are present in an arbitrary 1 cm width range along the direction orthogonal to the hairlines with an average frequency of 3 lines / cm or more and 80 lines / cm or less.
The galvanized steel sheet according to any one of claims 1 to 8. - 前記鋼板の表面において、前記亜鉛系めっき層における前記ヘアラインに対応する位置に、凹部が形成されている、
請求項1から請求項9のいずれか1項に記載の亜鉛系めっき鋼板。 On the surface of the steel sheet, a recess is formed at a position corresponding to the hairline in the zinc-based plating layer.
The galvanized steel sheet according to any one of claims 1 to 9. - 前記亜鉛系めっき層は、亜鉛系電気めっき層であり、
前記亜鉛系電気めっき層の平均付着量は、5g/m2以上40g/m2以下である、請求項1から請求項10のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plating layer is a zinc-based electroplating layer.
The zinc-based plated steel sheet according to any one of claims 1 to 10, wherein the average adhesion amount of the zinc-based electroplating layer is 5 g / m 2 or more and 40 g / m 2 or less. - 前記亜鉛系電気めっき層は、
Fe、Ni、およびCoからなる群より選択されるいずれか1つ以上の添加元素を合計で5質量%以上20質量%以下と、
Zn及び不純物からなる残部と、
を含有する、
請求項11に記載の亜鉛系めっき鋼板。 The zinc-based electroplating layer is
Any one or more additive elements selected from the group consisting of Fe, Ni, and Co are added in a total of 5% by mass or more and 20% by mass or less.
The balance of Zn and impurities,
Contains,
The zinc-based plated steel sheet according to claim 11. - 前記亜鉛系めっき層は、亜鉛系溶融めっき層であり、
前記亜鉛系溶融めっき層の平均付着量は、40g/m2超150g/m2以下である、
請求項1から請求項10のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plating layer is a zinc-based hot-dip plating layer.
The average adhesion amount of the zinc-based hot-dip plating layer is more than 40 g / m 2 and 150 g / m 2 or less.
The zinc-based plated steel sheet according to any one of claims 1 to 10. - 前記亜鉛系溶融めっき層は、
Al、およびMgからなる群より選択される何れか1つ以上の添加元素を合計で1質量%以上60質量%以下と、
Zn及び不純物から成る残部と、
を含有する、
請求項13に記載の亜鉛系めっき鋼板。 The zinc-based hot-dip plating layer is
Any one or more additive elements selected from the group consisting of Al and Mg are added in a total of 1% by mass or more and 60% by mass or less.
The balance of Zn and impurities,
Contains,
The zinc-based plated steel sheet according to claim 13. - 前記有機樹脂被覆層が着色顔料を有する、
請求項3に記載の亜鉛系めっき鋼板。 The organic resin coating layer has a coloring pigment.
The galvanized steel sheet according to claim 3. - 前記酸化物層の表面には、前記凹部と、前記凹部以外の領域である平坦部とが形成され、
前記凹部の平均深さは0.1μm以上3.0μm未満であり、
前記凹部の底部は前記酸化物層の下層の前記亜鉛系めっき層に到達し、
前記凹部に存在する前記酸化物層の平面視での面積率AR1と、前記平坦部に存在する前記酸化物層の平面視での面積率AR2との比AR1/AR2が0以上0.5以下である、
請求項1または請求項2に記載の亜鉛系めっき鋼板。 On the surface of the oxide layer, the recess and the flat portion which is a region other than the recess are formed.
The average depth of the recess is 0.1 μm or more and less than 3.0 μm.
The bottom of the recess reaches the zinc-based plating layer below the oxide layer and
The ratio AR1 / AR2 of the area ratio AR1 of the oxide layer existing in the recess in plan view to the area ratio AR2 of the oxide layer existing in the flat portion in plan view is 0 or more and 0.5 or less. Is,
The galvanized steel sheet according to claim 1 or 2. - 前記凹部の平均深さが0.1μm以上2.0μm未満である、請求項16に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to claim 16, wherein the average depth of the recesses is 0.1 μm or more and less than 2.0 μm.
- 前記亜鉛系めっき層が亜鉛系電気めっき層である、請求項17に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to claim 17, wherein the zinc-based plating layer is a zinc-based electroplating layer.
- 前記酸化物層が、亜鉛水酸化物及び亜鉛酸化物からなる群より選択される何れか1種以上を含む、請求項16から請求項18のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to any one of claims 16 to 18, wherein the oxide layer contains at least one selected from the group consisting of zinc hydroxide and zinc oxide.
- 前記酸化物層の平均厚みが0.05μm以上3.0μm未満である、請求項16から請求項18のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to any one of claims 16 to 18, wherein the average thickness of the oxide layer is 0.05 μm or more and less than 3.0 μm.
- 前記凹部は表面粗さRaA’が5nm超500nm以下である領域を含み、前記平坦部は表面粗さRaB’が500nm超5000nm以下である領域を含む、請求項16から請求項20のいずれか1項に記載の亜鉛系めっき鋼板。 Any one of claims 16 to 20, wherein the recess includes a region having a surface roughness RaA'of more than 5 nm and 500 nm or less, and the flat portion includes a region having a surface roughness RaB' of more than 500 nm and 5000 nm or less. The galvanized steel sheet described in the section.
- 前記凹部の長さ方向に沿った平均長さが1cm以上である、請求項16から請求項21のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to any one of claims 16 to 21, wherein the average length along the length direction of the recess is 1 cm or more.
- 前記凹部は、前記凹部の長さ方向に直交する方向に沿った任意の1cm幅の範囲に、平均して3本/cm以上80本/cm以下の頻度で存在する、請求項16から請求項22のいずれか1項に記載の亜鉛系めっき鋼板。 Claims 16 to 80, wherein the recesses are present in an arbitrary 1 cm width range along a direction orthogonal to the length direction of the recesses with an average frequency of 3 lines / cm or more and 80 lines / cm or less. The zinc-based plated steel sheet according to any one of 22.
- 前記亜鉛系めっき層の平均付着量は、5g/m2以上40g/m2以下である、請求項16から請求項23のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to any one of claims 16 to 23, wherein the average adhesion amount of the zinc-based plated layer is 5 g / m 2 or more and 40 g / m 2 or less.
- 前記酸化物層が第二成分としてFe、Ni、及びCoからなる群より選択される何れか1種以上の添加元素を含有する、請求項16から請求項24のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc according to any one of claims 16 to 24, wherein the oxide layer contains any one or more additive elements selected from the group consisting of Fe, Ni, and Co as the second component. System-plated steel plate.
- 前記亜鉛系めっき層は、Fe、Ni、及びCoからなる群より選択される何れか1種以上の添加元素を、これらの添加元素の合計で5質量%以上20質量%以下含有し、前記亜鉛系めっき層の残部はZn及び不純物である、請求項16から請求項25のいずれか1項に記載の亜鉛系めっき鋼板。 The zinc-based plating layer contains any one or more additive elements selected from the group consisting of Fe, Ni, and Co in a total of 5% by mass or more and 20% by mass or less of these additive elements, and the zinc. The zinc-based plated steel sheet according to any one of claims 16 to 25, wherein the balance of the system-based plating layer is Zn and impurities.
- 前記有機樹脂被覆層が黒色顔料を含有する、請求項3に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to claim 3, wherein the organic resin coating layer contains a black pigment.
- 前記有機樹脂被覆層が2層以上であり、最下層以外のいずれか1以上の層に前記黒色顔料が含有される、請求項27に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to claim 27, wherein the organic resin coating layer is two or more layers, and the black pigment is contained in any one or more layers other than the bottom layer.
- 前記有機樹脂被覆層が更にSi、P、及びZrから選択される何れか1種以上の添加元素を含有する、請求項28に記載の亜鉛系めっき鋼板。 The zinc-based plated steel sheet according to claim 28, wherein the organic resin coating layer further contains any one or more additive elements selected from Si, P, and Zr.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04193967A (en) * | 1990-11-27 | 1992-07-14 | Kobe Steel Ltd | Surface treated metallic material and its manufacture |
JP2004202988A (en) * | 2002-12-26 | 2004-07-22 | Nisshin Steel Co Ltd | Clear black coated metal plate utilizing appearance of metallic material |
JP2007131906A (en) * | 2005-11-09 | 2007-05-31 | Nippon Steel Corp | Zn-BASED ALLOY PLATED STEEL |
WO2015125887A1 (en) * | 2014-02-20 | 2015-08-27 | 新日鐵住金株式会社 | Plated steel |
JP2017218647A (en) * | 2016-06-09 | 2017-12-14 | 日新製鋼株式会社 | MOLTEN Zn-BASED PLATED STEEL SHEET HAVING LINEAR PATTERN |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6365086A (en) | 1986-09-06 | 1988-03-23 | Nippon Steel Corp | Black surface-treated steel sheet and its production |
WO2004094683A1 (en) * | 2003-04-18 | 2004-11-04 | Jfe Steel Corporation | Zinc hot dip galvanized steel plate excellent in press formability and method for production thereof |
JP4546848B2 (en) | 2004-09-28 | 2010-09-22 | 新日本製鐵株式会社 | High corrosion-resistant Zn-based alloy plated steel with hairline appearance |
WO2012030726A1 (en) | 2010-08-30 | 2012-03-08 | Ak Steel Properties, Inc. | Galvanized carbon steel with stainless steel-like finish |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04193967A (en) * | 1990-11-27 | 1992-07-14 | Kobe Steel Ltd | Surface treated metallic material and its manufacture |
JP2004202988A (en) * | 2002-12-26 | 2004-07-22 | Nisshin Steel Co Ltd | Clear black coated metal plate utilizing appearance of metallic material |
JP2007131906A (en) * | 2005-11-09 | 2007-05-31 | Nippon Steel Corp | Zn-BASED ALLOY PLATED STEEL |
WO2015125887A1 (en) * | 2014-02-20 | 2015-08-27 | 新日鐵住金株式会社 | Plated steel |
JP2017218647A (en) * | 2016-06-09 | 2017-12-14 | 日新製鋼株式会社 | MOLTEN Zn-BASED PLATED STEEL SHEET HAVING LINEAR PATTERN |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021181630A (en) * | 2019-04-17 | 2021-11-25 | 日本製鉄株式会社 | Zinc-based plated steel sheet |
JP7207472B2 (en) | 2019-04-17 | 2023-01-18 | 日本製鉄株式会社 | Galvanized steel sheet |
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