WO2018131681A1 - Tôle revêtue - Google Patents

Tôle revêtue Download PDF

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Publication number
WO2018131681A1
WO2018131681A1 PCT/JP2018/000650 JP2018000650W WO2018131681A1 WO 2018131681 A1 WO2018131681 A1 WO 2018131681A1 JP 2018000650 W JP2018000650 W JP 2018000650W WO 2018131681 A1 WO2018131681 A1 WO 2018131681A1
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WO
WIPO (PCT)
Prior art keywords
coating film
metal plate
coated metal
coating
chemical conversion
Prior art date
Application number
PCT/JP2018/000650
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English (en)
Japanese (ja)
Inventor
史生 柴尾
雅義 永冨
Original Assignee
新日鐵住金株式会社
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Application filed by 新日鐵住金株式会社 filed Critical 新日鐵住金株式会社
Priority to JP2018521447A priority Critical patent/JP6659838B2/ja
Publication of WO2018131681A1 publication Critical patent/WO2018131681A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • the present invention relates to a coated metal plate, and more particularly, to a painted metal plate that can increase whiteness while suppressing a decrease in glossiness.
  • the painted metal plate is used for electrical machinery and building materials.
  • pre-coated steel sheets that are pre-colored before processing are often used.
  • a zinc-based plated steel sheet is used as a base plate, and multiple layers are formed by performing each process of pretreatment (chemical conversion treatment, etc.), lower layer coating application, baking, upper layer coating application, baking, etc. A coating film is formed.
  • chromium compounds have been added to the chemical conversion coating and the lower coating to improve the corrosion resistance.
  • a rust preventive pigment is added to the lower layer coating film of the coating film having a plurality of layers.
  • search for useful compounds, mainly inorganic compounds, and studies on practical application are underway.
  • the rust preventive agent include calcium-modified silica, aluminum phosphate, and magnesium phosphate.
  • the chemical conversion coating has adhesion
  • the lower coating has adhesion and corrosion resistance
  • the upper coating has design, scratch resistance, stain resistance, chemical resistance, solvent resistance, etc. Each is required.
  • the pre-coated steel sheet is generally manufactured by a coating process that undergoes a number of steps to form a coating film as described above, unlike the process of forming a plating layer.
  • a coating process that undergoes a number of steps to form a coating film as described above, unlike the process of forming a plating layer.
  • studies have been made on making the coating film thinner, reducing the number of coating films, or making the coating film one layer.
  • Patent Document 1 discloses a resin-coated metal plate having a predetermined composite plating film layer, a chemical conversion treatment film layer, and a resin coating layer, and having excellent corrosion resistance and workability.
  • Patent Document 2 discloses a precoated steel sheet having a base treatment layer containing an organic resin, titanium oxide and tannin or tannic acid simultaneously on at least one surface of the steel sheet, and a coating layer containing titanium oxide as a white pigment. .
  • Patent Document 3 discloses a precoated steel sheet having a zinc-based plating layer, a chemical conversion coating, and a white coating film, and including titanium oxide and calcium-modified silica as a rust preventive pigment in the white coating film.
  • a pre-coated steel sheet having a colored coating instead of a white coating may add a white pigment so as to increase the whiteness of the coating for the purpose of toning. Even in such a case, when a white pigment is added to the coating film, the glossiness of the coating film decreases due to the above-described reason.
  • This invention is made in view of the said problem, and makes it a subject to provide the coating metal plate which can raise whiteness, suppressing the fall of glossiness.
  • the present inventors have increased the whiteness of the coating film while suppressing a decrease in glossiness by arranging a flat portion and a plurality of concave portions on the surface of the coating film. I found out that I can.
  • the coated metal plate according to one aspect of the present invention includes a metal plate and a coating film positioned on at least one plate surface of the metal plate, and the coating film is disposed on the outermost surface. And having a flat portion and a plurality of concave portions on the surface thereof, the average diameter of the concave portions is 0.20 to 4.0 ⁇ m, and the average depth of the concave portions is 20 to 200 nm.
  • the number density of the recesses with respect to the surface of the coating film may be 1 ⁇ 10 4 to 1 ⁇ 10 6 pieces / mm 2 .
  • the area ratio of the recesses to the surface of the coating film may be 1 to 40%.
  • the area ratio of the recesses to the surface of the coating film may be 20 to 40%.
  • the contour length L 1 of the concave portion, the circle of the recess when viewed the coating film from a thickness direction, the contour length L 1 of the concave portion, the circle of the recess The number of the concave portions satisfying 1.0 ⁇ L 1 / L 2 ⁇ 3.0 with respect to the circumferential length L 2 obtained from the equivalent diameter may be 95% or more.
  • the concave portion may have a convex portion on an inner surface thereof.
  • the average diameter of the protrusions is 0.1 to 1.5 ⁇ m, and the average height of the protrusions is It may be 5 to 90 nm.
  • the area ratio of the flat portion with respect to the surface of the coating film may be 60 to 99%.
  • the area ratio of the flat portion with respect to the surface of the coating film may be 60 to 80%.
  • the average surface roughness Ra of the flat portion may be less than 20 nm.
  • the thickness of the coating film may be 8.0 to 30 ⁇ m.
  • the coating film has a white pigment, and the content of the white pigment in the coating film is 40 to 70% by mass. It may be.
  • the coating film has a phosphoric acid-based anticorrosive pigment, and the phosphoric acid-based anticorrosive pigment is applied to the coating film. The content may be 1 to 15% by mass.
  • the coated metal plate according to any one of (1) to (13) may further include a chemical conversion treatment layer between the metal plate and the coating film.
  • FIG. 1 is a schematic cross-sectional view of a painted metal plate according to the present embodiment
  • FIG. 2 is a schematic plan view of the painted metal plate.
  • FIG. 1 shows a cut surface in which the plate thickness direction and the cutting direction are parallel to each other.
  • a coated metal plate 1 shown in FIG. 1 includes a metal plate 11, a chemical conversion treatment layer 13 disposed on one plate surface of the metal plate 11, and a coating film 15 disposed on the chemical conversion treatment layer 13.
  • the metal plate 11 is a substrate of the painted metal plate 1. Examples of the metal plate 11 include various metal plates such as steel (iron-based alloy), aluminum and its alloys, magnesium and its alloys.
  • Metal plate 11 Examples of the steel plate used for the metal plate 11 include well-known plated steel plates such as zinc-based plated steel plates and aluminum-based plated steel plates.
  • the base steel plate of the plated steel plate may be a normal steel plate (carbon steel) or a steel plate (alloy steel) containing an additive element such as chromium.
  • the base steel plate is preferably a steel plate in which the type and amount of additive elements and the metal structure are appropriately controlled so as to have a desired formability followability.
  • a zinc-based plating layer of a zinc-based plated steel sheet for example, a plating layer made of zinc, zinc, and at least one of aluminum, cobalt, tin, nickel, iron, chromium, titanium, magnesium, manganese, zirconium and vanadium
  • Known plating layers such as composite plating layers and various zinc-based alloy plating layers containing other metal elements or non-metal elements (for example, quaternary alloy plating layers with zinc, aluminum, magnesium, and silicon) can be used.
  • the other alloy components are not particularly limited except that the zinc-based plating layer contains the most zinc.
  • these zinc-based plating layers further include, as a small amount of different metal elements or impurities, cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, Copper, cadmium, arsenic and the like may be included, and inorganic substances such as silica, alumina, titania and the like may be included.
  • the plating solution for forming the plating layer may contain an organic additive (for example, diallylamine polymer, diallyldialkylammonium, etc.), and the plating layer to be formed It may contain carbon resulting from these organic additives.
  • examples of the galvanized steel sheet used for the metal plate 11 include a hot dip galvanized steel sheet, an electrogalvanized steel sheet, a zinc-nickel alloy plated steel sheet, and an alloyed hot dip galvanized steel sheet.
  • Examples of the aluminum-based plating layer of the aluminum-based plated steel sheet include a plating layer made of aluminum, an alloy plating layer of aluminum and at least one of silicon, zinc, and magnesium (for example, an alloy plating layer of aluminum and silicon, aluminum and the like).
  • a plating layer made of aluminum an alloy plating layer of aluminum and at least one of silicon, zinc, and magnesium (for example, an alloy plating layer of aluminum and silicon, aluminum and the like).
  • Well-known plating layers such as a zinc alloy plating layer, a ternary alloy plating layer of aluminum, silicon and magnesium
  • the other alloy components are not particularly limited except that the aluminum-based plating layer contains the most aluminum.
  • the zinc-based plated steel sheet and the aluminum-based plated steel sheet used for the metal plate 11 are combined with other types of plating layers (for example, iron plating layer, iron-phosphorus alloy plating layer, nickel plating layer, cobalt plating layer, etc.). It may be a multi-layer plated steel sheet.
  • the method for forming the plated layer of the plated steel sheet is not particularly limited.
  • electroplating, electroless plating, hot dipping, vapor deposition plating, dispersion plating, or the like can be used.
  • the plating layer can be formed by either a continuous method or a batch method. Further, after the plating layer is formed, a process such as a zero spangle process that is a uniform appearance process, an annealing process that is a modification process of the plating layer, and a temper rolling for adjusting the surface state or material may be performed.
  • the chemical conversion treatment layer 13 may be arrange
  • the chemical conversion treatment layer 13 is a film formed by performing chemical conversion treatment on the surface (plate surface) of the metal plate 11.
  • the chemical conversion treatment layer 13 improves the adhesion between the metal plate 11 and the coating film 15 by being interposed between the metal plate 11 and the coating film 15.
  • Such a chemical conversion treatment layer 13 is not particularly limited.
  • at least one selected from the group consisting of silica, a silane coupling agent, tannin, tannic acid, a zirconium compound, and a titanium compound, a polyester resin examples include a film formed using a composition (chemical conversion solution) containing at least one selected from the group consisting of urethane resins, epoxy resins, and acrylic resins.
  • the chemical conversion treatment layer 13 composed of such a film is particularly excellent in adhesion between the metal plate 11 and the coating film 15.
  • the adhesion amount of the chemical conversion treatment layer 13 is not particularly limited, and is preferably 10 to 800 mg / m 2 , more preferably 100 to 700 mg / m 2 .
  • the adhesion amount of the chemical conversion layer 13 is within the above range, the chemical conversion treatment layer 13 can be prevented from cohesive failure while sufficiently improving the corrosion resistance and the coating film adhesion.
  • the thickness of the chemical conversion treatment layer 13 is not particularly limited, and may be, for example, 0.005 to 0.7 ⁇ m.
  • the coating film 15 is a film that is located on at least one plate surface of the metal plate 11 and constitutes the outermost surface of the coated metal plate 1. As shown in FIGS. 1 and 2, the coating film 15 has a flat portion 151 and a plurality of concave portions 153 on its surface (film surface). As shown in FIG. 2, the plurality of recesses 153 are irregularly formed on the surface of the coating film 15 and form so-called substantially circular dimples.
  • the coating film 15 has a plurality of recesses 153 that contribute to the whiteness in addition to the flat portion 151 that contributes to the glossiness, so that it is possible to increase the whiteness while suppressing a decrease in the glossiness.
  • the glossiness and whiteness of the coating film 15 can be made sufficiently high.
  • the conventional coating film will be described.
  • the coating film which consists of a flat part which does not have a recessed part, it originates in a flat part, and since the regular reflection component with respect to incident light is large, it becomes a high glossiness value.
  • the diffuse reflection component is reduced accordingly, the whiteness becomes a low value.
  • the diffuse reflection component with respect to incident light increases in the entire area of the coating film surface (film surface). Becomes a high value.
  • the specular reflection component is reduced in the entire region of the film surface, so that the glossiness becomes a low value.
  • whiteness and glossiness have a trade-off relationship.
  • the coating film 15 includes a flat portion 151 and a plurality of concave portions 153.
  • incident light can be irregularly reflected by the geometric action of the recess 153.
  • the whiteness of the coating film 15 can be increased by the presence of the concave portion 153 separately from the effect of irregularly reflecting incident light by the white pigment.
  • the coated metal plate 1 it is possible to increase the whiteness of the coating film 15 due to the presence of the recess 153 and to maintain the glossiness of the coating film 15 due to the presence of the flat portion 151.
  • the coating film 15 becomes a coating film in which the whiteness is increased and the decrease in the glossiness is suppressed as compared with the conventional coating film in which the concave portion 153 is not present.
  • the color of the coating film 15 is not particularly limited.
  • the whiteness and glossiness of the coating film 15 can be simultaneously increased.
  • the white film is not added to the coating film 15 due to the presence of the recess 153 without adding an excessive white pigment, that is, while avoiding a decrease in the glossiness of the coating film 15. Can be given.
  • the average diameter of the recesses 153 is 0.20 to 4.0 ⁇ m.
  • the lower limit of the average diameter of the recess 153 is 0.7 ⁇ m, and preferably 0.9 ⁇ m.
  • the upper limit of the average diameter of the recess 153 is 3.0 ⁇ m, and preferably 2.5 ⁇ m.
  • the recess 153 can be specified as follows. First, using an atomic force microscope (AFM), the height data of the surface irregularities in a sample area of 10 ⁇ 10 ⁇ m including the entire contour of the concave portion 153 is 512 horizontal points ⁇ 512 vertical points (total 262144 points). ) Measure and record. Data of 110 points is extracted from the highest height data, and the arithmetic average value of 100 points excluding the top 10 points (10 high data points) is set as the reference height. The depth distance from the reference height toward the metal plate 11 is classified into a point that is 10 nm or less and a point that is more than 10 nm.
  • AFM atomic force microscope
  • a collective region in which the points exceeding 10 nm are formed with 99% or more is defined as a recess 153.
  • the gathering region that is the recess 153 may include, as an abnormal point, a point having a depth distance of 10 nm or less of less than 1%.
  • the concave portion 153 is a collective region including at least 60 points greater than 10 nm.
  • the area S of the recesses 153 including the entire contour is obtained by image processing.
  • This area S is the area of the recess 153 when the coating film 15 is viewed from the thickness direction.
  • the diameter D (equivalent circle diameter) of the recess 153 when the recess 153 is regarded as a perfect circle is obtained by the following equation.
  • the 10 ⁇ 10 ⁇ m AFM observation described above is performed at at least 20 locations, and each obtained from each observation surface
  • the arithmetic average value of the diameter D of the recess 153 is defined as the average diameter of the recess 153.
  • the average depth of the recess 153 is 20 to 200 nm.
  • the lower limit of the average depth of the recess 153 is 40 nm, and preferably 70 nm.
  • the emission of light from the inside of the concave portion 153 to the outside is limited in shape, so that incident light cannot be sufficiently irregularly reflected.
  • the upper limit of the average depth of the recess 153 is 150 nm, and preferably 120 nm.
  • each concave portion 153 110 points are extracted from the deeper depth data in the concave portion 153 specified by the above-described method, and 100 points excluding the top 10 points (deep data 10 points) are extracted. It can be determined by the height difference between the arithmetic average value and the reference height. Further, at the center of the plate surface excluding the range of 100 mm from the outermost edge of the coated metal plate 1, the above-mentioned 10 ⁇ 10 ⁇ m AFM observation is performed at at least 20 locations, and the depth of each recess 153 obtained from each observation surface Is the average depth of the recesses 153.
  • the recessed part 153 may have the convex part 155 on the inner surface.
  • incident light can be preferably irregularly reflected by the geometrical action of the convex portion 155. Therefore, it becomes possible to give whiteness to the coating film 15 without adding excessive white pigment, that is, while avoiding a decrease in the glossiness of the coating film 15.
  • the convex portion 155 is not shown for easy viewing of the drawing.
  • the average diameter of the convex portion 155 is not particularly limited. For example, it is more preferable that the average diameter of the convex portion 155 is 0.1 to 1.5 ⁇ m, and incident light can be irregularly reflected.
  • the lower limit of the average diameter of the convex portion 155 is 0.2 ⁇ m, and preferably 0.3 ⁇ m.
  • the upper limit of the average diameter of the convex part 155 is 1.0 ⁇ m, and preferably 0.7 ⁇ m.
  • the average diameter of the convex portion 155 is preferably 1.5 to 60% with respect to the average diameter of the concave portion 153.
  • the lower limit of the ratio of the average diameter of the convex portion 155 to the average diameter of the concave portion 153 is 10%, and preferably 20%.
  • the upper limit of the ratio of the average diameter of the convex portion 155 to the average diameter of the concave portion 153 is 50%, and preferably 40%.
  • the average height of the convex portion 155 is not particularly limited. For example, when the average height of the convex portions 155 is 5 to 90 nm, it is more preferable that incident light can be irregularly reflected.
  • the lower limit of the average height of the convex portions 155 is 15 nm, and preferably 25 nm.
  • the upper limit of the average height of the convex part 155 is 70 nm, and it is preferable that it is 50 nm.
  • the convex portion 155 can be determined as follows. First, based on the shape of the recess 153 specified by the above method, the center of gravity (geometric center) of the recess 153 when the coating film 15 is viewed from the thickness direction is obtained. Ten cut surfaces parallel to the plate thickness direction of the coated metal plate 1 are obtained while rotating by 18 degrees around the center of gravity. The two-dimensional profile of the concave portion 153 and the convex portion 155 appearing on each cutting plane is divided into two left-side and right-side two-dimensional profiles with the center of gravity of the concave portion 153 as a reference.
  • One local point having the deepest depth (the difference in height from the reference height is large) is specified from the local minimum points included in the left two-dimensional profile, and similarly, the local minimum point included in the right two-dimensional profile is the highest.
  • One minimum point having a deep depth (large difference in height from the reference height) is identified. That is, two minimum points are specified for one cut surface. Two minimum points are specified for each of the 10 cut surfaces.
  • a decagon representing the outline of the convex portion 155 is obtained. Can do.
  • a region surrounded by the decagon is referred to as a convex portion 155.
  • the area s of the protrusions 155 including the entire contour is obtained by image processing.
  • This area s is the area of the convex portion 155 when the coating film 15 is viewed from the thickness direction.
  • the diameter d (equivalent circle diameter) of the convex portion 155 when the convex portion 155 is regarded as a perfect circle is obtained by the following equation.
  • the above-mentioned 10 ⁇ 10 ⁇ m AFM observation is performed at at least 20 locations, and the diameter d of each convex portion 155 obtained from each observation surface
  • the arithmetic average value is defined as the average diameter of the convex portions 155.
  • the height of the convex portion 155 is obtained from the above 10 cut surfaces.
  • one maximum point having the highest height (small difference in height from the reference height) from the maximum point included in the region of the convex portion 155 is specified.
  • One maximum point is specified for each of the 10 cut surfaces.
  • the highest point is defined as the top of the convex portion 155.
  • the lowest point is set as the deepest portion of the convex portion 155.
  • the difference (distance along the plate thickness direction) between the top portion and the deepest portion is defined as the height of the convex portion 155.
  • the above-mentioned 10 ⁇ 10 ⁇ m AFM observation is performed at at least 20 locations, and the height of each convex portion 155 obtained from each observation surface
  • the arithmetic average value is defined as the average height of the convex portions 155.
  • the recesses 153 are irregularly arranged. However, in the coated metal plate 1 according to this embodiment, a plurality of recesses 153 formed in the coating film 15 may be aligned. .
  • the density of the recesses 153 is not particularly limited.
  • the number density of the recesses 153 with respect to the surface of the coating film 15 is more preferably 1 ⁇ 10 4 to 1 ⁇ 10 6 pieces / mm 2 , and whiteness can be increased while suppressing a decrease in glossiness.
  • the lower limit of the number density of the recesses 153 is 3 ⁇ 10 4 pieces / mm 2 , and preferably 9 ⁇ 10 4 pieces / mm 2 .
  • the upper limit of the number density of the recesses 153 is 1.5 ⁇ 10 5 pieces / mm 2 , and preferably 1.2 ⁇ 10 5 pieces / mm 2 .
  • the density of the recessed part 153 is the number density of the recessed part 153 with respect to the surface of the coating film 15 when the coating film 15 is seen from a plate thickness direction.
  • the number density is obtained based on the recess 153 specified by the above method.
  • the above-mentioned 10 ⁇ 10 ⁇ m AFM observation is performed at at least 20 locations so that the observation visual field is continuous at the central portion of the plate surface excluding the range of 100 mm from the outermost edge of the coated metal plate 1, and the concave portion 153 with respect to the observation surface is formed.
  • the number of existence is obtained, and the value obtained by dividing the number of existence by the observation area is defined as the density of the recesses 153.
  • the area ratio of the recess 153 is not particularly limited.
  • the area ratio of the recesses 153 with respect to the surface of the coating film 15 is 1 to 40%, and the whiteness can be increased while suppressing a decrease in glossiness.
  • the lower limit of the area ratio of the recess 153 is preferably 5%, 8%, or 20%.
  • the upper limit of the area ratio of the recessed part 153 is 35%, and it is preferable that it is 25%.
  • the area ratio of the recessed part 153 is the ratio of the recessed part 153 with respect to the surface of the coating film 15 when the coating film 15 is seen from a plate thickness direction.
  • the area ratio of the recess 153 is obtained by image processing based on the height data of the surface unevenness using AFM.
  • the above-mentioned 10 ⁇ 10 ⁇ m AFM observation is performed at at least 20 locations so that the observation visual field is continuous at the central portion of the plate surface excluding the range of 100 mm from the outermost edge of the coated metal plate 1, and the concave portion 153 for each observation surface.
  • the area ratio is calculated, and this arithmetic average value is taken as the area ratio of the recess 153.
  • the recess 153 preferably has a substantially circular outline. Specifically, the circumference when viewed coating 15 from a thickness direction, with respect to all of the recesses 153, the contour length L 1 of the recess 153 is determined from the diameter D of the recess 153 (circle equivalent diameter) It is preferable that the number of the concave portions 153 satisfying 1.0 ⁇ L 1 / L 2 ⁇ 3.0 with the length L 2 is 95% or more (and 100% or less). It is more preferable when the concave portion 153 satisfies the above conditions, and the whiteness can be increased while suppressing a decrease in the glossiness.
  • the lower limit of L 1 / L 2 When the lower limit of L 1 / L 2 is 1.0, it means that the recess 153 is a perfect circle. However, since it is industrially difficult to control the concave portion 153 to be a perfect circle, the lower limit of L 1 / L 2 may be 1.2, 1.4, or 1.6. On the other hand, in order to preferably achieve both high whiteness and high glossiness, the upper limit of L 1 / L 2 may be 2.8, 2.6, 2.4, or 2.0.
  • the contour length L 1 and the circumferential length L 2 of the recessed portion 153 can be specified as follows. Based on the recess 153 identified as described above, to identify the contour of the recess 153, obtaining the contour length L 1 of the recessed portion 153 by the image processing.
  • the contour length L 1 is the length of the contour of the recess 153 when viewed coating 15 from a thickness direction. Further, based on the diameter D of the recess 153, when regarded recesses 153 and perfect circle, the circumferential length L 2 of the recessed portion 153 obtained by the following equation.
  • L 2 ⁇ ⁇ D ( ⁇ : pi)
  • the above 10 ⁇ 10 ⁇ m AFM observation is performed in at least 20 locations at the center of the plate surface excluding the range of 100 mm from the outermost edge of the coated metal plate 1, and 95% in number of the recesses 153 including the entire contour. It is preferable that the above-mentioned recessed part 153 satisfies 1.0 ⁇ L 1 / L 2 ⁇ 3.0.
  • the flat portion 151 on the surface of the coating film 15 contributes to the glossiness.
  • the average surface roughness Ra of the flat portion 151 is preferably less than 20 nm.
  • the lower limit of the average surface roughness Ra of the flat portion 151 is not particularly limited and is preferably as small as possible.
  • the lower limit of the average surface roughness Ra of the flat portion 151 may be 1 nm.
  • the upper limit of the average surface roughness Ra of the flat portion 151 is 18 nm, and preferably 16 nm.
  • the flat portion 151 is a region on the surface of the coating film 15 other than the concave portion 153 specified as described above. Further, the surface roughness Ra of the flat portion 151 is obtained based on the two-dimensional profile of the flat portion 151 that appears on the cut surface parallel to the plate thickness direction of the coated metal plate 1. The surface roughness Ra is determined from at least a reference length of 3 ⁇ m or more. The surface roughness of each flat portion 151 obtained from each observation surface is obtained by performing the above-mentioned 10 ⁇ 10 ⁇ m AFM observation at at least 20 locations in the central portion of the plate surface excluding the range of 100 mm from the outermost edge of the coated metal plate 1. The arithmetic average value of Ra is defined as the average surface roughness Ra of the flat portion 151.
  • the area ratio of the flat portion 151 is not particularly limited.
  • the area ratio of the flat portion 151 with respect to the surface of the coating film 15 is more preferably 60 to 99%, and the whiteness can be increased while suppressing a decrease in glossiness.
  • the lower limit of the area ratio of the flat portion 151 is 65%, and preferably 75%.
  • the upper limit of the area ratio of the flat portion 151 is preferably 95%, 92%, or 80%.
  • the area ratio of the flat portion 151 is the ratio of the flat portion 151 to the surface of the coating film 15 when the coating film 15 is viewed from the thickness direction.
  • the area ratio of the flat portion 151 is obtained by image processing based on the height data of the surface irregularities using AFM.
  • the above-mentioned 10 ⁇ 10 ⁇ m AFM observation is performed at at least 20 locations so that the observation visual field is continuous at the central portion of the plate surface excluding the range of 100 mm from the outermost edge of the coated metal plate 1, and the flat portion with respect to each observation surface
  • the area ratio of 151 is obtained, and this arithmetic average value is defined as the area ratio of the flat portion 151.
  • the thickness (film thickness) of the coating film 15 is not particularly limited.
  • the thickness of the coating film 15 is 8.0 to 30 ⁇ m, it is more preferable, and both high whiteness and high gloss can be preferably achieved.
  • the background color is a color that easily absorbs incident light, both the diffuse reflection component and the regular reflection component with respect to the incident light are small, so it is difficult to increase the whiteness and the glossiness at the same time.
  • the base color can be preferably concealed.
  • the minimum of the thickness of the coating film 15 is 10 micrometers, and it is preferable that it is 13 micrometers.
  • the upper limit of the thickness of the coating film 15 is 25 ⁇ m, and preferably 20 ⁇ m.
  • the constituent material of the coating film 15 is not particularly limited as long as the surface shape described above can be formed.
  • the coating film 15 can contain a pigment and resin, for example.
  • the pigment examples include white pigments, colored pigments and rust preventive pigments.
  • the coating film 15 contains a relatively large amount of white pigment, the coating film 15 becomes a white coating film.
  • a metal plate having a white coating film is required to have high whiteness and high glossiness from the viewpoints of application and design.
  • the coating film 15 includes the flat portion 151 and the plurality of concave portions 153, so that both high whiteness and high glossiness can be achieved.
  • the white pigment is not particularly limited.
  • the white pigment include rutile type or anatase type titanium oxide (TiO 2 ), CaSO 4 , MgSO 4 , BaSO 4 , Al 2 O 3 , Sb 2 O 3 , and ZnO. These white pigments may be used alone or in combination of two or more.
  • titanium oxide whose surface is coated with Al 2 O 3 , Sb 2 O 3 , ZnO or the like can also be used.
  • BaSO 4 , Al 2 O 3 and titanium oxide are preferable from the viewpoint of concealability and high whiteness.
  • the content of the white pigment in the coating film 15 is not particularly limited.
  • the coating film 15 preferably has a white pigment, and the content of the white pigment with respect to the coating film 15 is preferably 40 to 70% by mass.
  • the lower limit of the content of the white pigment is preferably 40% by mass, 45% by mass, or 50% by mass with respect to the total mass of the coating film 15.
  • the upper limit of the content of the white pigment is preferably 70% by mass, 65% by mass, or 60% by mass with respect to the total mass of the coating film 15.
  • the colored pigment is not particularly limited.
  • a known pigment can be appropriately selected according to the intended color of the coating film 15.
  • examples of colored pigments include brown, aluminum, mica, carbon black, and cobalt blue.
  • the content of the colored pigment in the coating film 15 is not particularly limited, and can be appropriately selected according to the intended color of the coating film 15.
  • the coating film 15 preferably contains a rust preventive pigment as a pigment.
  • a rust preventive pigment the corrosion resistance of the whole coated metal plate 1 can be improved.
  • the antirust pigment is not particularly limited.
  • the rust preventive pigment include a phosphoric acid rust preventive pigment and a silica rust preventive pigment.
  • phosphoric acid-based rust preventive pigments are preferred because the corrosion resistance of the coated metal plate 1 can be sufficiently improved while preventing a decrease in glossiness.
  • Examples of phosphoric acid-based anticorrosive pigments include phosphates, orthophosphates and polyphosphates of metals such as magnesium and aluminum.
  • Examples of the phosphoric acid rust preventive pigment containing magnesium include magnesium dihydrogen phosphate (for example, manufactured by Junsei Chemical Co., Ltd.).
  • Examples of the phosphoric acid-based anticorrosive pigment containing aluminum include aluminum dihydrogen tripolyphosphate and a surface-treated product thereof using magnesium, calcium or zinc.
  • K-WHITE trademark
  • K-WHITE / # 105 zinc treatment
  • K-WHITE / Ca650 calcium treatment
  • K-WHITE / K-G105 magnesium treatment
  • phosphoric acid-based anticorrosive pigments particularly phosphoric acid-based anticorrosive pigments containing magnesium are preferable because of less reduction in glossiness due to addition.
  • the content of the phosphoric acid anticorrosive pigment in the coating film 15 is not particularly limited.
  • the coating film 15 has a phosphoric acid anticorrosive pigment and the content of the phosphoric acid anticorrosive pigment with respect to the coating film 15 is 1 to 15% by mass.
  • the lower limit of the content of the phosphoric acid anticorrosive pigment is preferably 1% by mass, 2% by mass, or 3% by mass with respect to the total mass of the coating film 15.
  • the upper limit of the content of the phosphoric acid anticorrosive pigment is preferably 15% by mass, 10% by mass, or 8% by mass with respect to the total mass of the coating film 15.
  • Resin functions as a binder for binding components such as pigments.
  • the resin constitutes the surface of the coating film 15.
  • the resin is not particularly limited.
  • the resin include an epoxy resin, a polyester resin, an acrylic resin, a urethane resin, a vinyl chloride resin, a fluorine resin, and a melamine resin.
  • the melamine resin include alkylated melamine resins such as methylated melamine resins and butylated melamine resins. These resins may be used alone or in combination of two or more.
  • the resin preferably contains an alkylated melamine resin, particularly a methylated melamine resin.
  • the coating film 15 is a white coating film
  • a polyester resin as the main resin in order to have excellent whiteness, adhesion, chemical resistance, and corrosion resistance.
  • the polyester resin preferably has a number average molecular weight of 3000 to 30000 and a glass transition temperature Tg of about 0 to 80 ° C.
  • the lower limit of the number average molecular weight is 5000, preferably 9000.
  • the upper limit of the number average molecular weight is 25000, preferably 23000.
  • the minimum of glass transition temperature Tg is 10 degreeC, and it is preferable that it is 20 degreeC.
  • the upper limit of the glass transition temperature Tg is 70 ° C, preferably 60 ° C.
  • the content of the resin in the coating film 15 is not particularly limited.
  • the lower limit of the resin content is preferably 30% by mass, 35% by mass, or 40% by mass with respect to the total mass of the coating film 15.
  • the lower limit of the resin content is preferably 60% by mass, 55% by mass, or 50% by mass with respect to the total mass of the coating film 15.
  • a melamine resin especially methylated melamine are preferable.
  • Isocyanate can also be used as a curing agent.
  • the coating film 15 may further contain a lubricant.
  • a lubricant When the coating film 15 contains a lubricant, effects such as an improvement in press workability and a reduction in handling scratches due to a reduction in the friction coefficient of the coating film surface can be obtained.
  • the lubricant include polyethylene, polypropylene, and fluorine compounds. These can be used alone or in combination of two or more depending on the processing application.
  • the content of the lubricant is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass with respect to the total mass of the coating film 15.
  • the coating film 15 may further contain a coupling agent.
  • a coupling agent By including the coupling agent in the coating film 15, it is possible to prevent a decrease in processing adhesion due to the addition of the rust preventive pigment.
  • a coupling agent include Si-based coupling agents and Ti-based coupling agents.
  • the addition amount of the Si-based and / or Ti-based coupling agent in the coating film 15 is not particularly limited.
  • the addition amount of the coupling agent can be 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the resin.
  • the coated metal plate 1 according to the present embodiment described above has a flat portion 151 and a plurality of concave portions 153 on the surface of the coating film 15, so that the whiteness can be increased while suppressing a decrease in glossiness.
  • Such a coated metal plate 1 is particularly useful as a painted metal plate that requires both high whiteness and high gloss.
  • the coated metal plate 1 that is adjusted so that whiteness is increased while the glossiness of the surface is high in this way is applied to, for example, an electric machine appliance such as a household electric machine appliance (home appliance) or a building material.
  • an electric machine appliance such as a household electric machine appliance (home appliance) or a building material.
  • the painted metal plate 1 can be a painted metal plate for electrical machine appliances, particularly a painted metal plate for household electrical machine appliances, or a painted metal plate for building materials.
  • the electric machine apparatus may have the above-described painted metal plate 1
  • the building material may have the above-described painted metal plate 1.
  • FIG. 3 is a schematic cross-sectional view of a painted metal plate 1A according to a modification of the above embodiment.
  • the chemical conversion treatment layer 13 was arrange
  • FIG. 4 is a schematic cross-sectional view of a painted metal plate 1B according to a modification of the above embodiment.
  • the coated metal plate 1 ⁇ / b> B includes a primer (undercoat coating film) 17 between the chemical conversion treatment layer 13 and the coating film 15.
  • the primer 17 improves the adhesion between the chemical conversion layer 13 and the coating film 15 and improves the corrosion resistance of the coated metal plate 1B by including, for example, a rust preventive pigment.
  • the primer 17 contains a rust preventive pigment
  • the rust preventive pigment in the coating film 15 can be omitted or reduced.
  • the coating film 15 can be configured with a composition for the purpose of design such as toning
  • the primer 17 can be configured with a composition for the purpose of improving corrosion resistance, and the functions of the layers can be separated.
  • the material constituting the primer 17 is not particularly limited.
  • various materials exemplified for the coating film 15 can be used as the primer 17.
  • the coated metal plate may have a chemical conversion treatment layer on the side where the coating film is not formed.
  • the coating metal plate may have a coating film on both surfaces.
  • the method of manufacturing the coated metal plate 1 according to this embodiment is as follows: A first step of applying a paint containing a resin and a liquid medium on the metal plate 11 (paint coating step); Removing a part or all of the liquid medium from the coating material, and forming a coating film while contacting an atmosphere containing a solvent (liquid medium) with the coating material (coating film forming process); Have The absolute value of the difference between the solubility parameter of the resin and the solubility parameter of the solvent is 0.5 or more and less than 2.0; The partial pressure of the solvent in the atmosphere is 0.005 to 0.2 atm.
  • the manufacturing method of the coating metal plate 1 which concerns on this embodiment may have a chemical conversion treatment process which forms the chemical conversion treatment layer 13 on the at least one surface of the metal plate 11 prior to the said 1st process.
  • the manufacturing method of the coated metal plate 1 according to the present embodiment will be described in order.
  • the metal plate 11 is prepared. As the metal plate 11, those described above can be used.
  • chemical conversion treatment is performed on at least one plate surface of the metal plate 11 to form a chemical conversion treatment layer 13.
  • the composition (chemical conversion treatment liquid) containing the constituent material of the chemical conversion treatment layer 13 is applied on the surface of the metal plate 11, and the liquid medium is removed by heating or the like, and the chemical conversion treatment layer 13 is formed. It can be done by fixing.
  • the chemical conversion treatment liquid examples include liquids in which the above constituent materials are dispersed or dissolved in a liquid medium.
  • the content of the resin in the chemical conversion treatment liquid may be 1.0 to 100 g / L.
  • the lower limit of the resin content is 2.0 g / L, preferably 5.0 g / L.
  • the upper limit of the resin content is 80 g / L, and preferably 60 g / L.
  • the total content of one or more selected from the group consisting of silica, silane coupling agent, tannin, tannic acid, zirconium compound, and titanium compound in the chemical conversion treatment solution is 0.01-100 g / L. That's fine.
  • the lower limit of this content is 0.1 g / L, preferably 0.5 g / L.
  • the upper limit of this content is 80 g / L, and preferably 60 g / L.
  • the above chemical conversion treatment liquid can sufficiently improve the stability of the chemical conversion treatment liquid while sufficiently improving the corrosion resistance and coating film adhesion of the chemical conversion treatment layer 13.
  • the liquid medium of the chemical conversion treatment liquid is not particularly limited.
  • various known organic solvents and water can be used as the liquid medium.
  • the liquid medium of the chemical conversion treatment liquid is water, the chemical conversion treatment liquid is easy to handle.
  • the method for applying the chemical conversion treatment liquid to the metal plate 11 is not particularly limited.
  • roll coating, ringer roll coating, air spray, airless spray, dipping method, curtain coating, etc. can be employed as the coating method.
  • the removal of the liquid medium in the chemical conversion treatment liquid and the formation and fixing of the chemical conversion treatment layer 13 are not particularly limited.
  • the chemical conversion treatment layer 13 can be formed by heating.
  • the heating method is not particularly limited.
  • a known method such as a hot air heating method, an induction heating method, or a near infrared heating method can be used as the heating method.
  • the heating temperature may be 40 to 200 ° C., for example.
  • the lower limit of the heating temperature is preferably 50 ° C, and the upper limit of the heating temperature is preferably 180 ° C.
  • the heating time may be, for example, 0.5 to 20 seconds.
  • the lower limit of the heating time is preferably 1 second, and the upper limit of the heating time is preferably 15 seconds.
  • the coating film 15 is formed on the metal plate 11 on which the chemical conversion treatment layer 13 is formed, that is, on the chemical conversion treatment layer 13.
  • a paint containing a resin and a liquid medium is applied on the metal plate 11 (first step).
  • the coating material only needs to contain a resin and a liquid medium, and preferably contains each component of the coating film 15 described above.
  • the blending ratio of each component in the paint can be appropriately selected and changed according to the composition of the coating film 15 to be formed and the physical properties such as the viscosity range necessary for application.
  • the liquid medium contained in the paint is not particularly limited.
  • various organic solvents such as ketone solvents such as cyclohexanone and methyl ethyl ketone, aromatic hydrocarbon solvents such as xylene, ether solvents such as dioxane, alcohol solvents such as n-butanol and ethanol, and water Is mentioned.
  • ketone solvents such as cyclohexanone and methyl ethyl ketone
  • aromatic hydrocarbon solvents such as xylene
  • ether solvents such as dioxane
  • alcohol solvents such as n-butanol and ethanol
  • water Is mentioned mentioned.
  • the absolute value of the difference between the solubility parameter of the liquid medium and the solubility parameter of the resin is 0.5 or more and less than 2.0.
  • an organic solvent having a predetermined solubility parameter difference can be brought into contact with the paint in a second step described later.
  • the lower limit of the absolute value of the difference in solubility parameter described above is 0.6, and preferably 0.7.
  • the upper limit of the absolute value of the difference between the solubility parameters described above is less than 1.8 and preferably less than 1.5.
  • solubility parameter of the liquid medium (solvent) and the solubility parameter of the resin can be experimentally determined based on the following cloud point titration method.
  • a poor solvent having a high SP value and a poor solvent having a low SP value are dropped into the sample solution, and the amount of the poor solvent required until turbidity is determined.
  • the above operation is performed, and the amount (volume) of the poor solvent required until turbidity is obtained for each.
  • the SP value ⁇ of the solution can be obtained by substituting the volume of the poor solvent required until the turbidity obtained and the SP value of the poor solvent into the following Equation 1.
  • VmL Volume of the poor solvent having a low SP value
  • Vmh Volume of the poor solvent having a high SP value
  • ⁇ mL SP value of the poor solvent having a low SP value
  • ⁇ mh SP value of the poor solvent having a high SP value
  • the method of applying the paint to the metal plate 11 is not particularly limited.
  • a coating method roll coating, ringer roll coating, air spray, airless spray, dipping method, curtain coating, electrostatic coating method, or the like can be employed.
  • the coating film 15 is formed by removing at least a part of the liquid medium from the paint while bringing the solvent into contact with the paint (second step).
  • the absolute value of the difference between the solubility parameter of the resin and the solubility parameter of the solvent is 0.5 or more and less than 2.0.
  • the reason why the plurality of recesses 153 are formed on the surface of the coating film 15 is unknown at this time, but is estimated as follows.
  • the resin contained in the paint greatly contributes to the formation of the surface shape of the coating film 15 as a binder.
  • the viscosity of the paint greatly increases.
  • the paint containing the resin comes in contact with the solvent in other local parts while repelling the solvent on a part of the contact surface. Dissolve.
  • the portion dissolved by contact with the solvent becomes the recess 153.
  • the convex portion 155 is simultaneously formed in the concave portion 153 together with the formation of the concave portion 153. If necessary, the protrusion 155 may be mechanically or chemically removed from the recess 153.
  • the solvent uniformly contacts the paint surface and dissolves the paint uniformly.
  • the recess 153 is not formed.
  • the absolute value of the difference between the solubility parameter of the resin and the solubility parameter of the solvent is 2.0 or more, the surface of the paint repels the solvent too much, and the solvent is too concentrated on a local part. Coarse recesses are formed on the surface of the coating film 15.
  • the absolute value of the difference between the solubility parameter of the resin and the solubility parameter of the solvent may be 0.5 or more and less than 2.0.
  • the lower limit of the absolute value of the difference in solubility parameter described above is 0.6, and preferably 0.7.
  • the upper limit of the absolute value of the difference between the solubility parameters described above is less than 1.8 and preferably less than 1.5.
  • FIG. 5 is a schematic diagram showing a method of bringing a paint into contact with a solvent in the second step of the method for manufacturing the coated metal plate 1 according to the present embodiment.
  • the metal plate 11 to which the coating material 15A is applied is heated by an arbitrary heating method such as a hot air heating method, an induction heating method, a near infrared heating method, etc., and then introduced into the baking furnace 100 shown in FIG. Is called.
  • the baking furnace 100 has a chamber 101, and the chamber 101 forms a space 103 therein. Further, the chamber 101 is provided with an inlet 105 and an outlet 107 for the metal plate 11, an air supply port 109, and an exhaust port 111.
  • a heating blower 113 is disposed on the space 103 side upper portion of the chamber 101, and an air supply port 109 is connected to the heating blower 113.
  • the heating blower 113 sucks ambient air from the air supply port 109, heats it, and sends hot air in the direction of the arrow in the figure.
  • the paint 15A carried on the metal plate 11 is heated, and at least a part of the liquid medium is removed from the paint 15A.
  • the metal plate 11 coated with the coating material 15 ⁇ / b> A is continuously passed through the baking furnace, the vapor of the liquid medium stays in the space 103.
  • the coating film 15 in which the above-mentioned recessed part 153 was formed is obtained when the vapor
  • the solvent partial pressure in the space 103 of the chamber 101 is controlled when the coating film 15 is formed (cured) in order to form the plurality of recesses 153. .
  • the solvent partial pressure was less than 0.005 atm.
  • the amount of hot air supplied from the inlet 109, the amount of outside air flowing from the inlet 105, the amount of exhaust from the outlet 111, the amount of leakage from the outlet 107, And the partial pressure of the solvent in the space 103 (atmosphere) is intentionally controlled to 0.005 to 0.2 atm by changing the heating temperature in the heating blower 113 from the conventional conditions.
  • the coating material 15A (resin) and the solvent are preferably in contact with each other, and the recess 153 is preferably formed. At this time, the smoothness of the flat portion 151 is also increased. As a result, a flat portion 151 and a plurality of concave portions 153 are formed on the surface of the coating film 15.
  • the lower limit of the solvent partial pressure in the space 103 is preferably 0.008 atm, 0.010 atm, or 0.015 atm.
  • the upper limit of the solvent partial pressure in the space 103 is preferably 0.15 atm, 0.12 atm, or 0.1 atm.
  • the partial pressure of the solvent in the space 103 includes the amount of hot air supplied from the air supply port 109, the amount of outside air flowing from the inlet 105, the amount of exhaust from the exhaust port 111, the amount of leakage from the outlet 107, and the heating blower. Control by changing the heating temperature at 113.
  • the amount of hot air supplied from the inlet 109, the amount of outside air flowing from the inlet 105, the amount of exhaust from the outlet 111, the amount of leakage from the outlet 107, and the heating temperature at the heating blower 113 are as follows. Since these values change, each condition may be appropriately adjusted so that the solvent partial pressure in the space 103 according to the purpose is obtained.
  • the temperature in the space 103 in the baking furnace 100 is not particularly limited.
  • the ultimate temperature of the metal plate may be 100 to 300 ° C. as the atmospheric temperature in the space 103.
  • the minimum of the ultimate temperature of a metal plate is 150 degreeC, and it is preferable that it is 200 degreeC.
  • the upper limit of the reached temperature of the metal plate is 270 ° C, and preferably 250 ° C.
  • the heating time of the metal plate 11 carrying the paint 15A is not particularly limited.
  • the heating time of the metal plate 11 may be 10 to 120 seconds.
  • the lower limit of the heating time of the metal plate 11 is 12 seconds, and preferably 15 seconds.
  • the upper limit of the heating time of the metal plate 11 is 90 seconds, and preferably 60 seconds.
  • the coated metal plate 1 having the flat portion 151 and the plurality of concave portions 153 on the surface of the coating film 15 is obtained.
  • Each of the above steps can be performed in a continuous coating line equipped with an apparatus corresponding to the above steps, for example, a coil coating line or a sheet coating line. As a result, the production efficiency of the coated metal plate 1 is improved.
  • the manufacturing method of the coating metal plate 1 which concerns on this embodiment is not limited to the method mentioned above.
  • the solvent brought into contact with the paint may not be derived from the liquid medium contained in the paint.
  • a solvent to be brought into contact with the paint can be separately supplied and brought into contact with the paint.
  • the solvent made to contact with a coating material is not limited to a vapor-form solvent,
  • a liquid or solid solvent can be used suitably.
  • the solvent can be brought into contact with the coating film 15 (paint 15A) using a droplet applying device such as a spraying device or an ink jet device.
  • the conditions in the examples are one example of conditions adopted to confirm the feasibility and effects of the present invention.
  • the present invention is not limited to this one condition example.
  • the present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
  • the chemical conversion treatment layer was formed with respect to one plate surface of the metal plate by the following method. First, the chemical conversion treatment liquid was applied to one surface of the metal plate with a roll coater. Then, it heated so that the ultimate temperature (PMT: Peak Metal Temperature) of a metal plate might be set to 60 degreeC. The coating amount of the chemical conversion treatment liquid on the coated surface was applied so that the total coating amount of the dry film was 300 mg / m 2 . The adhesion amount of each chemical conversion treatment film was measured by fluorescent X-rays. As the chemical conversion treatment solution, a chromate-free chemical conversion treatment solution “CT-E300N” manufactured by Nippon Parkerizing Co., Ltd. was used.
  • CT-E300N chromate-free chemical conversion treatment solution manufactured by Nippon Parkerizing Co., Ltd.
  • white coating film was formed on the chemical conversion treatment layer of the metal plate by the following method.
  • white paints (paints 1 to 18) containing 17% by mass of a resin, 50% by mass of a liquid medium, 3.0% by mass of a rust preventive pigment, and 30% by mass of a white pigment as shown in Table 1 were prepared.
  • the solid content in the white paint was 50% by mass.
  • titanium oxide was used as the white pigment, and the content of titanium oxide in the total solid content was 60% by mass.
  • the blending ratio described in the column of resin and liquid medium indicates the blending ratio of each component in the resin and liquid medium, respectively.
  • polyester is polyester resin “GK-140” manufactured by Toyobo Co., Ltd.
  • Metal-based melamine is methylated melamine resin “Cymel 303” manufactured by Cytec Co., Ltd.
  • Butylated melamine Is a butylated melamine resin “Super Peckamine J-820-60” manufactured by DIC Corporation
  • Magnnesium Phosphate is magnesium dihydrogen phosphate manufactured by Junsei Chemical Co., Ltd. R. “Sealdex C303” manufactured by Grace, respectively, is shown.
  • Solvesso 100 is a solvent sold by ExxonMobil
  • Cyclohexanone is “Anone” manufactured by Sankyo Chemical
  • Dioxane is “1,4-Dioxane” manufactured by Sankyo Chemical
  • Methodyl ethyl ketone is “MEK” manufactured by Sankyo Chemical Co., Ltd.
  • o-xylene is “Orthoxylene” manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • “Ethanol” is “Ethanol manufactured by Sankyo Chemical Co., Ltd.”
  • N-butanol is “butanol” manufactured by Sankyo Chemical Co., Ltd.
  • the SP value (solubility parameter) of the resin or liquid medium shown in Table 1 was experimentally determined as follows. Each test temperature was 20 ° C. ⁇ SP value measurement of resin> 0.5 g of resin and cyclohexanone (manufactured by Kanto Chemical Co., Inc.) were mixed so as to be 10 mL. The sample solution was obtained by stirring with a stirrer to dissolve the resin in the mixture. Next, poor solvents having different SP values were added dropwise until the sample solution became turbid. ⁇ For liquid media> 10 mL of various liquid media were used as sample solutions. Next, poor solvents having different SP values were added dropwise until the sample solution became turbid.
  • the SP value ⁇ of the sample solution was obtained by substituting the volume of the poor solvent required until the turbidity obtained and the SP value of the poor solvent into the above-described formula 1.
  • n-hexane manufactured by Kanto Chemical Co., Inc.
  • water manufactured by Wako Pure Chemical Industries, Ltd.
  • the values described in the literature were used as the SP values of n-hexane and water.
  • the paints 1 to 18 shown in Table 1 were applied to the plate surface of the galvanized steel sheet having the chemical conversion coating so as to have a predetermined dry film thickness using a slide curtain coater. Then, after baking in a hot air heating type baking furnace as shown in FIG. 5 so that the PMT becomes 220 ° C., water-cooling treatment is performed, and the pre-coated steel plate having the desired white coating film is dried by air blow (painted metal plate) )
  • the plate feeding speed (LS: Line Speed) was 80 to 200 m / min, and the heating time in the baking furnace (plate passing time in the baking furnace) was 10 to 30 seconds.
  • the liquid medium in the white paint volatilizes and becomes a solvent and stays in the internal space of the baking furnace chamber.
  • the supply amount of hot air from the supply port, the inflow amount of outside air from the metal plate inlet, the exhaust amount from the exhaust port, the metal plate outlet were adjusted. Thereby, the contact to the white coating film of the solvent was possible.
  • the white coating film on the outermost surface of the obtained coated metal plate was observed.
  • the characteristics of the recesses the presence / absence of the recesses, the average diameter, the average depth, the number density, the area ratio, and the contour shape were measured.
  • the average height and average diameter were measured as the characteristic of the convex part on the inner surface of a concave part.
  • the area ratio and average surface roughness Ra were measured as features of the flat portion.
  • the thickness (film thickness) of the white coating film was measured.
  • the surface of the white coating film of the coated metal plate was scanned using an atomic force microscope (NanoScope IIIa, manufactured by Digital Instruments).
  • a Si SPM Sccanning Probe Microscope
  • the measurement range was 10 ⁇ m ⁇ 10 ⁇ m, and 2.5 ⁇ 2.5 ⁇ m as required.
  • the flat part, the recessed part, and the convex part were specified by the method mentioned above, and said characteristic was evaluated.
  • L 1 / L 2 was calculated for each recess from the contour length L 1 of the recess and the circumferential length L 2 obtained from the equivalent circle diameter of the recess. Then, for all of the recesses observed, the recess are satisfied 1.0 ⁇ L 1 / L 2 ⁇ 3.0, it was evaluated as a number%.
  • the white coating film of the obtained coated metal plate was peeled off using a coating film peeling agent (“Neo River SP751”, manufactured by Sansai Kako Co., Ltd.), and the film thickness was calculated by a weight method.
  • a coating film peeling agent (“Neo River SP751”, manufactured by Sansai Kako Co., Ltd.)
  • the whiteness and glossiness of the obtained coated metal plate were measured.
  • L * value was measured using CR-400 manufactured by Konica Minolta.
  • 60 ° gloss was measured using a Multi Gloss 268 manufactured by Konica Minolta.
  • the thickness of the white coating film was less than 10 ⁇ m, the L * value of 87.0 or more was judged to be acceptable as the whiteness, and the 60 ° gloss was judged to be 71 or more as the glossiness.
  • the thickness of the white coating film was 10 ⁇ m or more, an L * value of 89.5 or more was judged to be acceptable as the whiteness, and a 60 ° gloss of 72 or more was judged to be acceptable as the glossiness.
  • Table 2 shows the evaluation results of the coated metal sheet having the produced white coating film. In any painted metal plate, the average surface roughness Ra of the flat portion was less than 20 nm.
  • the coated metal plates of Invention Examples 1 to 13 satisfied whiteness and glossiness at the same time.
  • the coated metal plates of Comparative Examples 1 to 11 were insufficient in either whiteness or glossiness.
  • Comparative Examples 1, 2, 5, and 6 since no concave portion was formed on the surface of the white coating film, the whiteness was not sufficient.
  • Comparative Examples 3 and 4 the average depth of the recesses was too deep, and the whiteness and glossiness were not sufficient.
  • Comparative Example 7 the average diameter of the recesses was too small, and the whiteness was not sufficient.
  • Comparative Example 8 the average depth of the recesses was too shallow, and the whiteness was not sufficient.
  • Comparative Examples 9 and 10 since the solvent partial pressure in the chamber was low, the whiteness was not sufficient.
  • Comparative Example 11 since the solvent partial pressure in the chamber was high, the whiteness and glossiness were not sufficient.
  • FIG. 6 is a graph showing the relationship between the whiteness (L * value) and the gloss (60 ° gloss) for the inventive examples and comparative examples in which the thickness of the white coating film is the same (16 ⁇ m). As shown in FIG. 6, it is clear that the inventive example has both high gloss and whiteness compared to the comparative example.
  • the scanning electron microscope (SEM: Scanning Electron Microscope) photograph which observed the surface of the white coating film of the invention example 1 in FIG. 7 is shown.
  • 8 and 9 show atomic force microscope images (oblique 45 °) of the surface of the white coating film of Invention Example 1 observed.
  • the scanning electron microscope (SEM) photograph which observed the surface of the white coating film of the comparative example 1 in FIG. 10 is shown.
  • the white coating film of Invention Example 1 had a plurality of recesses. Moreover, as shown in FIG. 9, the convex part was observed near the center part of the concave part. On the other hand, as shown in FIG. 10, no recess was observed in the white coating film of Comparative Example 1.
  • the chemical conversion treatment layer was formed with respect to one plate surface of the metal plate by the following method.
  • the chemical conversion solution was applied to one surface of the metal plate with a roll coater. Then, it heated so that PMT might be 60 degreeC.
  • the coating amount of the chemical conversion treatment liquid on the coated surface was applied so that the total coating amount of the dry film was 300 mg / m 2 .
  • the adhesion amount of each chemical conversion treatment film was measured by fluorescent X-rays.
  • the paints 19 to 27 shown in Table 3 were applied to the plate surface of the galvanized steel sheet having the chemical conversion coating so as to have a predetermined dry film thickness using a slide curtain coater. Then, after prebaking in a hot air heating type baking oven as shown in FIG. 5 so that the PMT is 220 ° C., water-cooling treatment is performed, and the precoated steel sheet (painted metal plate) having a desired colored coating film is dried by air blow ) The plate passing speed was 120 m / min, and the heating time in the baking furnace was 15 seconds.
  • the liquid medium in the colored paint volatilizes and becomes a solvent and stays in the internal space of the baking furnace chamber.
  • the supply amount of hot air from the supply port, the inflow amount of outside air from the metal plate inlet, the exhaust amount from the exhaust port, the metal plate outlet were adjusted. Thereby, the contact to the colored coating film of the solvent was possible.
  • the colored coating film on the outermost surface of the obtained coated metal plate was observed.
  • the flat part, the recessed part, and the convex part were specified by the method similar to the above, and each characteristic was evaluated.
  • the film thickness of the colored coating film was computed by the method similar to the above-mentioned.
  • the whiteness (L * value) and the glossiness (60 ° gloss) of the obtained coated metal plate were measured by the same method as described above. As the whiteness, an L * value of 27.0 or more was judged as acceptable, and as the glossiness, a 60 ° gloss of 50 or more was judged as acceptable. Table 4 shows the evaluation results of the coated metal sheet having the produced colored coating film. In any painted metal plate, the average surface roughness Ra of the flat portion was less than 20 nm.
  • the coated metal plates of Invention Examples 14 to 19 were given whiteness and at the same time had high gloss.
  • the painted metal plates of Comparative Examples 12 to 17 were not sufficiently whitened or the glossiness was remarkably reduced.
  • Comparative Example 12 since no concave portion was formed on the surface of the colored coating film, the whiteness was not sufficient.
  • Comparative Examples 13 and 14 the average depth of the recesses was too deep, and the glossiness was not sufficient.
  • Comparative Examples 15 and 16 the solvent partial pressure in the chamber was low, so the whiteness was not sufficient.
  • Comparative Example 17 since the solvent partial pressure in the chamber was high, the whiteness and glossiness were not sufficient.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Cette tôle revêtue comprend une tôle et un film de revêtement, le film de revêtement étant disposé sur la surface la plus à l'extérieur possédant une partie plate et une pluralité d'évidements, le diamètre moyen des évidements étant de 0,20-4,0 µm, et la profondeur moyenne des évidements étant de 20-200 nm.
PCT/JP2018/000650 2017-01-12 2018-01-12 Tôle revêtue WO2018131681A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0436746A (ja) * 1990-06-01 1992-02-06 Asahi Chem Ind Co Ltd 表面加工された金属光沢薄膜
JPH06198465A (ja) * 1993-01-11 1994-07-19 Osaka Prefecture 虹色発色加工方法
JP2001191021A (ja) * 2000-01-14 2001-07-17 Fujikura Kasei Co Ltd 粗面状塗膜および粗面状塗膜の形成方法
JP2002060977A (ja) * 2000-08-18 2002-02-28 Kobe Steel Ltd 際立った凹凸模様を有する着色皮膜被覆金属板
JP2008200662A (ja) * 2007-02-23 2008-09-04 Japan Crown Cork Co Ltd 非光沢面を有する塗装金属板及びその製造方法。
WO2013011868A1 (fr) * 2011-07-20 2013-01-24 新日鐵住金株式会社 Panneau

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0436746A (ja) * 1990-06-01 1992-02-06 Asahi Chem Ind Co Ltd 表面加工された金属光沢薄膜
JPH06198465A (ja) * 1993-01-11 1994-07-19 Osaka Prefecture 虹色発色加工方法
JP2001191021A (ja) * 2000-01-14 2001-07-17 Fujikura Kasei Co Ltd 粗面状塗膜および粗面状塗膜の形成方法
JP2002060977A (ja) * 2000-08-18 2002-02-28 Kobe Steel Ltd 際立った凹凸模様を有する着色皮膜被覆金属板
JP2008200662A (ja) * 2007-02-23 2008-09-04 Japan Crown Cork Co Ltd 非光沢面を有する塗装金属板及びその製造方法。
WO2013011868A1 (fr) * 2011-07-20 2013-01-24 新日鐵住金株式会社 Panneau

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