WO2019088123A1 - Feuille métallique revêtue et procédé de fabrication d'une feuille métallique revêtue - Google Patents

Feuille métallique revêtue et procédé de fabrication d'une feuille métallique revêtue Download PDF

Info

Publication number
WO2019088123A1
WO2019088123A1 PCT/JP2018/040384 JP2018040384W WO2019088123A1 WO 2019088123 A1 WO2019088123 A1 WO 2019088123A1 JP 2018040384 W JP2018040384 W JP 2018040384W WO 2019088123 A1 WO2019088123 A1 WO 2019088123A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating film
metal plate
coated metal
glass transition
resin
Prior art date
Application number
PCT/JP2018/040384
Other languages
English (en)
Japanese (ja)
Inventor
史生 柴尾
邦彦 東新
敬士 二葉
亜暢 小林
石塚　清和
岡田　克己
Original Assignee
新日鐵住金株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 MX2020004253A priority Critical patent/MX2020004253A/es
Priority to KR1020207013532A priority patent/KR102425956B1/ko
Priority to CN201880070229.9A priority patent/CN111278648B/zh
Priority to JP2019525038A priority patent/JP6624346B2/ja
Publication of WO2019088123A1 publication Critical patent/WO2019088123A1/fr

Links

Images

Classifications

    • 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
    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a coated metal sheet and a method of manufacturing the coated metal sheet.
  • Priority is claimed on Japanese Patent Application No. 2017-209460, filed Oct. 30, 2017, the content of which is incorporated herein by reference.
  • a coated metal plate coated with a coating film is used for automobiles, home appliances, building materials, civil engineering, machines, furniture, containers, etc., instead of conventional painted products to which painting is applied after processing. It has become like that.
  • Such a coated metal sheet is generally cut and applied after the paint is applied to the metal sheet.
  • a coated metal sheet is mainly used as an exterior material, it is often exposed to various solvents and chemicals, and thus often has solvent resistance and chemical resistance. Because they are exterior materials, they are usually colored and painted, and there are many coated metal plates, and the film thickness of such a coating is relatively thick because of the hiding property for color tone.
  • a metal-coated metal plate in which the appearance of the metal plate as the substrate is designed as it is, it is necessary to apply a clear coating containing no color pigment. In such a case, by reducing the film thickness of the clear coating film, the coated metal plate becomes excellent in metal appearance. Also, from the viewpoints of productivity and commerce, the thinner the film thickness of the clear coating film, the better.
  • Patent Document 1 discloses a coating method technology of a metal plate for coating a paint containing a solvent-soluble fluorine resin as a main component.
  • Patent Document 2 the processability, the stain resistance, and the scratch resistance are obtained by the coating film using the polyester resin having a high glass transition temperature, the polyester resin having a low glass transition temperature, and the aminoformaldehyde resin.
  • the art of a coated metal plate excellent in resistance and chemical resistance is disclosed.
  • Patent Document 3 a polyacrylic resin is applied to the upper layer, and a polyester resin is applied to the lower layer, and a technique of precoated metal excellent in stain resistance, chemical resistance, weather resistance and processability is disclosed. It is done.
  • Patent Document 4 discloses the technology of a coated metal plate which is excellent in processability, corrosion resistance (especially end face corrosion resistance), chemical resistance, etc. by a coating film obtained by mixing a specific polyurethane resin and a polyester resin. It is done.
  • the technique of the metal plate which is excellent in bending workability is disclosed by the following patent document 5 by the coating film which the melamine resin particle which is 50 nm or less in particle diameter disperse
  • Patent Document 6 discloses, in a coating film using an aminoblast resin such as melamine resin, a technology for concentrating the aminoblast resin on the surface layer of the coating film.
  • Japanese Patent Application Laid-Open No. 5-111675 Japanese Patent Application Laid-Open No. 7-331167 Japanese Patent Application Laid-Open No. 7-313929 Japan JP 2013-213281 Japanese Patent Application Laid-Open No. 2005-53002 Japanese Patent Application Laid-Open No. 2006-175815
  • the polyacrylic resin used by the technique of the said patent document 3 is inferior to workability, and when the coating film currently disclosed by the said patent document 3 is made into a clear coating film, barrier property is enough. Furthermore, it has poor chemical resistance.
  • the coating film disclosed in Patent Document 4 has insufficient barrier properties and is further inferior in chemical resistance.
  • the coating film is inferior in solvent resistance.
  • Patent Documents 1 to 6 do not disclose a technique for obtaining a coated metal plate excellent in metal appearance, chemical resistance and solvent resistance while suppressing the manufacturing cost.
  • an object of the present invention is to provide a coated metal sheet which is excellent in metal appearance, chemical resistance and solvent resistance, which is suppressed in manufacturing cost. And providing a method for producing such a coated metal sheet.
  • the present inventors formed a resin coating film including a first portion having a urethane bond skeleton and a second portion having a triazine ring skeleton on at least one surface of a metal plate.
  • a coated metal plate according to an aspect of the present invention comprises a metal plate and a first coating film located on at least one side of the metal plate and containing a resin, the first coating film comprising It has a first site having a urethane bond skeleton and a second site having a triazine ring skeleton.
  • the glass transition temperature of the first coating is 85 ° C. or more and 170 ° C. or less.
  • the second site When the second site is stained with osmium oxide and observed at a magnification of 100,000 using a transmission electron microscope, the second site is a dispersed second site in which particles having a number average particle diameter of 5 to 20 nm are dispersed, and A concentrated second portion is observed which is present at a depth of 15 nm from the surface of one coating film and in which particles having a number average particle diameter of 5 nm or more are not observed.
  • the coated metal plate according to the above (1) is characterized in that the N concentration N1 at a depth position of 0.2 ⁇ m from the surface of the first coating film from the interface between the first coating film and the metal plate
  • the ratio N1 / N2 to the N concentration N2 at the depth position of 0.2 ⁇ m on the first coating film side may be 1.2 or more.
  • the first coating film may have a plurality of the concentrated second portions.
  • the coated metal plate according to any one of the above (1) to (3) further comprises a second coating film between the first coating film and the metal plate;
  • the glass transition temperature may be equal to or less than the glass transition temperature of the first coating film.
  • the second coating film may contain a resin and have a urethane bond skeleton.
  • the second coating film may contain a resin and may have an epoxy group.
  • the second coating film may contain a resin and have a siloxane bond.
  • the second coating film is any one selected from the group consisting of P, V, Ti, Si and Zr. The above elements may be included.
  • the glass transition temperature of the first coating is higher by at least 5 ° C. than the glass transition temperature of the second coating. It is also good.
  • the film thickness of the second coating film may be 0.5 ⁇ m or more and 15 ⁇ m or less.
  • the film thickness of the first coating film may be 0.5 ⁇ m or more and 15 ⁇ m or less.
  • at least one of the first coating film and the second coating film may contain a colorant.
  • the second coating film may contain a black pigment as a colorant.
  • a texture may be formed on at least one surface of the metal plate.
  • a method of producing a coated metal sheet according to another aspect of the present invention is a method of producing a coated metal sheet having a predetermined first coating on at least one surface of a metal sheet, the method comprising the steps of First, a polyurethane resin (a) containing an anionic functional group and having a glass transition temperature of 75 ° C. to 160 ° C. on one side, a triazine ring-containing water-soluble curing agent (b), and an aqueous solvent A paint is applied, and the first paint film is formed by heating the metal plate to which the first paint is applied.
  • the triazine ring-containing water-soluble curing agent (b) may be a melamine resin containing an imino group.
  • the first paint contains the content (Wa) of the polyurethane resin (a) with respect to the total solid content and the total solid content.
  • the total content (Wa) + (Wb) of the content (Wb) of the triazine ring-containing water-soluble curing agent (b) satisfies the following formula (I), and the above with respect to the total solid content
  • the ratio (Wb) / (Wa) of the content (Wa) of the polyurethane resin (a) and the content (Wb) of the triazine ring-containing water soluble curing agent (b) to the total solid content is as follows: You may satisfy Formula (II).
  • the second paint may be applied on at least one side of the metal plate, and the second paint film may be formed by heating the metal plate coated with the second paint.
  • the glass transition temperature of the polyurethane resin (c) may be 5 ° C.
  • FIGS. 1A to 3 the overall configuration of a coated metal plate according to an embodiment of the present invention will be described.
  • 1A and 1B are explanatory views schematically showing an example of the structure of a coated metal plate according to the present embodiment
  • FIGS. 2A and 2B are other views of the structure of the coated metal plate according to the present embodiment
  • It is an explanatory view showing an example typically.
  • FIG. 3 is an explanatory view for explaining an upper-layer coating film of the coated metal sheet according to the present embodiment.
  • the coated metal plate 1 which concerns on this embodiment has the upper-layer coating film 13 as a 1st coating film on the single side
  • the upper layer coating film 13 may be provided on both sides of the metal plate 11, or the upper layer coating film 13 and the lower layer coating 15 may be provided on both sides of the metal plate 11.
  • the structure of the coated metal plate 1 which concerns on this embodiment is not limited to the structure shown to FIG. 1A-FIG. 2B,
  • the upper-layer coating film 13 and the lower-layer coating film on one side of the metal plate 11 A configuration in which the upper coating 13 or the lower coating 15 is provided on the other surface of the metal plate 11 is also feasible.
  • the upper layer coating film 13 which is an example of the first coating film has a first portion having a urethane bond skeleton (hereinafter also referred to as "urethane portion”) and a second portion having a triazine ring skeleton (hereinafter also referred to as "triazine portion”) And the resin coating film containing.
  • the glass transition temperature of the upper-layer coating film 13 is 80 degreeC or more and 170 degrees C or less.
  • the second part having a triazine ring skeleton is stained with osmium oxide and observed with a transmission electron microscope at a magnification of 100,000 times, the number average particle diameter is 5 nm.
  • the dispersed second portion (symbol 101 in FIG. 3) in which the above particles are dispersed, and a position from the surface of the upper layer coating film 13 to a depth of 15 nm, particles with a number average particle diameter of 5 nm or more are not observed Both of the concentrated second part (symbol 103 in FIG. 3) are present.
  • the coated metal plate 1 according to the present embodiment can be a coated metal plate having excellent metal appearance, chemical resistance and solvent resistance, without using an expensive resin such as a fluorocarbon resin, etc., by the above configuration. .
  • the reason is presumed as follows.
  • the urethane portion needs to have a relatively high glass transition temperature.
  • the upper layer coating film 13 is formed, a high cohesive force is generated in the urethane portion because the urethane portion has a high glass transition temperature.
  • the triazine moiety is not condensed alone, the triazine moiety is dispersed in the urethane moiety, and the urethane moiety and the triazine moiety are more easily bound.
  • a three-dimensional network structure is formed by bonding the highly solvent resistant triazine moiety to the urethane moiety.
  • the upper layer coating 13 has an increased barrier property (i.e., chemical resistance).
  • the glass transition temperature of the upper coating film 13 is set to 80 ° C. or more and 170 ° C. or less.
  • the triazine moiety forms a domain in the upper layer coating 13 and disperses in a granular form (reference numeral 101 in FIG. 3), and by thickening the surface layer of the upper layer coating 13 to form a concentrated portion 103,
  • the triazine moiety having high solvent resistance enhances the solvent resistance of the upper coating film 13.
  • the urethane portion and the triazine portion are likely to be preferentially bonded, as schematically shown in FIG.
  • the finely divided particulate triazine portion (hereinafter, also referred to as “triazine particulate matter 101”) is in a state of being concentrated in the surface layer of the upper layer coating film 13. From this point as well, the solvent resistance of the upper coating 13 is further improved.
  • micronized particulate triazine moiety (triazine particulate matter 101) is concentrated in the surface layer of the upper layer coating film 13, light scattering by the triazine moiety is suppressed, and as a result, the transparency of the upper layer coating film 13 is improved.
  • the gloss of the underlying metal plate 11 is easily visible from the outside. Thereby, in the coated metal plate 1 which concerns on this embodiment, a metal external appearance also improves.
  • the coated metal plate 1 according to the present embodiment has the above-described configuration, and without using an expensive resin such as a fluorine resin, it has a metal appearance, chemical resistance, and solvent resistance. It is estimated that it is excellent in sex.
  • the coated metal plate 1 In the coated metal plate 1 according to the present embodiment, various generally known metal plates can be used as the metal plate 11. Specifically, as the metal plate 11, for example, various metal plates and alloy plates such as steel plate, stainless steel plate, aluminum plate, aluminum alloy plate, titanium plate, copper plate and the like can be mentioned. In the coated metal plate 1 according to the present embodiment, various types of plating (not shown) may be applied to the surface of the metal plate 11. The type of plating is not particularly limited, and examples thereof include zinc plating, aluminum plating, copper plating, nickel plating, alloy plating of these, and the like.
  • the metal plate 11 is a plated steel sheet
  • there is a tendency to be inferior in chemical resistance so the effect of improving the chemical resistance by providing the upper coating 13 becomes more effective.
  • the plated steel plate used as the metal plate 11 is not particularly limited, and a galvanized steel plate, an electrogalvanized steel plate, a zinc-nickel alloy plated steel plate, a molten alloyed galvanized steel plate, an aluminum plated steel plate, an aluminum-zinc Generally known various plated steel plates such as alloyed plated steel plates and stainless steel plates can be applied.
  • a zinc-based plated steel sheet as the metal plate 11 is more preferable because the corrosion resistance is further improved.
  • the zinc-based plated steel sheet refers to zinc, such as zinc-plated galvanized steel sheet, zinc-nickel alloy plated steel sheet, hot-dip galvanized galvanized steel sheet, aluminum-zinc alloy coated steel sheet, etc. It refers to a plated steel plate in which an alloy with a metal is plated on the surface of the steel plate.
  • the galvanized steel sheet may be any of a galvanized steel sheet, an electrogalvanized steel sheet, and the like.
  • the surface of the metal plate 11 is textured, roughened, streaked (hairline), woven (satin), squared (hammer), etc. , And various textures may be formed.
  • the texture as described above is formed on the surface of the metal plate 11 Also, the metallic feeling recalled by such texture is easily visible from the outside.
  • the upper layer coating film 13 of the coated metal plate 1 has, as mentioned earlier, a urethane portion (a first portion having a urethane bond skeleton) and a triazine portion (a second portion having a triazine ring skeleton) And a resin coating film containing
  • part contained in the upper layer coating film 13 is demonstrated.
  • the urethane bond frame which the urethane part in the upper layer coating film 13 has can be confirmed by analyzing the upper layer coating film 13 by Fourier transform infrared spectroscopy and detecting the vibration peak attributed to the urethane bond. .
  • the triazine ring skeleton of the triazine moiety is a skeleton derived from the triazine ring contained in the melamine resin. That is, the triazine moiety is a moiety derived from the triazine ring contained in the melamine resin.
  • the triazine moiety was stained with osmium oxide as described earlier with reference to FIG. 3 and observed with a transmission electron microscope at a magnification of 100,000 to find particles with a number average particle diameter of 5 to 20 nm.
  • the second part of the dispersion type in which the particles are dispersed and the second part of the concentrated type which is present at a depth of 15 nm from the surface of the upper layer coating 13 and in which particles with a number average particle diameter of 5 nm or more are not observed Be done.
  • the concentration portion 103 has a range of positions from the surface layer of the upper layer coating film 13 to the depth d (15 nm) toward the metal plate 11 side. It exists inside.
  • the phrase “the triazine moiety is concentrated in the surface layer of the upper layer coating film 13” means a particulate triazine moiety (ie, triazine particles on the surface side of the upper layer coating film 13 opposite to the interface with the metal plate 11). It is shown that the object 101) is unevenly distributed in layers. That is, it is indicated that the region of the granular triazine site which is unevenly distributed in the layer constitutes the surface layer of the upper coating film 13.
  • the triazine moiety is unevenly distributed in a layer form the concentrated portion 103
  • the average concentration (average content) of the triazine moiety in the region where the triazine moiety is unevenly distributed is other than the uneven distribution portion. It means that it is 1.2 times or more of the average concentration of the triazine site in the region.
  • the triazine moiety according to the present embodiment is dispersed in particles of a number average particle diameter of 5 nm to 20 nm in the upper layer coating film 13 (in other words, the number average particle diameter of triazine particles 101 is 5 nm to 20 nm) And the surface layer within a depth of 15 nm from the surface of the upper layer coating film 13 (in other words, the depth d in FIG. 3 is 15 nm or less).
  • the triazine moiety is concentrated in the surface layer within a depth of 15 nm from the surface of the upper layer coating film 13 is unevenly distributed in a layer on the surface side of the upper layer coating film 13 opposite to the interface with the metal plate 11 It shows that the region of the particulate triazine site is present within 15 nm in depth from the surface of the upper layer coating 13. That is, it is shown that the region of the granular triazine site which is unevenly distributed in the layer constitutes the surface layer of the upper layer coating film 13 and has a thickness of 15 nm or less.
  • the number average particle size of the particulate triazine moiety i.e., triazine particulates 101
  • chemical resistance may decrease.
  • the number average particle size of the triazine site dispersed in the granular form exceeds 20 nm, the metallic appearance and the chemical resistance penetration of the coated metal plate 1 are lowered, or the metallic appearance, the chemical penetration and the processability are lowered. There is something to do.
  • the processability of the coated metal sheet 1 is lowered, a crack or the like occurs in the upper layer coating film 13 and the chemical resistance and the solvent resistance are also lowered.
  • the number average particle diameter of the triazine moiety (triazine particle 101) dispersed in the particles is more preferably 5 nm or more and 15 nm or less from the viewpoint of metal appearance, chemical permeability and solvent resistance.
  • the metal appearance and the solvent resistance may be lowered.
  • the particulate triazine portion is concentrated from the surface of the upper layer coating 13 to a depth of more than 15 nm (that is, the depth where the concentrated portion 103 is present is more than 15 nm from the surface of the upper layer coating 13)
  • the processability may be reduced.
  • a crack or the like occurs in the upper layer coating film 13 and the chemical resistance and the solvent resistance are also lowered.
  • a plurality of thickening portions 103 be formed in the upper layer coating film 13.
  • the barrier property is further improved, and suitable chemical resistance can be obtained.
  • the heating method in the upper layer coating film forming process described later is important. This point will be described later.
  • the N concentration N1 at a depth position of 0.2 ⁇ m from the surface of the upper layer coating 13 and the upper layer coating 13 from the interface between the upper layer coating 13 and the metal plate 11 N1 / N2 which is a ratio to the N concentration N2 at a depth position of 0.2 ⁇ m on the side is 1.2 or more.
  • N1 / N2 is 1.5 or more and 10 or less.
  • part in the upper layer coating film 13 are demonstrated.
  • the upper coating 13 to be analyzed is dyed with osmium oxide.
  • part in the upper layer coating film 13 is selectively dyed.
  • a coating film dyed with osmium oxide is cut along a film thickness direction using a microtome, a focused ion beam processing apparatus or the like to prepare a coating film sample whose cross section can be observed.
  • the thin film sample is observed at 100,000 ⁇ magnification using a transmission electron microscope. In this observation, the triazine site in the thin film sample is observed black in the STEM-BF (bright field) image and white in the STEM-HAADF (dark field) image.
  • part in the upper layer coating film 13 can be confirmed by the above analysis methods.
  • the triazine moiety in the upper coating film 13 is subjected to analysis of the coating film by energy dispersive X-ray spectroscopy or Fourier transform infrared spectroscopy to detect nitrogen and osmium, or to be attributed to a triazine ring It can also be confirmed by detecting a vibration peak.
  • the thickness of the region in which the particulate triazine moiety is concentrated is measured by the following method Value.
  • a thin film sample is observed at a magnification of 100,000 times by a transmission electron microscope to obtain a STEM-BF (bright field) image.
  • the obtained STEM-BF (bright field) image is binarized with, for example, the threshold 120.
  • the thickness of a layered region observed black from the surface of the upper layer coating film 13 is measured at any 20 locations, and the average value thereof is measured in the region where the triazine moiety is concentrated.
  • the position where the thickening portion 103 exists is to focus on the position of the lower end (the interface on the metal plate 11 side) of the thickness of the thickening portion 103 obtained as described above in the binarized image. Can be identified.
  • region observed in black in layer form is confirmed from the surface of the upper-layer coating film 13, it is considered that the granular triazine site
  • the number average particle diameter of the particulate triazine portion (the number average particle diameter of the triazine particles 101) is a value measured by the following method.
  • the thin film sample is observed at 500,000 ⁇ magnification by a transmission electron microscope to obtain a STEM-BF (bright field) image.
  • the obtained STEM-BF (bright field) image is binarized with, for example, the threshold 120.
  • calculation of the equivalent circle diameter is performed at 20 arbitrarily selected granular regions, and the average value thereof is determined as the number average particle diameter of the granular triazine portion.
  • the average concentration of the triazine moiety concentrated on the surface side of the upper layer coating 13 can be measured as follows. That is, the distribution in the depth direction of the N element concentration from the surface layer side to the metal plate direction of the upper layer coating film 13 is measured, and the N element concentration N1 at a position of 0.2 ⁇ m from the outermost layer, the metal plate or the lower layer The ratio N1 / N2 of the concentration of the N element to N2 at a position 0.2 ⁇ m on the surface side from the boundary with the coating film is determined. Elemental analysis in the direction of depth can be examined by a known method, for example, using Glow Discharge Optical Emission Spectroscopy (GD-OES), Auger Electron Spectroscopy (AES), etc. It is possible.
  • GD-OES Glow Discharge Optical Emission Spectroscopy
  • AES Auger Electron Spectroscopy
  • the glass transition temperature (Tg) of the upper coating film 13 is 85 ° C. or more and 170 or less.
  • the glass transition temperature of the upper layer coating 13 is less than 85 ° C., the chemical resistance of the coated metal sheet 1 is reduced.
  • the glass transition temperature of the upper layer coating film 13 exceeds 170 ° C., the processability of the coated metal sheet 1 is reduced.
  • the glass transition temperature of the upper layer coating film 13 is preferably 100 ° C. or more and 170 ° C. or less, more preferably 110 ° C. or more, from the viewpoint of chemical resistance and solvent resistance (particularly, chemical resistance penetration). It is 165 ° C. or less.
  • the glass transition temperature of the upper layer coating film 13 is more than the glass transition temperature of the lower layer coating film 15.
  • the adhesion between the upper coating film 13 and the lower coating film 15 is reduced, and the chemical resistance is lowered. There is.
  • the glass transition temperature of the upper layer coating film 13 is higher than the glass transition temperature of the lower layer coating film 15 by 5 ° C. or more.
  • the difference between the glass transition temperature of the upper layer coating film 13 and the lower layer coating film 15 and the glass transition temperature is 5 ° C. or more, the adhesion between the upper layer coating film 13 and the lower layer coating film 15 is further improved. It becomes easier to improve the quality.
  • the glass transition temperature of the upper layer coating film 13 is more preferably higher than the glass transition temperature of the lower layer coating film 15 in the range of 10 ° C. to 50 ° C.
  • the glass transition temperature of the upper coating film 13 is higher by 10 ° C. or more than the glass transition temperature of the lower coating film 15, chemical resistance can be easily enhanced.
  • the glass transition temperature of the upper layer coating film 13 is higher than the glass transition temperature of the lower layer coating film 15 in the range of 50 ° C. or less, the decrease in the coating film hardness is easily suppressed.
  • the glass transition temperature (Tg) is a value measured by the following method. First, the coating film to be measured is peeled off or scraped to prepare a measurement sample. And a glass transition point temperature is calculated
  • DSC method differential scanning calorimetry
  • the upper-layer coating film 13 does not have a silica.
  • the chemical resistance of the upper coating film 13 is deteriorated.
  • the upper layer coating film 13 does not have at least one metal complex compound selected from zinc, aluminum and titanium.
  • At least one metal complex compound selected from zinc, aluminum and titanium for example, zinc stearate, zinc gluconate, zinc picolinate, zinc citrate, zinc acetylacetonate, aluminum acetate, aluminum stearate ,
  • the lower layer coating film 15 is not particularly limited, and polyurethane resin, epoxy resin, acrylic resin, polyester resin, phenol resin, polyolefin resin, alkyd resin, Well-known resin coating films, such as melamine resin and silicone resin, can be applied.
  • resin coating film it is also possible to use known additives such as a silane coupling agent.
  • the lower layer coating film 15 has at least a first portion (hereinafter also referred to as a "urethane portion") having a urethane bond skeleton from the viewpoint of metal appearance, chemical resistance and solvent resistance.
  • a first portion hereinafter also referred to as a "urethane portion”
  • it further comprises a moiety having at least one of an epoxy group and a siloxane bond skeleton (hereinafter, the moiety having an epoxy group is also referred to as “epoxy moiety” and the moiety having a siloxane bond skeleton is also referred to as “siloxane moiety”). It is preferable that it is such a resin coating film.
  • the lower coating film 15 preferably contains a compound having at least one element selected from the group consisting of P, V, Ti, Si and Zr in addition to the above urethane site. .
  • the urethane portion when the urethane portion further has an anionic functional group, the dispersibility of the urethane portion in the aqueous medium (water-based paint) is improved, and the film forming property of the lower layer coating 15 is enhanced.
  • the adhesion to the metal plate 11 is improved, and the barrier property (that is, chemical resistance) of the lower coating film 15 is enhanced.
  • the chemical resistance of the lower coating film 15 is also improved by including a urethane portion and at least one of an epoxy group and a siloxane bond skeleton.
  • the lower coating film 15 as a resin coating film having at least a urethane portion, the transparency of the lower coating film 15 is improved, and the metal appearance also becomes good.
  • compounds having at least one element selected from the group consisting of P, V, Ti, Si and Zr generally function as a rust inhibitor in general, but Such compounds may be contained.
  • the corrosion resistance of the coated metal sheet 1 can be further improved.
  • the urethane bond skeleton of the urethane moiety is a skeleton derived from a polyurethane resin. That is, the urethane moiety is a moiety derived from a polyurethane resin, and can be further referred to as a moiety which may have an anionic functional group.
  • the epoxy moiety having an epoxy group is a moiety derived from an epoxy resin. That is, the epoxy group of the epoxy site is an epoxy group residue which did not react with the urethane site derived from the polyurethane resin.
  • the siloxane bond skeleton of the siloxane moiety is a skeleton derived from a silicone resin having a siloxane bond or a silane coupling agent capable of forming a siloxane bond.
  • the urethane bond skeleton of the urethane moiety in the lower coating film 15, the epoxy group of the epoxy moiety, and the siloxane bond skeleton of the siloxane moiety are coated with the lower layer by energy dispersive X-ray spectroscopy or Fourier transform infrared spectroscopy.
  • the film 15 can be analyzed to confirm the element constituting the corresponding bond or functional group or the vibration peak attributed to the corresponding bond or functional group. Further, the presence of a compound having at least one element selected from the group consisting of P, V, Ti, Si and Zr in the lower coating film 15 causes such a compound to be obtained by energy dispersive X-ray spectroscopy. It can be confirmed by whether or not the contained element is detected.
  • the glass transition temperature of the lower coating film 15 is preferably equal to or less than the glass transition temperature of the upper coating film 13.
  • the glass transition temperature of the lower coating film 15 is more preferably in the range of 80 ° C. or more and 170 or less and not more than the glass transition temperature of the upper coating film 13.
  • the chemical resistance may decrease.
  • the glass transition temperature of the lower coating film 15 exceeds 170 ° C., the processability may be lowered.
  • the lower coating film 15 may be cracked and the like, and the chemical resistance and the solvent resistance may also be lowered.
  • the glass transition temperature of the lower coating film 15 is more preferably equal to or less than the glass transition temperature of the upper coating film 13 from the viewpoints of chemical resistance and solvent resistance (in particular, chemical resistance penetration). It is in the range of ° C to 170 ° C.
  • the film thickness of the above upper layer coating film 13 is 0.5 micrometer or more and 15 micrometers or less.
  • the film thickness of the upper layer coating film 13 is less than 0.5 ⁇ m, the chemical resistance of the coated metal plate 1 may decrease.
  • the film thickness of the upper layer coating film 13 exceeds 15 ⁇ m, the transparency of the upper layer coating film 13 may be reduced and the metal appearance may be reduced.
  • the film thickness of the upper layer coating film 13 is more preferably 1 ⁇ m or more and 10 ⁇ m or less from the viewpoint of metal appearance and chemical resistance permeability.
  • the film thickness of the lower coating film 15 is preferably 0.5 ⁇ m to 15 ⁇ m. .
  • the film thickness of the lower coating film 15 is more preferably more than 1.0 ⁇ m and 15 ⁇ m or less.
  • the upper coating film 13 and / or the lower coating film 15 as described above may contain a colorant.
  • a coloring agent By incorporating a coloring agent into the upper coating 13 and / or the lower coating 15, the color tone of the product can be adjusted, and it becomes possible to apply to various applications.
  • the color pigment is a black pigment
  • the chemical resistance may be lowered.
  • Such a decrease in chemical resistance is considered to be due to the fact that the black pigment in the upper layer coating film 13 facilitates the penetration of chemicals.
  • the black pigment concentration in the lower coating film 15 is not particularly limited, but is preferably 0.5% by mass or more and 20% by mass or less based on the total solid content of the lower coating film 15, for example. .
  • coloring may be insufficient.
  • the black pigment concentration in the lower coating film 15 exceeds 20% by mass, chemical resistance and corrosion resistance may be reduced.
  • the upper layer coating film 13 is a polyurethane resin (a) having a glass transition temperature of 75 ° C. or more and 160 ° C. or less and a triazine ring-containing water soluble curing agent It is preferable that it is a resin coating film (For example, the resin coating film containing the crosslinked material of a polyurethane resin and a water-soluble melamine resin) which hardened the upper layer coating material containing water-soluble melamine resin (b) and an aqueous solvent.
  • the resin coating film formed from the upper layer paint has a glass transition temperature of 85 ° C. or more and 170 ° C.
  • the water-soluble melamine resin (b) is in the form of particles dispersed in the upper layer coating film 13 and those in which the water-soluble melamine resin (b) is concentrated on the surface side of the upper layer coating film 13.
  • the glass transition temperature of the said polyurethane resin (a) is the polyurethane resin which the lower layer coating film 15 as follows contains. It is preferable that it is more than the glass transition temperature of (c).
  • the polyester resin is inferior in chemical resistance to the polyurethane resin, so it is necessary to increase the film thickness of the upper layer coating film in order to obtain the same chemical resistance. .
  • the film thickness of the upper layer coating film is increased, it is not preferable because a desired metal appearance can not be obtained in the case of forming a clear coating film.
  • the lower layer coating film 15 is specifically a glass transition of the polyurethane resin (a) of the upper layer coating film 13 in glass transition temperature.
  • a polyurethane resin (c) having a temperature or less an epoxy resin (d), a silane coupling agent (e), and P, V, Ti, Si and Zr
  • a resin coating film obtained by curing a lower layer coating containing at least one of a rust inhibitor (f) containing an aqueous solvent and an aqueous solvent for example, a resin coating film containing a crosslinked product of a polyurethane resin (c) and an epoxy resin (d)
  • coated metal plate 1 which concerns on this embodiment was demonstrated in detail.
  • the coated metal plate 1 according to the embodiment as described above can be used for automobiles, home appliances, building materials, civil engineering, machines, furniture, containers, and the like.
  • FIG. 4 is a flow chart showing an example of the flow of the method of producing a coated metal sheet according to the present embodiment.
  • the method of manufacturing the coated metal plate includes a texture forming step (step S101) of forming a predetermined texture on the surface of the metal plate 11 as necessary, as shown in FIG. 4 as an example, and a metal plate as necessary.
  • a lower coating film forming step (step S103) for forming the lower coating film 15 on the upper layer 11 and an upper coating film forming step (step S105) for forming the upper coating film 13 on the metal plate 11 or the lower coating film 15; Have.
  • the texture forming step and the lower layer coating forming step may be carried out as required.
  • step S105 is implemented among the three steps shown in FIG.
  • the upper layer coating film forming step includes a polyurethane resin (a) having an anionic functional group and having a glass transition temperature of 75 ° C. or more and 160 ° C. or less, and a water soluble melamine resin (b) which is a triazine ring-containing water soluble curing agent
  • a polyurethane resin (a) having an anionic functional group and having a glass transition temperature of 75 ° C. or more and 160 ° C. or less
  • a water soluble melamine resin (b) which is a triazine ring-containing water soluble curing agent
  • the upper coating film 13 is formed by coating the lower coating film 15) and heating and cooling the metal plate coated with the upper coating material.
  • the method for producing a coated metal sheet according to the present embodiment is the coated metal sheet according to the present embodiment (that is, a coated metal sheet excellent in metal appearance, chemical resistance, and solvent resistance) by the above-described method. Can be manufactured while suppressing costs. The reason is guessed as follows.
  • the melamine resin is less compatible with the polyurethane resin and thus hardly coexists with the polyurethane resin.
  • the self-condensed particles become larger, a phenomenon occurs in which the melamine resin is concentrated on the surface layer of the coating film.
  • the method for producing a coated metal sheet according to the present embodiment by employing the polyurethane resin (a) containing an anionic functional group, the polyurethane resin (a) and the triazine ring-containing in an aqueous medium
  • the water-soluble melamine resin (b) which is a water-soluble curing agent, is uniformly mixed and coexistent.
  • the upper layer paint in such a state is formed on the metal plate 11 (or on the lower layer coating film 15) and heated, the self-shrinkage of the water-soluble melamine resin (b) is suppressed, and the water-soluble melamine resin (b)
  • the reaction with the polyurethane resin (a) will occur preferentially.
  • the polyurethane resin (a) when vaporization (drying) of the aqueous solvent proceeds by heating, the polyurethane resin (a) is in a molten state.
  • the viscosity is increased because the glass transition temperature is as high as 75 ° C. or more and 160 ° C. or less.
  • high cohesion is generated and the diffusion speed of the melamine resin (b) is decreased.
  • the self-shrinkage of the water-soluble melamine resin (b) is suppressed, and the reaction between the water-soluble melamine resin (b) and the polyurethane resin (a) is preferentially generated.
  • the melamine resin (b) having low compatibility with the polyurethane resin (a) is concentrated to the surface layer of the coating film, the self-shrinkage of the water-soluble melamine resin (b) is suppressed, and the polyurethane resin (a) React preferentially with
  • the reaction product of the water-soluble melamine resin (b) reacted with the polyurethane resin (a) in the upper layer coating film 13 And the reaction product resulting from the self-shrinkage of the water-soluble melamine resin (b) coexist.
  • the upper layer coating 13 is dispersed in the form of particles and the upper layer coating 13 is concentrated in the surface layer.
  • the polyurethane resin (a) has a high cohesive force, so that the reaction between the water-soluble melamine resin (b) and the polyurethane resin (a) It occurs preferentially. Therefore, the micronized particulate water-soluble melamine resin (b) is concentrated in the surface layer of the upper layer coating film 13 to form a concentrated portion 103 as shown in FIG.
  • the micronized particulate water-soluble melamine resin (b) which was not concentrated, forms the triazine particulates 101 as shown in FIG.
  • the lower coating film 15 is formed using a polyurethane resin (c) having a glass transition temperature of 80 ° C. to 160 ° C. and a glass transition temperature lower than that of the polyurethane resin (a).
  • a polyurethane resin (c) having a glass transition temperature of 80 ° C. to 160 ° C. and a glass transition temperature lower than that of the polyurethane resin (a).
  • the high adhesion between the upper coating 13 and the lower coating 15 can be realized.
  • the polyurethane resin (a) containing an anionic functional group the dispersibility of the urethane portion in the aqueous medium (water-based paint) is improved, and as a result, the film forming property of the upper coating 13 is enhanced. High adhesion between the coating 13 and the lower coating 15 is realized.
  • the method of producing a coated metal sheet according to the present embodiment is a coated metal sheet according to the present embodiment (that is, a coated metal sheet excellent in metal appearance, chemical resistance and solvent resistance) Can be manufactured at low cost.
  • the upper layer coating film forming step first, an upper coating, which is an example of the first coating, is prepared.
  • the upper layer paint contains a polyurethane resin (a), a water soluble melamine resin (b) which is a triazine ring-containing water soluble curing agent, and an aqueous solvent.
  • the polyurethane resin (a) is a polyurethane resin containing an anionic functional group and having a glass transition temperature of 75 ° C. or more and 160 ° C. or less.
  • the glass transition temperature of the polyurethane resin (a) is the polyurethane resin used for the lower coating film 15 It is preferable that it is more than the glass transition temperature of (c).
  • a polyurethane resin having a urethane bond for example, a high glass transition Point temperature polyester resins are difficult to manufacture.
  • a polyurethane resin having a high glass transition temperature has a very high melt viscosity, it is difficult to coat (form a coated film) unless a paint dispersed in an aqueous medium is used. For this reason, by providing the anionic functional group to the polyurethane resin, it becomes possible to disperse in the aqueous medium together with the water-soluble melamine resin.
  • the polyurethane resin (a) is, for example, polyvalent such as ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane and the like.
  • polyurethane resin (a) for example, polyether polyurethane resin (polyurethane resin having a polyether skeleton), polyester polyurethane resin (polyurethane resin having a polyester skeleton), polyether polyester polyurethane resin (polyether skeleton and polyester skeleton) Polyurethane resin etc. is preferable. Coatings using these polyurethane resins are likely to have improved chemical resistance and solvent resistance.
  • the polyether polyurethane resin, the polyester polyurethane resin, and the polyether polyester polyurethane resin can be obtained by using at least one of a polyether polyol and a polyester polyol as polyhydric alcohols.
  • the polyether polyols are, for example, polyethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol and copolymers thereof.
  • polyester polyols include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or dialkyl esters of dibasic acids, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol Glycols such as 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethyl alcohol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol and the like It can be obtained by reaction.
  • the polyester polyol can be obtained, for example, by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly ( ⁇ -methyl- ⁇ -valerolactone) and the like.
  • the glass transition temperature of the polyurethane resin (a) is 75 ° C. or more and 160 ° C. or less. If the glass transition temperature of the polyurethane resin (a) is less than 75 ° C., the chemical resistance will decrease. On the other hand, when the glass transition temperature of the polyurethane resin (a) exceeds 160 ° C., the processability is lowered. When the processability is lowered, the upper coating film 13 is cracked and the like, and the chemical resistance and the solvent resistance are also lowered.
  • the glass transition temperature of the polyurethane resin (a) is preferably 100 ° C. or more and 160 ° C. or less from the viewpoints of chemical resistance and solvent resistance (particularly, chemical resistance permeability).
  • the glass transition temperature of various resins including the above-mentioned polyester resin can be measured according to the differential scanning calorimetry (DSC method) of the plastic transition temperature measurement method (JIS K 7121 1987).
  • water-soluble melamine resin (b) As the water-soluble melamine resin (b) which is a triazine ring-containing water-soluble curing agent, generally known water-soluble melamine resins (imino-type melamine resin, methylol-type melamine resin, completely alkyl etherified melamine resin, etc.) may be used it can. Examples of commercially available water-soluble melamine resins include water-soluble melamine resins such as those manufactured by Nippon Carbide, Ornex, and DIC.
  • the water-soluble melamine resin (b) as described above it is particularly preferable to use a melamine resin containing an imino group (imino-type melamine resin).
  • a melamine resin containing an imino group By using a melamine resin containing an imino group, the particulate water-soluble melamine resin is easily concentrated in the surface layer of the upper layer coating film 13, so that the solvent resistance can be more easily improved.
  • water solubility shows that the dissolution amount of the object substance with respect to 100 mass parts of water of 25 degreeC is 5 mass parts or more (preferably 10 mass parts or more).
  • the colorant to be dispersed in the upper layer paint containing the components as described above is not particularly limited, and known colorants can be appropriately used.
  • a colorant for example, various inorganic pigments such as titanium oxide, zinc oxide, calcium carbonate, aluminum oxide, barium sulfate, aluminum, iron oxide, copper-chromium composite oxide, carbon black, cyanine, quinacridone, etc.
  • various organic pigments of the above, various dyes and the like can be used.
  • the colorant to be used is a black pigment such as carbon black or a metal oxide exhibiting black color
  • the chemical resistance may decrease, so the concentration in the upper layer paint is limited or dispersed in the lower layer paint. It is preferable to disperse in the lower layer paint.
  • the type of carbon black dispersed in the upper layer paint is not particularly limited, and for example, known carbon blacks such as furnace black, ketjen black, acetylene black, channel black and the like can be used.
  • the particle size of the carbon black used is not particularly limited as long as there is no problem in the dispersibility in the paint, the quality of the coating film, and the paintability, but the primary particle size of about 10 to 120 nm is used Cheap.
  • the primary particle size of 10 to 120 nm is used Cheap.
  • the type of metal oxide exhibiting black color is not particularly limited, and, for example, known black pigments such as triiron tetraoxide and copper-chromium composite oxide can be used.
  • aqueous solvent examples include water or a mixed solution of water and a lower alcohol. Such an aqueous solvent may contain 50% by mass or more (preferably 80% by mass or more) of water.
  • a solvent typified by an organic solvent it is not preferable because the melamine particles are dispersed and present in the coating film and the surface is not concentrated.
  • an aqueous solvent is used. It is possible to concentrate melamine particles on the surface without using an amine compound.
  • distilled water ion exchange water, ultrapure water, ultrafiltered water, etc.
  • ion exchange water ion exchange water
  • ultrapure water ultrafiltered water
  • C1-C4 alcohol such as methanol, ethanol, butanol, isopropyl alcohol etc.
  • the content (Wa, unit: mass%) of the polyurethane resin (a) to the total solid content and the content (Wb) of the water-soluble melamine resin (b) to the total solid content The total content (Wa) + (Wb) of (unit: mass%) satisfies the following formula (11), and the content (Wa) of the polyurethane resin (a) and the water solubility
  • the ratio (Wb) / (Wa) of the content (Wb) of the melamine resin (b) preferably satisfies the following formula (13). 90 mass% ⁇ (Wa) + (Wb) ⁇ 100 mass% formula (11) 0 ⁇ (Wb) / (Wa) ⁇ 1 formula (13)
  • the total content (Wa) + (Wb) satisfies the following formula (15), and the ratio (Wb) / (Wa) is as follows: It is more preferable to satisfy the equation (17) of 95 mass% ⁇ (Wa) + (Wb) ⁇ 100 mass% formula (15) 0.1 ⁇ (Wb) / (Wa) ⁇ 0.3 formula (17)
  • the upper layer paint preferably does not have silica.
  • the upper layer coating film 13 contains silica, and as a result, the chemical resistance of the upper layer coating film 13 is deteriorated.
  • the upper layer paint preferably does not have at least one metal complex compound selected from zinc, aluminum and titanium.
  • At least one metal complex compound selected from zinc, aluminum and titanium for example, zinc stearate, zinc gluconate, zinc picolinate, zinc citrate, zinc acetylacetonate, aluminum acetate, aluminum stearate ,
  • the method of forming (coating) the upper layer coating on the metal plate 11 or the lower layer coating 15 in the upper layer coating forming step is not particularly limited, and, for example, a roll coating method, a ringer roll coating method, an air spray Well-known film-forming methods (coating method), such as a method, an airless spray method, an immersion method, can be utilized.
  • a roll coating method such as a method, an airless spray method, an immersion method
  • film formation is performed in a continuous coating line called a coil coating line or sheet coating line, complete with a film forming apparatus (coating apparatus) for performing these known film forming methods (coating methods)
  • the coating operation efficiency is good and a large amount It is more preferable because production is possible.
  • the method for cooling the upper layer coating film 13 after heating is not particularly limited, but for example, a known method such as water cooling (spray, submersion, etc.), air cooling (spray of nitrogen gas, etc.), etc. can do.
  • heating is performed under the condition that the heating time from the heating start to the highest reaching temperature is 1 second to 30 seconds, and from the highest reaching temperature to 30 ° C. It is preferable to form the upper coating film 13 by cooling under the condition that the cooling time is 0.1 seconds or more and 5 seconds or less.
  • the heating time and the cooling time are measured by detecting the temperature of the metal plate with a thermocouple.
  • the self-shrinkage of the water-soluble melamine resin (b) is further suppressed, and 0.1 as described above
  • the cooling is performed in a short time of 2 seconds to 5 seconds, the diffusion of the water-soluble melamine resin (b) is suppressed.
  • the water-soluble melamine resin (b) reacted with the polyurethane resin (a) forms a domain, and is dispersed in the upper layer coating 13 in particles having a number average particle diameter of 5 nm to 20 nm. It tends to be in the state of being concentrated in the surface layer within 15 nm in depth from the surface of. For this reason, in the coated metal plate 1 manufactured, the metal appearance, the chemical resistance and the solvent resistance can be further easily improved.
  • the heating time is less than 1 second, the reaction between the polyurethane resin (a) and the water-soluble melamine resin (b) may be insufficient and the chemical resistance and the solvent resistance may be lowered.
  • the heating time exceeds 30 seconds, the water-soluble melamine resin (b) tends to be self-condensed, the self-condensed particles become large, and the phenomenon occurs that the film is concentrated to the surface layer. In the coated metal plate 1, the metal appearance and the chemical resistance may decrease.
  • the cooling time is less than 0.1 seconds
  • the upper layer coating film 13 may be cracked as a result of rapid cooling.
  • the cooling time exceeds 5 seconds, diffusion of the water-soluble melamine resin (b) occurs, and the metal appearance and chemical resistance permeability may decrease in the manufactured coated metal plate 1.
  • the heating time is preferably 1 second or more and 20 seconds or less from the viewpoint of metal appearance, chemical resistance, and solvent resistance. Moreover, it is preferable that cooling time is 0.1 second or more and 2 seconds or less from the same viewpoint.
  • the maximum reaching temperature and the holding time thereof are not particularly limited, and may be, for example, 0.1, after appropriately setting the maximum reaching temperature to be the boiling point or more of the aqueous solvent according to the aqueous solvent used.
  • the holding time may be set in the range of seconds to 5 seconds.
  • the concentrated portion 103 is also formed at depth positions other than the surface layer.
  • the lower layer coating-film formation process in the manufacturing method of the coated metal plate which concerns on this embodiment is demonstrated.
  • the lower coating film forming step is not particularly limited, and a known lower coating is used as an example of the second coating, and the lower coating 15 is formed by a known method. It can be formed.
  • the lower coating film forming step contains an anionic functional group, and the glass transition temperature is not higher than the glass transition temperature of the polyurethane resin (a)
  • the lower layer paint containing at least one of the rust preventive agent (f) and the aqueous solvent is formed into a film and heated on at least one surface of the metal plate 11 and then cooled to form the lower layer coating film 15 Is preferred.
  • the glass transition temperature of the polyurethane resin (c) is preferably equal to or less than the glass transition temperature of the polyurethane resin (a).
  • the glass transition temperature of the polyurethane resin (c) is equal to or lower than the glass transition temperature of the polyurethane resin (a)
  • the adhesion between the lower coating 15 and the upper coating 13 is improved, and the chemical resistance is further improved. It will be easier.
  • the glass transition temperature of the polyurethane resin (c) is a value within the range of 80 ° C. or more and 160 ° C. or less, and less than or equal to the glass transition temperature of the polyurethane resin (a) (preferably, the glass transition temperature of the polyurethane resin (a) It is more preferable that the temperature is lower than 5 ° C.). If the glass transition temperature of the polyurethane resin (c) is less than 80 ° C., the chemical resistance may decrease. On the other hand, when the glass transition temperature of the polyurethane resin (c) exceeds 160 ° C., the processability may be lowered. When the processability is lowered, the lower coating film 15 is cracked and the like, and the chemical resistance and the solvent resistance are also lowered.
  • the glass transition temperature of the polyurethane resin (c) is preferably in the range of 100 ° C. or more and 160 ° C. or less from the viewpoints of chemical resistance and solvent resistance (in particular, in terms of chemical resistance).
  • the polyurethane resin (c) may be a polyurethane resin containing a polyurethane resin having a glass transition temperature of 80 ° C. to 160 ° C. and a polyurethane resin having a glass transition temperature of 20 ° C. to 60 ° C.
  • chemical resistance can be further improved.
  • polyurethane resin (c) the various polyurethane resin illustrated by the polyurethane resin (a) can be mentioned.
  • Epoxy resin (d) examples include bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, aliphatic epoxy resin and the like. Among these resins, since the aliphatic epoxy resin is hardly discolored by baking, it is particularly preferable to use as the epoxy resin (d).
  • epoxy resins (d) are not particularly limited, and various commercially available epoxy resins (d) can be used, and the glass transition temperature is within the above range. It is possible to synthesize such a thing by itself and use it appropriately.
  • the silane coupling agent (e) is not particularly limited, and various known silane coupling agents can be used.
  • a silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino) Ethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, bis (trimethoxysilylpropyl) amine, 3-glycidoxypropyltrimethoxysilane, 3-glylic Examples thereof include cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane
  • a rust inhibitor containing at least one element selected from the group consisting of P, V, Ti, Si and Zr as a rust inhibitor (f) is used. It is possible to use.
  • the corrosion resistance of the lower coating film 15 can be improved by incorporating the rust inhibitor (f) in the lower coating material.
  • P-containing compounds that function as antirust agents (f) include phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like, salts thereof, and aminotri (methylene phosphonic acid ), Phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid) and salts thereof, organic phosphoric acids such as phytic acid, and salts thereof Etc. can be mentioned.
  • phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like, salts thereof, and aminotri (methylene phosphonic acid )
  • Phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylene phosphonic acid), di
  • V which functions as a rust inhibitor (f) for example, vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, Examples thereof include vanadium oxyacetylacetonate, vanadium acetylacetonate, vanadium trichloride, phosphorus vanadomolybdic acid and the like.
  • an organic compound having at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group and a phosphonic acid group in a pentavalent vanadium compound A salt of oxovanadium cation and an inorganic acid anion such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, or an organic acid anion such as formic acid, acetic acid, propionic acid, butyric acid or oxalic acid
  • chelates of vanadyl compounds with organic acids such as vanadyl glycolate and vanadyl dehydroascorbate can be used.
  • Ti-containing compound which functions as a rust inhibitor (f) examples include, for example, titanium oxalate potassium, titanyl sulfate, titanium chloride, titanium lactate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium 2-ethyl oxide -1-Hexanolate, tetraisopropyl titanate, tetra-n-butyl titanate, titania sol, titanium hydrofluoric acid or salts thereof and the like can be mentioned.
  • Examples of compounds containing Si that function as antirust agents include Snowtex C, Snowtex O, Snowtex N, Snowtex S, Snowtex UP, Snowtex PS-M, and Snowtex PS-L.
  • Colloidal silica such as Snowtex 20, Snowtex 30, Snowtex 40 (all manufactured by Nissan Chemical Industries, Ltd.), Adelite AT-20N, Adelite AT-20A, Adelight AT-20Q (both manufactured by Asahi Denka Kogyo Co., Ltd.)
  • aerosols such as Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil MOX 80, Aerosil MOX 170 (all manufactured by Nippon Aerosil Co., Ltd.) and the like.
  • Zr which functions as an antirust agent (f) for example, zirconyl nitrate, zirconyl acetate, zirconyl sulfate, ammonium zirconium carbonate, potassium zirconium carbonate, sodium zirconium carbonate, zirconium acetate, zirconium hydrofluoric acid or the same Salt etc. can be mentioned.
  • the colorant to be dispersed in the lower layer paint containing the components as described above is not particularly limited as in the case of the upper layer paint, and known materials can be suitably used.
  • a coloring agent for example, various inorganic pigments such as titanium oxide, zinc oxide, calcium carbonate, aluminum oxide, barium sulfate, aluminum, iron oxide, carbon black and the like, various organic pigments such as cyanine and quinacridone, Various dyes and the like can be used.
  • aqueous solvent water, a mixed solution of water and a lower alcohol, or the like can be used as in the above-mentioned upper layer paint.
  • the aqueous solvent preferably contains 50% by mass or more (preferably 80% by mass or more) of water.
  • distilled water ion exchange water, ultrapure water, ultrafiltered water, etc.
  • ion exchange water ion exchange water
  • ultrapure water ultrafiltered water
  • C1-C4 alcohol such as methanol, ethanol, butanol, isopropyl alcohol etc.
  • the content of the polyurethane resin (c), the epoxy resin (d), the silane coupling agent (e) and the rust inhibitor (f) as described above is not particularly limited, and the lower coating film 15
  • the content of each component may be appropriately determined in accordance with the characteristics to be obtained.
  • the content of the polyurethane resin (c) can be in the range of 30 to 95% by mass
  • the content of the epoxy resin (d) can be in the range of 1 to 5% by mass It is possible.
  • the content of the silane coupling agent (e) can be, for example, in the range of 10 to 40% by mass
  • the content of the antirust agent (f) is, for example, in the range of 1 to 15% by mass It is possible to do inside.
  • the content of each component is within the above range so that the total content of these polyurethane resin (c), epoxy resin (d), silane coupling agent (e) and rust inhibitor (f) is 100% by mass. It may be determined appropriately.
  • the upper layer paint and the lower layer paint may contain known additives such as a wax, a leveling agent, an antifoamer, a thickener, a dispersant, etc. Good. That is, in the coated metal sheet according to the present embodiment, the upper coating film 11 and the lower coating film 15 may contain any of these known additives.
  • the surface of the metal sheet 11 to which the upper layer paint as described above is applied is, as required, textured, roughened, streaks (hair lines), weaves (satins), squares Various textures such as (hammer) may be formed.
  • the method and apparatus for forming the various textures as described above are not particularly limited, and various known ones can be appropriately used.
  • Example shown below is only an example of the manufacturing method of the coating metal plate which concerns on this invention, and a coating metal plate only, and the manufacturing method of the coating metal plate which concerns on this invention, and a coating metal plate is limited to the following example. It is not something to be done.
  • the plating adhesion amount of ZL was 20 g / m 2 per one side, and the amount of nickel in the plating layer was 12% by mass. Moreover, the plating adhesion amount of GI, SD, GL, and ZAM was 60 g / m 2 per one side, respectively. The plating adhesion amount of GA was 45 g / m 2 per one side. The plating adhesion amount of EG was 20 g / m 2 per one side.
  • the reaction liquid was cooled to 40 ° C., and then 20.00 g of triethylamine (boiling point 89 ° C.) was added to obtain an acetonitrile solution of a polyurethane prepolymer. 300 g of this solution is dispersed in 70. 00 g of water using a homodisper to form an emulsion, the solution is kept at 40 ° C., 21 g of ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane as a chain extender, and ethylenediaminehydrazine The chain extension reaction was carried out by adding 18 g of monohydrate.
  • the acetonitrile used at the time of polyurethane prepolymer synthesis was distilled off at 50 ° C. under a reduced pressure of 150 mmHg to obtain a self-made polyurethane resin B.
  • the triethylamine used as a raw material is removed at the refinement
  • the upper layer paint and the lower layer paint were respectively manufactured by using the materials shown in Tables 1 to 7 and mixing predetermined amounts of each material with water according to the description of Table 8 and Table 9.
  • the main resin-2 was blended at a ratio of 15 parts by mass with respect to 100 parts by mass of the main resin-1.
  • the lower layer paint manufactured as mentioned above was each coated with a roll coater so as to obtain a predetermined film thickness with a dry film thickness.
  • the film of the lower layer paint is heated (dried) under the condition that the maximum temperature of the metal plate reaches 150 ° C and the heating time from the start of heating to the maximum temperature is 10 seconds Cured).
  • the coated metal plate was sprayed with water by a spray, and water cooling was performed under the condition that the cooling time from the maximum reaching temperature to 30 ° C. was 1 second.
  • attainment temperature at the time of a heating was 1 second.
  • the upper layer paint manufactured as mentioned above was each coated with a roll coater so as to have a predetermined film thickness with a dry film thickness.
  • the film temperature of the upper layer paint is heated (dry-cured) under the condition that the maximum temperature of the metal plate reaches 230 ° C and the heating time from the start of heating to the maximum temperature is 10 seconds. did.
  • One second after reaching the highest reaching temperature spray the water onto the painted metal plate with a spray, and one second after reaching the highest reaching temperature, wipe the water onto the painted metal plate with a spray.
  • Water cooling was performed under the condition that the cooling time from the highest temperature to 30 ° C. was 1 second.
  • attainment temperature at the time of a heating was 1 second.
  • the composition of the upper-layer coating film and the lower-layer coating film was analyzed about the sample of each manufactured coated metal plate. Specifically, the upper coating film and the lower coating film constituting site (urethane bond skeleton (UB), triazine ring skeleton (TR), epoxy group (EP), presence of siloxane bond (silane) derived from silane coupling agent)
  • the coating film was analyzed using a Fourier transform infrared spectrophotometer (FT-IR, PerkinElmer Frontier), and it was judged based on whether or not the vibration peak shown below was observed. When it was done, it described in the table as "presence".
  • Urethane bond backbone (UB): 1540cm -1 are observed in the vicinity of the N-H vibrational peak of bending vibration, and the vibration peak triazine ring skeleton of C O stretching vibration is observed near 1730cm -1 (TR): 1550,1450,815Cm -1 vibrational peak epoxy group derived from triazine ring observed in the vicinity (EP): 910cm -1 from epoxy groups observed in the vicinity of the vibration peak siloxane bond: 1050 cm -1 Si observed in the vicinity Peak of -O-Si stretching vibration
  • the thickness (depth of concentration) of the concentrated portion present in the surface layer, and the number average particle diameter (particle diameter) of the particulate triazine portion (water soluble melamine resin) ) Were each measured.
  • an N concentration N1 at a depth of 0.2 ⁇ m from the surface of the first coating and an N concentration N2 at a depth of 0.2 ⁇ m from the interface between the first coating and the metal plate on the first coating side The ratio of N1 / N2 (concentration factor) was measured according to the method described above.
  • the glass transition temperature (Tg) of each coating film was measured according to the method described above for each of the manufactured coated metal sheet samples.
  • the coated metal sheet corresponding to the example of the present invention is excellent in metal appearance, chemical resistance, solvent resistance and processability. .
  • the processability is lowered compared to the other examples, and the processing is performed. It can be seen that the chemical resistance and the solvent resistance decrease when the In addition, when the glass transition temperature of the lower coating film 15 is higher than the glass transition temperature of the upper coating film 13 (Example 146), it can be seen that the chemical resistance is inferior to that of the other examples.
  • the commercially available resin, silane coupling agent and rust inhibitor used to form the upper layer coating film and the lower layer coating film are as follows.
  • Polyurethane resin for upper layer coating film Polyurethane resin 4 in Test Example 1
  • Polyurethane resin for lower layer coating Polyurethane resin 3 in Test Example 1
  • Water-soluble melamine resin Melamine resin 2 in Test Example 1
  • Epoxy resin Epoxy resin 1 in Test Example 1
  • Silane Coupling Agent Silane Coupling Agent 1 in Test Example 1
  • Rust inhibitor Rust inhibitor 2 in Test Example 1
  • Wax Chemipearl S100 (Mitsui Chemical Co., Ltd.)
  • the upper layer paint was prepared by mixing predetermined amounts of the above-mentioned polyurethane resin, melamine resin and wax in the composition according to Table 11, respectively.
  • the lower layer paint was prepared by mixing predetermined amounts of the above-mentioned polyurethane resin, epoxy resin, silane coupling agent, rust inhibitor and coloring agent in the composition according to Table 11, respectively.
  • the lower layer paint produced as described above was coated by a roll coater to a dry film thickness of 0.5 ⁇ m.
  • the film of the lower layer paint is heated (dried) under the condition that the maximum reached plate temperature of the metal plate is 150 ° C and the heating time from the start of heating to the maximum reached temperature is 5 seconds Cured).
  • the coated metal plate was sprayed with water by a spray, and water cooling was performed under the condition that the cooling time from the maximum reaching temperature to 30 ° C. was 1 second.
  • attainment temperature at the time of a heating was 1 second.
  • the upper layer paint produced as described above was coated by a roll coater to a dry film thickness of 10 ⁇ m.
  • the film temperature of the upper layer paint is heated (dry-cured) under the condition that the maximum temperature of the metal plate reaches 230 ° C and the heating time from the start of heating to the maximum temperature is 10 seconds. did.
  • One second after reaching the highest reaching temperature spray the water onto the painted metal plate with a spray, and one second after reaching the highest reaching temperature, wipe the water onto the painted metal plate with a spray.
  • Water cooling was performed under the condition that the cooling time from the highest temperature to 30 ° C. was 1 second.
  • attainment temperature at the time of a heating was 1 second.
  • the total content (Wa) + (Wb) of the polyurethane resin (a) and the water-soluble melamine resin (b) used in the upper layer coating film 13 is 90 mass% or more and 100 mass It turns out that the chemical-resistance permeability of the manufactured coated metal plate improves more because it becomes% or less and ratio (Wb) / (Wa) becomes more than 0 and 1 or less.
  • the upper layer paint 3 in Test Example 1 was used as the upper layer paint, and the lower layer paint 8 in Test Example 1 was used as the lower layer paint.
  • the lower layer paint produced as described above was coated by a roll coater to a dry film thickness of 1.0 ⁇ m.
  • the film of the lower layer paint is heated (dried) under the condition that the maximum reached plate temperature of the metal plate is 150 ° C and the heating time from the start of heating to the maximum reached temperature is 5 seconds Cured).
  • the coated metal plate was sprayed with water by a spray, and water cooling was performed under the condition that the cooling time from the maximum reaching temperature to 30 ° C. was 1 second.
  • attainment temperature at the time of a heating was 1 second.
  • the upper layer paint produced as described above was coated with a roll coater to a dry film thickness of 8 ⁇ m.
  • the induction heating furnace blown with hot air, the upper layer of the metal plate so that the heating time from the start of heating to the maximum reaching temperature and the holding time at 40 to 100 ° C become the conditions shown in Table 12
  • the paint film was heated (dried and cured).
  • the coated metal plate was sprayed with water by spraying, and water cooling was carried out under the condition that the cooling time from the maximum reaching temperature to 30 ° C. was the time shown in Table 12.
  • attainment temperature at the time of a heating was 1 second.
  • the heating time from the heating start to the highest reaching temperature is heated under the condition of 1 second to 30 seconds, and the cooling time from the highest reaching temperature to 30 ° C.
  • the obtained coated metal sheet is excellent in metal appearance, chemical resistance, processability and solvent resistance, in particular, It was excellent in chemical resistance.
  • a plurality of concentrated layers are provided in the first coating film produced by the method of holding at a temperature of 40 to 100 ° C. for 1 to 20 seconds, and then heating to 200 ° C. for 1 to 10 seconds, and then cooling. It was formed (Examples 315, 316, 317). When a plurality of concentrated layers were formed on the first coating, all of the metal appearance, chemical resistance, processability and solvent resistance were excellent.
  • FIGS. 5A-5D show cross-sectional TEM images of the upper coating film 13 of Example 303
  • FIG. 5 B shows the upper coating film 13 of Example 303 stained with osmium oxide as a TEM- It shows an elemental mapping image of osmium when observed by EDX.
  • FIG. 5C is an enlarged view of a central portion of the upper coating film 13 in the cross-sectional TEM image in FIG. 5A.
  • black particles appear in the cross-sectional TEM image.
  • FIG. 5D is an enlarged view of one such black granular material.
  • the regions corresponding to FIGS. 5C and 5D are confirmed in FIG. 5B, it can be seen that the elements of osmium are dispersed in such regions. Therefore, it can be understood that the portion of the dispersed osmium corresponds to the triazine particles 101. That is, it can be seen that the black particles in FIGS. 5C and 5D are triazine particles 101.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Coating With Molten Metal (AREA)

Abstract

La présente invention concerne une feuille métallique revêtue, comprenant une feuille métallique et un premier film de revêtement contenant de la graisse qui est disposé au moins sur une surface de la feuille métallique, le premier film de revêtement comprenant une première région comprenant un squelette de liaison uréthane et une seconde région comprenant un squelette de cycle triazine ; le premier film de revêtement comprenant une température de transition vitreuse de 85 à 170 °C ; et, lorsque la seconde région est colorée avec de l'oxyde d'osmium et observée avec un microscope électronique de type transmission dans un rapport de grossissement de 100 000, une seconde région dispersive, dans laquelle sont dispersées des particules comprenant un diamètre de particule moyen en nombre qui n'est pas inférieur à 5 nm, et une seconde région concentrée, dans laquelle de telles particules comprenant un diamètre de particule moyen en nombre qui n'est pas inférieur à 5 nm ne sont pas trouvées, étant observées.
PCT/JP2018/040384 2017-10-30 2018-10-30 Feuille métallique revêtue et procédé de fabrication d'une feuille métallique revêtue WO2019088123A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
MX2020004253A MX2020004253A (es) 2017-10-30 2018-10-30 Lamina de metal prepintada y metodo de fabricacion para lamina de metal prepintada.
KR1020207013532A KR102425956B1 (ko) 2017-10-30 2018-10-30 도장 금속판 및 도장 금속판의 제조 방법
CN201880070229.9A CN111278648B (zh) 2017-10-30 2018-10-30 涂装金属板和涂装金属板的制造方法
JP2019525038A JP6624346B2 (ja) 2017-10-30 2018-10-30 塗装金属板及び塗装金属板の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017209460 2017-10-30
JP2017-209460 2017-10-30

Publications (1)

Publication Number Publication Date
WO2019088123A1 true WO2019088123A1 (fr) 2019-05-09

Family

ID=66332537

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/040384 WO2019088123A1 (fr) 2017-10-30 2018-10-30 Feuille métallique revêtue et procédé de fabrication d'une feuille métallique revêtue

Country Status (5)

Country Link
JP (1) JP6624346B2 (fr)
KR (1) KR102425956B1 (fr)
CN (1) CN111278648B (fr)
MX (1) MX2020004253A (fr)
WO (1) WO2019088123A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004338397A (ja) * 2003-04-25 2004-12-02 Nippon Steel Corp 加工性に優れた非脱膜型潤滑めっき鋼板
JP2010285666A (ja) * 2009-06-12 2010-12-24 Nippon Parkerizing Co Ltd 金属材料用水系表面処理剤及び表面被覆金属材料
WO2013161621A1 (fr) * 2012-04-27 2013-10-31 日本パーカライジング株式会社 Tôle d'acier galvanisée traitée en surface qui présente une excellente résistance à la corrosion de face enroulée et d'extrémité et procédé de fabrication de cette dernière
JP2015129248A (ja) * 2014-01-09 2015-07-16 関西ペイント株式会社 熱交換器アルミニウムフィン用の皮膜形成方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05111675A (ja) 1991-10-22 1993-05-07 Asahi Glass Kooto & Resin Kk 金属板の塗装方法
JPH07313929A (ja) 1994-05-21 1995-12-05 Yodogawa Steel Works Ltd プレコートメタルとそのロール塗装方法
JPH07331167A (ja) 1994-06-08 1995-12-19 Sumitomo Metal Ind Ltd 被覆組成物とこれを塗装した塗装金属板
WO2001072524A1 (fr) * 2000-03-25 2001-10-04 Union Steel Manufacturing Co., Ltd. Procede de fabrication d'une plaque d'acier revetue par transfert de motif grave
JP4116945B2 (ja) 2003-08-06 2008-07-09 新日本製鐵株式会社 曲げ加工性に優れるプレコート金属板
JP4324094B2 (ja) 2004-12-24 2009-09-02 新日本製鐵株式会社 加工性および耐汚染性に優れる塗装金属板
JP5295549B2 (ja) * 2007-11-07 2013-09-18 株式会社Ａｄｅｋａ 塗料組成物
JP6255160B2 (ja) 2012-03-05 2017-12-27 新日鐵住金株式会社 クロメートフリー塗装金属板および水性塗料組成物
JP6291773B2 (ja) * 2013-10-03 2018-03-14 東洋インキＳｃホールディングス株式会社 樹脂組成物、活性エネルギー線重合性接着剤、及び積層体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004338397A (ja) * 2003-04-25 2004-12-02 Nippon Steel Corp 加工性に優れた非脱膜型潤滑めっき鋼板
JP2010285666A (ja) * 2009-06-12 2010-12-24 Nippon Parkerizing Co Ltd 金属材料用水系表面処理剤及び表面被覆金属材料
WO2013161621A1 (fr) * 2012-04-27 2013-10-31 日本パーカライジング株式会社 Tôle d'acier galvanisée traitée en surface qui présente une excellente résistance à la corrosion de face enroulée et d'extrémité et procédé de fabrication de cette dernière
JP2015129248A (ja) * 2014-01-09 2015-07-16 関西ペイント株式会社 熱交換器アルミニウムフィン用の皮膜形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T ECHNICAL DATASHEET CYMEL 385 RESIN, March 2017 (2017-03-01), Retrieved from the Internet <URL:https://www.palmerholland.com/Assets/User/Documents/Product/40580/5022/MITM00250.pdf> [retrieved on 20180115] *

Also Published As

Publication number Publication date
JPWO2019088123A1 (ja) 2019-11-14
KR102425956B1 (ko) 2022-07-28
CN111278648B (zh) 2021-11-05
JP6624346B2 (ja) 2019-12-25
MX2020004253A (es) 2020-07-29
KR20200069343A (ko) 2020-06-16
CN111278648A (zh) 2020-06-12

Similar Documents

Publication Publication Date Title
JP5108820B2 (ja) プレコート金属材料用水系表面処理剤、表面処理金属材料及びプレコート金属材料
CN103906578B (zh) 具有金属色调外观的无铬酸盐预涂金属板及其制造中使用的水系涂料组合物
US5578669A (en) Water-based polyurethane coating composition
CN104246010B (zh) 损伤部及端面耐腐蚀性优异的表面处理镀锌系钢板及其制造方法
JP5183586B2 (ja) プライマー兼用水系塗装下地処理剤、表面処理金属材料及びプレコート金属材料
JP2006328445A (ja) プレコート金属材料用水系表面処理剤、表面処理方法及びプレコート金属材料の製造方法
KR101290878B1 (ko) 복층 표면 처리 강판에 사용하는 접착층 형성용 조성물
KR101166212B1 (ko) 표면 처리 금속판
CN103547446B (zh) 面板
JP5369986B2 (ja) 塗装金属材とそれを用いてなる筐体
TW202225425A (zh) 熔融Ａｌ－Ｚｎ－Ｓｉ－Ｍｇ－Ｓｒ系鍍敷鋼板、表面處理鋼板及塗裝鋼板
TW202223118A (zh) 熔融Ａｌ－Ｚｎ－Ｓｉ－Ｍｇ系鍍敷鋼板、表面處理鋼板及塗裝鋼板
JP6350768B1 (ja) プレコート金属板
JP6255160B2 (ja) クロメートフリー塗装金属板および水性塗料組成物
JP7143786B2 (ja) 塗装金属板およびその製造方法
WO2019088123A1 (fr) Feuille métallique revêtue et procédé de fabrication d&#39;une feuille métallique revêtue
JP2011037083A (ja) 塗装金属材およびこれを用いてなる筐体ならびに塗料組成物
JP2010247396A (ja) 塗装金属板およびこれを用いてなる電子機器筐体
JP2008254313A (ja) プレコート金属板、これを成形加工した金属成形体及びプレコート金属板の製造方法
JP5602486B2 (ja) 塗装鋼板、加工品および薄型テレビ用パネル
JP2010247347A (ja) プレコート冷延鋼板およびこの製造方法
JP2022018854A (ja) 表面処理鋼板
JP6742142B2 (ja) めっき溶接形鋼及びめっき溶接形鋼の製造方法
JP6796100B2 (ja) 被覆めっき鋼板
JP2011038138A (ja) 塗装金属材およびこれを用いてなる筐体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019525038

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18873732

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207013532

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18873732

Country of ref document: EP

Kind code of ref document: A1