WO2019159385A1 - 塗装金属板 - Google Patents

塗装金属板 Download PDF

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Publication number
WO2019159385A1
WO2019159385A1 PCT/JP2018/014978 JP2018014978W WO2019159385A1 WO 2019159385 A1 WO2019159385 A1 WO 2019159385A1 JP 2018014978 W JP2018014978 W JP 2018014978W WO 2019159385 A1 WO2019159385 A1 WO 2019159385A1
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WIPO (PCT)
Prior art keywords
metal plate
fluororesin
layer
coated metal
mass
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PCT/JP2018/014978
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English (en)
French (fr)
Japanese (ja)
Inventor
克明 佐藤
尾和　克美
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日新製鋼株式会社
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Application filed by 日新製鋼株式会社 filed Critical 日新製鋼株式会社
Priority to KR1020207023058A priority Critical patent/KR102486942B1/ko
Priority to CN201880087419.1A priority patent/CN111819078B/zh
Publication of WO2019159385A1 publication Critical patent/WO2019159385A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—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 vinyl resins; comprising acrylic 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints

Definitions

  • the present invention relates to a painted metal plate.
  • the coated metal plate is generally excellent in durability, weather resistance, and design properties, and is suitably used for exterior building materials, for example.
  • painted metal plates for exterior building materials painted metal plates having a coating film made of fluororesin are suitable for painted metal plates that require long-term durability.
  • a fluororesin-based coated metal plate has a transparent coating film made of a mixed resin of polyvinylidene fluoride and an acrylic resin on a stainless steel plate surface, and the transparent coating film has a specific crystallinity and hardness.
  • a fluororesin-based coated stainless steel plate is known (for example, see Patent Document 1), and has a fluoro-colored layer containing a fluororesin, an acrylic resin, an inorganic fired pigment, and an organic pigment on the surface of the steel plate.
  • a fluororesin-based coated steel sheet having a coating film made of polyester having a specific glass transition temperature on the back surface of the steel sheet is known (for example, see Patent Document 2).
  • Fluorine resin is known to crystallize over time. That is, the fluororesin has a property that molecules relatively easily move in a temperature range higher than a glass transition temperature (for example, about ⁇ 40 ° C. for polyvinylidene fluoride) and a property that it has crystallinity. Therefore, the fluororesin tends to change from an irregular molecular arrangement structure (amorphous structure) to a regular molecular arrangement structure (crystal structure) in a temperature range above the glass transition temperature.
  • a glass transition temperature for example, about ⁇ 40 ° C. for polyvinylidene fluoride
  • Fluorine resin also has the property that, when crystallized, the bonding force between molecular chains becomes strong. Therefore, the ductility of the fluororesin-based coating film may decrease over time as the crystallization of the fluororesin progresses over time.
  • a coated metal sheet having a fluororesin-based coating film has a high ductility of the fluororesin-based coating film.
  • the coating film may be broken.
  • Patent Document 3 Patent Document 4, Patent Document 4
  • Patent Document 6 a method for graft polymerization of an acrylic resin on the fluororesin has also been proposed (see, for example, Patent Document 6).
  • the fluororesin coating film has a difference in workability depending on the crystal type of the fluororesin. Specifically, the ⁇ -type crystal of the fluororesin is lower in processability than the ⁇ -type crystal. It is said that it is not preferable to generate in a coating film (for example, refer patent document 7, nonpatent literature 1).
  • PVDF polyvinylidene fluoride
  • an object of the present invention is to provide a coated metal plate having a fluororesin layer having pigment particles and having high workability even after long-term storage.
  • the fluororesin layer contains a polyvinylidene fluoride-based fluororesin and an acrylic resin, and the polyvinylidene fluoride-based fluororesin has more ⁇ -type crystals than ⁇ -type crystals of the fluororesin. As a result, it was found that the workability was not easily lowered even after long-term storage, and thus the present invention was completed.
  • one embodiment of the present invention relates to a painted metal plate having a metal plate and a fluororesin layer.
  • the fluororesin layer includes a polyvinylidene fluoride fluororesin, an acrylic resin, and pigment particles.
  • a coated metal plate having a fluororesin layer and having high workability even after long-term storage.
  • FIG. 1A is a schematic diagram showing the magnitude of stress applied when the fluororesin layer is stretched
  • FIG. 1B shows the stretch of the fluororesin when the fluororesin layer is stretched immediately after the formation of the fluororesin layer
  • FIG. 1C is a schematic diagram showing a state in which the concentration of tensile stress is relaxed by the growth of voids, and FIG. 1C shows that after a certain time has elapsed since the formation of the fluororesin layer, the fluororesin is difficult to stretch and cracks are likely to grow. It is a schematic diagram which shows a mode.
  • Painted metal plate A first embodiment of the present invention relates to a painted metal plate having a metal plate and a fluororesin layer.
  • Metal plate can be selected from known metal plates as long as the effects of the present embodiment can be obtained.
  • Examples of the metal plate include cold rolled steel sheet, galvanized steel sheet, Zn—Al alloy plated steel sheet, Zn—Al—Mg alloy plated steel sheet, aluminum plated steel sheet, stainless steel sheet (austenite, martensite, ferrite, ferrite -Including martensite two-phase systems), aluminum plates, aluminum alloy plates and copper plates.
  • the metal plate is preferably a plated steel plate or a stainless steel plate from the viewpoint of corrosion resistance and weight reduction, and is preferably a plated steel plate from the viewpoint of cost effectiveness.
  • the metal plate is preferably a molten 55% Al—Zn alloy-plated steel plate, a Zn—Al—Mg alloy-plated steel plate or an aluminum-plated steel plate from the viewpoint of further improving the corrosion resistance.
  • zinc-based plated steel sheets are preferable, and zinc-based plated steel sheets containing magnesium such as Zn—Al—Mg alloy-plated steel sheets are more preferable.
  • the thickness of the metal plate can be appropriately determined based on the use of the coated metal plate.
  • the thickness of the metal plate is preferably 0.2 to 3.0 mm when the application of the coated metal plate is an exterior building material, and 0.25 to 2 from the viewpoint of further improving the workability. 0.0 mm is preferred.
  • Fluororesin layer is a resin layer disposed in contact with the surface of the metal plate or via another layer.
  • the fluororesin layer contains a fluororesin and a base resin constituting the film structure of the fluororesin layer, and pigment particles dispersed in the base resin. It is preferable that the said fluororesin layer is a layer which comprises the outermost surface of the said coating metal plate from a viewpoint of raising the weather resistance of a coating metal plate more.
  • the thickness of the fluororesin layer is preferably 50 ⁇ m or less.
  • the thickness of the fluororesin layer can be represented by an average value of the distance from the bottom surface to the surface at a plurality of locations (for example, 10 locations arbitrarily selected) of the fluororesin layer.
  • the thickness is 50 ⁇ m or less, it is not necessary to increase the coating amount of the coating material when producing the fluororesin layer, and when the coating film is heated and cured, ) And other coating defects can be made difficult to occur.
  • the thickness of the fluororesin layer can be appropriately determined based on various factors including pigment particle content, color tone and ultraviolet shielding degree, and degree of processing at the time of forming the coated metal plate. .
  • the thickness of the fluororesin layer can be further reduced.
  • required by a fluororesin layer becomes low, when the said processing degree is low, it is possible to make the thickness of a fluororesin layer small.
  • the thickness of the fluororesin layer is large from the viewpoint of reducing the elongation deformation strain.
  • the thickness of the fluororesin layer cannot be generally specified, for example, the degree of processing is equivalent to the degree of 4T bending, and the pigment particles (for example, titanium oxide particles) that are color pigments
  • the thickness of the fluororesin layer is preferably 20 ⁇ m or more, and more preferably 25 ⁇ m or more.
  • the L value of the pigment particles (for example, iron-chromium-based calcined pigment particles) that are the above-mentioned degree of processing and color pigments is 70 or less
  • the thickness of the fluororesin layer is preferably 15 ⁇ m or more. More preferably, it is 18 ⁇ m or more.
  • the fluororesin is a polyvinylidene fluoride resin.
  • the fluororesin is a resin that is a main component of the base resin, and imparts durability, chemical resistance, heat resistance, wear resistance, weather resistance, corrosion resistance, stain resistance, and the like to the fluororesin layer.
  • the above fluororesin may be one kind or more.
  • the fluororesin component that is a polyvinylidene fluoride resin include polyvinylidene fluoride (PVDF) that is a homopolymer of 1,1-difluoroethylene, and a copolymer of 1,1-difluoroethylene and hexafluoropropylene. Includes coalescence.
  • the fluororesin is more preferably a copolymer of 1,1-difluoroethylene and hexafluoropropylene, and the content of the copolymer is preferably a fluororesin.
  • the total mass is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.
  • Content of the said fluororesin in the said base resin can be suitably determined in the range with which the effect of this Embodiment is acquired, for example, is 50 to 85 mass% with respect to the total mass of base resin. It is preferable that it is 70 mass% or more and 85 mass% or less.
  • the above fluororesin is at least partially crystallized.
  • crystal structures of fluororesins ⁇ -type crystals and ⁇ -type crystals are known.
  • the fluororesin is characterized in that the proportion of ⁇ -type crystals (crystallinity) is higher than the proportion of ⁇ -type crystals (crystallinity).
  • the degree of crystallinity (Ic ⁇ / Ia) of the ⁇ -type crystal is set to 2.5 or less from the viewpoint of suppressing a decrease in workability.
  • the crystallinity (Ic ⁇ / Ia) of the ⁇ -type crystal is preferably 1.2 or more and 2.0 or less because workability is improved, and is 1.4 or more and 2.0 or less. It is more preferable because workability is further improved.
  • the crystallinity (Ic ⁇ / Ia) of the ⁇ -type crystal is preferably less than 1.2 because workability is increased, and less than 0.8 is more preferable because workability is further increased.
  • the crystallinity of the ⁇ -type crystal may increase as time elapses from the formation of the fluororesin layer due to the crystallization of the fluororesin. Even in such a case, the crystallinity (Ic ⁇ / Ia) of the ⁇ -type crystal in the coated metal plate is preferably less than 1.5. In the coated metal plate of the present embodiment, the ⁇ -type crystal probably inhibits the growth of the ⁇ -type crystal, and therefore the crystallinity of the ⁇ -type crystal (Ic ⁇ / Ia) is 1.2 even if the change with time occurs. May be less than
  • the lower limit of the crystallinity (Ic ⁇ / Ia) of the ⁇ -type crystal can be zero.
  • the coated metal plate in which the fluororesin has the above characteristics has sufficient ductility even though the fluororesin layer contains pigment particles, and thus has sufficient workability.
  • the reason assumed by the present inventors will be described below with reference to FIG. 1A, FIG. 1B, and FIG. 1C schematically showing how voids are generated when the fluororesin layer is stretched.
  • FIGS. 1A, 1B, and 1C when tensile stress is applied to the base resin 110 in which the pigment particles 120 are dispersed in the vertical direction in the figure, stress is applied to the base resin 110. (The magnitude of stress at each position is indicated by the length of the arrow).
  • the molecular chains of the fluororesin constituting the coating film that are oriented randomly before the constricted deformation are oriented in the tensile direction due to the tensile stress. For this reason, when a certain amount of tensile stress is applied to the constricted deformed portion, the molecular chain that has already been oriented is not easily stretched any more, even if tensile stress is applied further. For this reason, the “parts that have not been constricted yet (molecular chains that are not oriented)” around the constricted deformed portion are constricted and deformed.
  • Such propagation of molecular chain orientation is elongation deformation of the resin coating.
  • the high ductility of the resin-made coating film results from the propagation of the above-described orientation of the molecular chain progressing throughout the coating film without breaking the molecular chain.
  • the stress required for the orientation of the molecular chain is higher in the crystallized resin than in the amorphous resin. This is because the bond strength between regularly folded crystal molecular chains is high.
  • the molecular chains are more oriented and easily deformed, and the fluororesin layer is also easily deformed in width.
  • voids 130 are generated in the tensile direction in which the fluororesin cannot be stretched, and the voids 130 grow in the tensile direction (see FIG. 1B).
  • concentration of tensile stress is alleviated by the stretching of the fluororesin and the growth of the voids 130.
  • the fluororesin layer after a certain time has passed since the formation of the fluororesin layer, in the stretching, the voids generated from the pigment particles 120 grow in the direction perpendicular to the tensile direction, and eventually When the fluororesin layer is broken, it is considered that ductility is lowered and workability is lowered.
  • the base resin contains an acrylic resin in addition to the fluororesin
  • the ⁇ -type crystals of the fluororesin phase separate together with the acrylic resin to form a fine structure.
  • Such a fine phase-separated structure inhibits molecular chain orientation, thus making it more difficult for constriction deformation to occur, and as a result, the ductility of the fluororesin layer after a certain period of time is further reduced. It is done.
  • the ⁇ -type crystal of the fluororesin hardly generates the fine phase separation structure.
  • the fluororesin layer containing more ⁇ -type crystals and less ⁇ -type crystals is liable to undergo width deformation due to constriction deformation, and cracks in the direction perpendicular to the stretching direction are less likely to occur.
  • the tensile stress applied to the fluororesin layer by stretching is easily relaxed, and the ductility of the fluororesin layer is also increased.
  • the ductility of the fluororesin layer after aging may decrease, and the crystallinity of the ⁇ -type crystals (Ic ⁇ / Ia) is 2.5 or less.
  • Acrylic resin is contained in the base resin from the viewpoint of suppressing excessive crystallization of the fluororesin, the viewpoint of increasing the dispersibility of the pigment particles, and the viewpoint of increasing the adhesion of the base resin.
  • the acrylic resin may be one kind or more.
  • examples of the acrylic resin include a polymer of an acrylic monomer such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, or a copolymer of a monomer containing the acrylic monomer.
  • the Content of the said acrylic resin in the said base resin can be suitably determined in the range in which the effect of this Embodiment is acquired, for example, 15 to 50 mass% with respect to the total mass of base resin It is preferable that it is 15 mass% or more and 30 mass% or less.
  • the mass ratio (FR: AR) of the fluororesin (FR) and the acrylic resin (AR) in the base resin is preferably 50:50 to 85:15. If the acrylic resin content is in the above range, the properties of the fluororesin such as weather resistance, corrosion resistance, and contamination resistance can be fully exerted. On the other hand, the adhesion of the fluororesin layer is not significantly reduced. Sufficient workability of the plate can be maintained.
  • the acrylic resin is preferably softer. From such a viewpoint, the acrylic resin has a glass transition temperature (Tg) of 30 ° C. or lower. preferable. An acrylic resin having a Tg of 30 ° C. or lower is less likely to be cured during storage of the coated metal plate, and therefore can suppress a decrease in workability of the coated metal plate after long-term storage. From the above viewpoint, the Tg of the acrylic resin is more preferably 20 ° C. or less, and more preferably 10 ° C. or less. The Tg of the acrylic resin can be a value calculated from the monomer composition by the formula of FOX or a value measured by differential thermal analysis (DTA).
  • DTA differential thermal analysis
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 50,000 or more and 200,000 or less, and more preferably 70,000 or more and 150,000 or less.
  • the acrylic resin is preferably a copolymer of methyl methacrylate, ethyl acrylate, and an ester compound of (meth) acrylic acid and an alcohol having 1 to 6 carbon atoms.
  • the copolymer is imparted with an appropriate hardness by methyl methacrylate and moderately softened by ethyl acrylate.
  • the fine ⁇ type in advance Forming the crystal prevents the formation of a fine phase separation structure between the ⁇ -type crystal and the acrylic resin and maintains the improvement in adhesion by the acrylic resin, which is considered to improve the workability.
  • the copolymer has a structure ratio derived from methyl methacrylate of 10% by mass or more and 50% by mass or less, and a ratio of structure derived from ethyl acrylate is 40% by mass. It is preferable that the ratio of the structure derived from the said ester compound is 10 to 50 mass%.
  • the proportion of the structure derived from methyl methacrylate is 10% by mass to 30% by mass, and the proportion of the structure derived from ethyl acrylate Is 60 mass% or more and 80 mass% or less, and it is preferable that the ratio of the structure originating in the said ester compound is 10 mass% or more and 30 mass% or less.
  • the fluororesin layer contains pigment particles dispersed in the base resin.
  • the pigment particles may be colored pigment particles, gloss modifier particles, or extender pigment particles. One or more pigment particles may be used.
  • the colored pigment particles may be either organic colored pigments or inorganic colored pigment particles that are generally available as colored pigments for paints.
  • the colored pigment particles are non-transparent and give a color tone to the fluororesin layer to form a colored coating film.
  • inorganic coloring pigments examples include titanium oxide, chromium oxide, carbon black, iron black, iron oxide yellow, titanium yellow, bengara, bitumen, cobalt blue, cerulean blue, ultramarine blue, cobalt green, and molybdenum red. It is.
  • organic coloring pigments examples include quinacridone red, resol red B, brilliant scarlet G, pigment scarlet 3B, brilliant carmine 6B, lake red C, lake red D, permanent red 4R, Bordeaux 10B, fast yellow G, fast yellow.
  • 10G Para Red, Watching Red, Benzidine Yellow, Benzidine Orange, Bon Maroon L, Bon Maroon M, Brilliant Fast Scarlet, Vermillion Red, Phthalocyanine Blue, Phthalocyanine Green, Fast Sky Blue, and Aniline Black.
  • the colored pigment particles may be particles of a composite oxide fired pigment containing a metal component.
  • the calcined pigment include CoAl, CoCrAl, CoCrZnMgAl, CoNiZnTi, CoCrZnTi, NiSbTi, CrSbTi, FeCrZnNi, MnSbTi, FeCr, FeCrNi, FeNi, FeCrNiMn, FeZn, CoCr, MnCo, and SnZnTi.
  • the colored pigment particles may be metallic pigment particles.
  • the metallic pigment particles include Al flakes, resin-coated Al flakes, metal oxide-coated Al flakes, Ni flakes, Cu flakes, and stainless steel flakes.
  • the colored pigment particles may be pearl pigment particles.
  • the pearl pigment particles include titanium oxide-coated mica, iron oxide-coated mica, and titanium oxide-iron oxide-coated mica.
  • the number average particle diameter of the colored pigment particles can be appropriately determined within the range in which the effect of the present embodiment can be obtained, but is usually 3 ⁇ m or less, preferably 0.01 ⁇ m or more and 1.5 ⁇ m or less. .
  • the number average particle diameter of the colored pigment particles is preferably 2.0 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • the number average particle diameter is 2.0 ⁇ m or less, it is usually possible to contain up to 5% by volume of color pigment particles in the fluororesin layer, and if the number average particle diameter is 0.5 ⁇ m or less. It becomes possible to contain up to 20% by volume of color pigment particles in the fluororesin layer.
  • the gloss modifier particles can be used for the purpose of imparting a desired gloss to the fluororesin layer or for the purpose of forming irregularities on the top surface of the fluororesin layer.
  • the gloss adjusting agent particles may be one kind or more.
  • the material of the gloss modifier particles include inorganic materials including silica and calcium carbonate, and resin materials such as acrylic resin, urethane resin, benzoquamine resin, styrene resin, polyethylene resin, polypropylene resin, and fluorine resin. Is included.
  • the number average particle diameter of the gloss modifier particles contained in the fluororesin layer is preferably 3 ⁇ m or less. Since the average particle size of commercially available gloss modifier particles is usually more than 3 ⁇ m, when using commercially available gloss modifier particles, particles having a particle size of 3 ⁇ m or less are separated and used by classification, or The content is preferably 1% by volume or less.
  • the content of the gloss modifier particles in the fluororesin layer varies depending on, for example, the particle size of the gloss modifier particles, but the desired design is achieved by blending the gloss modifier particles in the fluororesin layer. In view of the above, it is preferably 0.2% by volume or more and 1.0% by volume or less.
  • the gloss modifier particles in the fluororesin layer have a larger particle size (for example, the number average particle size is greater than 3 ⁇ m).
  • the content is preferably 0.2% by volume or more.
  • the said content is 1.0 volume% or less from a viewpoint of the workability after storage.
  • the extender pigment particles are pigments contained in the fluororesin layer from the viewpoints of adjusting the hardness of the fluororesin layer and reducing the cost of the paint (the effect of increasing the bulk), and generally do not affect the color tone of the fluororesin layer. . Since extender pigment particles are usually less expensive than fluororesin, it is preferable that the fluororesin layer contains extender pigment particles as long as the effects of the present embodiment are obtained.
  • the extender pigment particles preferably have a high visible light transmittance.
  • One or more extender pigment particles may be used. Examples of extender pigment particles include particles such as barium sulfate, titanium oxide, silica and calcium carbonate.
  • the number average particle size of the extender particles is preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
  • content of the extender pigment particle in a fluororesin layer is 0.1 volume% or more and 10 volume% or less.
  • the coated metal plate may further have a layer other than the fluororesin layer as long as the effect of the present embodiment is obtained.
  • the other layers include a chemical conversion treatment layer, an undercoat layer, and an intermediate coat layer.
  • the metal plate, the chemical conversion treatment layer, the undercoat layer, and the fluororesin layer are preferably laminated in this order, and the metal plate, the chemical conversion treatment layer, the undercoat layer, More preferably, the coating layer and the fluororesin layer are laminated in this order.
  • Chemical conversion layer The chemical conversion layer is disposed directly on the metal plate, that is, between the metal plate and the fluororesin layer, for the purpose of improving the adhesion and corrosion resistance of the coated metal plate.
  • a chemical conversion treatment layer is a layer formed in contact with the surface of a metal plate, and is comprised with the composition adhering to the surface of the metal plate by the pre-coating process. Examples of the chemical conversion treatment layer include a non-chromate film and a chromate film. Both are films formed by rust prevention treatment.
  • the non-chromate film is preferable from the viewpoint of enhancing the corrosion resistance and reducing the environmental load in the production and use of the coated metal plate, and the chromate film is preferable from the viewpoint of increasing the corrosion resistance.
  • non-chromate coatings examples include Ti-Mo composite coatings, fluoroacid coatings, phosphate coatings, resin coatings, resins and silane coupling agent coatings, silica coatings, silica and silane coupling agent coatings Films, zirconium-based films, and zirconium and silane coupling agent-based films are included.
  • the adhesion amount of the non-chromate film can be appropriately determined according to the type.
  • the adhesion amount of the Ti—Mo composite film is preferably 10 mg / m 2 or more and 500 mg / m 2 or less in terms of total Ti and Mo
  • the adhesion amount of the fluoroacid-based film is in terms of fluorine or total metal It is preferably 3 mg / m 2 or more and 100 mg / m 2 or less in terms of element
  • the amount of the phosphate coating deposited is preferably 0.1 mg / m 2 or more and 5 g / m 2 or less in terms of phosphorus element.
  • the adhesion amount of the resin film is preferably 1 mg / m 2 or more and 500 mg / m 2 or less in terms of resin, and the adhesion amount of the resin and the silane coupling agent film is 0.1 mg / m in terms of Si.
  • the adhesion amount of the silica-based coating is possible in terms of Si is 0.1 mg / m 2 or more 200 mg / m 2 or less
  • the adhesion amount of the silica and silane coupling agent-based coating is preferably in terms of Si is 0.1 mg / m 2 or more 200 mg / m 2 or less
  • adhesion quantity of the zirconium-based coating, in terms of Zr It is preferably 0.1 mg / m 2 or more and 100 mg / m 2 or less
  • the adhesion amount of the zirconium and silane coupling agent-based film is 0.1 mg / m 2 or more and 100 mg / m 2 or less in terms of Zr. Is preferred.
  • chromate film examples include a coating type chromate film and a phosphoric acid-chromic acid system chromate rust preventive film.
  • the adhesion amount of these chromate films is preferably 20 g / m 2 or more and 80 g / m 2 or less in terms of chromium element.
  • the undercoat layer is disposed between the metal plate and the fluororesin layer from the viewpoint of enhancing the adhesion and corrosion resistance of the fluororesin layer in the coated metal plate.
  • the undercoat layer is formed on the surface of the metal plate or, if the chemical conversion treatment layer is prepared, on the surface of the chemical conversion treatment layer.
  • the undercoat layer is made of resin.
  • the resin include fluorine resin, polyester resin, modified silicon resin, acrylic resin, epoxy resin, phenoxy resin, urethane resin, and vinyl chloride resin.
  • the undercoat layer may further contain additives such as rust preventive pigment particles, colored pigment particles, metallic pigment particles, pearl pigment particles, extender pigment particles, and gloss modifier particles.
  • additives such as rust preventive pigment particles, colored pigment particles, metallic pigment particles, pearl pigment particles, extender pigment particles, and gloss modifier particles.
  • anticorrosive pigment particles include non-chromium anticorrosive pigment particles including modified silica, vanadate, magnesium hydrogen phosphate, magnesium phosphate, zinc phosphate, and aluminum polyphosphate, and chromium.
  • examples include particles of chromium-based anticorrosive pigments including strontium acid, zinc chromate, barium chromate, calcium chromate and the like.
  • colored pigment particles examples include titanium oxide, chromium oxide, carbon black, iron black, iron oxide yellow, titanium yellow, bengara, bitumen, cobalt blue, cerulean blue, ultramarine, cobalt green, molybdenum red, quinacridone red, and risol.
  • Aniline Racks include CoAl, CoCrAl, CoCrZnMgAl, CoNiZnTi, CoCrZnTi, NiSbTi, CrSbTi, FeCrZnNi, MnSbTi, FeCr, FeCrNi, FeNi, FeCrNiMn, FeZn, CoCr, MnCo, and particles such as SnZnTi.
  • Examples of the metallic pigment particles include Al flakes, resin-coated Al flakes, metal oxide-coated Al flakes, Ni flakes, Cu flakes, and stainless steel flakes.
  • Examples of the pearl pigment particles include titanium oxide-coated mica, iron oxide-coated mica, and titanium oxide-iron oxide-coated mica.
  • Examples of the extender particles include particles such as barium sulfate, titanium oxide, silica and calcium carbonate.
  • Examples of the gloss modifier particles include inorganic materials such as silica and calcium carbonate, and resin materials such as acrylic resin, urethane resin, benzoquaminamine resin, styrene resin, polyethylene resin, polypropylene resin, and fluorine resin. .
  • the content of the additive in the undercoat layer can be determined as appropriate as long as the effect of the present embodiment is obtained. For example, by adding a pearl pigment to the fluororesin layer and providing an undercoat layer having low lightness between the fluororesin layer and the metal plate, it is possible to impart a unique color tone and radiance to the pearl pigment. Further, for example, by adding pigment particles having a large particle size of about several tens of ⁇ m to the undercoat layer, unevenness is formed at the interface between the undercoat layer and the fluororesin layer, thereby further improving the adhesion of the fluororesin layer. Moreover, low glossiness can be further enhanced by the formation or development of irregularities on the surface of the coated metal plate. For example, the content of the anticorrosive pigment in the undercoat layer is preferably 10% by volume or more and 70% by volume or less.
  • the intermediate coating layer is disposed between the undercoat layer and the fluororesin layer from the viewpoint of enhancing the adhesion and corrosion resistance between the layers in the coated metal plate.
  • the intermediate coating layer is also made of resin.
  • the resin include fluorine resin, polyester resin, modified silicon resin, acrylic resin, epoxy resin, phenoxy resin, urethane resin, and vinyl chloride resin.
  • the intermediate coat layer may further contain the above additives as long as the effects of the present embodiment can be obtained.
  • the additive for example, the same additive as described in the fluororesin layer can be used.
  • the thickness of a fluororesin layer can be determined in consideration of presence of the said other layer.
  • the thickness of the fluororesin layer is preferably 10 ⁇ m or more and 35 ⁇ m or less from the viewpoint of improving design properties, corrosion resistance, and workability over time.
  • the said coated metal plate can be produced based on the production method of a well-known coating film.
  • the coated metal plate includes a step of forming a film of the fluororesin layer (fluorine resin paint) on the metal plate, and curing the film of the fluororesin paint to form an ⁇ -type crystal and a ⁇ -type crystal. And the step of producing the fluororesin layer having the above-mentioned characteristics with respect to the degree of crystallinity.
  • the above-mentioned paint is a liquid composition containing the material of each layer described above.
  • the coating material is prepared, for example, by dispersing the above-described material of each layer in a solvent.
  • the solvent include hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ethers such as cellosolve, and ketones such as methyl isobutyl ketone, methyl ethyl ketone, isophorone, and cyclohexanone.
  • the paint may further contain other additives in the solvent.
  • the additive include a curing agent, a curing catalyst, and a hydrophilizing agent.
  • the curing agent crosslinks the base resins when the paint is cured (baked).
  • the curing agent can be appropriately selected from known crosslinking agents and curing agents according to the type of base resin, baking conditions, and the like.
  • curing agents include melamine compounds, isocyanate compounds, and both.
  • the melamine compound include an imino group type, a methylol imino group type, a methylol group type or a fully alkyl group type melamine compound.
  • the isocyanate compound may be aromatic, aliphatic, or alicyclic, and examples include m-xylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, and block compounds thereof.
  • the curing catalyst is a component that accelerates the curing of the film or the crosslinking of the base resin, and can be appropriately selected from known components having such a catalytic action.
  • the content of the curing catalyst in the paint can be appropriately determined within a range where sufficient storage stability of the paint can be obtained, and is, for example, 10 to 30% by volume.
  • the hydrophilizing agent is suitable as an additive for the fluororesin layer, and can be contained in the fluororesin paint in an amount of, for example, 30% by volume or less from the viewpoint of preventing rain stains on the fluororesin layer.
  • the hydrophilizing agent include a partial hydrolysis condensate of tetraalkoxysilane.
  • the coating can be performed by a known method such as roll coating, curtain flow coating, spray coating, or dip coating.
  • the coating amount of the paint is appropriately adjusted according to the desired thickness of each layer described above.
  • the coating of at least the upper layer of the two layers that directly overlap each other can be applied by a non-contact coating method such as curtain flow coating or spray coating (so-called wet-on-wet coating without contact with the object to be coated is possible.
  • the lower coating film can be cured at the same time as the upper coating film at the same time, so before applying the coating for the upper layer, It is possible to omit the step of curing the coating film.
  • the fluororesin layer is disposed directly on the other layer described above, a coating film for the other layer is formed, and then the fluororesin coating film is formed by a non-contact coating method. Then, it is possible to cure (by heating) the other layer and the film of the fluororesin coating layer overlapping therewith.
  • the coating film can be cured by a known method in which the coating is baked on a metal plate.
  • a metal plate to which the above paint such as a fluororesin paint is applied is heated so that the ultimate temperature is 200 to 260 ° C.
  • the step of producing the fluororesin layer is performed at a temperature at which the film in which the fluororesin coating is cured by the heating is reduced from the temperature (200 ° C.) higher than the melting temperature of the fluororesin, so that the molecular motion of the fluororesin is reduced and the crystal is difficult to grow.
  • This is a crystallization step of cooling to (70 ° C.) at a cooling rate of 130 ° C./second or more.
  • the cooling rate is preferably faster, and is preferably 250 ° C./second or more.
  • the cooling of the colored coating after baking can be performed by a known method such as air cooling, water cooling, cooling, contact with a cooling member, or a combination thereof.
  • the crystallization step may be performed immediately after curing of the fluororesin coating film by heating or after the cured film having a temperature lower than the melting temperature is heated to a temperature equal to or higher than the melting temperature. May be.
  • the crystal structure of the fluororesin substantially disappears at a temperature equal to or higher than the melting point temperature of the fluororesin.
  • the method for manufacturing a coated metal plate may further include other steps than the above-described steps within a range where the effect of the present embodiment can be obtained.
  • the other steps include a chemical conversion treatment step for forming a chemical conversion treatment film, a step for forming an undercoat layer, and a step for forming an intermediate coating layer.
  • an aqueous chemical conversion treatment liquid for forming a chemical conversion treatment film is applied to the surface of the metal plate by a known method such as a roll coating method, a spin coating method, or a spray method. This can be done by drying the plate without washing it with water. From the viewpoint of productivity, the drying temperature and drying time of the metal plate are preferably, for example, 60 to 150 ° C. and 2 to 10 seconds at the ultimate temperature of the metal plate.
  • the step of forming the undercoat layer can be performed by applying a paint for the undercoat layer (undercoat paint) and thereby curing the film.
  • the undercoat paint may contain the solvent and the additive as necessary.
  • the undercoat paint is prepared by uniformly mixing and dispersing the above-described materials.
  • the undercoat paint is applied to the metal plate by a known method described above for the overcoat paint in an application amount that provides a dry film thickness of 1 to 10 ⁇ m (preferably 3 to 7 ⁇ m).
  • the coating film of the paint is produced by, for example, baking onto the metal plate by heating the metal plate at a temperature of 180 to 260 ° C. at the temperature reached by the metal plate.
  • the step of forming the intermediate coating layer can also be performed by applying a coating material for the intermediate coating layer (intermediate coating material) and curing the film thereby, similarly to the step of forming the undercoat layer.
  • the intermediate coating material may also contain the solvent and the additive as necessary, in addition to the material of the intermediate coating layer.
  • the intermediate coating is also prepared by uniformly mixing and dispersing the above-described materials.
  • the intermediate coating is preferably applied in a coating amount of 3 to 20 ⁇ m (preferably 5 to 15 ⁇ m), for example, by the above-mentioned known method.
  • the coating layer is produced by, for example, baking onto a metal plate by heating the metal plate at a temperature of 180 to 260 ° C. at a temperature reached by the metal plate.
  • a non-chromate antirust treatment solution containing the following components in the following amounts is applied, and the coated steel sheet after application is dried at 100 ° C. without washing, and 10 mg in terms of Ti.
  • a non-chromate rust preventive treatment with an adhesion amount of / m 2 was performed.
  • the following epoxy resin-based paint containing the following components in the following amounts is applied, and the above-mentioned temperature of the plated steel sheet is 200 ° C.
  • the plated steel sheet after application of was heated to obtain a plated steel sheet having a chromate-free coating film with a dry film thickness of 5 ⁇ m. This is the original coating.
  • the following clear paint is “NSC680” manufactured by Nippon Paint Industrial Coatings Co., Ltd. Phosphate mixture 15% by volume Barium sulfate 5% by volume Silica 1% by volume Above clear paint
  • fluororesin paint 1 to fluororesin paint 25
  • Polyvinylidene fluoride (“Kynar 500” manufactured by Arkema, “Kynar” is a registered trademark of the company) was prepared as a fluororesin. This is designated as fluororesin 1.
  • copolymer resins of 1,1-difluoroethylene (VDF) and hexafluoropropylene (HFP) (“Kynar Flex LBG” manufactured by Arkema, “Kynar Flex” are registered trademarks of the company) were prepared as fluororesins. This is designated as fluororesin 2.
  • acrylic resins polymers containing methyl methacrylate (MMA), ethyl methacrylate (EMA), and ethyl acrylate (EA) in different compounding ratios were synthesized by a conventional method to obtain acrylic resins 1 to 5.
  • Table 1 shows the weight ratio of the monomers used for the synthesis of the acrylic resins 1 to 5, the weight average molecular weight (Mw) determined by GPC (styrene conversion), and the glass transition temperature (Tg).
  • titanium oxide (“JR-805” manufactured by Teika Co., Ltd., average particle size: 0.29 ⁇ m) was prepared.
  • the fluororesin and the acrylic resin are blended at a mass ratio shown in Table 2, and pigment particles are blended in an amount of 30% by mass (15% by volume) based on the total mass of the coating solvent component (isophorone) and solids. And mixed. Thereafter, the obtained mixture was filtered through a 500 mesh filter to remove aggregated particles from the mixture, and fluororesin paint 1 to fluororesin paint 24 were prepared.
  • the fluororesin coating material 25 is a blend of polyvinylidene fluoride and acrylic resin, and contains 30% by mass of acrylic resin with respect to 70% by mass of polyvinylidene fluoride.
  • the acrylic resin contained in the fluororesin paint 25 is a copolymer resin of 65% by mass of MMA and 35% by mass of EA, the weight average molecular weight (Mw) measured by GPC is 140,000, and the glass transition.
  • the temperature (Tg) is 50 ° C.
  • Fluororesin paint 2 is applied to the surface of the coated original plate, the coated original plate coated with fluororesin paint 2 is heated so that the temperature reached by the plated steel sheet is 250 ° C., and then immersed in 20 ° C. water. It was cooled with water, then taken out of the water, wiped with gauze, and dried in a room at 23 ° C. At this time, the cooling rate from 200 ° C. to 70 ° C. was 250 ° C./second. Thus, a coated metal plate 1 having a coating film (fluororesin layer) having a thickness of 20 ⁇ m made of the fluororesin coating 2 on the surface of the coating original plate was produced.
  • the coated metal plate 1 was left in an environment of 60 ° C. for 7 days, and then Ic ⁇ / Ia was measured again.
  • the said stationary conditions are the conditions which reproduced the crystallization and ductility fall of the fluororesin by long-term normal temperature storage.
  • Each of the painted metal plates 2 to 30 was produced in the same manner as the painted metal plate 1 except that the fluororesin paint 1 and the fluororesin paint 3 to the fluororesin paint 25 were used in place of the fluororesin paint 2.
  • the coated metal plate 19 and the painted metal plate 20 were immersed in water at 40 ° C. and 60 ° C., cooled with water, then taken out of the water, wiped with gauze, and dried in a room at 23 ° C. At this time, the cooling rates of 200 ° C. to 70 ° C. were 160 ° C./second and 130 ° C./second, respectively.
  • the coated metal plate 23 to the coated metal plate 25 were heated after the coating original plate coated with the fluororesin coating was allowed to cool without being immersed in water to form a coating film. The cooling rate at this time was 1 ° C./second.
  • Fluorine resin paint No. 1 used to fabricate painted metal plate 1 to painted metal plate 30 Table 3 shows Ic ⁇ / Ia and Ic ⁇ / Ia immediately after painting by cooling condition (water cooling or standing cooling) and wide-angle X-ray analysis, and Ic ⁇ / Ia after storage.
  • Table 4 shows the evaluation results of painted metal plate 1 to painted metal plate 30.
  • the coated metal plate 1 to painted metal plate 20 having Ic ⁇ / Ia of less than 2.5 and Ic ⁇ / Ia larger than Ic ⁇ / Ia have any workability immediately after coating or after storage. It was also expensive.
  • the coated metal plate 10 the coated metal plate 11, the painted metal plate 13, wherein the fluororesin contains a copolymer of 1,1-difluoroethylene and hexafluoropropylene in an amount of 50% by mass or more based on the total mass of the fluororesin.
  • the painted metal plate 14 the painted metal plate 16, and the painted metal plate 17, the coated metal plate 1, the painted metal plate 2, the painted metal plate 4, and the painted metal plate 5 in which the content of the copolymer is less than 50% by mass.
  • the workability after storage was higher than that of the painted metal plate 7 and the painted metal plate 8.
  • the ratio of the structure from which acrylic resin is derived from methyl methacrylate is 10 mass% or more and 30 mass% or less
  • the ratio of the structure derived from ethyl acrylate is 60 mass% or more and 80 mass% or less
  • the ester Paint metal plate 2 paint metal plate 3, paint metal plate 5, paint metal plate 6, paint metal plate 8, paint metal plate 8, which is a copolymer resin whose proportion of the structure derived from the compound is 10% by mass or more and 30% by mass or less.
  • the painted metal plate 9 the painted metal plate 11, the painted metal plate 12, the painted metal plate 14, the painted metal plate 15, the painted metal plate 17, the painted metal plate 18, the painted metal plate 19 and the painted metal plate 20, ⁇ -type crystals are formed. It was not generated.
  • the acrylic resin has a glass transition temperature (Tg) of 10 ° C. or less, a painted metal plate 3, a painted metal plate 6, a painted metal plate 9, a painted metal plate 12, a painted metal plate 15, a painted metal plate 18, and a painted metal.
  • Tg glass transition temperature
  • the coated metal plate of the present invention exhibits high workability even after storage even if it is a fluororesin-based coating film. Therefore, further spread of fluororesin-based coated metal plates is expected, especially as a material for exterior building materials.

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