WO2007013232A1 - Plaque ayant deja un revetement et procede servant a produire celle-ci - Google Patents

Plaque ayant deja un revetement et procede servant a produire celle-ci Download PDF

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Publication number
WO2007013232A1
WO2007013232A1 PCT/JP2006/311891 JP2006311891W WO2007013232A1 WO 2007013232 A1 WO2007013232 A1 WO 2007013232A1 JP 2006311891 W JP2006311891 W JP 2006311891W WO 2007013232 A1 WO2007013232 A1 WO 2007013232A1
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WIPO (PCT)
Prior art keywords
coating
coating layer
layer
metal plate
color tone
Prior art date
Application number
PCT/JP2006/311891
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English (en)
Japanese (ja)
Inventor
Kohei Ueda
Hiroshi Kanai
Kengo Yoshida
Hiroyasu Furukawa
Original Assignee
Nippon Steel Corporation
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 Nippon Steel Corporation filed Critical Nippon Steel Corporation
Priority to JP2007528370A priority Critical patent/JP4808717B2/ja
Priority to CN200680027553XA priority patent/CN101232994B/zh
Publication of WO2007013232A1 publication Critical patent/WO2007013232A1/fr

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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
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • 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
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding

Definitions

  • the present invention relates to a pre-coated metal plate excellent in design and corrosion resistance and a method for producing the same, and in particular, bright red, yellow, and orange colors.
  • Pre-coated metal plates are being used. This metal plate is a metal plate that has been pre-treated for metal and is coated with paint, and is generally used after being formed and processed.
  • a continuous coating facility called a coil coating line having a coating facility called a rollco overnight or a curtain co
  • a coating facility called a rollco overnight or a curtain co
  • a coating defect called “boiling” is also likely to occur. Therefore, in the case of a conventional precoated metal plate, the thickness of a single layer is
  • each layer is about 1 to 25 m, and in the case of multiple layers, the thickness of each layer is about l to 25 ⁇ m It is common to be.
  • the coating color of the pre-coated metal plate is colored to a color other than white and black
  • the color other than white and black is low in concealment.
  • the color will be transparent, resulting in a blackish color.
  • red, yellow, and orange colors are used, this tendency is generally strong.
  • a thick film (generally over 50 m) must be applied. This pre-coated metal sheet is applied to the coil coating grain. When manufacturing with, boiling defects occur.
  • a pre-coated metal sheet was prepared using the same coating material (known as a three-coat model in which a corrosion-resistant coating film, intermediate coating film, and colored top coating film were laminated) using generally known coating materials for pre-coated metal sheets.
  • pre-coated metal sheets are baked in a short time unlike automotive paints. Therefore, in order to prevent the occurrence of “boiling” defects, it is necessary to coat each layer with a thick film like automotive paints. Have difficulty. Therefore, it must be painted with a thin film Therefore, it is difficult to achieve both the appearance and the corrosion resistance with the pre-coated metal sheet because it is not possible to express a vivid appearance when coated with a thin film. Therefore, the present invention has been made in view of these problems.
  • a new and improved pleated metal plate with excellent corrosion resistance and excellent appearance design because it can produce vivid colors even when the coating thickness is reduced to prevent the occurrence of the above-mentioned boiling defects. And its manufacturing method. Disclosure of the invention
  • a colored coating layer (hereinafter referred to as a top coating layer).
  • the coating layer containing a large amount of Ti (hereinafter referred to as the intermediate coating layer) can be concealed by the intermediate coating layer.
  • the color of the top coating layer painted on it can be vividly expressed.
  • at least the intermediate coating layer and the top coating layer can be coated simultaneously in multiple layers. Liquid-liquid interface at the interface between the film layer and the top coating layer.
  • the present invention has been completed based on such knowledge, and the gist of the present invention is as follows.
  • the primer coating layer includes one or both of S i and P,
  • the pre-coated metal sheet having a vivid color tone wherein the intermediate coating layer contains a Ti-based additive.
  • the coloring pigment other than the Ti-based additive in the top coating layer is red.
  • the top coating layer is colored with a pigment of any one of red, yellow or orange, and the intermediate coating layer is added with a Ti-based additive in addition to a red-based pigment.
  • the maximum height from the center line of the waviness of the interface is the height measured from the center line of the layer located above the interface.
  • the pre-coating metal plate having a vivid color tone according to any one of the above (1) to (7), characterized by being 50% or less.
  • the thicknesses of the primer coating layer, the intermediate coating layer and the top coating layer are in the range of 1 to 30 xm, respectively, and the total coating thickness of the multilayer coating layer is 5
  • the outermost coating layer (A) has a glass transition temperature of 5 to 30, and (B) 2 2.5 NZmm 2 in terms of universal hardness under a load of 5 mN. (C) The elongation at break at 23 ° C is 100% or more, and (D) The specular gloss of the outermost coating film is 60 ° for the incident angle and the light receiving angle, respectively. According to any one of (1) to (1 ⁇ ) above, which is 60% or more when measured under conditions Pre-coated metal plate with vivid colors.
  • a vivid color tone characterized by applying at least two of the primer coating layer, intermediate coating layer and top coating layer on one or both sides of the metal plate by the multilayer simultaneous coating method.
  • FIG. 1 is a schematic cross-sectional view of a precoated metal plate of the present invention.
  • FIGS. 2A and 2B are diagrams for explaining the interface between the lower coating layer and the upper coating layer of the precoated metal sheet according to the present invention.
  • FIG. 3 is a diagram for explaining the Ra evaluation method for the coating film interface of the precoated metal sheet.
  • FIG. 4 is a diagram for explaining the interface when the lower layer of the multilayer simultaneous coating contains a pigment.
  • Fig. 5 is a schematic perspective view of a slide hopper type force-tensile coating device.
  • FIG. 6 is an explanatory diagram showing the bending method of the method for measuring the elongation at break of the coating film of a preco-metal plate.
  • FIG. 7 is a schematic diagram for explaining a pretreatment metal plate production processing line.
  • FIG. 8 is a diagram showing a mouth-to-peed test method for evaluating the coating strength of a precoated metal sheet.
  • a primer coating layer 12 on one side or both sides of a metal plate 1 1 (on only one side in FIG. 1), a primer coating layer 12, an intermediate coating layer 1 3, and a top coating layer 14 Even if it is a multi-layer pre-coated metal sheet that is formed by sequentially laminating a multi-layer coating, and the top coating layer is colored with a color other than white or black, the primer coating layer is S One or both of i and P are included, and there is a trace interface between the intermediate coating layer and the top coating layer in the multilayer coating layer, and fine irregularities at the interface
  • the size of the metal plate is 0.3 to 0.8 m in terms of centerline average roughness (R a), and the intermediate coating layer contains a Ti-based additive to conceal the color of the metal plate. can do.
  • the top coating layer does not contain a Ti-based additive, or when the paint layer is colored in any of red, yellow, or orange, the effect of concealing the color of the metal plate is further improved. Demonst
  • a steel plate, an aluminum plate, a titanium plate, or the like can be used as the metal plate serving as the base of the precoated metal plate of the present invention, but the metal plate is not limited to these.
  • steel plates that can be used include cold-rolled steel sheets, hot-rolled steel sheets, zinc-plated steel sheets, alloyed zinc-plated steel sheets, zinc-ferrous alloy-plated steel sheets, zinc-alloy alloy-plated steel sheets, aluminum-plated steel sheets
  • steel plate examples include chrome plated steel plate, nickel plated steel plate, zinc-nickel alloy plated steel plate, and tin plated steel plate.
  • the steel sheet can be subjected to surface treatment (pre-painting treatment) if necessary.
  • Surface treatment includes washing with water, washing with hot water, pickling, alkaline degreasing, grinding, polishing, and chromate treatment , Zinc phosphate treatment, composite oxide film treatment and other non-chromate treatments. These can be used alone or in combination for pre-painting of steel sheets.
  • the primer coating layer refers to a coating layer that is applied directly on a metal plate or directly on a metal plate that has been subjected to chemical conversion treatment.
  • the intermediate coating film is a coating layer applied on the primer coating layer, and the top coating layer is a coating layer applied on the intermediate coating layer.
  • the top coating layer may be one layer or two or more layers.
  • the top coating layer is one layer, only the coating layer colored with a color other than white or black can be painted.
  • a metallic layer is formed on the colored layer.
  • a clear coating layer containing a pigment or a clear coating layer containing no pigment can be laminated.
  • the primer coating layer is provided with a metal plate protection function.
  • a compound containing Si or P has an antifungal function, and since the color of the compound is white, an intermediate coating layer and a top coating colored in a bright primary color are formed thereon. When the layer is applied as a thin film, the color of the colored layer becomes vivid.
  • One way to include Si or P in the primer coating layer is to add a compound containing Si or P into the primer coating layer.
  • the compound containing S i and P generally known compounds such as silica, Ca ion exchange silica, zinc phosphate, aluminum tripolyphosphate, and the like can be used. wear. These compounds may be those commercially available as reagents or those commercially available as industrial products such as pigments. These compounds may be added in combination.
  • the “, Ca ion exchange system” force or aluminum dihydrogen tripolyphosphate has a beautiful coating appearance. It is particularly suitable because of its excellent corrosion resistance.
  • Ca ion exchange silica “SHIELDEX (registered trademark)” manufactured by GRACE, and “K—WHITE” manufactured by Tika, etc. can be used for aluminum tripolyphosphate.
  • the addition amount of S i compound or P compound can be changed as necessary, but the addition amount of S i compound or P compound, or the combined addition amount when these are used in combination or in multiple types, It is more preferable that it is 5 to 60 mass% in the dry coating film. If it is less than 5 m s s%, the corrosion resistance is poor, and if it exceeds 60 m s s%, the coating film becomes brittle and the workability may be poor. In addition, other pigments and compounds may be added to the primer coating layer as necessary.
  • the precoated metal sheet of the present invention has a liquid-liquid interface trace interface between the intermediate coating layer and the top coating layer in the multilayer coating.
  • the liquid-liquid interface trace interface is formed due to the liquid-liquid interface between the multi-layer liquid layers when the multi-layer liquid layers are simultaneously applied by the multi-layer simultaneous application method adopted by the present invention. This is a unique interface that is never seen when the upper layer is applied after the lower layer is applied (drying and baking).
  • the low magnification magnified photograph of about 500 times shows undulation at the interface between the upper and lower coating films
  • the pitch of the waviness (distance P in the figure) is about 0.5 to 1 mm.
  • the coating layer interface 105 is observed at a higher magnification of 500.000 times, as shown schematically in FIG. 2B corresponding to an enlarged view of the portion indicated by B in FIG. In 10 5, fine irregularities with a unique shape derived from the liquid-liquid interface are recognized.
  • the pre-coated metal sheet of the present invention has a liquid interface trace interface derived from multilayer simultaneous coating between the intermediate coating layer and the top coating layer in the multilayer coating, and the liquid By measuring the size of the fine irregularities at the interface trace interface with the centerline average roughness (R a) method to be 0.3 to 0.8 zm (hereinafter referred to as “the centerline average roughness of the interface” (R
  • the Ra of the interface between each coating inter-layer intermediate coating layer and the top coating layer is less than 0.3 ⁇ m, it is difficult to conceal the color of the original plate and it is difficult to express a vivid coating color. It becomes a black and cloudy paint color.
  • the adhesion at the interface between both coating layers is also improved, which is more preferable.
  • the adhesion at the interface of the coating film may be reduced.
  • the adhesion of the coating is maintained by physical bonds such as chemical bonding, hydrogen bonding, and van der Waals force between coatings. 0. By doing this, in addition to these adhesive forces, adhesion due to the anchor effect is imparted. However, if it exceeds 0.8 ⁇ m, the gloss when applied to the top paint is affected, which may reduce the gloss.
  • corrugation of the interface between the upper and lower coating layers formed by multilayer simultaneous coating is used to represent the surface roughness of the material. It can be specified by calculating the center line average roughness Ra (JISB 0 6 0 1).
  • Ra can be obtained by regarding the curve of the interface 105 when observed at a magnification of 500,000 as a roughness curve. For example, by cutting a coated metal plate, embedding it in resin, and polishing it, the cross section perpendicular to the surface of the coating film is smoothed, and after taking a photograph with a scanning microscope of 500,000 times, Ra of the interface can be obtained.
  • the Ra of the interface covers the photograph with a transparent sheet used for HP, and after tracing the unevenness of the interface precisely, as shown in Fig. 3, the area of the vertical line part is Measured with an image processing device, the average value can be obtained from the following equation.
  • the value of the center line average roughness Ra is generally 0.3 ⁇ m or more, and at least 0.25 It was found to be about ⁇ m, and the upper limit was generally about 0.7 to 0.8 m. This relationship is also recognized in the case of three or more coating films formed by simultaneous multi-layer coating. In this case, the center line average observed at a high magnification of 500,000 at the interface between two adjacent layers.
  • the roughness Ra is generally 0.3 m or more and at least about 0.25 m, and the upper limit is generally about 0.7 to 0.8 / ⁇ m.
  • the Ra of the interface is 0.15 to 0.25 m.
  • the difference from the coating film layer according to the present invention was clear when viewed from a 500.times.
  • the maximum measured from the center line C of the undulation peak 1 1 1 and the valley 1 1 3 of the interface 1 0 5 shown in Fig. 2A It is desirable that the height H does not exceed 50% of the thickness t of the top film layer expressed as the distance from the center line C to the top surface of the top coating layer. This is because unevenness in color may be observed when this value power exceeds 50%.
  • the thickness t expressed as the distance from the center line of the wrinkled interface to the upper surface of the top coating layer as described above is defined as the average thickness of the top coating layer.
  • the thickness expressed as the distance from the lower surface of the intermediate coating layer to the center line of the interface with the top coating layer is defined as the average thickness of the intermediate coating layer.
  • t is the thickness of the top coat layer that is simultaneously applied immediately above the intermediate coating layer.
  • the intermediate coating layer 10 1 contains pigment 10 7
  • the maximum height H when the pigment 1 0 7 protrudes from the interface 1 1 1 is determined by regarding the contour 1 0 7 a of the portion protruding from the interface 1 1 1 of the pigment 1 0 7 as the interface.
  • Multi-layer simultaneous coating is a method in which multiple layers of coating liquid such as Slot Daiko Yui or Slide Hopper type curtain co
  • the coating film of the precoated metal sheet of the present invention is formed using a multilayer simultaneous coating apparatus.
  • Fig. 5 shows a schematic perspective view of a typical slide hopper type curtain coating device.
  • the slide hopper 1 is provided with a paint supply hole 8 and a slit 6 through which three layers of paint are quantitatively sent out by a gear pump (not shown) or the like.
  • a chain-shaped force guide 3 is provided so as to be in contact with both ends of the lip 7 A of the slide surface 7.
  • a paint pan 5 is installed below the lip 7 A, and the force ten guide 3 hangs down to the bottom of the paint pan 5.
  • the paint P is uniformly supplied in the width direction from the paint supply holes 8 of the slide hopper 1 through the slit 6 to the slide surface 7 and is laminated on the slide surface 7.
  • the laminated paint is spread by the curtain guide 3 when it falls from the tip of the slide surface 7 (the lip 7 A) to the paint pan 5, it is It flows down as a uniform liquid film.
  • a strip-shaped metal plate such as the steel strip 2
  • a plurality of layers of paint can be applied simultaneously on the surface of the steel strip 2.
  • the paint film is a multi-layer (laminate) curtain 4
  • the stable film thickness that is, about 20 hi dry film thickness
  • the top coating layer is referred to as the upper layer
  • the intermediate coating layer is referred to as the lower layer
  • the top coating layer or the intermediate coating layer may be composed of two or more layers.
  • it is preferable to add a leveler to the upper layer because the Ra of the interface between the upper layer and the lower layer can be controlled.
  • the surface tension of the paint is adjusted, and the degree of color tone is improved compared to the case where no leveler is added to the upper layer.
  • the upper layer coating will not spread over the lower layer coating. It is thought that the force that the upper layer paint wets and spreads works to suppress the force that disturbs the interface between the upper and lower layers due to Marangoni convection and widens the interface. And the difference in surface tension between the upper and lower layer paint is more than 1. S in NZ m, 5 m N / The inventors have found that if it is less than m, the Ra at the interface between the upper layer and the lower layer after baking the coating layer is 0.3 to 0.8 m, which is suitable.
  • the surface tension of the upper layer is lower than the surface tension of the lower layer.
  • the Ra at the interface between the upper layer and the lower layer can be controlled to 0.3 to 0.8 m. This phenomenon makes it easier for the lower layer coating to spread on the lower layer (another layer of paint that is formed together in a multi-layer simultaneous coating, or a steel plate or a primer layer above it). This is presumed to be due to the suppression of the rising phenomenon.
  • the difference in surface tension between the upper layer (top coating layer) and the lower layer (intermediate coating layer) is 0.
  • the inventors have found that when it is 3 mN / m or more and less than 3.7 mN / m, the Ra of the interface between the upper layer and the lower layer becomes 0.3 to 0.8 _ m, which is suitable. Found out.
  • the leveler is a kind of paint surface conditioner, which is also called a leveling agent, and is an additive having the property of making the paint surface uniform.
  • levelers that can be used in the present invention include acrylic levelers and silicone levelers.
  • silicone-based homogenol L 1 0 0 (Kao Co.), B YK 0 8 0, B YK '1 4 1, B YK 0 6 5, B YK 0 6 6, B YK 0 70, B YK 0 8 8 (BYK-Chemie) and the like.
  • the leveler in the coating film of the product pre-coated steel sheet manufactured by multilayer simultaneous coating peels off the coating film of the product, extracts unreacted polymer in the solvent, and heats and concentrates the solvent after extraction. Later, it can be detected by infrared absorption spectrometry.
  • the precoated metal sheet of the present invention needs to contain a Ti-based additive in the intermediate coating layer.
  • Ti compounds, especially titanium oxide, as Ti-based additives, when added to the coating film have high concealability of the coating film and have a high effect of concealing the color of the base plate (metal plate). By coating this under the top coating layer, the color of the coating can be made more vivid.
  • titanium oxide, barium titanate, or strontium titanate can be used as the Ti compound contained in the intermediate coating layer.
  • a commercially available product may be used.
  • a type in which the surface of these titanium compounds is coated with another metal or resin may be used.
  • Commercially available titanium oxides such as “Yuyip J-Tika ⁇ ⁇ ⁇ ⁇ I X” manufactured by Ishihara Sangyo Co., Ltd. can be used.
  • the particle size of the Ti-based additive in the intermediate coating is preferably 0.1 to 0 •
  • the particle size of the Ti-based additive is less than 0 • 1 m, the concealment effect may be unpredictable, and if it is greater than 0.3 m, the Ra of the interface between the top coating and the intermediate coating is more than necessary. This is because it may be enlarged.
  • the particle size of the Ti-based additive in the intermediate coating film is not particularly limited. For example, considerably large particles can be used, and those having a particle size outside the above range can be used if necessary.
  • the amount of Ti-based additive added to the intermediate coating can be selected as necessary, but is preferably 40 m'ass% or more in the dry coating. More preferably, it is 40 to 60 mass%. If it is less than 40 mass%, the concealability is insufficient, and there is a risk that vivid primary colors will not appear when the top coating is applied.
  • a paint with 40 mass% or more of a Ti-based additive added to the intermediate coating and a dip coating are applied in a multilayer coating, the intermediate coating layer and the top coating layer
  • the Ti-based additive tends to thicken at the interface, so that visible light is more easily diffused and reflected near the interface, resulting in increased concealment and a more vivid primary color. However, if it exceeds 60 mass%, the coating film becomes brittle and the workability may be inferior. If necessary, other pigments and compounds may be further added to the intermediate coating layer.
  • the top coating layer of the pre-coated metal sheet of the present invention is colored with a color other than white or black, especially when it does not contain a T i additive, or is red, yellow or orange. It is more effective if it is colored with any color. Furthermore, if it contains no Ti-based additives and is colored in any of red, yellow or orange colors, it can produce a very vivid color tone.
  • Typical examples of pigments containing T i include titanium oxide, but these have very strong whiteness, so if they are included in the top layer, colored primary colors such as red, orange, and yellow are colored. There is a risk that the color will be light and the vivid color will not be expressed.
  • the intermediate coating layer of the precoated metal sheet of the present invention is colored in any of red, yellow or orange
  • the intermediate coating layer is also added to the Ti-based additive in red. If it is colored with any color of yellow, yellow or orange, it is suitable because a vivid primary color is developed even if the additive amount of the Ti-based additive is less than 40 mass%.
  • the intermediate coating film is colored with any of red, yellow, or orange colors
  • the T i type is concealed by the synergistic effect of the hiding effect of the original plate and the T i type additive. Additive amount of additive Even if it is less than 40 mass%, a vivid primary color is developed.
  • the intermediate coating layer is colored with any of red, yellow, or orange in addition to the Ti-based additive
  • this intermediate coating and top coating can be applied simultaneously in multiple layers.
  • the Ti additive in the intermediate coating film slightly diffuses into the top coating layer in the wet state, so the interface between the intermediate coating layer and the top coating layer Ti-based additives tend to thicken, so that visible light is more diffusely reflected near the interface, resulting in increased concealment and more vivid primary colors.
  • the amount of the Ti-based additive added is not particularly specified when the intermediate coating layer is also colored in any of red, yellow, or orange. However, 5 to 60 mass% is preferable.
  • the hiding property is insufficient if it is less than 40 mass%, and therefore there is a possibility that vivid primary colors may not be developed when the top coating is applied. If it exceeds 60 mass%, the coating film becomes brittle and the workability may be inferior.
  • the glazing coating When the glazing coating is colored with a color other than white or black, it can be colored with a generally known pigment.
  • a generally known pigment For example, in order to give red, orange or yellow coloration, each color pigment or dye can be added to the coating.
  • Generally known pigments and dyes can be used.
  • a commercially available product may be used.
  • red pigments include, for example, inorganic red pigments such as cadmium red and silver red, carmine 6 B, lake red C, organic soluble azo red pigments such as watching red, permanent red, and lake.
  • Red 4 R organic insoluble azo red pigments such as naphthol red, condensed azo red pigments such as chromophthale red, etc.
  • Yellow pigments include, for example, yellow lead, yellow iron oxide, cadmium Inorganic yellow face such as yellow, disazoero, monoazoero, 'condensed yellow
  • organic orange pigments such as molybdenum orange, inorganic orange pigments such as molybdenum orange, and organic orange pigments such as disazo orange and permanen-orange can be used.
  • the type and amount of facial pigment can be selected as needed.
  • For the top coating layer a commercially available coating that has already been colored may be used.
  • the particle size of the pigment used in the top coating is not limited, but is preferably smaller than Ra, more preferably 0.3 m or less.
  • the particle size of the pigment of the top coating film is small, it is preferable to obtain a deep color tone especially when the particle size is 0.1 lim or less.
  • thermosetting resins As a binder for all coating layers of the precoated metal sheet of the present invention, generally known resins can be used.
  • polyester resin, epoxy resin, urethane resin, acrylic resin, fluorine resin, melamine resin, etc. can be used.
  • These resins may be thermoplastic or thermosetting.
  • the thermosetting type is more suitable from the viewpoint of the scratching properties of the coating film.
  • crosslinking agents such as aminoplast resins such as melamine, isocyanates, etc. may be added to the above known resins.
  • each coating layer of the precoated metal sheet of the present invention that is, each of the primer coating layer, the intermediate coating layer and the top coating layer is in the range of 1 to 30 m, and It is more preferable that the total thickness of the multilayer coating film including the coating layer is 50 m or less. If the film thickness of each of the primer coating, intermediate coating, and top coating is less than 1, the primer coating has corrosion resistance, and the intermediate coating has concealment. In the case of a coating film, the color tone may be inferior. Also, if the film thickness of each of the primer coating, intermediate coating, and top coating is more than 30, a coating defect called boiling may occur. Furthermore, even if the total film thickness of the primer coating, intermediate coating, and top coating exceeds 50 / m, coating defects called boiling may occur.
  • the growth rate is defined differently depending on the literature, and is described below to avoid confusion.
  • the method for measuring the elongation at break of each coating film is a coating film obtained by peeling each coating layer coated on a pre-coated metal plate from the metal plate, or has a peelability such as Teflon (registered trademark) in advance.
  • a metal plate that has already been painted is closely bonded and bent at 180 ° with the coating layer side facing outward in an atmosphere of 23 ° C, and the coating at the curvature part is applied.
  • the presence or absence of cracks was observed with a microscope, and if no cracks were observed, it was possible to determine that the elongation at break of the coating was 100% or more (hereinafter, this method is the bending method). ).
  • this method is the bending method.
  • the 180 ° tightly bent material (pre-coated metal plate) 10 is viewed from the cross-sectional direction, there is no distortion at the center of the bent portion of the material in the thickness direction. A part called the neutral plane that does not occur is generated.
  • ⁇ s (2 ⁇ t-2 ⁇ (t / 2)) X 1 0 0/2 ⁇ (t / 2)
  • the pleco-coherent metal plate is bent closely at 18 ° with the coating side facing outward, it can be assumed that the elongation of the coating has reached 100%. If no cracks are observed in the paint film, the elongation at break of the paint film can be considered to be 100% or more. Microscopic observation of cracks in the coated metal plate that has been bent tightly can be observed from the surface of the paint film or from the cross section.
  • a method for measuring the elongation at break of the coating film in the present invention either a method obtained by a tensile test of a coating film or a method in which a coated metal plate is closely adhered and bent and observed for occurrence of cracks is observed. May be adopted.
  • the elongation at break of any one of the coating films to be applied to the precoated metal sheet of the present invention is less than 100%, cracking or peeling of the coating film may occur in the processed part when it is ground into a severe shape. Caused by poor appearance There is a risk that the corrosion resistance at the machined part will be poor.
  • the type of binder resin is more suitable because the polyester resin has high flexibility and the elongation at break tends to be high.
  • the lower the Tg of the coating resin the more likely it is that the elongation at break tends to be higher, so it is more suitable.
  • Higher molecular weights are more suitable because the elongation at break tends to be higher.
  • a lower crosslink density is more suitable because the elongation at break tends to be higher.
  • the crosslink density can be adjusted by changing the amount and type of curing agent. In general, the lower the added amount, the lower the crosslink density, and the lower the number of functional groups the crosslinker has, the lower the crosslink density.
  • polyester Z melamine type or polyester / isocyanate type as a binder resin in order to make the elongation at break of the coating film 100% or more.
  • the number average molecular weight of the polyester resin is more preferably from 1 00 0 0 to 5 0 00 0 0. If the number average molecular weight is less than 100000, the processability may be inferior. If the number average molecular weight is more than 500, it may be difficult to form a paint by dissolving in a solvent.
  • the glass transition temperature of polyester resin (hereinafter referred to as Tg) is more preferably 30 ° C or less.
  • Tg glass transition temperature of polyester resin
  • the number average molecular weight of the whole mixed polyester resin is from 1 00 0 0 to 5 0 0 0 0.
  • Pylon registered trademark
  • Desmophen registered trademark manufactured by Sumika Bayer Urethane Co., Ltd.
  • melamine resin When a melamine resin is used as the cross-linking agent, generally known melamine resins such as fully alkyl methylated melamine, butylated melamine, and imino group mixed alkylated melamine can be used.
  • commercially available products such as Mitsui Cytec “Cymel (registered trademark)”, “My Coat (registered trademark)” manufactured by Dainippon Ink & Chemicals, Inc., “Super Becamine (registered trademark)”, etc. manufactured by Dainippon Ink & Chemicals, Inc. can be used.
  • two or more of these resins may be mixed and used.
  • the amount of melamine resin added is more preferably 5 to 30 parts by mass of melamine solids with respect to 100 parts by mass of polyester resin solids. If the melamine solid content is less than 5 parts by mass with respect to 100 parts by mass of the polyester resin, the amount of the crosslinking agent is too small, and the coating film may not be cured and may not form a film after dry baking. . If the melamine solid content exceeds 30 parts by mass, the coating film becomes too hard and hard, and the elongation at break at 23 ° C is less than 100%. There is a risk of poor shape.
  • isocyanate When isocyanate is used as the cross-linking agent, commercially available isocyanates such as “Sumidule (registered trademark)” and “Desmodur (registered trademark)” manufactured by Sumika Bayer Urethane can be used.
  • the amount of isocyanate added is preferably within the range of 0.8 to 1.2 equivalent ratio of OH number of polyester resin and NCO value of isocyanate. Outside this range, the coating film may become uncured, and the coating film may become so-called “sticky” with viscosity.
  • the outermost coating layer of the coating layers has (A) a glass transition temperature of 5 to 30 ° C and (B) a hardness at 23 ° C.
  • the universal hardness under a load of 5 mN is 2.5 N / mm 2 or more.
  • the elongation at break at 23 ° C is 100% or more.
  • the specular gloss of the outermost coating layer is 60 ° for the incident angle and the light receiving angle, respectively. Preferably, it is 60% or more when measured under the above conditions.
  • Tg as the bulk of the coating after adding them.
  • the T g of the coating film may be measured using a differential scanning calorimeter (generally called DSC) after peeling off the coating film applied to the pre-coated metal plate, or as a pre-coated metal plate. Measurements may be made using a thermomechanical analyzer (generally called TMA). In addition, it may be measured by other generally known methods. It is known that there are some errors in the Tg of the coating film depending on the measuring equipment and measurement conditions.
  • the coating film T g is measured when measured by any one of a plurality of generally known T g measuring methods, that is, a method using DSC or a method using TMA. If the temperature is in the range of 5 to 30 ° C, it is included in the present invention. Since the Tg of the coating film is mainly governed by the Tg of the binder resin, the coating film Tg can be adjusted by controlling the Tg of the binder resin. '' Because it can be considered that the Tg of the binder resin is almost correlated with the Tg of the coating film, the Tg of the binder resin used is more preferably 5 to 30 ° C. It is also possible to mix multiple resins with different Tg and set the total Tg of the mixed resin to 5 to 30 ° C.
  • the coating film T g is less than 5 ° C, the hardness of the entire coating film is too low, and it is difficult to ensure a universal hardness of 2.5 NZmm 2 or more at 23 ° C and 5 mN load. Therefore, it is unsuitable. Also, if the coating film Tg is more than 30, when the precoated metal sheet is processed, This is not suitable because of a decrease in gloss.
  • the coating film Tg is more preferably 10 to 28 ° C.
  • the coating hardness of Pleco Ichigo Metal Plate can be adjusted mainly by the type and amount of cross-linking agent contained in the coating.
  • the universal hardness is the DIN 5 0 3 5 9-1 in Germany. Refers to the coating film hardness measurement method described, and is a diamond pyramid with a face angle of 1 36 ° (same as the indenter used in the picker hardness test described in JIS — Z— 2 2 4 4) The hardness is calculated from the indentation depth under the applied load condition. Note that the universal hardness in the present invention is generally known under the conditions of a temperature of 23 ° C. and an indentation load of 5 mN and using a micro hardness meter described in this DIN standard.
  • Addition of other curing agents such as melamine resin, isocyanate, etc. is more suitable because the coating film hardness increases.
  • melamine resin or isocyanine is effective, and the universal hardness increases as the amount added is increased. Universal hardness tends to be higher for melamine curing agents than isocyanate curing agents.
  • the addition amount of the melamine resin is more preferably 5 to 120 parts by mass with respect to 100 parts by mass of the main resin solid content. If the amount of melamine resin added to 100 parts by mass of the main resin is less than 5 parts by mass, the universal hardness at 23 ° C may be less than 2.5 NZ mm 2 .
  • the elongation at break may be less than 100%. If the universal hardness at 23 ° C is less than 2.5 N / mm2, it is not suitable because galling of the coating tends to occur when press molding is performed under severe conditions.
  • the universal hardness may change depending on the type and amount of pigment added. In some cases, the degree can be adjusted.
  • the specular intensity of the coating film is 60% or more when measured in an unprocessed state with an incident angle and a light receiving angle of 60 °.
  • the specular gloss at 60 ° is less than 60%, this mode is meaningless because the gloss reduction of the coating film at the forming part is not noticeable. If the specular gloss is 80% or more, this effect is more effective, and this is more preferable.
  • the specular gloss of the coating film refers to the specular gloss described in JIS K. 5 6 0. 0. 4.7: 1 9 9 9.
  • the gloss of the paint film generally has 80% or more unless adjusted with a matting agent. When adjusting the gloss to a low level, it can be adjusted using a matting agent such as silica. It can also be adjusted using other commonly known gloss modifiers.
  • the pre-coated metal sheet of the present invention further includes an interface other than the interface between the intermediate coating layer and the top coating layer, such as a primer coating layer.
  • the centerline average roughness (R a) is the size of at least one interface between each layer, such as between the top layer and the intermediate coating layer, or between the top coating layers when there are multiple top coating layers. It is more preferable that the thickness is 0.3 to 0.8 m. If the size of the fine irregularities at the interface between coating layers is less than 0.3 m in Ra, the adhesion at the coating layer interface may be reduced.
  • the adhesion of the coatings is maintained by physical bonds such as chemical bonds, hydrogen bonds, and van der Waals forces between the coatings. 0.
  • the length By setting the length to 3 m or more, in addition to these adhesion forces, adhesion force due to the anchor effect is imparted. However, it is not preferable to exceed 0. 0, because the appearance when the top paint is applied may be affected and the gloss may decrease.
  • the primer coating layer is in contact with the base metal plate, and the intermediate coating layer or the top coating layer is usually applied on top of this.
  • a resin with excellent adhesion such as an epoxy resin, is used so that it adheres to the top coating, or because it is added as one of the components in the primer coating layer,
  • the size of the fine irregularities at the interface with these coatings is Ra
  • a certain degree of adhesion is secured even outside the range of 0.3 to 0.8 im.
  • the intermediate coating layer or the top coating layer if adhesion is imparted to the coating itself, other coating performance may be degraded. Therefore, since the intermediate coating layer and the top coating layer tend to be inferior in adhesion compared to the primer coating layer, the adhesion is further improved when the Ra of these interfaces is within the above range. Therefore, it is preferable. It should be noted that the adhesion between the primer coating layer and the intermediate coating layer is also improved if Ra is within the above range, or a resin that does not consider adhesion can be used. It is more suitable because of the advantages such as.
  • the centerline average roughness (R a) representing the size of the fine irregularities at the interface is determined by the following method (ie, basically JIS-B-0606-1-1980). 2). That is, after taking a vertical cross-section of the interface where the surface roughness Ra is to be measured with a photomicrograph, tracing the unevenness curve of the interface), and stipulated in JIS-B- 0 6 0 1 — 1 9 8 2
  • the centerline average roughness Ra of this interface can be determined according to a predetermined formula (see the example below).
  • Multi-layer simultaneous coating means' slot die coater
  • it is a method in which multiple layers of a coating solution such as a slide hopper curtain curtain are applied to the base material in a stacked state, and then the applied multiple layers of coating solution are dried and baked at the same time.
  • simultaneous multi-layer coating allows the coating liquid of each layer to slightly mix near the interface of the multilayer coating, thereby generating irregularities (that is, Ra) at the interface.
  • irregularities that is, Ra
  • the size of the fine irregularities Ra at the coating interface is 0.3 to 0.8 / im.
  • Multi-layer simultaneous coating method is a method of coating by laminating different coatings from two or more parallel slits as typified by slide hopper type force. Can be used.
  • Figure 7 shows an example of curtain coating of a multilayer film on a steel strip as a production line for pre-coated metal sheets.
  • the steel strip wound around the coil is unwound by an uncoiler 41, and passed through an accumulator 42, a chemical conversion device 47, a prime converter 45, and an induction heating furnace 43.
  • a slide type slide hopper type curtain coating device 4 9 is arranged at the subsequent position, and a multilayer film is applied to the surface of the traveling steel sheet 11 by curtain coating.
  • An induction heating furnace 51 is installed downstream of the curtain coating device 4 9 as equipment for drying and baking the applied paint. After that, the steel sheet passes through an accumulator 53 and is wound up by a recoiler 44 as a steel strip that has been processed.
  • the size of the slide hopper type curtain coating equipment is, for example, a slit width of 200 mm above and below, and a slit spacing of 500 mm, and the height to the steel sheet to be coated is 1 5 0 m hi.
  • Steel sheet is multilayered A multilayer coating film is formed on the steel plate by moving under the lidco.
  • dry and bake in an induction heating furnace After two-layer coating, dry and bake in an induction heating furnace.
  • the thickness of the coating film is, for example, 2 to 15 ⁇ m for the intermediate coating layer and 0.5 to 15 m for the top coating layer.
  • the heating rate in the induction heating furnace is 2 to 10 ° C / s, and the ultimate temperature of the steel sheet after baking is 2200 to 2300 ° C.
  • the pre-coated metal sheet of the present invention is a roll coat overnight coating, a dip coating, a dip coating, a tension coating, an evening coating, except that at least the intermediate coating film and the top coating film are coated and baked by a multilayer simultaneous coating method. It is possible to paint by repeating commonly-known coating methods, such as roller power one-wheeler, sliding hopper type curtain flowco overnight, etc., and by repeating the method of coating and baking each layer one by one. However, it is more suitable to use the method in which two or more layers are coated and baked at the same time by the multi-layer simultaneous coating method, because it can be painted on the current 2-coat 2-bake coating line. .
  • a general pre-coated metal sheet production line (generally called a coil coating line or CCL) is generally used for two-coat coating, so it is difficult to apply three or more layers.
  • CCL coil coating line
  • the above-mentioned problem can be solved by using the multi-layer simultaneous coating method.
  • drying baking method for coating generally known drying 'baking methods such as a hot air oven', a direct flame oven, a far-infrared oven, an induction heating oven, and the like can be used.
  • additives such as antifoaming agent, leveling agent, slipping agent, wax, delustering agent, etc. are required in the primer, intermediate coating and top coating used in the present invention. It may be added accordingly.
  • the metal material may be an alloy material. Examples include steel plates, stainless steel plates, aluminum plates, aluminum alloy plates, titanium plates, and copper plates. The surface of these materials may be applied. Types of plating include zinc plating, aluminum plating, copper plating, nickel plating, and the like. These alloys may be used. In the case of steel sheets, hot dip galvanized steel sheets, electrogalvanized galvanized steel sheets, zinc-nickel alloy galvanized steel sheets, molten alloyed galvanized steel sheets, aluminum galvanized steel sheets, aluminum-zinc alloy galvanized steel sheets, etc. Known steel plates and plated steel plates can be applied.
  • the surface of the metal plate used in the present invention is more preferably subjected to a known chemical conversion treatment because the adhesion between the metal plate and the coating layer is improved.
  • a known chemical conversion treatment zinc phosphate-based chemical conversion treatment, coating chromate treatment, electrolytic chromic acid treatment, reaction chromate treatment, chromate-free chemical conversion treatment, etc. can be used.
  • Non-chromate chemical conversion treatments are known to have been treated with an aqueous solution containing a silane coupling agent, a zirconium compound, a titanium compound, dinin or tannic acid, resin, silica, etc.
  • JP 9 2 3 JP 9 1 2 4 1 5 7 6, JP 2 0 0 1 — 8 9 8 6 8, JP 2 0 0 1 — 3 1 6 8 4 5 , JP 2 0 0 2-6 0 9 59, JP 2 0 0 2-3 8 2 8 0, JP 2 0 0 2-2 6 6 0 8 1, JP 2 0 0 3 — 2 5 3 4 6
  • a known technique described in Japanese Laid-Open Patent Publication No. 4 may be used.
  • Byron (registered trademark) 6 3 CS” (T g: 7 ° C, number average molecular weight: 2 00 0 0), an amorphous polyester resin manufactured by Toyobo Co., Ltd., and amorphous resin manufactured by Toyobo Co., Ltd.
  • Polyester resin “Byron (registered trademark) 2 0 0” (T g: 67 ° C, number average molecular weight: 1 7 0 0 0), “Byron (registered trademark) 2 2 0” (T g: 5 3 ° C, number average molecular weight: 3 00 0), "Byron (registered trademark) GK 8 90" (T g: 17 ° C, number average molecular weight: 1 1 0 0 0) used as binder resin It was. Since “Byron (registered trademark) 20 0” and “Byron (registered trademark) 2 20” are in the form of pellets or flakes, they are organic solvents (cyclohexanone by mass ratio: Solvesso 15).
  • melamine resin a fully alkyl methylated melamine resin (hereinafter referred to as melamine resin) manufactured by Mitsui Cytec Co., Ltd., was used.
  • a reaction catalyst 1.0% by mass of “Cyalist 60.2” manufactured by Mitsui Cytec was added to the total resin solids.
  • the clear paint used in the experiment was prepared according to the above procedure.
  • paints made using the polyester resin “Byron (registered trademark) 6 3 CS” are polymer low-T g paints
  • paints using “Byron (registered trademark) 2 2 0” are polymers.
  • Ti system titanium oxide
  • Ti system titanium oxide
  • a clear coating of “Flex Coat 200 HQ” (hereinafter referred to as a commercially available high-working intermediate coating) made by Nippon Fine Coings, which is a commercially available paint, and a product made by Nippon Fine Co., Ltd.
  • a clear paint of “Nippes Super Coat 200 HQ” (hereinafter referred to as a commercially available low-process intermediate coat) with the addition of 50% by mass of the above-mentioned titanium oxide.
  • Table 1 shows the details of the prepared intermediate coating.
  • top paint was prepared by adding red, yellow and orange coloring pigments to the clear paint.
  • Commercially available naphthol red was used for red pigments
  • commercially available disazo yellow was used for yellow pigments
  • commercially available disazopyrazolone orange was used for orange pigments.
  • a titanium oxide “Yuypeku CR 95” manufactured by Ishihara Sangyo Co., Ltd. was also added for comparison.
  • the red paint of “Frecoco Tote 200 HQ” hereinafter referred to as “commercial high-processed glass paint”
  • commercial high-processed glass paint a paint for pre-coated metal sheets manufactured by Nippon Fine Coatings, Inc. Toppe Super Coat 2 0 0 "( We have also prepared a commercially available low-painting top paint).
  • a clear paint without any pigment was used as the top clear paint to be coated on these colored coating layers.
  • the anti-glare pigments used in this experiment are “Topol C” (hereinafter referred to as “Cr-based”), a chromium anti-glare pigment made by Toho Pigment, and aluminum dihydrogen triphosphate made by Tika.
  • a titanium oxide “Yuypeku CR 95” Ti-based pigment
  • Ishihara Sangyo Co., Ltd. was added as needed. Details of the prepared primer paint are shown in Table 1.
  • no leveler is added to all intermediate coatings.
  • the acrylic leveler manufactured by Nippon Paint Co., Ltd. is used as the leveler in all top coatings, and the surface tension between the intermediate coating and the top coating.
  • the difference between the maximum value and the minimum value of the measured value is less than 2 mNZm when the difference between the maximum value and the minimum value is 1.2 mN / m or more and less than 5 mN / m and each surface tension is measured 5 times. The addition amount was adjusted appropriately for each paint.
  • BYK-Chemie's silicone additive B YK 1 4 1 is added to all top clear paints, and the level tension of the top paint to which the leveler used for coating is added is adjusted.
  • the difference is 0.3 mN Nom or more and less than 3.7 mNZm, and when the surface tension is measured 5 times as the paint of each layer, the difference between the maximum and minimum values obtained is 2 Adjust the addition amount appropriately so that it is less than mNZm. It was.
  • the amount of leveler added was determined by measuring the surface tension of the paint 5 times using a dinome (B YK—Chemie Gmb H) each time a drop of the leveler was dropped into the paint with a spot. The method was repeated until the above range was reached.
  • the prepared original plate was spray degreased with a 2% by weight, 50 ° C aqueous solution of alkaline degreasing solution “(— 4 3 3 6” manufactured by Nihon Parkerizing Co., Ltd. “CT—E 3 0 0 N”, a chromate-free chemical conversion process, was applied in a mouthful and dried in a hot air oven.
  • the final plate temperature was 60 ° C.
  • the amount of chromate-free treatment was applied so that the total solid content would be 20 g / m 2 , and then one side of the chemical-treated metal plate.
  • the prepared primer paint is applied on the other side, and on the other side, a single color of “FL 1 0 0 HQ”, which is the back side paint made by Nihon Fine Coatings, is applied on a rollco.
  • the metal plate reached a temperature of 2 10 ° C. In dry cured. Then after drying baking, the painted metal plate subjected wipe the water in a spray, and water-cooled.
  • the intermediate coating and the top coating were simultaneously laminated in a slide hopper-type curtain co shown in Fig. 5, and hot air was blown into them.
  • the coated films were dried and cured at the same time under the condition that the ultimate temperature of the metal plate was 230 ° C.
  • the coated metal plate was sprayed with water and cooled with water to obtain a three-layer pre-coated metal plate (the coating method in this procedure is called “painting method (i ) ").
  • the primer paint Furthermore, in the process of painting the primer paint, three layers of primer paint, intermediate paint, and top paint are simultaneously applied in three layers using a slide hopper set curtain coater in an induction heating furnace blown with hot air.
  • the laminated coatings were dried and cured at the same time under the condition that the ultimate temperature of the metal plate was 230 ° C. After drying and baking, the coated metal plate was wiped with a spray and cooled with water to obtain a three-layer pre-coated metal plate (the coating method in this procedure was called “painting method (iii) ' ").
  • a two-layer pre-coated metal sheet was also produced by applying only one layer of top paint on the primer coating and baking it on the primer coating.
  • the coating method in this procedure is called “Coating method (V)”.
  • V The coating method
  • the roll peripheral speed and paint viscosity for the roll coater are used, and the coating pressure and paint viscosity for the slide hopper type curtain coater are used. It was controlled by adjusting.
  • the film thickness of the back coating was 5 ⁇ m in terms of dry film thickness.
  • Each film thickness was measured with an electromagnetic film thickness meter “LE-2200 J” manufactured by KET, and the vertical cut surface of each sample was observed with a microscope to determine the film thickness to be obtained. I reconfirmed.
  • Table 2 shows the details of the pre-coated metal sheet produced.
  • the appearance of the surface of the pre-coated metal sheet that had been coated with the top coating was evaluated by visual observation and observation with a 10 ⁇ magnifier. Appearance evaluation focused on both the color tone and the occurrence of boiling defects.
  • the color tone X is when the color of the paint film appears to be dark, or it is clearly white and light
  • ⁇ is the color when the color appears slightly dark. The case where it appeared vivid with no blackness was rated as ⁇ , and the case where it looked vivid without any darkening was rated as ⁇ .
  • the intermediate level between ⁇ and ⁇ was evaluated as ⁇ .
  • boiling defects ⁇ if no boiling defects are observed visually or with a loupe, ⁇ if no very small boiling defects are observed with a loupe, apparently visible boiling defects If X was found, it was evaluated as X.
  • Cut scratches were made on the surface of the pre-coated metal sheet that had been coated with the top coating, and a salt spray test was carried out according to the method described in JISK 5400.9.1. Salt water was sprayed on the surface of the test piece with the crosscut. The test time was 2400 hours. Then, the film swell width from the cut on the surface side was measured, and ⁇ when the bulge width of the cut part was 3 mm or less on one side, and ⁇ , when the bulge width of the cut butt part was more than 3 mm and less than 5 mm on one side. The case where the bulge bulge width was over 5 mm on one side was evaluated as X.
  • the pre-coated metal plate is cut vertically so that the cross-section of the coating film can be observed, the cut pre-coated metal plate is embedded in the resin, and then the cross-section is polished. Take a cross-sectional picture of the membrane 1. Next, photograph of transparent resin sheet (using commercially available OHP sheet) The top and bottom of the film were accurately traced on the film interface. And figure
  • the area of the vertical line was measured with an image processor, and Ra was calculated from the following formula (I I) as the average value.
  • the pre-coated metal plate was bent at 180 ° (additional bending X) in a 23 ° C atmosphere so that the surface with the top coating was on the outside.
  • the processed part was observed with a 10Ox microscope to investigate the presence or absence of cracks in the paint film.
  • the machined part of the pre-coated metal sheet was cut vertically so that a new surface could be observed, and the cross-section was polished after the cut pre-coated metal sheet was embedded in resin.
  • the cross section was observed with a double and a 500 ⁇ microscope. We then observed the presence or absence of cracks in each coating layer.
  • each coating layer was observed, and when all the coating layers were not cracked by observing them with a 500 ⁇ magnification microscope, the elongation at break of the coating was set to 100% or more. If the coating film of one or more layers is very slightly cracked with a 10Ox microscope and clearly cracked with a 500x microscope, the estimated elongation is only 10 ⁇ , assuming that cracks occurred in one or more layers with a microscope of 10 times, the elongation at break of the coating was clearly less than 100%, and was evaluated as X .
  • Adhesive tape was affixed to the coating surface of the processed part of the pre-coating metal plate that was bent by the measurement of the elongation at break of the coating film, and the remaining state of the coating film was visually observed when it was peeled off vigorously. .
  • the evaluation of coating film peeling was evaluated as “X” when there was no peeling of the coating film, and “X” when there was a clear peeling in the coating film when slight peeling was observed in the coating film. 6.
  • Measurement of glass transition temperature of precoated metal sheet The T g of the coating film was measured with a thermomechanical analyzer “SSC 5200 series TMAZSS 120C” manufactured by Seiko Denshi. A probe probe was used for the measurement.
  • the draw bead test is known as a test method for evaluating the slidability during press molding and the scratching property of the material due to the mold.
  • the mold galling of the paint film that occurs during press forming is reproduced, and the pre-coated metal sheet that is prone to galling of the paint film during press forming is However, peeling of the paint film due to galling is observed.
  • sample 6 3 was sandwiched between convex mold 6 1 and concave mold 6 2 having the shape and dimensions shown in Fig.
  • the prepared pre-coated metal sheet was deep-drawn into a rectangular tube shape so that the evaluation surface (the surface to which the back coating film was not applied) was outside the molded product.
  • the molds used for the rectangular tube formation were the following conditions. In other words, the punch size was 40 mm square, the punch corner R was 5 mm, the punch shoulder R was 5 mm, and the die MR was 5 mm. The surface roughness of the mold is 0.1 as Ra. The mirror finish was less than m.
  • the blank size of the material was a circle with a diameter of ⁇ 100 mm, and the wrinkle pressure was 0.8 t. Three molding heights of 20 mm, 25 mm, and 30 mm were used.
  • the presence or absence of coating film peeling or cracking (hereinafter referred to as processability) of the processed part of the pre-coated metal plate was observed visually and with a 10 ⁇ microscope. If no peeling or cracking is observed even when observed by the method, ⁇ , peeling or cracking is observed under the microscope, but if these are not visually observed, ⁇ , peeling or cracking is observed visually. If it was found, it was evaluated as X. Also, the glossiness of the molded product was visually observed and evaluated as ⁇ when no gloss reduction was observed in the processed part, and X when there was a clear decrease in gloss.
  • Tables 3 to 5 show the evaluation results of the pre-coated metal plates produced.
  • the pre-coated metal plates of the present invention (Examples PCM—No. 1 to 20 and 22 to 30) all have a liquid interface at the interface between the intermediate coating layer and the top coating layer. A trace interface was observed, but when it was colored red, yellow, or orange, it was able to express a vivid color without being blackish or white. There was no generation of boiling defects, and the design looked good.
  • each layer is applied by baking, and the surface roughness Ra of the interface between the intermediate coating layer and the top coating layer is less than 0.3 in (Comparative Example PCM-2 1)
  • the intermediate coating layer and the top layer have a liquid-liquid interface at the interface, and Ra of the fine irregularities of the interface is adjusted to 0.3 to 0.8 / X m.
  • Examples PCM—No. 1 to 20 and 2 2 to 30 have a more vivid appearance.
  • the added amount of titanium pigment contained in the intermediate coating film is less than 40 mass% (Example PCM—No. 9)
  • the coating appearance of the top coating film tends to be slightly blackish If it exceeds 60 mass% (Example PCM—No. 9), the elongation at break tends to be slightly lower than 100%, and there is a concern that the workability is poor.
  • the added amount of titanium pigment in the coating is more preferably 40 to 60 mass%.
  • the elongation at break of the coating film is less than 100% (Example p CM—NO 2.
  • the coating film used for the precoated metal sheet of the present invention preferably has a breaking elongation of 100% or more.
  • the Ra of the fine irregularities at the interface between the intermediate coating film and the top coating film is outside the range of 0.3 to 0.8 m (Example PCM-No. 2 1 ), Coating film adhesion is lost when severe processing is applied Therefore, Ra of the fine irregularities at the interface is more preferably 0.3 to 0.8 m.
  • Ra of the fine irregularities at each coating interface can be set to 0.3 to 0.8 ⁇ m.
  • the precoated metal sheet of the present invention with a thin primer coating (Example PCM—No. 2 2) tended to be slightly inferior in corrosion resistance.
  • Example PCM—No. 2 3 When the film thickness of the intermediate coating film is thin (Example PCM—No. 2 3), the color of the original plate cannot be completely concealed. It was a tendency to take on.
  • Example PCM—No. 2 4 When the film thickness of the top coating is thin (Example PCM—No. 2 4), the color of the top coating is thin and the white color of the intermediate coating tends to show through slightly. It was.
  • the thickness of each coating layer was thick (Example PCM—No. 25, 2 6, 2 7), extremely fine boiling defects tended to occur. Therefore, it is more preferable that the film thickness of each coating film of the precoated metal plate of the present invention is 1 to 3 Oim and the total film thickness is less than 50 m. It was.
  • any pre-coated metal plate of the present invention may be used as long as it is a known metal plate.
  • the primer coating of the precoated metal sheet of the present invention contains an anti-glare pigment other than Si and P, for example, a Cr anti-glare pigment (Comparative Example PCM—No. 3 1) or an intermediate coating
  • a Cr anti-glare pigment Comparative Example PCM—No. 3 1
  • the ones that did not contain Ti-based additives were not suitable because the color tone was poor when the top coating was applied, and vivid colors could not be expressed.
  • a coating containing a Ti-based additive in the top coating film (Example PCM-N o. Since the color tone has become dry, it is more preferable that the top coating does not contain a T i additive in order to express vivid red, orange, and yellow colors. It is.
  • the primer coating, intermediate coating and top coating of the pre-coated metal plate of the present invention are based on commercially available coatings, and the primer coating layer contains either Si or P or both.
  • the intermediate coating layer containing a Ti-based additive is used, and the top coating layer is colored in a color other than white or black (Example P CM-N o. 1 5, 1 6) is effective.
  • the coating film adhesion is excellent and more suitable.
  • VOC volatile organic solvents
  • the pre-coated metal plates (PCM-2, PCM-17, PCM-45 to PCM_49) according to the examples of the present invention have high gloss. Regardless of this, the gloss reduction in the processed part when deep drawing is small is small, and in the draw bead test that reproduces coating galling during continuous press, coating galling is unlikely to occur. There was no peeling or cracking of the coating film at the part, which was good.
  • the T g of the coating film is preferably 30 ° C or less.
  • Table 5 shows the evaluation results of molded products molded using precoated powder metal plates PCM-2, PCM-17, PCM-4 5 to PCM-4 9. Molded products formed using pre-coated metal sheets within the range expected in the present invention have a 60 ° specular gloss and an appearance of 60% or more, and cracks in the coating film in the processed part. There was no occurrence of peeling or peeling, and the appearance was excellent. However, those with a Tg of more than 30 ° C (PCM—17) have a lower gloss retention after processing than the other ones, which is just over 60%. T g is more preferably 30 ° C. or less.
  • the T g of the coating film exceeds 30 ° C, and the Ra of the interface with the top coating layer deviates from 0.3 to 0.8 '(PCM—48, PCM -4 9) are all 6 0. Specular gloss is less than 60%.
  • the present invention is applicable to a pre-coated metal plate excellent in design and corrosion resistance and a manufacturing method thereof. In particular, it has a design appearance of bright red, yellow, and orange colors and is used for home appliances. Pre-coated metal with excellent corrosion resistance, coating film workability, and excellent scratch resistance in applications such as building materials, civil engineering, machinery, automobiles, furniture, and containers Applicable to board.

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  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Cette invention concerne une plaque de métal ayant déjà un revêtement, laquelle a une excellente résistance à la corrosion et, même lorsqu'on diminue l'épaisseur du film de revêtement pour empêcher la survenue de défauts de travail du bain, peut développer une couleur vive et a un excellent aspect ; et un procédé servant à produire celle-ci. La plaque de métal ayant déjà un revêtement est une plaque de métal ayant déjà un revêtement multicouche comprenant un film de revêtement multicouche formé par superposition d'une couche de film de revêtement primaire, d'une couche de film de revêtement intermédiaire et d'une couche de film de revêtement de finition dans cet ordre sur un côté ou les deux côtés d'une plaque de métal. La plaque de métal ayant déjà un revêtement est caractérisée en ce que la couche de film de revêtement primaire contient du P et/ou du Si, une interface à trace interfaciale liquide-liquide est présente entre la couche de film de revêtement intermédiaire et la couche de film de revêtement de finition dans le film de revêtement multicouche, la taille des fines parties convexes et concaves de l'interface à trace interfaciale liquide-liquide est de 0,3 à 0,8 µm en termes de rugosité moyenne par rapport à la ligne centrale (Ra) et la couche de film de revêtement intermédiaire contient un additif de type Ti.
PCT/JP2006/311891 2005-07-28 2006-06-07 Plaque ayant deja un revetement et procede servant a produire celle-ci WO2007013232A1 (fr)

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JP2007528370A JP4808717B2 (ja) 2005-07-28 2006-06-07 プレコート金属板及びその製造方法
CN200680027553XA CN101232994B (zh) 2005-07-28 2006-06-07 预涂金属板及其制造方法

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JP2008265209A (ja) * 2007-04-23 2008-11-06 Nippon Steel Corp プレコート金属板
WO2011034216A1 (fr) * 2009-09-17 2011-03-24 新日本製鐵株式会社 Matériau métallique enduit et procédé de fabrication associé
WO2011034214A1 (fr) * 2009-09-17 2011-03-24 新日本製鐵株式会社 Feuille de métal prérevêtue et son procédé de fabrication
US9933550B2 (en) 2008-12-03 2018-04-03 Nippon Steel & Sumitomo Metal Corporation Coated metal material and method of production of same
CN111788335A (zh) * 2018-05-25 2020-10-16 日本制铁株式会社 表面处理钢板
CN113659157A (zh) * 2021-08-12 2021-11-16 惠州市亿纬新能源研究院 一种膜电极及其制备方法和应用

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MY165606A (en) * 2015-04-28 2018-04-16 Nippon Steel & Sumitomo Metal Corp Pre-coated metal sheet
CN109772916B (zh) * 2019-03-20 2024-03-15 江铃集团山东华岳车辆部件有限公司 自动喷涂石墨乳的模具冷却润滑装置
JP7107474B1 (ja) * 2021-12-03 2022-07-27 日本製鉄株式会社 Ｚｎ系めっき鋼板

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WO2011034216A1 (fr) * 2009-09-17 2011-03-24 新日本製鐵株式会社 Matériau métallique enduit et procédé de fabrication associé
WO2011034214A1 (fr) * 2009-09-17 2011-03-24 新日本製鐵株式会社 Feuille de métal prérevêtue et son procédé de fabrication
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CN111788335A (zh) * 2018-05-25 2020-10-16 日本制铁株式会社 表面处理钢板
CN111788335B (zh) * 2018-05-25 2022-07-26 日本制铁株式会社 表面处理钢板
CN113659157A (zh) * 2021-08-12 2021-11-16 惠州市亿纬新能源研究院 一种膜电极及其制备方法和应用

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