WO2011048930A1 - Tôle d'acier prérevêtue et son procédé de fabrication - Google Patents

Tôle d'acier prérevêtue et son procédé de fabrication Download PDF

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Publication number
WO2011048930A1
WO2011048930A1 PCT/JP2010/067315 JP2010067315W WO2011048930A1 WO 2011048930 A1 WO2011048930 A1 WO 2011048930A1 JP 2010067315 W JP2010067315 W JP 2010067315W WO 2011048930 A1 WO2011048930 A1 WO 2011048930A1
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Prior art keywords
steel sheet
coating layer
clear coating
layer
fine particles
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PCT/JP2010/067315
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English (en)
Japanese (ja)
Inventor
大熊俊之
古田彰彦
佐藤進
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Ｊｆｅ鋼板株式会社
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Application filed by Ｊｆｅ鋼板株式会社 filed Critical Ｊｆｅ鋼板株式会社
Priority to CN201080046784.1A priority Critical patent/CN102574363B/zh
Priority to KR1020147010533A priority patent/KR20140057677A/ko
Priority to KR1020127008088A priority patent/KR101423405B1/ko
Priority to SG2012014643A priority patent/SG178943A1/en
Priority to AU2010309188A priority patent/AU2010309188B2/en
Publication of WO2011048930A1 publication Critical patent/WO2011048930A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/24—Titanium dioxide, e.g. rutile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms

Definitions

  • the present invention relates to a pre-coated steel sheet used as an exterior material of an electrical equipment product, an interior / exterior material for a building, a member for a road, or the like.
  • the present invention relates to a precoated steel sheet excellent in workability, weather resistance, aesthetic durability, environmental cleanability and the like, and a method for producing the same.
  • Pre-coated steel sheets do not need to be painted after forming, and can be omitted from processing manufacturers and work environments can be improved, so various materials for electrical equipment products and exterior materials such as roofs and walls of buildings, It is used in a wide range of interior materials such as partitions.
  • Such pre-coated steel sheets are usually used after being subjected to various processing including 90 ° bending and 180 ° bending by press forming, roll forming or emboss forming, and therefore require excellent workability and coating film durability. Is done. For this reason, as the resin for the coating film used for the pre-coated steel sheet, a thermosetting polyester resin that forms a cured coating film by baking at 200 ° C. or higher, a fluorine resin having excellent weather resistance, and the like are used. Yes.
  • pre-coated steel sheets In recent years, the need for high performance and high functionality for pre-coated steel sheets has increased, and aesthetic durability is particularly required. That is, the appearance of pre-coated steel sheets is impaired by adhesion of fungi, algae, mold, etc., airborne smoke, various oily mists, exhaust gas, combustion products such as carbon black, and other substances over a long period of time. Measures to prevent this are required.
  • pre-coated steel sheets that have been individually provided with functions such as antibacterial / anti-fungal functions and anti-contamination functions, there are those that have been developed so far, but for pre-coated steel sheets that function in combination with other functions, The fact is that it has not been developed yet.
  • the pre-coated steel sheet provided with antibacterial and antifungal functions is obtained by dispersing a compound containing silver, copper, or the like in the coating film.
  • the antibacterial action of these compounds suppresses or kills the growth of mold, fungi, and algae on the coating surface.
  • the pre-coated steel sheet to which the anti-contamination function is imparted is one that keeps the surface of the coating film as hydrophilic as possible, thereby washing away contaminating components adhering to the surface together with rain water and suppressing the deposition of deposits.
  • a precoated steel sheet having an antibacterial function and a contamination resistance function there is one using a method of decomposing organic substances and the like attached by a photocatalyst.
  • a substance having photocatalytic activity is dispersed in a coating film on the surface of the steel sheet to decompose organic substances adhering to the generated active oxygen.
  • the technology using this photocatalyst decomposes surface deposits such as organic substances adhering to the surface of the steel sheet and at the same time gradually decomposes the coating film itself as a matrix.
  • Patent Documents 1 to 3 As a countermeasure against this, conventionally, as a matrix coating film of a photocatalyst, there has been proposed to use an inorganic material, a fluororesin, or an organic-inorganic composite which is not easily decomposed (Patent Documents 1 to 3). Further, a method has been proposed in which a photocatalyst layer containing a photocatalyst and a fluororesin wax is formed on at least one surface of a metal plate via a protective film formed of an inorganic paint (Patent Document 4).
  • a member is also proposed in which a surface layer is formed by dispersing a fluorocatalyst having a lubricating effect and a buffering effect on a photocatalytic coating film using silica or the like on a substrate as a matrix (Patent Documents 5 and 6).
  • the photocatalytic film layer has a high refractive index, it tends to exhibit an interference color due to unevenness in the amount of the photocatalytically active substance attached.
  • the surface of the base substrate to be processed is highly glossy or has a flat surface with a small surface roughness, there is a problem that the aesthetic appearance is impaired, for example, the processing unevenness is noticeable and the interference color looks streak.
  • the photocatalyst film is dispersed in islands on the base material and deposited in a discontinuous manner, so that the design and durability are excellent, and cracks do not occur.
  • Methods that can be kept stable have been proposed (Patent Documents 7 and 8).
  • the photocatalytically active substance is dispersed in the inorganic coating film, it has excellent weather resistance such as discoloration, but the coating film itself is poor in flexibility.
  • the coating film is applied to the precoated steel sheet as it is, there is a big problem that cracks are likely to occur when bending or drawing is performed, and the coating film peels off.
  • Patent Document 2 relates to a steel plate in which a photocatalytically active substance is dispersed in a fluororesin coating film.
  • a photocatalytically active substance is dispersed in a fluororesin coating film.
  • the coating film as a matrix is decomposed by the photocatalyst. This drawback can be solved by increasing the thickness of the coating film.
  • the film thickness is increased, the flexibility becomes poor, and a new problem arises that workability is lowered.
  • Patent Document 3 relates to a surface-treated metal obtained by dispersing a photocatalytically active substance in a coating film made of an organic-inorganic composite. Although it is slightly superior in workability, in order to satisfy the workability level required for the pre-coated steel sheet, it is necessary to reduce the film thickness, resulting in a decrease in the photocatalytic function.
  • the coated metal plate disclosed in Patent Document 4 also has a problem that when it is applied to an exterior material, the coating film as a matrix is decomposed by the photocatalyst.
  • Patent Documents 5 and 6 are effective in preventing scratches and scratches, but the photocatalytic film is scratched when processing involving deformation such as press molding is performed. Due to problems such as easy attachment, application as a pre-coated steel sheet is difficult.
  • Patent Document 7 requires a complicated method for forming a photocatalytic film in an island shape, and requires a special apparatus for stable film formation.
  • the disclosed technology is difficult to apply to pre-coated steel sheets because damage such as scratches on the photocatalyst film is inevitable when processing such as press molding or roll molding is performed.
  • the object of the present invention is to solve the above-mentioned problems of the conventional technology and to make the photocatalyst layer (film), which is the outermost layer, discontinuous (network-like), so that processing unevenness and interference color can be reduced.
  • the photocatalyst layer film
  • various properties such as high weather resistance, aesthetic durability, and decomposition resistance to photocatalysts
  • An object of the present invention is to provide an excellent precoated steel sheet and a method for producing the same.
  • the inventors have proposed a new technique according to the following summary configuration as a method effective for realizing the above-described object, by solving the above-described problems of the prior art.
  • the present invention includes a clear coating layer (A) in which the main component is composed of a silicon compound and contains water-repellent fine particles dispersedly on at least one surface of a steel plate substrate, and the main component laminated on the clear coating layer (A). And a clear film layer (B) containing titanium oxide fine particles exhibiting photocatalytic activity as a pre-coated steel sheet.
  • At least a part of the water-repellent fine particles in the clear coating layer (A) protrudes from the surface of the clear coating layer (B) and is dispersed in an island shape; (2) The contact angle between the surface of the clear coating layer (B) and water is 22 to 60 degrees, (3) At least a part of the water-repellent fine particles in the clear coating layer (A) has a particle diameter larger than the film thickness of the clear coating layer (A).
  • the water-repellent fine particles in the clear coating layer (A) are made of fluorine resin particles, fluorine resin copolymer resin particles, silicon resin particles, or particles obtained by coating these resins on the surface.
  • the silicon compound in the clear film layer (A) is an acrylic silicon resin
  • titanium oxide particles in the clear coating layer (B), it adhered amount per one side, is 10mg / m 2 ⁇ 2000mg / m 2 in terms of TiO 2
  • the clear coating layer (B) is mainly composed of a mixture of anatase type crystalline titanium oxide fine particles and amorphous titanium oxide
  • the steel sheet substrate has a chemical conversion film and a resin film formed thereon on at least one surface of a zinc-based plated steel sheet, and the resin film contains a rust preventive pigment.
  • the colored resin layer is mainly composed of an organosol-baked fluororesin having a mass ratio of polyvinylidene fluoride and acrylic resin of 85:15 to 50:50, Is a more preferable solution.
  • a clear coating layer (A) mainly composed of a silicon compound and a clear coating layer (B) mainly composed of titanium oxide fine particles exhibiting photocatalytic activity are sequentially laminated on at least one surface of a steel plate substrate.
  • the water-repellent fine particles are dispersed and contained in the clear coating layer (A), and the coating amount of the clear coating layer (B) on the portion where the water-repellent fine particles are present and in the vicinity thereof
  • a method for producing a pre-coated steel sheet is proposed in which at least a part of the water-repellent fine particles is dispersed from the surface of the clear coating layer (B) in an island shape by suppressing the above.
  • At least a part of the water-repellent fine particles in the clear coating layer (A) may have a particle size larger than the film thickness of the clear coating layer (A). This is a more preferable solution.
  • a clear coating layer (A) containing water-repellent particles as a base layer is laminated on the surface of a steel plate substrate, and further, titanium oxide fine particles having photocatalytic activity are further dispersed on the clear coating layer (B) which is the outermost layer is not formed in the portion where the water-repellent particles of the clear coating layer (A) are present and becomes discontinuous (network-like).
  • the pre-coated steel sheet is subjected to bending or drawing, cracks are less likely to occur in the clear coating layer (B).
  • the water-repellent fine particles in the clear coating layer (A) exposed on the surface of the precoated steel sheet have a function as a lubricant or a buffer, and therefore when subjected to bending or drawing, Generation
  • the clear coating layer (A) having a silicon compound as a main component is provided between the colored resin layer on the steel plate substrate surface and the clear coating layer (B) which is the outermost layer, it is clear.
  • the coating layer (B) is effectively decomposed against the photocatalyst, and the lower colored resin layer is prevented from being decomposed and deteriorated by direct contact with the photocatalyst, and has good workability, weather resistance and aesthetic durability. It can be set as the precoat steel plate which has.
  • the basic structure of the precoated steel sheet of the present invention is that a clear film layer (A) containing water repellent fine particles dispersed and containing a silicon compound as a main component on at least one surface of a steel sheet substrate, and the clear film layer (A) A clear coating layer (B) containing titanium oxide particles having photocatalytic activity is sequentially laminated thereon.
  • the clear coating layer (A) is characterized in that water-repellent fine particles are dispersed and contained, whereby the clear coating layer (B) as an upper layer is contained in the clear coating layer (A).
  • the water-repellent fine particles are repelled to form a discontinuous state (network), and at least a part of the water-repellent fine particles protrudes from the surface of the clear coating layer (B) and is dispersed in an island shape.
  • the clear coating layer (A) is exposed on the surface of the steel sheet, and the water-repellent fine particles serve as a lubricant and a buffer.
  • the water-repellent fine particles serve as a lubricant and a buffer.
  • the precoated steel sheet of the present invention has a chemical conversion coating 2 on at least one surface of a zinc-based plated steel sheet 1 and a resin film (primer layer) formed thereon, as shown in FIG. 3, a colored resin layer 4) and two types of clear coating layers (clear coating layer (A) 5 and clear coating layer (B) 6) are sequentially laminated.
  • the zinc-based plated steel sheet 1 suitably used in the present invention, those that can be formed, such as electrogalvanized steel sheet, hot-dip galvanized steel sheet, hot-dip zinc-5 mass% aluminum alloy-plated steel sheet, hot-dip zinc-55 mass% aluminum alloy
  • the thickness of the plated steel sheet is not particularly limited, but is preferably about 0.2 to 1.6 mm from the viewpoint of forming.
  • the chemical conversion coating 2 is first formed on the one or both sides of the galvanized steel sheet 1 prior to forming the primer layer 3. This chemical conversion coating 2 is formed in order to strengthen the adhesion between the zinc-based plated steel sheet 1 and the primer layer 3 and to provide corrosion resistance.
  • Examples of the chemical conversion treatment film 2 suitably used in the present invention include a phosphate treatment film, a chromate treatment film, a silica-containing chromate treatment film, a chromate-free rust preventive comprising various metal oxides, and an organic resin alone. Or it consists of a composite, and in order to improve adhesiveness and corrosion resistance in particular, it is preferably composed of a thin film containing an organic resin and a metal oxide, a phosphoric acid compound and / or chromic acid.
  • the organic resin it is desirable to use a water-dispersible resin, for example, an acrylic resin or a urethane resin dispersed with an emulsifier.
  • chromic acid acts as a binder for obtaining adhesion between the chemical conversion treatment film and the zinc-based plating layer.
  • the organic resin acts to improve adhesion between the chemical conversion film and a primer layer described later.
  • chromium content in a chemical conversion treatment film is 20 mg / m ⁇ 2 > or more in metal chromium conversion amount. This is because when the chromium content is less than 20 mg / m 2 , the corrosion resistance as the precoated steel sheet cannot be obtained sufficiently.
  • the chromate-free rust preventive agent used as the chemical conversion coating component is silicic acid and / or silicic acid compound, calcium or calcium compound, zirconic acid and / or zirconic acid compound, vanadic acid and / or vanadic acid compound, molybdic acid. It preferably contains one or more of compounds, phosphoric acid and / or phosphoric acid compounds, and the content is 0.3 to 3.0 g / m 2 .
  • the reason for making the amount of this chromate-free rust inhibitor 0.3 to 3.0 g / m 2 is that if it is less than 0.3 g / m 2 , the corrosion resistance and adhesion as a pre-coated steel sheet cannot be obtained. This is because if it exceeds 0.0 g / m 2 , the workability is lowered.
  • the binder for example, a water dispersible acrylic resin or urethane resin may be used.
  • the primer layer 3 is first formed as a first film on the surface of the chemical conversion film 2 formed on at least one surface of the zinc-based plated steel sheet 1 as described above.
  • the primer layer 3 is made of a thermosetting resin containing a rust preventive pigment, and includes a chemical conversion treatment film 2 and an upper film described later (colored resin layer 4, clear film layer (A) 5, clear film layer (B) 6). It is a layer formed in order to obtain adhesion and corrosion resistance.
  • the layer thickness of the primer layer 3 is preferably 2 ⁇ m or more and 10 ⁇ m or less. If the layer thickness is less than 2 ⁇ m, sufficient rust prevention properties cannot be obtained. This is not preferable.
  • thermosetting resin that is the main component of the primer layer 3 is not particularly limited, but it is preferable to use one or more of polyester resins, epoxy resins, and the like.
  • a polyester resin or the like can be used.
  • some epoxy resins are partially replaced with urethane resins, phenol resins, amino resins, etc., and epoxy compounds comprising bisphenols such as bisphenol A, bisphenol F, bisphenol AD, and epihalohydrin or ⁇ -methyl epihalohydrin.
  • copolymers of these can be used.
  • monocarboxylic acid or dicarboxylic acid modified products, mono, di or polyalcohol modified products, mono or diamine modified products, mono, di or polyphenol modified products of these epoxy compounds can also be used as epoxy resins.
  • the reason for limiting the main body of the primer layer 3 to the thermosetting resin is that when a room temperature drying resin or a thermoplastic resin is used, when an upper film (colored resin layer, clear film layer) is formed thereon, This is because deformation and deterioration accompanying softening occur depending on the baking temperature, and there is a problem that strong adhesion to the upper layer film cannot be obtained.
  • a polyisocyanate compound and / or an amino resin can be used as the curing agent for the primer layer 3.
  • the polyisocyanate compound hexamethylene diisocyanate (hereinafter referred to as HDI) and derivatives thereof obtained by a general production method, tolylene diisocyanate (hereinafter referred to as TDI) and derivatives thereof 4.4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) and Its compounds, xylylene diisocyanate (hereinafter referred to as XDI) and derivatives thereof, isophorone diisocyanate (hereinafter referred to as IPDI) and derivatives thereof, trimethylhexamethylene diisocyanate (hereinafter referred to as TMDI) and derivatives thereof, hydrogenated TDI and derivatives thereof, hydrogenated MDI and Compounds such as derivatives thereof, hydrogenated XDI and derivatives thereof can be used.
  • HDI hexam
  • a polyisocyanate compound blocked with a blocking agent such as phenol, cresol, aromatic secondary amine, tertiary alcohol, lactam, or oxime, which can be used as a one-pack type paint.
  • This blocked polyisocyanate compound can be stored in a single liquid and can be easily used as a paint.
  • the amino resin used for the curing agent there are resins obtained by reacting urea, benzoguanamine, melamine and the like with formaldehyde, and those obtained by alkyl etherification with alcohols such as methanol and butanol. Specifically, methylated urea resin, n-butylated benzoguanamine resin, methylated melamine resin, n-butylated melamine resin, iso-butylated melamine resin and the like can be mentioned.
  • the blending ratio of the curing agent in the primer layer 3 is preferably 9 to 50% by mass in the resin solid content, and if it is less than 9% by mass, the coating film hardness is insufficient, and 50% by mass. This is because if the thickness is too high, the processability is insufficient.
  • a curing catalyst such as p-toluenesulfonic acid, tin octoate, dibutyltin dilaurate or the like may be used for the primer layer 3 according to the purpose or application.
  • extender pigments such as calcium carbonate, kaolin, and clay, color pigments such as titanium oxide, dial, mica, carbon black, and aluminum powder, and various additives such as antifoaming agents and leveling agents may be added.
  • the primer layer 3 when the pre-coated steel sheet is formed, or when it is used outdoors for a long period of time, coating bulge and plating corrosion from a cut edge portion or a coating scratch portion are prevented.
  • 5% by mass to 50% by mass of an antirust pigment is contained.
  • the content of the rust preventive pigment is less than 5% by mass, there is no effect of improving the corrosion resistance, and when it exceeds 50% by mass, the workability deteriorates with a decrease in the flexibility of the coating film, which is not preferable. .
  • rust preventive pigments As rust preventive pigments, chromate, silica pigment, phosphite pigment, calcium compound, aluminum oxide, zirconic acid or / and zirconic acid compound, vanadic acid or / and vanadic acid compound, molybdate compound, It is preferable to use one or a mixture of two or more of phosphoric acid and / or phosphoric acid compounds. Among them, it is preferable to use chromate from the viewpoint of further improving rust prevention.
  • the colored resin layer 4 is formed on the primer layer 3 described above.
  • a resin excellent in adhesiveness with the primer layer 3 and capable of continuous coating in a pre-coated steel sheet manufacturing facility for example, a polyester resin, a fluorine resin, an acrylic resin, a urethane resin, Resins in which these components are combined are advantageously suitable.
  • polyvinylidene fluoride and acrylic resin as the main resin of the colored resin layer 4 are 85: It is preferable to use an organosol baking type fluororesin blended in a ratio of 15 to 50:50, more preferably 85:15 to 75:25. This is because, by using an organosol-type baking type fluororesin that is a mixture of polyvinylidene fluoride and an acrylic resin, it is possible to suppress crystallization of polyvinylidene fluoride, which is a crystalline resin, and durability (resistance to weathering). ) And processability can be improved, and furthermore, the adhesion between the primer layer 3 as the lower layer of the colored resin layer 4 and the clear film layer (A) 5 as the upper layer can be improved. is there.
  • thermoplastic acrylic resin As the acrylic resin contained in the organosol-based baking type fluororesin, a thermoplastic acrylic resin and a thermosetting acrylic resin can be used alone or in combination.
  • thermoplastic acrylic resins from the viewpoint of compatibility with polyvinylidene fluoride, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic
  • monomer polymers such as acid amyl, or a copolymer of these monomers with acrylic acid, styrene, or the like can be used.
  • thermosetting acrylic resin is composed of an acrylic resin having a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a glycidyl group or an isocyanate group, and a curing agent such as an alkylated melamine, a polyol or a polyamide. Can be used.
  • the colored resin layer 4 controls the color tone of the appearance of the precoated steel sheet, and titanium oxide, petal, mica, carbon black, fired black, titanium yellow, yellow iron oxide, phthalocyanine blue, phthalocyanine are included in the coating film.
  • Blends various color pigments such as green. This color pigment is contained in an amount of about 15% by mass to 60% by mass. The reason is that the target hue can be formed as a stable and concealed coating film within the range of this content.
  • additives such as a gloss adjusting agent such as synthetic silica, an antifoaming agent for improving coating workability, a surface adjusting agent, and an anti-scratch agent for a coating film can be blended as necessary.
  • the colored resin layer 4 is preferably 8 to 25 ⁇ m thick. If the layer thickness is less than 8 ⁇ m, the color tone becomes unstable as the concealing property decreases, and sufficient durability, workability and corrosion resistance of the processed part cannot be obtained. On the other hand, if the layer thickness exceeds 25 ⁇ m, film defects such as occurrence of cracks (foaming) are likely to occur, and further cracks occur due to an increase in internal strain at the time of processing, which is not preferable.
  • the colored resin layer 4 is applied to the surface of the primer layer 3 of the galvanized steel sheet by a conventional method for producing a precoated steel sheet, for example, a chemical solution diluted with an organic solvent, using a roll coater or a curtain coater. It can be formed continuously by baking at a temperature of about 0C.
  • the clear coating layer (A) 5 is formed on the colored resin layer 4 and provides mutual adhesion between the clear coating layer (B) 6 as an upper layer and the colored resin layer 4 as a lower layer. It has a function to improve. Further, the clear coating layer (A) 5 functions to suppress the colored resin layer 4 from being decomposed and deteriorated over time by the photocatalytic action of the titanium oxide fine particles blended in the clear coating layer (B) 6. Also have.
  • the main component of the clear coating layer (A) 5 is a silicon compound such as acrylic silicon resin, trialkoxysilane and its condensate, acrylic silicate and its condensate, organohydroxysilane and its condensate, or a composition thereof and silica. It is particularly preferable to use an acrylic silicon resin.
  • acrylic silicone resin it is possible to use a composite, copolymerized or cross-linked with another cross-linking agent, or a cross-linked one using an acrylate or silicon-containing cross-linking agent. it can.
  • the acrylate component of the acrylic silicone resin has the function of improving the flexibility of the clear coating layer (A) 5 and improving the adhesion with the colored resin layer 4 as the lower layer.
  • alkyl-containing acrylic monomers and oligomers or polymers such as methyl acrylate and methyl methacrylate, hydroxyl-containing acrylic monomers and oligomers or polymers such as 2-hydroxyethyl acrylate, and ethylenic unsaturated compounds such as acrylic acid.
  • carboxylic acid monomers, oligomers or polymers, and acrylic monomers, oligomers or polymers containing amide groups or glycidyl groups can be used.
  • the silicon component of the acrylic silicon resin strengthens the adhesiveness with the clear coating layer (B) 6 formed in the upper layer, and the clear coating layer (A) by the photocatalyst contained in the clear coating layer (B) 6. 5 itself has a function of suppressing decomposition and deterioration.
  • Examples of the silicon component include alkoxysilane compounds such as methyltriethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane, hydrolysates thereof, or one of condensates thereof. Two or more types can be used.
  • the layer thickness of the clear coating layer (A) 5 is preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the upper limit thickness of the clear coating layer (A) 5 is not particularly defined, but when the composition itself is poor in flexibility, it is preferably a thinner film, particularly 1 ⁇ m, in order to suppress deterioration of workability. By setting it as the following, favorable workability can be obtained irrespective of the kind of composition.
  • the present invention is characterized in that the water-repellent fine particles 7 are dispersed and contained in the clear film layer (A) 5. That is, the clear film layer (B) 6 as an upper layer is repelled by the water-repellent fine particles 7 in the clear film layer (A) 5 and is not covered in and around the portion where the fine particles 7 are present.
  • the coating layer (B) 6 is not formed in a continuous film shape. As a result, when processed as a pre-coated steel sheet, the occurrence of cracks and the like in the clear coating layer (B) 6 is suppressed, and the deterioration of aesthetics due to processing unevenness, streak-like interference color, etc. can be prevented. it can.
  • fluorine-based resin particles such as polytetrafluoroethylene, polychlorotrifluoroethylene, or perfluoroalkoxy fluororesin, tetrafluoroethylene / hexafluoride, etc.
  • Fluorine resin copolymer resin particles such as polypropylene copolymer or ethylene / tetrafluoroethylene copolymer, silicon resin particles, or particles coated with these resins on the surface, especially fine particles made of fluorine resin Is preferred.
  • water-repellent fine particles 7 made of polytetrafluoroethylene are used, and fine particles 7 having a particle diameter larger than the film thickness are formed in the clear coating layer (A) 5 as shown in FIG.
  • the fine particles 7 are exposed on the surface of the clear coating layer (A) 5, that is, the surface of the precoated steel plate, and the fine particles 7 are used as a lubricant or a buffer when the precoated steel plate is bent. It can act more effectively and suppress the occurrence of scratches and the like.
  • fluororesin fine particles 7 include Dionion TF micro powder manufactured by Sumitomo 3M Limited.
  • the particle diameter of the water-repellent fine particles 7 is preferably an (average) particle diameter of 0.3 to 10 ⁇ m because the water-repellent effect is reduced when the particle diameter is less than 0.3 ⁇ m, and the clear coating layer (B) 6 is formed in a continuous film shape, causing problems such as uneven appearance (interference color) and lowering of workability.
  • the clear coating layer (A) 5 has a problem. In order to disperse, it is necessary to make the thickness of the clear coating layer (A) 5 sufficiently thick, which is disadvantageous in terms of cost and it becomes difficult to stably form the clear coating layer (A) 5 itself. It is.
  • the blending amount of the water-repellent fine particles 7 in the clear coating layer (A) 5 is preferably about 0.5 to 20% by mass, more preferably 1 to 10% by mass in terms of solid content. If the blending amount is less than 0.5% by mass, the above effect cannot be obtained, and if it exceeds 20% by mass, the film becomes cloudy or difficult to paint, which is not preferable.
  • various additives such as silica fine particles, a dispersant, a coupling agent or an ultraviolet absorber may be added within a range that does not change the color tone.
  • a method for forming the clear coating layer (A) 5 in a continuous coating line there is a method in which a solution diluted in an organic solvent is applied and baked by a curtain coater, a roll coater or a die coater.
  • an acrylic silicon resin is used as the main component of the clear coating layer (A) 5, it is preferably baked at a temperature of about 150 to 200 ° C. after coating.
  • the clear coating layer (B) 6 that is the outermost layer of the precoated steel sheet of the present invention will be described.
  • the clear coating layer (B) 6 is formed on the clear coating layer (A) 5.
  • the clear coating layer (B) 6 is used as an aqueous dispersion, for example, by a roll coating method in a continuous coating line.
  • the clear coating layer (B) 6 is not coated on or near the water-repellent fine particles 7 and is formed in a discontinuous state (network shape).
  • the clear coating layer (B) is not covered in the vicinity of the water-repellent fine particles 7 contained and dispersed in the clear coating layer (A) and in the vicinity thereof, and the water-repellent fine particles are not clear.
  • the contact angle between the surface of the clear coating layer (B) and water is 60 degrees or less, preferably 22 to 50 degrees. This is because when the contact angle of water exceeds 60 degrees, the self-cleaning effect (the effect of self-cleaning rain-stained dirt outdoors by rain) cannot be obtained. Clearly obtained at 50 degrees or less.
  • the contact angle of water is less than 22 degrees, the effect (formability as a pre-coated steel plate, wiping off attached dirt) due to the water-repellent fine particles contained and dispersed in the clear coating layer (A) may be reduced. Is not preferable.
  • anatase type crystalline titanium oxide as the titanium oxide fine particles having a high level of photocatalytic activity.
  • anatase type crystalline titanium oxide those having a particle diameter of about 0.001 to 0.2 ⁇ m are optimal in terms of paintability and photocatalytic properties.
  • Examples include ST-01, ST-21, ST-30L manufactured by Ishihara Sangyo Co., Ltd.
  • anatase type crystalline titanium oxide exhibits activity with respect to light having a short wavelength in the ultraviolet region, and therefore, when a precoated steel sheet is used as an exterior member, it can exhibit photocatalytic properties by ultraviolet rays contained in sunlight. it can.
  • a pre-coated steel sheet is used as an interior member, it is preferable to use a visible light responsive anatase type crystalline titanium oxide.
  • a visible light responsive titanium oxide an oxide doped with nitrogen, sulfur or carbon is used. Titanium, oxygen-deficient titanium oxide, dye-sensitized titanium oxide, metal-supported titanium oxide, or the like can be used.
  • the clear coating layer (B) 6 may be blended with amorphous titanium oxide together with the above anatase type crystalline titanium oxide.
  • the mixing ratio of the anatase type crystalline titanium oxide and the amorphous titanium oxide is preferably 10:90 to 80:20 by mass ratio.
  • Amorphous titanium oxide has the effect of improving the stability of the coating chemical and improving the action of the film as a binder, and the workability and durability of the film.
  • the clear coating layer (B) 6 has a titanium oxide particle adhesion amount per one surface of a zinc-based plated steel sheet of 10 mg / m 2 to 2000 mg / m 2 in terms of TiO 2 , more preferably 50 mg / m 2 to 2000 mg. / M 2 .
  • the adhesion amount is less than 10 mg / m 2 , the photocatalytic characteristics are greatly deteriorated or a uniform film cannot be formed.
  • the adhesion amount exceeds 2000 mg / m 2 , various forming processes are performed as a precoated steel sheet. When this occurs, cracks and peeling occur in the film, and in some cases, the cracks may propagate to the lower colored resin layer 4.
  • the clear coating layer (B) 6 includes, in addition to the fine titanium oxide particles, one or more of metal oxides and compounds such as silicon, aluminum and zirconium, or phosphate compounds as binders and additives for forming the coating.
  • metal oxides and compounds such as silicon, aluminum and zirconium, or phosphate compounds as binders and additives for forming the coating.
  • An inorganic compound may be contained.
  • the clear coating layer (B) 6 may contain an antibacterial agent such as a silver compound and an adsorbent such as activated carbon or zeolite as long as the color tone is not changed. It can be further increased.
  • the clear coating layer (B) 6 As a method of forming the clear coating layer (B) 6 on the clear coating layer (A) 5 which is a lower layer in a continuous coating line, water or There is a method in which a chemical solution diluted in an organic solvent is applied by a roll coater or a die coater and baked at a temperature of about 180 to 250 ° C.
  • the present invention is provided with the clear coating layer (A) 5 containing a water-repellent substance and the clear coating layer (B) 6 containing photocatalyst particles on one or both sides of a steel plate substrate.
  • the clear coating layer (B) 6 serving as the upper layer has a clear coating layer (A) 5 It is repelled by the water-repellent fine particles 7 and is not covered in the vicinity of the fine particles 7 and the vicinity thereof, and the water-repellent fine particles 7 are exposed from the surface of the precoated steel plate (clear coating layer (B) 6).
  • Each of the coating layers is formed on at least one side of the steel plate substrate, but the same coating layer may be formed on the other side (back side), and after the chemical conversion treatment on the back side, You may form what is called a service coat of 1 coat and 1 bake used in a normal precoat steel plate.
  • Example 1 of the present invention a molten 55% aluminum-zinc alloy having a thickness of 0.5 mm obtained by applying a silica-containing coating-type chromate treatment as a steel plate substrate so that the amount of adhesion is 40 mg / m 2 in terms of metal chromium.
  • a plated steel sheet (with a coating amount of 80 g / m 2 on one side) was used.
  • This hot dip galvanized steel sheet is coated with a melamine curable polyester resin paint “Precolor Primer FX-2 (manufactured by BASF Coating Japan)” containing about 20% by mass of strontium chromate as a rust preventive pigment.
  • the primer layer (a-1) was formed by coating with a bar coater so as to have a thickness of 5 ⁇ m and baking at about 230 ° C. for 60 seconds.
  • an organosol-based baking type fluororesin “Precolor No. 8800 (manufactured by BASF Coating Japan Co., Ltd.)” having a weight ratio of polyvinylidene fluoride and acrylic resin of 80:20 is used as a coloring pigment.
  • a paint (b-1) in which titanium oxide and calcined black are mixed with calcined silica for surface adjustment is applied with a bar coater so that the dry coating thickness is 22 ⁇ m, and then baked at about 240 ° C. for 60 seconds to be colored.
  • a resin layer gloss value 10 by 60 degree gloss method was formed.
  • an acrylic silicon resin solution having a weight average molecular weight of about 20,000 comprising n-butyl acrylate and methyl methacrylate as an acrylic component and ⁇ -methacryloxypropyltriethoxysilane as a silicon component is formed on the colored resin layer.
  • a coating material (c-1) containing 5% by mass of polytetrafluoroethylene fine particles having an average particle size of 4 ⁇ m (Dinion TF9207 manufactured by Sumitomo 3M Limited) was applied with a bar coater so that the dry film thickness was 2 ⁇ m. Thereafter, the film was dried at about 150 ° C. for 30 seconds to form a clear film layer (A).
  • an amorphous titanium oxide dispersion “Nippon Parkerizing Co., Ltd.” is used so that ST-21 manufactured by Ishihara Sangyo Co., Ltd. as anatase-type titanium oxide has a solid content ratio of 20 mass%.
  • the aqueous dispersion (d-1) mixed with “PTI-5600” was applied with a roll coater so that the adhesion amount was 150 mg / m 2 in terms of TiO 2 , and then dried at about 200 ° C. for 20 seconds.
  • a clear coating layer (B) was formed to obtain a precoated steel sheet of the present invention (Invention Example 1).
  • the aqueous dispersion liquid of the said kind (d-1) was apply
  • the type (b-2) of the colored resin layer in Table 1 is a melamine curable polyester resin in which titanium oxide and carbon black are mixed as a color pigment ("Precolor No. 3800" (manufactured by BASF Coatings Japan). ), A thickness of 15 ⁇ m, and a gloss value of 60.
  • the type (c-2) of the clear coating layer (A) is obtained by adding polytetrafluoroethylene fine particles (Sumitomo 3M Dyneon TF9205) having an average particle size of 8 ⁇ m to the same acrylic silicon resin solution as the type (c-1). The solid content ratio is 3% by mass.
  • Type (c-3) is the same acrylic silicon resin solution as type (c-1) and does not contain water-repellent fine particles.
  • (C-4) is an acrylic resin emulsion paint
  • the type (c-5) is 30% of the powder of the type (d-1) with respect to the solution of the type (c-3) in a solid content ratio.
  • water-repellent fine particles (Sumitomo 3M Dionine TF9207) are mixed so that the solid content ratio is 3%.
  • the type (d-2) of the clear coating layer (B) is obtained by removing the anatase-type titanium oxide from the type (d-1), and the type (d-3) is the type (d-1).
  • Water-repellent fine particles (Sumitomo 3M Dionine TF9207) are mixed in an aqueous dispersion so that the solid content ratio is 3%.
  • the precoated steel plate of Comparative Example 3 does not contain water-repellent fine particles in the clear coating layer (A) 5
  • the clear coating layer (B) 6 to be formed was formed in a continuous film shape, and processing scratches were generated on the surface.
  • the clear coating layer (B) since the clear coating layer (B) does not contain titanium oxide, the aesthetic durability effect by the photocatalyst cannot be exhibited.
  • the clear coating layer (A) is an acrylic resin emulsion paint. Since the silicon compound and water-repellent fine particles were not contained, the clear coating layer (A) was decomposed and deteriorated by the photocatalyst, and deterioration in weather resistance and workability was recognized.
  • Comparative Example 8 is an example in which the photocatalyst particles are interposed together with the water-repellent fine particles in the clear coating layer (A). As shown in the cross-sectional view of FIG. 7A and the plan view of FIG. The fine particles 7 are exposed from the surface of the clear coating layer (A) 5.
  • the pre-coated steel sheet of Comparative Example 8 showed excellent bending workability due to the effect of the water-repellent fine particles 7, but the photocatalyst particles 8 penetrated into the clear coating layer (A) 5, so that the weather resistance decreased. I have.
  • the pre-coated steel sheet of the present invention and the production method thereof are excellent in workability, weather resistance, aesthetics, etc., and of course are suitable as exterior materials for electrical equipment products and interior / exterior materials for buildings. Can also be used in applications where the above performance is required.

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Abstract

La présente invention concerne une tôle d'acier prérevêtue comportant une couche de photocatalyseur (pellicule protectrice) comme couche la plus extérieure. Ladite tôle permet d'empêcher une diminution de l'apparence esthétique provoquée par l'inégalité de traitement ou des stries colorées interférentielles du fait de la formation de la couche photocalytique comme couche discontinue (réseau). Cette tôle d'acier prérevêtue présente les performances requises pour une tôle d'acier prérevêtue, telles que l'égalité de l'apparence et l'aptitude au traitement, et présente en outre diverses excellentes propriétés telles qu'un degré élevé de tenue aux intempéries, une durabilité de l'apparence esthétique, et une résistance à la décomposition avec le photocatalyseur. Elle concerne également un procédé de fabrication de la tôle d'acier prérevêtue. La tôle d'acier prérevêtue comprend une tôle d'acier de base, une couche de revêtement transparente (A) formée au-dessus d'au moins une surface de la base, la couche (A) comprenant un composé silicium comme composant principal et de fines particules hydrofuges étant dispersées dans celle-ci, et une couche de revêtement transparent (B) superposée sur la couche de revêtement transparent (A), la couche (B) contenant, comme composant principal, de fines particules d'oxyde de titane révélant une activité photocatalytique.
PCT/JP2010/067315 2009-10-19 2010-09-28 Tôle d'acier prérevêtue et son procédé de fabrication WO2011048930A1 (fr)

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CN201080046784.1A CN102574363B (zh) 2009-10-19 2010-09-28 预涂钢板及其制造方法
KR1020147010533A KR20140057677A (ko) 2009-10-19 2010-09-28 프리코트 강판 및 그 제조방법
KR1020127008088A KR101423405B1 (ko) 2009-10-19 2010-09-28 프리코트 강판 및 그 제조방법
SG2012014643A SG178943A1 (en) 2009-10-19 2010-09-28 Precoated steel sheet and process for producing same
AU2010309188A AU2010309188B2 (en) 2009-10-19 2010-09-28 Precoated steel sheet and process for producing the same

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EP3187747A4 (fr) * 2014-08-28 2018-05-02 NHK Spring Co., Ltd. Élément de suspension pour véhicules

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JP2013244613A (ja) * 2012-05-23 2013-12-09 Jfe Galvanizing & Coating Co Ltd プレコート鋼板
JP6112975B2 (ja) * 2012-05-31 2017-04-12 新日鐵住金株式会社 耐汚染性に優れるプレコート金属板
KR101500195B1 (ko) * 2013-11-13 2015-03-06 주식회사 포스코 내오염성이 우수한 강판 및 그 제조방법
JP6274953B2 (ja) * 2014-04-09 2018-02-07 新日鐵住金ステンレス株式会社 クリヤ塗装ステンレス鋼板
WO2016159306A1 (fr) * 2015-03-31 2016-10-06 新日鐵住金株式会社 Tôle en acier galvanisé
JP6298513B2 (ja) * 2015-10-19 2018-03-20 イビデン株式会社 トイレブース用化粧板及びトイレブース
JP6200477B2 (ja) * 2015-11-09 2017-09-20 イビデン株式会社 抗ウィルス性化粧板、抗ウィルス性化粧板の機能回復方法及び抗ウィルス性付与組成物
JP6200567B2 (ja) * 2015-11-09 2017-09-20 イビデン株式会社 化粧板
US20170190139A1 (en) * 2015-12-30 2017-07-06 Atieh Haghdoost Coatings and coated surfaces with selected surface characteristics and features
CN107471795B (zh) * 2016-06-07 2019-08-23 上海劲嘉建材科技有限公司 复合饰面板及其制备方法
JP6043889B1 (ja) * 2016-09-16 2016-12-14 日新製鋼株式会社 塗装金属板

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CN102574363A (zh) 2012-07-11
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KR101423405B1 (ko) 2014-07-24

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