WO2015140837A1 - 塗装鋼板および外装建材 - Google Patents
塗装鋼板および外装建材 Download PDFInfo
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- WO2015140837A1 WO2015140837A1 PCT/JP2014/001666 JP2014001666W WO2015140837A1 WO 2015140837 A1 WO2015140837 A1 WO 2015140837A1 JP 2014001666 W JP2014001666 W JP 2014001666W WO 2015140837 A1 WO2015140837 A1 WO 2015140837A1
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- WIPO (PCT)
- Prior art keywords
- steel sheet
- coated steel
- aggregate
- film
- undercoat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—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
- B05D7/14—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
- B05D7/16—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 using synthetic lacquers or varnishes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B05D7/54—No clear coat specified
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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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- 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
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- 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
- B32B2419/00—Buildings or parts thereof
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
Definitions
- the present invention relates to a coated steel sheet having excellent corrosion resistance and scratch resistance, and an exterior building material including the coated steel sheet.
- red rust is a problem.
- an area where salt damage is not a problem non-salt damage area
- red rust is generated in exposed parts of the steel base such as the end face of the coated steel sheet and the bent part, and deterioration of the appearance due to this occurs.
- the occurrence of such red rust can be effectively prevented by subjecting the steel sheet to a chromate-based chemical conversion treatment or by adding a chromic acid-based rust preventive pigment to the undercoat film.
- a coated steel sheet that does not cause elution of hexavalent chromium has been demanded.
- Manganese phosphate or manganese phosphite as a rust preventive pigment as a technology to prevent the occurrence of red rust in exposed areas of steel without using chromate conversion treatment liquid and chromic acid rust preventive pigment.
- Patent Document 1 Manganese phosphate and manganese phosphite elute at an early stage in the steel substrate and form a protective film. As a result, it is possible to prevent the occurrence of red rust in the exposed portion of the steel base without using the chromate-based chemical conversion treatment liquid and the chromic acid-based rust preventive pigment.
- the coated steel sheet when using a coated steel sheet as an exterior building material, the coated steel sheet may be required to have scratch resistance.
- a technique for improving the scratch resistance of a coated steel sheet it has been proposed to add silica particles having a particle size of 1 to 5 ⁇ m in the undercoat film (see Patent Document 2).
- silica particles in the undercoat film By adding silica particles in the undercoat film to increase the surface roughness of the undercoat film, the contact area between the undercoat film and the topcoat film increases and the adhesion strength of the topcoat film to the undercoat film improves. To do. Thereby, the improvement of the scratch resistance of the coated steel plate is realized.
- Patent Document 1 As means for improving both corrosion resistance and scratch resistance of a coated steel sheet, refer to Patent Document 1 and Patent Document 2, and a rust preventive pigment (for example, manganese phosphate or manganese phosphite) that easily dissolves in an undercoat film. It is conceivable to add silica particles capable of increasing the surface roughness of the undercoat film. However, according to the preliminary experiments by the present inventors, it was found that the coated steel sheet obtained in this way is excellent in scratch resistance, but the corrosion resistance is drastically lowered with time. .
- a rust preventive pigment for example, manganese phosphate or manganese phosphite
- An object of the present invention is to provide a coated steel sheet excellent in both corrosion resistance and scratch resistance, and an exterior building material including the painted steel sheet.
- the present inventors have found that the above-mentioned problems can be solved by adding a rust preventive pigment and an aggregate which is a primary particle, which are easily eluted to the undercoat film, and further studies are completed to complete the present invention. I let you.
- the present invention relates to the following coated steel sheets and exterior building materials.
- An undercoating film comprising a steel plate, an anticorrosive pigment and an aggregate as primary particles, disposed on the steel plate, and an overcoating film disposed on the undercoating film.
- the rust preventive pigment includes divalent tin salt, trivalent vanadium salt, tetravalent vanadium salt, tetravalent molybdenum salt, oxycarboxylate, ascorbic acid, phosphite and hypophosphite.
- a coated steel sheet which is one or more compounds selected from the group consisting of: [2] The coated steel sheet according to [1], wherein the aggregate satisfies the following formulas (1) and (2).
- D 10 ⁇ 0.6T (1) D 90 ⁇ 2.0T (2)
- D 10 is 10% particle diameter of the aggregate in the cumulative particle size distribution based on the number ([mu] m).
- D 90 is the 90% particle size ( ⁇ m) of the aggregate in the cumulative particle size distribution based on the number.
- T is the film thickness ( ⁇ m) of the portion where the aggregate is not present in the undercoat coating film.
- [3] The coated steel sheet according to [1] or [2], wherein the ratio of the aggregate to the solid content of the undercoat coating film is 1% by volume or more and less than 10% by volume.
- An exterior building material comprising the coated steel sheet according to any one of [1] to [4].
- the coated steel sheet according to the present invention includes a steel sheet (coating raw sheet), an undercoat film formed on the steel sheet, and an overcoat film formed on the undercoat film.
- a steel sheet coating raw sheet
- an undercoat film formed on the steel sheet an undercoat film formed on the steel sheet
- an overcoat film formed on the undercoat film an overcoat film formed on the undercoat film.
- the kind of steel plate used as a coating original plate is not specifically limited.
- coated original sheets include cold-rolled steel sheets, galvanized steel sheets, Zn-Al alloy-plated steel sheets, Zn-Al-Mg alloy-plated steel sheets, aluminum-plated steel sheets, stainless steel sheets (austenite, martensite, ferrite, Martensite two-phase system).
- the coated original sheet is preferably a molten 55% Al—Zn alloy plated steel sheet.
- the steel sheet may be subjected to known coating pretreatments such as degreasing and pickling.
- board thickness of a steel plate is not specifically limited, According to the use of a coated steel plate, it can set suitably. For example, the thickness of the steel plate is about 0.1 to 2 mm.
- the steel plate (painted original plate) may be subjected to chemical conversion treatment from the viewpoint of improving the corrosion resistance and coating film adhesion (scratch resistance) of the coated steel plate.
- the type of chemical conversion treatment is not particularly limited. Examples of the chemical conversion treatment include chromate treatment, chromium-free treatment, phosphate treatment and the like. From the viewpoint of reducing environmental load, a chromium-free chemical conversion treatment is preferable.
- the chemical conversion treatment can be performed by a known method.
- the chemical conversion solution may be applied to the surface of the steel sheet by a roll coating method, a spin coating method, a spray method, or the like, and dried without being washed with water.
- the drying temperature and drying time are not particularly limited as long as moisture can be evaporated. From the viewpoint of productivity, the drying temperature is preferably in the range of 60 to 150 ° C. as the ultimate plate temperature, and the drying time is preferably in the range of 2 to 10 seconds.
- the adhesion amount of the chemical conversion treatment film is not particularly limited as long as it is within a range effective for improving corrosion resistance and coating film adhesion.
- the adhesion amount may be adjusted so that the total Cr conversion adhesion amount is 5 to 100 mg / m 2 .
- the Ti-Mo composite coating has a range of 10 to 500 mg / m 2
- the fluoroacid-based coating has a fluorine equivalent or total metal element equivalent deposit of 3 to 100 mg / m 2.
- the adhesion amount may be adjusted.
- the adhesion amount may be adjusted so as to be 5 to 500 mg / m 2 .
- the undercoat coating film is formed on the surface of the steel plate or the chemical conversion coating.
- the undercoat coating film contains a rust preventive pigment and an aggregate, and improves the corrosion resistance and coating film adhesion (scratch resistance) of the coated steel sheet.
- the type of resin (base resin) constituting the undercoat coating film is not particularly limited.
- Examples of the resin constituting the undercoat coating include epoxy resin, acrylic resin, polyester, and the like.
- the rust preventive pigment is blended in the undercoat coating film from the viewpoint of improving the corrosion resistance.
- a compound having a standard electrode potential lower than the standard electrode potential of nitrate ion (0.832 V) is blended in the undercoat film as a rust preventive pigment.
- a compound having a lower standard electrode potential than nitrate ions as a rust preventive pigment, it is possible to decompose nitrate ions that have reached the steel base exposed part from the outside and suppress the occurrence of red rust in the steel base exposed part. .
- corrosion resistance can be remarkably improved by adding a compound having a standard electrode potential of less than 0.6V.
- the standard electrode potential is lower than the standard electrode potential of nitrate ion (0.832 V)
- a compound having a voltage of 0.6 V or more decomposes nitrate ions that inhibit corrosion resistance, but is exposed metal other than the steel substrate, particularly potential. Reacts preferentially with the base plating layer metal.
- the undercoating film includes a divalent tin salt, a trivalent vanadium salt, a tetravalent vanadium salt, a tetravalent molybdenum salt, an oxycarboxylate, ascorbic acid, a phosphite, and hypoxia.
- phosphates are blended.
- the standard electrode potential of phosphorous acid is 0.28V
- the standard electrode potential of vanadium (IV) oxide is 0.52V
- the standard electrode potential of vanadium (III) oxide is 0.53V
- the standard electrode potential of molybdenum (IV) is 0.32 V
- the standard electrode potential of tin (II) is 0.09 V
- the standard electrode potential of hypophosphorous acid is 0.50 V
- ascorbic acid The standard electrode potential of 0.34V
- the standard electrode potential of tartaric acid is 0.24V
- the standard electrode potential of phosphoric acid is 0.90V
- the standard electrode potential of vanadium oxide (V) is 1. 24V
- the standard electrode potential of molybdenum (VI) oxide is 0.61V.
- the total blending amount of the rust preventive pigment is not particularly limited, but is preferably in the range of 1 to 50% by volume, and preferably in the range of 5 to 20% by volume with respect to the solid content of the undercoat.
- the total blending amount is less than 1% by volume, the corrosion resistance may not be improved effectively.
- the total blending amount is more than 50% by volume, there is a possibility that coating property, workability and / or coating film adhesion may be impaired.
- another rust preventive pigment may be further blended.
- a metal phosphate having a low solubility may be further blended as a rust preventive pigment in order to maintain the corrosion resistance for a longer period.
- “low solubility” means that the solubility at 25 ° C. is 0.5 (g / 100 g-H 2 O) or less.
- metal phosphates include magnesium phosphate (0.02), calcium phosphate (0.003), zinc phosphate (0.002), magnesium hydrogen phosphate (0.025), hydrogen phosphate.
- the numerical value described after each compound name is the solubility of the compound (g / 100 g-H 2 O, 25 ° C.).
- the solubility of calcium hypophosphate is 16.7
- the solubility of calcium phosphite is 1.00
- the solubility of strontium phosphite is 1.10
- the solubility of barium phosphite is 0.687. is there.
- an aggregate is blended from the viewpoint of improving the scratch resistance.
- the contact area between the undercoat film and the topcoat film increases and the adhesion strength of the topcoat film to the undercoat film improves. To do. Thereby, the damage resistance of a coated steel plate can be improved.
- a compound (antirust pigment) having a standard electrode potential lower than that of nitrate ions has a high solubility, and thus is easily eluted from the undercoat film.
- the rust preventive pigment is more likely to elute through the gaps in the aggregate, and the corrosion resistance may be lost in a short period of time. There is.
- the “pore particle” means a particle including a pore that can be a passage for a rust preventive pigment, and is a concept including an aggregate of fine particles and a particle having a porous structure.
- the “primary particles” mean particles that do not contain pores that can be used as a path for anticorrosive pigments.
- the primary particle may have a recessed part which does not become a passage of a rust preventive pigment.
- the aggregate is composed of primary particles (resin particles) made of a resin such as acrylic resin, polyurethane, polyester, melamine resin, urea resin, and polyamide; from inorganic compounds such as glass, silicon carbide, boron nitride, zirconia, and alumina / silica.
- Primary particles (inorganic particles) The shape of these primary particles is preferably substantially spherical, but may be other shapes such as a cylindrical shape or a disk shape.
- the particle size of the aggregate is not particularly limited, but preferably satisfies the following formulas (1) and (2).
- D 10 is 10% particle size of the aggregate in the cumulative particle size distribution based on the number ([mu] m).
- D 90 is the 90% particle diameter ( ⁇ m) of the aggregate in the cumulative particle size distribution based on the number.
- T is the film thickness ( ⁇ m) of the portion where no aggregate is present in the undercoat coating film. If the following formula (1) is not satisfied, the surface roughness of the undercoat coating film becomes small and the scratch resistance may not be effectively improved. If the following formula (2) is not satisfied, the aggregate tends to be detached from the undercoat coating film, and the scratch resistance may be reduced.
- D 10 ⁇ 0.6T (1)
- D 90 ⁇ 2.0T (2)
- the particle size of the said Formula (1) and Formula (2) is measured by the Coulter counter method, for example, even if it is a particle size measured by the other measuring method, said Formula (1) and Formula ( If 2) is satisfied, scratch resistance can be effectively improved.
- the particle size of the aggregate in the undercoat film can be measured by the following procedure. First, the coated steel plate is cut and the cut surface is polished. Next, the cut surface is observed with an electron microscope to obtain a cross-sectional image of the undercoat coating film. Next, the long side length and short side length are measured for all aggregates present in the field of view of the cross-sectional image, and the individual average particle size is calculated. Next, the number of particles is counted from the smallest particle size, and the particle diameter at 10% of the total particle number is calculated as D 10 , and the particle diameter at 90% is calculated as D 90 .
- the amount of the aggregate is not particularly limited, but is preferably in the range of 1% by volume or more and less than 10% by volume with respect to the solid content of the undercoat coating film. If the total blending amount is less than 1% by volume, scratch resistance may not be improved effectively. Moreover, since there are few aggregates which become a barrier with respect to elution of a rust preventive pigment, a rust preventive pigment elutes excessively and there exists a possibility that corrosion resistance may be lost in a short period of time. When the total blending amount is 10% by volume or more, the elution of the rust preventive pigment is excessively inhibited and the corrosion resistance may be lowered.
- the thickness of the undercoat coating film is not particularly limited, but is preferably in the range of 1 to 10 ⁇ m. When the film thickness is less than 1 ⁇ m, the corrosion resistance may not be sufficiently improved. On the other hand, if the film thickness is more than 10 ⁇ m, it becomes easy for cracks to occur when the paint is dried, and the appearance of the coated steel sheet deteriorates (such as the occurrence of cracks when the paint is dried), or the workability of the coated steel sheet decreases. There is a fear. Moreover, even if the film thickness of the undercoat coating film exceeds 10 ⁇ m, the effect on cost is small.
- the undercoat coating film can be formed by a known method.
- an undercoat paint containing a base resin, a rust preventive pigment, and an aggregate may be applied to the surface of a coating original plate (steel plate) and baked at an ultimate plate temperature of 150 to 280 ° C. for 10 to 60 seconds.
- the baking temperature is less than 150 ° C., the paint cannot be sufficiently baked, and the function of the undercoat film may not be sufficiently exhibited.
- the baking temperature is higher than 280 ° C., the adhesion between the undercoat film and the topcoat film may be reduced due to excessive baking.
- the method for applying the undercoat paint is not particularly limited, and may be appropriately selected from methods used for producing precoated steel sheets. Examples of such a coating method include a roll coating method, a flow coating method, a curtain flow method, a spray method, and the like.
- the top coat film is formed on the undercoat film.
- the top coat film improves the design and corrosion resistance of the coated steel sheet.
- the type of resin (base resin) constituting the top coat film is not particularly limited.
- the resin constituting the top coat film include polyester, epoxy resin, acrylic resin and the like. These resins may be cross-linked by a curing agent.
- the type of the curing agent may be appropriately selected according to the type of resin to be used, baking conditions, and the like.
- the curing agent include melamine compounds and isocyanate compounds.
- the melamine compound include an imino group type, a methylol imino group type, a methylol group type or a fully alkyl group type melamine compound.
- the top coat film may be transparent, but may be colored by blending an arbitrary color pigment.
- coloring pigments include inorganic pigments such as titanium oxide, calcium carbonate, carbon black, iron black, titanium yellow, bengara, bitumen, cobalt blue, cerulean blue, ultramarine blue, cobalt green, and molybdenum red; CoAl, CoCrAl, CoCrZnMgAl, Composite oxide calcined pigments containing metallic components such as CoNiZnTi, CoCrZnTi, NiSbTi, CrSbTi, FeCrZnNi, MnSbTi, FeCr, FeCrNi, FeNi, FeCrNiMn, CoCr, Mn, Co, SnZnTi; Metallic pigments such as Al, resin-coated Al, Ni ; And Resol Red B, Brilliant Scarlet G, Pigment Scarlet 3B, Brilliant Carmine 6B, Lake Red C, Lake Red D, Permanent Treasure 4
- the film thickness of the top coat film is not particularly limited, but is preferably in the range of 5 to 30 ⁇ m. If the film thickness is less than 5 ⁇ m, the desired appearance may not be imparted. On the other hand, when the film thickness is more than 30 ⁇ m, it becomes easy for cracks to occur when the paint is dried, and the appearance of the coated steel sheet deteriorates (such as the occurrence of cracks when the paint is dried), or the workability of the coated steel sheet decreases. There is a fear.
- the top coat film can be formed by a known method.
- a top coating containing a base resin, a color pigment, and an extender may be applied to the surface of a coating original plate (steel plate) and baked at an ultimate plate temperature of 150 to 280 ° C. for 20 to 80 seconds.
- the baking temperature is less than 150 ° C., the paint cannot be sufficiently baked and the function of the top coat film may not be sufficiently exhibited.
- the baking temperature exceeds 280 ° C., characteristics such as molding, weather resistance, and corrosion resistance may not be sufficiently exhibited due to oxidative degradation of the resin due to excessive baking.
- the method for applying the top coat is not particularly limited, and may be appropriately selected from methods used for producing precoated steel sheets. Examples of such a coating method include a roll coating method, a flow coating method, a curtain flow method, a spray method, and the like.
- the coated steel sheet according to the present invention may have a coating film (back coating film) on the surface opposite to the surface on which the undercoat coating film and the top coating film are formed.
- the back coating film may have a one-coat configuration or a two-coat configuration.
- the kind of resin which comprises a back surface coating film, the kind of pigment, etc. are not specifically limited.
- a back coating film can be formed by applying a known paint by a known method.
- the coated steel sheet according to the present invention contains a rust preventive pigment that easily elutes in the undercoat coating film, it is possible to prevent red rust from occurring in exposed portions of the steel substrate such as end faces and bent parts of the coated steel sheet. Moreover, since the coated steel plate which concerns on this invention contains the aggregate which consists of primary particles in undercoat, it is excellent in scratch resistance, preventing the excessive elution of a rust preventive pigment. That is, the coated steel sheet according to the present invention is excellent in short-term and long-term corrosion resistance and scratch resistance. Therefore, the coated steel sheet according to the present invention is suitable as an exterior building material of a building that is used, for example, in a portion that is exposed to the outside air and can be irradiated with sunlight.
- An undercoat paint was applied to the surface of the chemical-treated coating original plate with a roll coater and dried at an ultimate plate temperature of 200 ° C. for 30 seconds to form an undercoat film with a thickness of 2 to 8 ⁇ m.
- a commercially available epoxy-based clear paint (NSC680; Nippon Fine Coatings Co., Ltd.) based on the addition of 5% by volume of barium sulfate as an extender pigment, and the antirust pigments shown in Tables 1 and 2 What added the aggregate was prepared.
- the particle diameters (D 10 and D 90 ) of the aggregate are the particle diameters in the cumulative particle size distribution based on the number measured by the Coulter counter method, and are adjusted using a sieve.
- a top coat was applied to the surface of the undercoat with a roll coater and dried at an ultimate plate temperature of 220 ° C. for 45 seconds to form a top coat with a thickness of 10 ⁇ m.
- a commercially available polyester-based clear paint (CA; Nippon Fine Coatings Co., Ltd.) prepared by adding 7% by volume of carbon black as a coloring pigment was prepared.
- Tables 1 and 2 show the composition of the undercoat film on the prepared coated steel sheet.
- A1 is acrylic resin particles (primary particles) (Art Pearl J-4P; Negami Industrial Co., Ltd.).
- A2 is acrylic resin particles (primary particles) (Toughtic FH-S010; Toyobo Co., Ltd.).
- A3 is acrylic resin particles (primary particles) (Toughtic FH-S005; Toyobo Co., Ltd.).
- A4 is acrylic resin particles (primary particles) (Toughtic FH-S008; Toyobo Co., Ltd.).
- A5 is acrylic resin particles (primary particles) (Art Pearl J-5P; Negami Industrial Co., Ltd.).
- A6 is acrylic resin particles (primary particles) (Art Pearl J-7P; Negami Industrial Co., Ltd.).
- B is urethane resin particles (primary particles) (Art Pearl P-800T; Negami Industrial Co., Ltd.).
- C is glass particles (primary particles) (EMB-10; Potters Barotini Co., Ltd.).
- D is hard silica particles (pore particles) (Silicia 430; Fuji Silysia Chemical Ltd.).
- a is magnesium phosphite (Taihei Chemical Industrial Co., Ltd.).
- b is vanadium tetroxide.
- c is vanadium (III) oxide.
- d molybdenum oxide (IV).
- e tin (II) oxide.
- f magnesium hypophosphite (Taihei Chemical Industry Co., Ltd.).
- g manganese phosphite (Kikuchi Color Co., Ltd.).
- h is ascorbic acid.
- i tartaric acid.
- j magnesium phosphate (Kikuchi Color Co., Ltd.).
- k zinc phosphate (Kikuchi Color Co., Ltd.).
- l is aluminum phosphate (Taihei Chemical Industrial Co., Ltd.).
- m manganese phosphate (Kikuchi Color Co., Ltd.).
- n vanadium oxide (V).
- o molybdenum oxide (VI).
- the amount of aggregate and rust preventive pigment is a ratio (% by volume) to the solid content of the undercoat coating film.
- Corrosion resistance test A plate was cut out from each coated steel plate by shearing to prepare a test piece by 2T bending. This test piece has a cut end face and a bent portion, and the steel substrate and the plated metal are exposed at those places.
- Each test piece was installed outdoors (non-salt damage area) in Kiryu City, Gunma Prefecture, and air exposure tests were conducted for 2 months and 1 year. Each test piece was installed at an inclination angle of 35 ° southward. The bending portion was positioned on the lower side of the test piece. Two months and one year after the start of exposure, the area ratio of the red rust occurrence part in the steel base exposed part of the cut end face and the bent part was measured. When the area ratio of the red rust occurrence portion is less than 10%, “ ⁇ ”, when it is 10% or more and less than 30%, “ ⁇ ”, when it is 30% or more and less than 60%, “ ⁇ ”, when it is 60% or more “ ⁇ ”. If “ ⁇ ”, “ ⁇ ” or “ ⁇ ”, it can be said that the coated steel sheet has the necessary corrosion resistance.
- Evaluation results Table 3 shows the evaluation results of the corrosion resistance test and scratch resistance test of each coated steel sheet.
- the coated steel sheets of No. 38 and 39 in which no aggregate was added to the undercoat coating film were inferior in scratch resistance.
- the coated steel sheets of Nos. 31, 32, and 37 in which the aggregate composed of pore particles was added to the undercoat coating film were excellent in scratch resistance, but were inferior in long-term corrosion resistance.
- the reason why the coated steel sheets of No. 31 and 32 are inferior in long-term corrosion resistance is that the aggregate is pore particles, so that the rust preventive pigment is exposed to the outside through a gap (pore) in the aggregate in a short period of time. It is thought that it was eluted.
- the coated steel sheet of No. 37 was inferior in short-term corrosion resistance because the standard electrode potential of the rust preventive pigment was higher than that of nitrate ions.
- the coated steel sheets No. 1 to 30 in which the predetermined rust preventive pigment and the aggregate composed of primary particles were added to the undercoat film were excellent in short-term and long-term corrosion resistance and scratch resistance.
- the coated steel sheet according to the present invention is excellent in both corrosion resistance and scratch resistance.
- coated steel sheet according to the present invention is excellent in both corrosion resistance and scratch resistance, it is useful for exterior building materials of buildings, for example.
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- General Chemical & Material Sciences (AREA)
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Abstract
Description
[2]前記骨材は、以下の式(1)および式(2)を満たす、[1]に記載の塗装鋼板。
D10≧0.6T …(1)
D90<2.0T …(2)
[ここで、D10は、個数基準の累積粒度分布における前記骨材の10%粒子径(μm)である。D90は、個数基準の累積粒度分布における前記骨材の90%粒子径(μm)である。Tは、前記下塗り塗膜における前記骨材が存在しない部分の膜厚(μm)である。]
[3]前記下塗り塗膜の固形分に対する前記骨材の割合は、1体積%以上かつ10体積%未満である、[1]または[2]に記載の塗装鋼板。
[4]前記鋼板は、クロムフリーの化成処理が施されている、[1]~[3]のいずれか一項に記載の塗装鋼板。
[5][1]~[4]のいずれか一項に記載の塗装鋼板を含む外装建材。
塗装原板となる鋼板の種類は、特に限定されない。塗装原板の例には、冷延鋼板、亜鉛めっき鋼板、Zn-Al合金めっき鋼板、Zn-Al-Mg合金めっき鋼板、アルミニウムめっき鋼板、ステンレス鋼板(オーステナイト系、マルテンサイト系、フェライト系、フェライト・マルテンサイト二相系を含む)などが含まれる。耐食性、軽量化および対費用効果の観点からは、塗装原板は、溶融55%Al―Zn合金めっき鋼板であることが好ましい。鋼板は、脱脂や酸洗などの公知の塗装前処理が施されていてもよい。鋼板の板厚は、特に限定されず、塗装鋼板の用途に応じて適宜設定されうる。たとえば、鋼板の板厚は、0.1~2mm程度である。
下塗り塗膜は、鋼板または化成処理皮膜の表面に形成されている。下塗り塗膜は、防錆顔料および骨材を含み、塗装鋼板の耐食性や塗膜密着性(耐傷付き性)などを向上させる。
D10≧0.6T …(1)
D90<2.0T …(2)
上塗り塗膜は、下塗り塗膜の上に形成されている。上塗り塗膜は、塗装鋼板の意匠性や耐食性などを向上させる。
本発明に係る塗装鋼板は、下塗り塗膜および上塗り塗膜が形成された面の反対側の面にも塗膜(裏面塗膜)を有していてもよい。裏面塗膜は、1コート構成であってもよいし、2コート構成であってもよい。また、裏面塗膜を構成する樹脂の種類や、顔料の種類なども特に限定されない。たとえば、公知の塗料を公知の方法で塗布することで、裏面塗膜を形成することができる。
本発明に係る塗装鋼板は、下塗り塗膜に溶出しやすい防錆顔料を含むため、塗装鋼板の端面や曲げ加工部などの鋼素地露出部における赤錆の発生を防止することができる。また、本発明に係る塗装鋼板は、下塗り塗膜に一次粒子からなる骨材を含むため、防錆顔料の過度の溶出を防止しつつ、耐傷付き性に優れている。すなわち、本発明に係る塗装鋼板は、短期および長期の耐食性、ならびに耐傷付き性に優れている。したがって、本発明に係る塗装鋼板は、例えば外気に露出し、かつ太陽光に照射されうる部分に使用される、建築物の外装建材として好適である。
塗装原板として、溶融55%Al-Znめっき鋼板(基材:SPCC、両面めっき付着量:150g/m2)を準備した。塗装原板の表面をアルカリ脱脂した後、塗布型のクロムフリー化成処理液(パルコートCT-E200;日本パーカライジング株式会社)を用いて化成処理を施した。
(1)耐食性試験
各塗装鋼板からせん断加工により板材を切り出し、2T曲げ加工を行うことで試験片を準備した。この試験片には切断端面および曲げ加工部が存在しており、それらの箇所で鋼素地およびめっき金属が露出している。
塗装鋼板の取り扱い時および施工時における傷付きを想定して、クレメンス型引掻き硬度試験機を用いて耐傷付き性試験を行った。各塗装鋼板からせん断加工により2枚の板材(評価用板材および引掻用板材)を切り出した。水平に配置された評価用板材の表面に対して45°の傾斜となるように、引掻用板材を評価用板材の上に設置した。引掻用板材に所定の荷重を加えた状態で、引掻用板材で評価用板材の塗膜を引っ掻き、めっき層が見えたときの最小の荷重を評価値として記録した。評価値が1000g以上の場合を「◎」、800g以上1000g未満の場合を「○」、500g以上800g未満の場合を「△」、500g未満の場合を「×」と評価した。「◎」、「○」または「△」であれば、その塗装鋼板は、必要な耐傷付き性を有しているといえる。
各塗装鋼板の耐食性試験および耐傷付き性試験の評価結果を表3に示す。
Claims (5)
- 鋼板と、
前記鋼板の上に配置された、防錆顔料と一次粒子である骨材とを含む下塗り塗膜と、
前記下塗り塗膜の上に配置された上塗り塗膜と、
を有し、
前記防錆顔料は、2価のスズ塩、3価のバナジウム塩、4価のバナジウム塩、4価のモリブデン塩、オキシカルボン酸塩、アスコルビン酸、亜リン酸塩および次亜リン酸塩からなる群から選択される1種または2種以上の化合物である、
塗装鋼板。 - 前記骨材は、以下の式(1)および式(2)を満たす、請求項1に記載の塗装鋼板。
D10≧0.6T …(1)
D90<2.0T …(2)
[ここで、D10は、個数基準の累積粒度分布における前記骨材の10%粒子径(μm)である。D90は、個数基準の累積粒度分布における前記骨材の90%粒子径(μm)である。Tは、前記下塗り塗膜における前記骨材が存在しない部分の膜厚(μm)である。] - 前記下塗り塗膜の固形分に対する前記骨材の割合は、1体積%以上かつ10体積%未満である、請求項1または請求項2に記載の塗装鋼板。
- 前記鋼板は、クロムフリーの化成処理が施されている、請求項1~3のいずれか一項に記載の塗装鋼板。
- 請求項1~4のいずれか一項に記載の塗装鋼板を含む外装建材。
Priority Applications (5)
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EP14886591.8A EP3121001A4 (en) | 2014-03-19 | 2014-03-24 | Coated steel sheet and exterior building material |
US15/124,545 US9765223B2 (en) | 2014-03-19 | 2014-03-24 | Coated steel sheet and exterior building material |
KR1020167023242A KR101725231B1 (ko) | 2014-03-19 | 2014-03-24 | 도장 강판 및 외장 건재 |
RU2016140857A RU2635583C1 (ru) | 2014-03-19 | 2014-03-24 | Стальной лист с покрытием и конструкционный материал для наружного использования |
CN201480077100.2A CN106132697B (zh) | 2014-03-19 | 2014-03-24 | 涂装钢板及外装建材 |
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CA2962729C (en) * | 2014-09-30 | 2019-08-06 | Nippon Steel & Sumitomo Metal Corporation | Coated metal sheet for automobile excellent in rust resistance in low temperature running environments |
JP6323825B1 (ja) * | 2017-11-27 | 2018-05-16 | 有限会社カオル | 紙粉除去方法 |
JP7094864B2 (ja) * | 2017-12-27 | 2022-07-04 | 日鉄鋼板株式会社 | 塗装金属板 |
CN108912995B (zh) * | 2018-07-25 | 2020-10-20 | 江西恒毅科技有限公司 | 一种环保型水性双组份聚氨酯防腐面漆及其制备方法 |
JP7500924B2 (ja) * | 2019-07-04 | 2024-06-18 | Toppanホールディングス株式会社 | プリント鋼板 |
CN115233096B (zh) * | 2022-07-13 | 2023-01-31 | 首钢集团有限公司 | 一种冷轧钢及其制备方法 |
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TWI558545B (zh) | 2016-11-21 |
EP3121001A4 (en) | 2017-08-09 |
TW201536538A (zh) | 2015-10-01 |
EP3121001A1 (en) | 2017-01-25 |
KR20160106764A (ko) | 2016-09-12 |
CN106132697A (zh) | 2016-11-16 |
US9765223B2 (en) | 2017-09-19 |
US20170015837A1 (en) | 2017-01-19 |
KR101725231B1 (ko) | 2017-04-10 |
JP2015178225A (ja) | 2015-10-08 |
CN106132697B (zh) | 2017-12-05 |
RU2635583C1 (ru) | 2017-11-14 |
JP5568191B1 (ja) | 2014-08-06 |
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