WO2012001981A1 - Tôle d'acier revêtue présentant une excellente résistance à la corrosion et aux alcalis - Google Patents

Tôle d'acier revêtue présentant une excellente résistance à la corrosion et aux alcalis Download PDF

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WO2012001981A1
WO2012001981A1 PCT/JP2011/003750 JP2011003750W WO2012001981A1 WO 2012001981 A1 WO2012001981 A1 WO 2012001981A1 JP 2011003750 W JP2011003750 W JP 2011003750W WO 2012001981 A1 WO2012001981 A1 WO 2012001981A1
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Prior art keywords
steel sheet
coated steel
zirconium
coating film
pigment
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PCT/JP2011/003750
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English (en)
Japanese (ja)
Inventor
大久保　謙一
尾和　克美
上田　耕一郎
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日新製鋼株式会社
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Priority claimed from JP2010149013A external-priority patent/JP5829799B2/ja
Application filed by 日新製鋼株式会社 filed Critical 日新製鋼株式会社
Priority to CN201180041712.2A priority Critical patent/CN103097576B/zh
Priority to PCT/JP2011/003750 priority patent/WO2012001981A1/fr
Publication of WO2012001981A1 publication Critical patent/WO2012001981A1/fr

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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides

Definitions

  • the present invention relates to a coated steel sheet having excellent corrosion resistance and alkali resistance.
  • JP 2003-343844 A Japanese Patent Laying-Open No. 2005-055142 JP 2008-170149 A JP 2005-186287 A
  • the present invention has been made in view of such a point, and an object of the present invention is to provide a coated steel sheet excellent in corrosion resistance and alkali resistance that can maintain corrosion resistance even in a strong alkaline corrosive environment.
  • the present inventor has found that the above problem can be solved by forming a chemical conversion treatment film containing a predetermined titanium compound and a zirconium compound and further forming a primer coating film containing a predetermined phosphate and barium sulfate on the chemical conversion film. Further studies were made to complete the present invention.
  • this invention relates to the following heat-resistant non-adhesive coating steel plates. [1] It has a steel plate, a chemical conversion coating formed on the surface of the steel plate, a primer coating formed on the surface of the chemical conversion coating, and a top coating formed on the surface of the primer coating.
  • the primer coating film includes an organic resin, pigment A composed of one or two compounds selected from the group consisting of magnesium phosphate and zirconium phosphate, and pigment B composed of barium sulfate;
  • the content of the pigment A and the content of the pigment B are 20 to 100 parts by mass with respect to 100 parts by mass of the organic resin.
  • the total content of the pigment A and the pigment B in the primer coating is 40-160 parts by weight relative to the organic resin 100 parts by weight, the coated steel plate.
  • the organic resin includes one kind or two or more kinds of resins selected from the group consisting of polyethersulfone resin, polyphenylsulfide resin, polyimide resin, and polyamideimide resin. Coated steel sheet according to any one of the above.
  • a coated steel sheet having excellent heat resistance, corrosion resistance, water (humidity) resistance and alkali resistance can be provided. Therefore, according to the present invention, it is possible to provide a coated steel sheet that can be used for a long time even in a strongly alkaline corrosive environment.
  • FIG. 1A is a photograph of a processed part of a painted steel plate No. 7-1.
  • FIG. 1B is a photograph of the processed part of No. 7-2 coated steel sheet.
  • the coated steel sheet of the present invention is formed on the surface of the steel sheet (coating raw sheet), the chemical conversion coating formed on the surface of the steel sheet, the primer coating formed on the surface of the chemical conversion coating, and the surface of the primer coating.
  • a top coating film That is, in the coated steel sheet of the present invention, a chemical conversion treatment film, a primer coating film, and a top coating film are sequentially laminated on the steel sheet surface.
  • the kind of steel plate used as a coating original plate is not specifically limited.
  • coated steel sheets include galvanized steel sheets (electrical Zn plating, hot dip Zn plating), galvannealed steel sheets (alloyed hot dip Zn plating alloyed after hot dip Zn plating), zinc alloy galvanized steel sheets (molten) Zn-Mg plating, hot-dip Zn-Al-Mg plating, hot-dip Zn-Al plating), hot-dip Al-plated steel plate, hot-dip Al-Si-plated steel plate, stainless steel plate and the like. From the viewpoint of improving the corrosion resistance in a high temperature environment, a molten Al—Si plated steel sheet is preferred.
  • the steel sheet used as the coating original sheet is preferably a molten Al—Si plated steel sheet that is further annealed after the plating layer is formed.
  • defects such as cracks and peeling may occur in the plating layer, and the base steel may be exposed. If the base steel is exposed in this way, red rust will occur at the part where the base steel is exposed in a severe corrosive environment such as the inside of a microwave oven or microwave oven having a steam function. May decrease.
  • a molten Al—Si plated steel sheet that is further annealed after forming the plating layer may be used.
  • the molten Al—Si plating layer can be softened.
  • the molten Al—Si plating layer does not generate cracks or peels off even when combined with compression and tension, and can be deformed following the processing. Therefore, even if composite processing is performed, defects such as cracks and peeling that expose the underlying steel do not occur, and the processed portion corrosion resistance can be improved.
  • the molten Al—Si plated steel sheet on which the plated layer is formed may be held at 350 to 500 ° C. for 30 minutes or longer (see Japanese Patent Application Laid-Open No. 62-50454).
  • the thickness of the alloy layer formed at the interface between the plating layer and the base steel can be reduced by adjusting the cooling rate from when it is pulled up from the molten Al-Si plating bath to annealing.
  • the workability of the Al—Si plating layer can be further improved. Specifically, a steel plate (steel strip) pulled up from a molten Al—Si plating bath (bath temperature of 640 ° C.
  • the chemical conversion treatment film includes 1) a fluoride of titanium or a fluoride of zirconium, 2) an oxide of titanium or a hydroxide of titanium, and 3) an oxide of zirconium or a hydroxide of zirconium.
  • the chemical conversion treatment film 1) contains a fluoride of titanium or a fluoride of zirconium. These fluorides dissolve in water and liberate fluorine ions. The liberated fluorine ions react with the underlying coating original plate at the damaged part of the coating film to form an insoluble metal salt, thereby providing self-repairing properties.
  • the chemical conversion treatment film includes 2) titanium oxide or titanium hydroxide, and 3) zirconium oxide or zirconium hydroxide. These oxides and hydroxides are almost insoluble in water and alkaline aqueous solutions, and form a strong barrier film on the surface of the painted base plate, improving the corrosion resistance, water resistance (humidity) and alkali resistance of the coated steel sheet. Can be made.
  • the titanium oxide when the corrosion resistance was compared with only the chemical conversion coating formed, the titanium oxide was able to improve the corrosion resistance more than the zirconium oxide.
  • the hydroxide of titanium can improve the corrosion resistance more than the hydroxide of zirconium. This is presumably because the titanium oxide (hydroxide) becomes an inorganic polymer during the formation of the chemical conversion film, and forms a stronger barrier film than the zirconium oxide (hydroxide).
  • the zirconium oxide when the corrosion resistance was compared with the primer coating and the top coating formed on the chemical conversion coating, the zirconium oxide improved the coating adhesion and corrosion resistance more than the titanium oxide. I was able to.
  • zirconium hydroxide can improve coating film adhesion and corrosion resistance more than titanium hydroxide. This is presumed to be because zirconium oxide (hydroxide) acts as a cross-linking agent for organic resins, thereby improving coating film adhesion and coating film density.
  • the combination of the oxide or hydroxide of titanium and the oxide or hydroxide of zirconium can improve the barrier property, the adhesion of the coating film and the denseness of the coating film, resulting in corrosion resistance. It is considered that the water resistance (humidity) and alkali resistance can be further improved.
  • these oxides and hydroxides are necessary components for imparting corrosion resistance, they are insoluble and therefore almost cannot be expected for self-healing properties.
  • the chemical conversion coating of the coated steel sheet of the present invention provides self-healing properties by blending a fluoride of titanium and a fluoride of zirconium, and an oxide or hydroxide of titanium and an oxide or hydroxide of zirconium In addition, the barrier properties, coating film adhesion and coating film denseness were improved. Therefore, the chemical conversion film of the coated steel sheet of the present invention can exhibit excellent corrosion resistance, water (humidity) resistance, and alkali resistance.
  • the film thickness of the chemical conversion coating is not particularly limited, but is preferably adjusted so that the total metal equivalent adhesion amount of titanium and zirconium is in the range of 3 to 100 mg / m 2 .
  • the total metal conversion adhesion amount is less than 3 mg / m 2 , corrosion resistance, water resistance (wet) resistance and alkali resistance cannot be sufficiently provided.
  • the total metal equivalent adhesion amount is more than 100 mg / m 2 , the processability of the coating film may be deteriorated.
  • the total metal equivalent adhesion amount of titanium and zirconium can be measured by ICP analysis or the like.
  • Molar ratio of fluoride (total content of titanium fluoride and zirconium fluoride) to oxide and hydroxide (total content of titanium oxide and hydroxide and zirconium oxide and hydroxide) Is preferably in the range of 0.2 to 3.
  • the molar ratio is less than 0.2, the self-repairing property cannot be sufficiently imparted, so that the corrosion resistance of the damaged part may be lowered.
  • the molar ratio is more than 3, the amount of soluble components increases, so that the water resistance and alkali resistance may be lowered.
  • the molar ratio of the total of zirconium oxide and hydroxide to the total of titanium oxide and hydroxide is preferably in the range of 0.4 to 2.
  • the molar ratio is less than 0.4, the crosslinking effect of the coating film by the oxide and hydroxide of zirconium and the effect of improving the coating film adhesion cannot be sufficiently exhibited, so that the corrosion resistance, water resistance (humidity) and Alkali resistance may be reduced.
  • the molar ratio is more than 2
  • the barrier effect of the oxide and hydroxide of titanium cannot be sufficiently exhibited, so that the corrosion resistance, water resistance (humidity) and alkali resistance may be lowered.
  • the chemical conversion treatment film may contain other optional components.
  • the chemical conversion treatment film may contain an organic resin such as polyphenol in order to further improve the adhesion with the primer coating film.
  • the chemical conversion treatment film may contain oxides, such as Si, Al, and Mg, and a metal compound for barrier property improvement.
  • the chemical conversion film may contain a soluble phosphate or an oxyacid salt such as Mo or V having an oxidizing property in order to further improve the self-repairing property. Oxidizing nitric acid and the oxyacid salt promote the formation of an inorganic polymer of an oxide of titanium or zirconium and promote the dissociation of fluoride when a chemical conversion treatment solution is applied. Therefore, the ratio of the fluoride, oxide and hydroxide of the chemical conversion film can be controlled by blending these oxidizing compounds.
  • the chemical conversion treatment film can be formed by a known method. For example, if a chemical conversion treatment solution containing titanium fluoride salt or zirconium fluoride salt is applied to the surface of the coating original plate by a method such as roll coating, spin coating, or spraying, it is dried without washing with water. Good.
  • 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 primer coating film contains one or two kinds of rust preventive pigments (pigment A) and barium sulfate (pigment B) selected from the group consisting of magnesium phosphate and zirconium phosphate based on an organic resin.
  • the organic resin used as the base of the primer coating is not particularly limited, but 1 or 2 selected from the group consisting of polyethersulfone resin, polyphenylsulfone resin, polyimide resin, and polyamideimide resin from the viewpoint of imparting heat resistance.
  • the above heat resistant resin is preferable.
  • magnesium phosphate, zirconium phosphate or a combination thereof is used as the rust preventive pigment (Pigment A).
  • barium sulfate is blended in the primer coating to suppress elution of the anticorrosive pigment, but elution of magnesium phosphate and zirconium phosphate can be suppressed by barium sulfate.
  • barium sulfate hardly suppresses elution with respect to other rust preventive pigments (calcium-based, silicate-based, zinc phosphate, etc.).
  • the content of magnesium phosphate and zirconium phosphate is preferably in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the base organic resin. When content is less than 20 mass parts, corrosion resistance cannot fully be exhibited. On the other hand, when the content is more than 100 parts by mass, the elution amount of the rust preventive pigment increases, and the water resistance and alkali resistance may be lowered.
  • Barium sulfate (pigment B) suppresses excessive elution of magnesium phosphate and zirconium phosphate (pigment A) in an alkaline atmosphere. This suppression is presumably because the eluted phosphate ions and barium ions react and re-deposit. Thereby, since the elution amount of magnesium phosphate and zirconium phosphate can be reduced and water permeability resistance and ion resistance resistance can be maintained, water resistance and alkali resistance can be imparted.
  • the content of barium sulfate is preferably in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the base organic resin.
  • the content is less than 20 parts by mass, elution of magnesium phosphate and zirconium phosphate cannot be sufficiently suppressed.
  • the content exceeds 100 parts by mass, the primer coating film becomes porous, and the water resistance may be lowered.
  • the total content of magnesium phosphate and zirconium phosphate (pigment A) and barium sulfate (pigment B) is preferably in the range of 40 to 160 parts by mass with respect to 100 parts by mass of the organic resin.
  • the corrosion resistance cannot be exhibited sufficiently.
  • the primer coating film becomes porous, and the water resistance may be lowered.
  • the mass ratio of barium sulfate (pigment B) to phosphoric acid anticorrosive pigment (pigment A) is preferably in the range of 0.5 to 1.6.
  • the mass ratio is less than 0.5, elution of magnesium phosphate and zirconium phosphate cannot be sufficiently suppressed.
  • the mass ratio is more than 1.6, the elution of magnesium phosphate and zirconium phosphate is suppressed excessively, so that the corrosion resistance may be lowered.
  • the primer coating may be transparent, but may be colored by adding an arbitrary coloring pigment.
  • the color pigment include titanium oxide, carbon black, chromium oxide, iron oxide and the like.
  • the primer coating film may be added with scaly inorganic additives, inorganic fibers, etc. to improve the coating film hardness and wear resistance.
  • the flaky inorganic additive include glass flake, graphite flake, synthetic mica flake, synthetic alumina flake, silica flake and the like.
  • the inorganic fiber include potassium titanate fiber, wollastonite fiber, silicon carbide fiber, alumina fiber, alumina silicate fiber, silica fiber, rock wool, slag wool, glass fiber, carbon fiber and the like.
  • the film thickness of the primer coating is not particularly limited, but is preferably in the range of 0.5 to 30 ⁇ m. When the film thickness is less than 0.5 ⁇ m, the effects of corrosion resistance and coating film adhesion may not be sufficiently obtained. Moreover, when a primer coating film is a colored coating film, in order to conceal a coating original plate, the film thickness of 3 micrometers or more is preferable. On the other hand, when the film thickness is more than 30 ⁇ m, the surface of the coating film becomes a cocoon skin shape and the appearance is deteriorated, and a crack is easily generated when baking.
  • the primer coating can be formed by a known method.
  • a primer paint containing an organic resin, magnesium phosphate or zirconium phosphate (pigment A), barium sulfate (pigment B), etc. may be applied to the surface of the chemical conversion treated steel sheet and baked.
  • the method for applying the primer paint is not particularly limited, and may be appropriately selected from the methods used for the production of 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 drying temperature is preferably in the range of 200 ° C. to 400 ° C. as the ultimate plate temperature, and the drying time is preferably in the range of 20 to 180 seconds.
  • the drying temperature is the ultimate plate temperature. More preferably, the temperature is in the range of 300 ° C. to 400 ° C., and the drying time is more preferably in the range of 30 to 180 seconds. If it is dried within this range, the base resin is sufficiently cured, so that the characteristics are easily exhibited.
  • the top coating is not particularly limited, but a coating containing a fluororesin based on a heat resistant resin is preferable from the viewpoint of heat resistance and easy cleaning (non-adhesiveness).
  • the heat resistant resin contained in the top coating film may be the same as or different from the heat resistant resin contained in the primer coating film.
  • the heat resistant resin contained in the top coating film is a polyethersulfone resin, a polyphenylsulfone resin, a polyimide resin, a polyamideimide resin, or a combination thereof.
  • a heat-meltable fluororesin having a melting point of 270 ° C. or higher is preferable from the viewpoint of imparting heat resistance and easy cleaning.
  • fluororesins include polymers or copolymers such as tetrafluoroethylene, hexafluoroethylene, perfluoroalkyl vinyl ether, and chlorotrifluoroethylene.
  • a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer is particularly preferable from the viewpoint of durability of easy washing and heat resistance.
  • the content of the fluororesin is preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the heat resistant resin.
  • the content is less than 10 parts by mass, the easy cleaning property cannot be exhibited sufficiently.
  • the content exceeds 200 parts by mass, the adhesion of the top coating to the primer coating tends to decrease.
  • the top coating may be transparent, but may be colored by adding an arbitrary coloring pigment.
  • the color pigment include titanium oxide, carbon black, chromium oxide, iron oxide and the like.
  • a dark color (black) heat reflective pigment having an average reflectance of 10% or less and an average reflectance of 20% or more in the wavelength range of 750 to 2500 nm (near infrared) into the top coating film.
  • dark (black) near-infrared reflective pigments include calcined pigments containing Fe 2 O 3 , Cr 2 O 3 , CoO or combinations thereof.
  • the content of the dark (black) near-infrared reflective pigment is preferably in the range of 5 to 35 parts by mass with respect to the organic resin. When the content is less than 5 parts by mass, a dark color tone cannot be imparted. On the other hand, when the content is more than 35 parts by mass, the cohesive force of the coating film is lowered, and the processability may be inferior.
  • a scale-like inorganic additive or inorganic fiber may be added to the top coating film to improve the coating film hardness and wear resistance.
  • the flaky inorganic additive include glass flake, graphite flake, synthetic mica flake, synthetic alumina flake, silica flake and the like.
  • the inorganic fiber include potassium titanate fiber, wollastonite fiber, silicon carbide fiber, alumina fiber, alumina silicate fiber, silica fiber, rock wool, slag wool, glass fiber, carbon fiber and the like.
  • the film thickness of the top coating is not particularly limited, but is preferably in the range of 5 to 40 ⁇ m.
  • the film thickness is less than 5 ⁇ m, the easy cleaning property cannot be maintained sufficiently.
  • the film thickness is more than 40 ⁇ m, the surface of the coating film becomes a cocoon skin shape and the appearance is deteriorated, and a crack is easily generated when baking.
  • the film thickness of the top coating film is preferably in the range of 5 to 20 ⁇ m.
  • the top coating can be formed by a known method.
  • a top paint containing an organic resin, a fluororesin (preferably in the form of particles), a color pigment, or the like may be applied to the surface of the primer-coated steel sheet and baked.
  • the method for applying the top 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 drying temperature is preferably in the range of 200 ° C. to 450 ° C. as the ultimate plate temperature, and the drying time is preferably in the range of 20 to 180 seconds.
  • the drying temperature is more preferably in the range of 300 ° C. to 400 ° C. at the ultimate plate temperature.
  • the drying time is more preferably in the range of 30 to 180 seconds. If it is dried within this range, the base resin is sufficiently cured, so that the characteristics are easily exhibited.
  • the top coating contains a heat-meltable fluororesin
  • the drying temperature is more preferably in the range of 350 ° C. to 450 ° C. as the ultimate plate temperature, and the drying time is more preferably in the range of 60 to 180 seconds. When it is dried within this range, a sufficient amount of the fluororesin can be moved to the surface of the top coating film to exhibit excellent easy cleaning (non-adhesiveness).
  • the primer coating is prevented from becoming porous due to excessive outflow of the anticorrosive pigment from the primer coating, And ion permeability are improved.
  • the barrier property and the self-repairability of a chemical conversion treatment film are improved by including a predetermined titanium compound and a zirconium compound in a chemical conversion treatment film.
  • the coated steel sheet of the present invention is excellent in water resistance (humidity), alkali resistance, and corrosion resistance, and can maintain corrosion resistance even in a highly alkaline corrosive environment.
  • Example 1 Preparation of coated steel plate
  • a molten Al-9Si plated steel plate having a thickness of 0.5 mm and a coated amount on one side of 40 g / m 2 was prepared.
  • a predetermined amount of chemical conversion treatment liquid having the composition shown in Table 1 (Example: No. 1-1 to No. 1-7, Comparative Example: No. 1-8 to No. 1-10) is applied to the surface of the original coating plate. It was coated with a bar coater so as to be dried at a final plate temperature of 100 ° C. for 10 seconds, and then subjected to chemical conversion treatment steel plates shown in Table 2 (Example: No. 2-1 to No. 2-11, Comparative Example: No. 2-12 to No.
  • the molar ratio of fluoride to oxide and hydroxide on the surface of each chemical conversion treated steel sheet was measured by X-ray photoelectron spectroscopy (XPS; ESCA). Specifically, after Ti and Zr peaks were separated into waveforms of X—F, X—O and X—OH (X: Ti, Zr), each component was quantified to identify the ratio.
  • the amount of fluoride measured here corresponds to the total content of fluoride of titanium and fluoride of zirconium contained in the chemical conversion film.
  • the measured amounts of oxides and hydroxides correspond to the total content of titanium oxides and hydroxides and zirconium oxides and hydroxides contained in the chemical conversion coating.
  • the molar ratio of titanium and zirconium corresponds to the molar ratio of titanium oxide and hydroxide to zirconium oxide and hydroxide.
  • the primer coatings shown in Table 3 were formed on the surface of the chemical conversion treated steel plates (No. 2-1 to No. 2-15).
  • a bar coater so as to have a predetermined film thickness
  • 30 seconds at a final plate temperature of 220 ° C. (No. 3-1 paint) or 60 seconds at a final plate temperature of 320 ° C. (No. 3-14) 3-2 to 14 paints) were baked to prepare primer-coated steel sheets.
  • the top coating No. 4-1 to No.
  • Table 4 The coated steel sheets shown in Table 5 (Example: No. 5-1 to No. 5-23, Comparative Example: No. 5-24 to No. 5-40) were produced by baking.
  • NEOFRON AP Daikin Industries, Ltd.
  • Polyflon M (Daikin Industries, Ltd.) was used as the hexafluoroethylene polymer.
  • Neophron NP (Daikin Industries, Ltd.) was used.
  • test piece 50 mm x 50 mm was cut out from each coated steel sheet, and a work adhesion test was performed. Each test piece was subjected to 180-degree contact bending (inner R: 1 mm). After a cellophane tape was applied to the bending portion of each test piece, the tape was peeled off perpendicularly to the bending ridgeline, and the residual ratio of the coating film was measured to evaluate the work adhesion.
  • Water resistance test A test piece (50 mm x 50 mm) was cut out from each coated steel sheet and subjected to a water resistance test. After each test piece was immersed in hot water of 95 ° C. or higher for 120 hours, a lattice-like cut was made in the coating so that 100 squares of 1 mm square could be formed. After applying a cellophane tape to the part of each test piece where the cut was made, the tape was peeled off perpendicularly to the surface of the test piece, the remaining rate of the coating was measured, and the water resistance was evaluated.
  • Alkali Resistance Test A test piece (50 mm ⁇ 50 mm) was cut out from each coated steel sheet and a water resistance test was performed. Each test piece was immersed in an aqueous NaOH solution (pH 14) of 95 ° C. or higher, and the time for the occurrence of coating swelling was measured to evaluate alkali resistance. The case where the film swelling occurs is “ ⁇ ” when the time is 120 hours or more, “ ⁇ ” when the time is 80 hours or more and less than 120 hours, “ ⁇ ” when the time is 24 hours or more and less than 80 hours, 2 hours or more and 24 hours The case of less than “ ⁇ ” and the case of less than 2 hours were evaluated as “x”.
  • Corrosion resistance test A test piece (150 mm x 70 mm) was cut out from each coated steel sheet and subjected to a corrosion resistance test. The upper and lower ends of each test piece were sealed with polyester tape, and a cross-cut was made in the center, followed by a salt spray test (5% NaCl, 35 ° C., 500 hours). After the test, the maximum bulge piece width of the left and right ends of each test piece and the maximum bulge piece width of the crosscut portion were measured to evaluate the corrosion resistance.
  • ⁇ if the maximum blister width is less than 0.5 mm, “ ⁇ ” if it is 0.5 mm or more and less than 1 mm, “ ⁇ ” if it is 1 mm or more and less than 2 mm, and “ ⁇ ” if it is 2 mm or more and less than 3 mm. The case of 3 mm or more was evaluated as “x”.
  • the coated steel sheets of the present invention (coated steel sheets No. 5-1 to No. 5-23) showed good results in all of the processed part adhesion, water resistance, alkali resistance and corrosion resistance. It was.
  • the coated steel sheet of No. 5-35 in which the chemical conversion film does not contain titanium oxide and hydroxide, was inferior in the corrosion resistance of the cross-cut portion. This is considered because the barrier effect by the oxide and hydroxide of titanium could not be exhibited.
  • the coated steel sheet of No. 5-34 in which the chemical conversion coating did not contain zirconium oxide and hydroxide, was inferior in corrosion resistance at the end face. This is considered to be because the effect of improving the coating film cross-linking effect and coating film adhesion by zirconium oxide and hydroxide could not be exhibited.
  • the coated steel sheets of No. 5-37 and No. 5-38 in which the chemical conversion coating film did not contain titanium fluoride and zirconium fluoride, had inferior corrosion resistance at the crosscut portion. This is presumably because the self-healing effect by fluorine ions could not be exhibited.
  • the coated steel sheet No. 5-29 with a low zirconium phosphate content in the primer coating film was inferior in corrosion resistance. This is presumably because the corrosion resistance by zirconium phosphate could not be exhibited.
  • the coated steel sheet No. 5-27 having a high zirconium phosphate content was inferior in alkali resistance. This is thought to be because the elution amount of zirconium phosphate was large and the primer coating became porous.
  • the coated steel sheet No. 5-30 in which zinc phosphate was blended instead of magnesium phosphate and zirconium phosphate had poor alkali resistance. This is probably because elution of zinc phosphate could not be suppressed and the primer coating became porous.
  • the coated steel plate No. 5-28 which has a low barium sulfate content in the primer coating, was inferior in alkali resistance.
  • the coated steel sheet No. 5-31 in which barium sulfate was not blended in the primer coating film was inferior in alkali resistance. This is presumably because the elution of magnesium phosphate and zirconium phosphate could not be sufficiently suppressed, and the primer coating became porous.
  • the coated steel sheet No. 5-26 with a high barium sulfate content was inferior in water resistance. This is thought to be because the primer coating became porous due to an excess amount of barium sulfate.
  • the coated steel plate No. 5-24 which has a small total content of pigment A and pigment B in the primer coating film, was inferior in corrosion resistance. This is presumably because the ratio of the pigment to the organic resin was small, and sufficient corrosion resistance could not be imparted.
  • the coated steel sheets of No. 5-25, No. 5-36 and No. 5-39 having a large total content of pigment A and pigment B in the primer coating film were inferior in water resistance. This is probably because the primer coating became porous due to an excessive amount of pigment.
  • the coated steel sheet of No. 5-40 in which the chemical conversion film was not formed was inferior in all of the adhesion to the processed part, water resistance, alkali resistance and corrosion resistance.
  • the coated steel sheet of No. 5-32 in which the primer coating film was not formed was inferior in all of the processed part adhesion, water resistance, alkali resistance and corrosion resistance.
  • the coated steel sheet No. 5-33 in which the top coating film was not formed was inferior in corrosion resistance.
  • the coated steel sheet of the present invention is excellent in corrosion resistance, water resistance and alkali resistance.
  • Example 2 it shows that the process part corrosion resistance of a coated steel plate can also be improved by annealing the coating layer of a coating original plate.
  • the coating original plate A and the coating original plate B are different only in that an annealing treatment is performed after the plating layer is formed.
  • coated steel plates (Examples: Nos. 7-1 to 7-2) were produced under the same conditions as the No. 5-3 coated steel plates of Example 1.
  • the coated steel sheet of No. 7-1 using the painted original sheet A is the same as the coated steel sheet of No. 5-3 in Example 1.
  • the chemical conversion solution of No. 1-1 shown in Table 1 is applied to the surface of the coating original plate so that the Ti adhesion amount becomes 1.2 mg / m 2 and the Zr adhesion amount becomes 2.3 mg / m 2.
  • the film was applied with a bar coater and dried at a final plate temperature of 100 ° C. for 10 seconds to form a chemical conversion coating.
  • the primer coating of No. 3-3 shown in Table 3 was applied to the surface of the chemical conversion treated steel plate with a bar coater so as to have a film thickness of 4 ⁇ m, and baked at a final plate temperature of 320 ° C. for 60 seconds to form a primer coating film. Formed.
  • Processed part corrosion resistance test A test piece was cut out from each coated steel sheet and a processed part corrosion resistance test was performed. After performing 180 degree
  • FIG. 1 is a photograph of a processed part of a coated steel sheet after a wet test.
  • 1A is a photograph of a processed part of No. 7-1 coated steel sheet (painted original sheet A; no annealing treatment)
  • FIG. 1B is a photograph of No. 7-2 coated steel sheet (painted original sheet B; with annealing treatment). It is a photograph of the processed part.
  • red rust was generated in the processed part. This is presumably because cracks occurred in the plating layer or the like during processing, and the base steel was exposed.
  • red rust did not occur at all in the No. 7-2 coated steel sheet using the coated original sheet B with the plated layer annealed. This is considered to be because the plating layer was annealed and softened to suppress cracks in the plating layer during processing.
  • the coated steel sheet of the present invention can also improve the corrosion resistance of the processed part by using a coated original sheet having a plated layer annealed.
  • Example 3 In Example 3, it is shown that the heat reflection characteristics of the coated steel sheet can be improved by adding a near-infrared reflective pigment to the top coating film.
  • Example 1 No. 5 of Example 1 except that the top paint of No. 8-1 or No. 8-2 shown in Table 8 is used instead of the top paint of No. 4-1 shown in Table 4.
  • a coated steel sheet Example: Nos. 9-1 to 9-2 was produced under the same conditions as those of the coated steel sheet No. -3.
  • the top paint of No. 4-1 and the top paint of Nos. 8-1 to 8-2 differ in whether or not black pigments are blended. Further, the top paint of No. 8-1 and the top paint of No. 8-2 differ in whether or not the blended black pigment is a near-infrared reflective (heat reflective) black pigment.
  • the chemical conversion solution of No. 1-1 shown in Table 1 is applied to the surface of the coating original plate so that the Ti adhesion amount becomes 1.2 mg / m 2 and the Zr adhesion amount becomes 2.3 mg / m 2.
  • the film was applied with a bar coater and dried at a final plate temperature of 100 ° C. for 10 seconds to form a chemical conversion coating.
  • the primer coating of No. 3-3 shown in Table 3 was applied to the surface of the chemical conversion treated steel plate with a bar coater so as to have a film thickness of 4 ⁇ m, and baked at a final plate temperature of 320 ° C. for 60 seconds to form a primer coating film. Formed.
  • Table 8 shown in Table 8 was applied to the surface of the primer coated steel plate with a bar coater to a film thickness of 10 ⁇ m, and baked at a final plate temperature of 380 ° C. for 60 seconds.
  • the coated steel sheets shown in Table 9 (Examples: Nos. 9-1 and 9-2) were prepared.
  • Heat Reflection Test A heat reflectivity test was performed on each coated steel sheet (No. 9-1 to 9-2). A heating chamber (width 34 cm ⁇ depth 36 cm ⁇ height 23 cm) was prepared using the coated steel plate of No. 9-1 or No. 9-2 as a wall material, and a glass ceramic plate was installed in the heating chamber. The heating chamber was heated by infrared using a glass ceramic plate, and the temperature of the wall surface of the heating chamber was measured over time. Table 10 shows the measurement results of the ceiling surface temperature of the heating chamber.
  • the coated steel sheet of the present invention can improve the heat reflection characteristics of the coated steel sheet by adding a near-infrared reflective pigment to the top coating film.
  • the coated steel sheet of the present invention is excellent in heat resistance, corrosion resistance, water resistance and alkali resistance, it is useful, for example, as a precoated steel sheet for members in a heating chamber of a superheated cooker having a steam supply function.

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Abstract

Cette invention concerne une tôle d'acier revêtue apte à garder une résistance à la corrosion même dans des environnements corrosifs fortement alcalins, et présentant une excellente résistance à la corrosion et aux alcalis. Ladite tôle d'acier revêtue comprend une tôle d'acier, une couche de revêtement traitée par conversion chimique formée sur la surface de la tôle d'acier, une couche de revêtement primaire formée sur la surface de la couche de revêtement traitée par conversion chimique, et une couche de revêtement de finition formée sur la surface de la couche de revêtement primaire. La couche de revêtement traitée par conversion chimique comprend un fluorure de titane ou un fluorure de zirconium, un oxyde ou un hydroxyde de titane et un oxyde ou un hydroxyde de zirconium. La couche de revêtement primaire comprend une résine organique, un pigment anticorrosif comprenant un ou deux composés indépendamment choisis dans le groupe comprenant le phosphate de magnésium et le phosphate de zirconium, et un sulfate de baryum.
PCT/JP2011/003750 2010-06-30 2011-06-30 Tôle d'acier revêtue présentant une excellente résistance à la corrosion et aux alcalis WO2012001981A1 (fr)

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PCT/JP2011/003750 WO2012001981A1 (fr) 2010-06-30 2011-06-30 Tôle d'acier revêtue présentant une excellente résistance à la corrosion et aux alcalis

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WO2014009004A1 (fr) * 2012-07-10 2014-01-16 Tata Steel Nederland Technology B.V. Bande, tôle ou flan d'acier thermoformable revêtu(e), et procédé de fabrication de celle/celui-ci
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers
WO2022210200A1 (fr) 2021-03-31 2022-10-06 日本製鉄株式会社 Feuille d'acier plaquée pré-revêtue et produit moulé
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

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CN103468128B (zh) * 2013-08-14 2015-06-17 苏州康华净化系统工程有限公司 一种耐腐蚀净化车间彩钢板
CN103600526B (zh) * 2013-10-31 2015-09-09 苏州扬子江新型材料股份有限公司 一种耐磨耐火彩色涂层钢板
JP6530885B2 (ja) * 2013-12-18 2019-06-12 東洋製罐株式会社 表面処理鋼板、有機樹脂被覆金属容器、及び表面処理鋼板の製造方法
JP5568191B1 (ja) * 2014-03-19 2014-08-06 日新製鋼株式会社 塗装鋼板および外装建材
TW201538309A (zh) * 2014-03-27 2015-10-16 Nisshin Steel Co Ltd 化學轉化處理鋼板及其製造方法以及化學轉化處理液
US20170336013A1 (en) * 2014-10-22 2017-11-23 Nisshin Steel Co., Ltd. Chemical conversion-treated steel pipe
CN110387174A (zh) * 2019-07-01 2019-10-29 深圳华美板材有限公司 一种水性疏水疏油彩涂板及其制造工艺

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WO2014009004A1 (fr) * 2012-07-10 2014-01-16 Tata Steel Nederland Technology B.V. Bande, tôle ou flan d'acier thermoformable revêtu(e), et procédé de fabrication de celle/celui-ci
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
WO2022210200A1 (fr) 2021-03-31 2022-10-06 日本製鉄株式会社 Feuille d'acier plaquée pré-revêtue et produit moulé
KR20230159860A (ko) 2021-03-31 2023-11-22 닛폰세이테츠 가부시키가이샤 프리코트 도금 강판 및 성형품

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