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WO2022044195A1 - Tôle d'acier revêtue et procédé de fabrication de tôle d'acier revêtue - Google Patents

Tôle d'acier revêtue et procédé de fabrication de tôle d'acier revêtue Download PDF

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Publication number
WO2022044195A1
WO2022044195A1 PCT/JP2020/032350 JP2020032350W WO2022044195A1 WO 2022044195 A1 WO2022044195 A1 WO 2022044195A1 JP 2020032350 W JP2020032350 W JP 2020032350W WO 2022044195 A1 WO2022044195 A1 WO 2022044195A1
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Prior art keywords
steel sheet
coated steel
phosphate
less
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2020/032350
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English (en)
Japanese (ja)
Inventor
颯 永山
雅典 松野
晋 上野
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Nippon Steel Corp
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Nippon Steel Corp
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Publication date
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Priority to PCT/JP2020/032350 priority Critical patent/WO2022044195A1/fr
Publication of WO2022044195A1 publication Critical patent/WO2022044195A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • 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

Definitions

  • the present invention relates to a coated steel sheet and a method for manufacturing a coated steel sheet.
  • Steel sheets used for the exterior and roof of buildings may be required to have a black appearance in order to enhance their design.
  • a coated steel sheet in which a coating film (coating) is formed on the surface of a galvanized steel sheet, some methods have been proposed in which the appearance of the galvanized steel sheet is blackened by blackening the coating film.
  • Patent Document 1 contains a predetermined amount of a compound having two nickel ions or cobalt ions, an ammonium ion or a primary amino group, a nitrate ion, and a fluoride on the surface of a zinc-based plating material. It is described that the zinc-based plating material can be blackened by contacting with a treatment liquid having a pH of 2.0 to 4.8.
  • a hot-dip galvanized steel sheet or a hot-dip galvanized steel sheet is treated with zinc phosphate in a zinc phosphate-treated bath containing a predetermined amount of Fe 2+ , Mn 2- and Ni 2+ . It is stated that the lightness index can be 20-40.
  • the appearance of the galvanized steel sheet can be blackened by surface-treating the galvanized steel sheet with a predetermined treatment liquid.
  • the coated steel sheet used for the exterior and roof of a building is also required to have corrosion resistance that suppresses the generation of white rust for a long period of time. Not high enough. Therefore, conventionally, in order to improve the corrosion resistance of a galvanized steel sheet, a chrome sealing film and an organic film have been formed on the surface of a phosphate-treated layer formed by zinc phosphate treatment or the like.
  • the chrome sealing film has an effect of enhancing the adhesion of the organic film while enhancing the corrosion resistance of the coated steel sheet (for example, the organic film is sufficiently adhered even after being processed).
  • the present invention has been made in view of the above points, and the appearance of the coated steel sheet having a chromium-free sealing film and an organic film that does not substantially contain chromium (Cr) is sufficiently blackened and is further blackened. It is an object of the present invention to provide a coated steel sheet having sufficiently improved corrosion resistance and adhesion of a processed portion, and a method for manufacturing such a coated steel sheet.
  • the coated steel sheet according to the embodiment of the present invention for solving the above problems has a steel sheet, a zinc-based plating layer, and a total adhesion amount of Ni and Co of 20 mg / m 2 or more and 100 mg / m 2 or less, and is a treated layer.
  • the surface brightness (L *) of the coated steel sheet is 55 or less.
  • the method for manufacturing a coated steel plate according to an embodiment of the present invention for solving the above problems includes a step of preparing a plated steel plate having a zinc-based plating layer and contacting the zinc-based plating layer with Ni and Co.
  • a chemical conversion treatment solution containing a group 4 metal oxidase, a group 1 metal or a salt thereof, and an ammonium ion and having a pH of 7.0 or more and 9.0 or less is applied in contact with the phosphate treatment layer. It has a step of forming a chrome-free sealing film and a step of contacting with the chrome-free sealing film to form an organic film.
  • a coated steel sheet having a chromium-free sealing film and an organic film that substantially does not contain chromium (Cr) the appearance is sufficiently blackened, and the corrosion resistance and the adhesion of the processed portion are sufficient.
  • Enhanced coated steel sheets, and methods for manufacturing such coated steel sheets are provided.
  • An embodiment of the present invention relates to a painted steel sheet in which a coating film is formed on the surface of the steel sheet.
  • a coating film is formed on the surface of the steel sheet.
  • a steel sheet, a zinc-based plating layer, a phosphate-treated layer, a chrome-free sealing film, and an organic-based film are laminated in this order, and the surface brightness (L *) is 55 or less. Is.
  • the steel sheet may be any steel sheet that can form a zinc-based plating layer, may be carbon steel containing low carbon steel, medium carbon steel, high carbon steel, or the like, or may be an alloy steel containing Mn, Cr, Si, Ni, or the like. But it may be.
  • the steel plate may be a killed steel containing Al killed steel or the like, or may be a rimmed steel. When good press formability is required, a steel sheet for deep drawing containing low-carbon Ti-added steel, low-carbon Nb-added steel, or the like is preferable as the steel sheet. Further, a high-strength steel plate in which the amounts of P, Si, Mn and the like are adjusted to specific values may be used.
  • the zinc-based plating layer is a plating layer containing zinc as a main component.
  • the plating constituting the zinc-based plating layer is described from Zn plating (pure zinc plating), Zn—Al alloy plating, Zn—Mg alloy plating, Zn—Ni alloy plating, Zn—Al—Mg alloy plating, and the like. It can be selected according to the application of the surface-treated zinc-based plated steel plate.
  • the zinc-based plating layer may be a plating layer formed by any known method such as an electroplating method, a hot-dip plating method, and a vapor deposition plating method.
  • the zinc-based plating layer is preferably a plating layer formed by a hot-dip plating method because a zinc-based plating layer having a larger amount of adhesion can be easily produced.
  • the zinc-based plating layer preferably contains Al of 0.1% by mass or more and 22.0% by mass or less in order to enhance the corrosion resistance of the coated steel sheet.
  • the zinc-based plating layer preferably has an adhesion amount of 100 g / m 2 or more in order to enhance the durability of the zinc-based plating layer when the coated steel sheet is used as an exterior building material in a relatively harsh environment such as a beach area. ..
  • Phosphate-treated layer is a layer containing phosphate crystals formed on the surface of the zinc-based plating layer.
  • the phosphate-treated layer is a film having a phosphate anion and having a plurality of phosphate crystals composed of compounds capable of forming sparingly water-soluble crystals arranged on the surface of the zinc-based plating layer.
  • phosphate crystals include magnesium phosphate, manganese phosphate, zinc phosphate, iron phosphate, zinc iron phosphate, zinc phosphate calcium and the like.
  • the phosphate treatment layer contains Ni and Co. Both Ni and Co give the coated steel sheet a black appearance, presumably by substituting and precipitating fine particles on the surface of the zinc-based plating layer to produce a light scattering effect. From the viewpoint of better blackening the appearance of the coated steel sheet, the total amount of Ni and Co adhered to the phosphate-treated layer is 20 mg / m 2 or more. On the other hand, from the viewpoint of suppressing the deterioration of the corrosion resistance of the coated steel sheet due to the above-mentioned substitution precipitation inhibiting the precipitation of phosphate crystals, the total adhesion amount of Ni and Co in the phosphate-treated layer is 100 mg / m. 2 or less.
  • the total amount of Ni and Co adhered to the phosphate-treated layer is preferably 30 mg / m 2 or more and 80 mg / m 2 or less, and 40 mg / m 2 or more and 70 mg / m 2 or less. More preferred.
  • the phosphate-treated layer may contain metal elements such as Mn, Mg, Ca, and Fe, or an aliphatic amine as other components.
  • the amount of the phosphate-treated layer adhered is such that the amount of the phosphate crystals adhered is increased and the thickness of the precipitation layer due to Ni and Co deposited at the position where the phosphate crystals are not adhered is increased to increase the thickness of the coated steel plate.
  • the temperature should be 2.0 g / m 2 or more.
  • the phosphate-treated layer is used.
  • the amount of adhesion shall be 7.0 g / m 2 or less.
  • the amount of the phosphate-treated layer adhered is preferably 2.5 g / m 2 or more and 7.0 g / m 2 or less, and 3.0 g / m 2 or more and 6.0 g / m 2 or less. It is more preferable to have.
  • the brightness (L *) of the surface of the coated steel sheet is 55 by appropriately controlling the total amount of Ni and Co adhered to the phosphate-treated layer and the amount of adhesion of the phosphate-treated layer.
  • it can be preferably 50 or less, more preferably 40 or more and 50 or less.
  • the brightness (L *) is a value measured by a spectral reflection measurement method based on JIS K 5600-4-5 (1999) using a spectroscopic color difference meter.
  • the 60 ° gloss value of the surface of the coated steel sheet is obtained by appropriately controlling the total amount of Ni and Co adhered to the phosphate-treated layer and the amount of adhesion of the phosphate-treated layer. It can be 10 or less, preferably 8 or less, and more preferably 5 or less.
  • the 60 ° gloss value is a value measured in accordance with JIS K 5600-4-5 (1999).
  • Chromium-free sealing film is a film containing an oxygenate of a Group 4 metal and a Group 1 metal or a salt thereof formed on the surface of the phosphate-treated layer.
  • the chromium-free sealing film is a chemical conversion treatment formed by a chemical conversion treatment liquid containing an oxidase of a group 4 metal, a salt of the group 1 metal or a salt thereof, and an ammonium ion and having a pH of 7.0 or more and 9.0 or less. It is a film.
  • the above-mentioned group 4 metal oxygen salt improves the corrosion resistance (flat portion corrosion resistance and processed portion corrosion resistance) of the coated steel sheet by forming a dense chemical conversion treatment film (chromium-free sealing film).
  • the Group 4 metals include Ti, Zr and Hf.
  • the above-mentioned group 4 metal oxyate salt is a salt of an inorganic acid containing a group 4 metal atom and an oxygen atom.
  • the above salts include hydrides, ammonium salts, alkali metal salts, alkaline earth metal salts and the like.
  • the oxygen salt of the Group 4 metal is preferably an ammonium salt of an inorganic acid containing a Group 4 metal atom and an oxygen atom, and is zirconium ammonium carbonate. Is preferable.
  • the amount of the oxygen acid salt of the Group 4 metal adhered to the chromium-free sealing film is 2 mg / m 2 or more and 80 mg / m 2 or less in terms of Group 4 metal atom. It is preferable that it is 5 mg / m 2 or more and 30 mg / m 2 or less.
  • the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid to provide adhesion between the chromium-free sealing film and the phosphate-treated layer, and between the chromium-free sealing film and the organic film. Improves adhesion. Further, the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid, suppresses the bond between the Group 4 metal and phosphorus in the chemical conversion treatment, and gels the chemical conversion treatment liquid by these bonds. By suppressing the formation, the long-term storage stability (stability) of the chemical conversion treatment liquid is enhanced.
  • the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid, making it difficult for water to be removed when the chemical conversion treatment liquid is dried, and the chromium-free sealing film is excessively dried during production. It is possible to suppress the occurrence of cracks due to the cracking.
  • the Group 1 metals include Li, Na, K and the like. Of these, the Group 1 metal is preferably Na from the viewpoint of further enhancing the adhesion to the phosphate-treated layer and the organic film and further suppressing the generation of cracks.
  • the Group 1 metal may be a phosphate such as sodium diphosphate, potassium diphosphate and sodium tripolyphosphate, or 1-hydroxyethylidene-1,1-bisphosphonate disodium, and 1-hydroxyethylidene. It may be an organic phosphonic acid such as -1,1-diphosphonate pentasodium, or it may be another compound such as a hydroxide of a Group 1 metal.
  • the Group 1 metals are sodium tripolyphosphate and 1-hydroxyethylidene. It is preferably -1,1-bisphosphonate disodium or 1-hydroxyethylidene-1,1-diphosphonate pentasodium.
  • the amount of the Group 1 metal or its salt in the chromium-free sealing film is Group 4. It is preferable that the amount of the Group 1 metal atom is 0.5 parts by mass or more and 21 parts by mass or less with respect to 100 parts by mass of the metal atom. Similarly, the amount of the Group 1 metal or a salt thereof in the chrome-free sealing film is preferably an amount such that the molar ratio of the Group 1 metal atom to the Group 4 metal atom is 0.02 or more and 0.8 or less. ..
  • the amount of the chrome-free sealing film adhered is not particularly limited, but can be 3 mg / m 2 or more and 1000 mg / m 2 or less, and 5 mg / m 2 or more and 500 mg / m 2 or less from the viewpoint of improving spot weldability. Is preferable.
  • the chromium-free sealing film contains oxides, hydroxides or fluorides of V, Mo, P, Ti or Si in order to further enhance the corrosion resistance of the coated steel sheet in a situation where salt water such as seawater is applied. You may.
  • the chromium-free sealing film contains substantially no hexavalent chromium. Specifically, four 50 mm ⁇ 50 mm test pieces were cut out from the coated steel sheet, immersed in 100 mL of boiling pure water for 10 minutes, and then the hexavalent chromium eluted in the pure water was added to JIS H8625 (JIS H8625). 1993) It is below the detection limit when quantified by the concentration analysis method based on the "diphenylcarbazide colorimetric method" of 2.4.1 of the annex.
  • the chemical conversion treatment liquid containing each of the above components is usually acidic.
  • the phosphate treatment layer or the zinc-based plating layer may be partially dissolved in the chemical conversion treatment liquid.
  • these layers are partially dissolved in the chemical conversion treatment liquid, the brightness of the coated steel sheet becomes high, the appearance of the coated steel sheet becomes uneven, and the components of these layers are mixed in the chromium-free sealing film and each of them is used. The properties expected of the layer may not be fully exhibited.
  • a chromium-free sealing film is formed by using a chemical conversion treatment liquid having a pH of 7.0 or more and 9.0 or less.
  • the method for adjusting the pH is not particularly limited, it is preferable to adjust the pH to the above range with ammonium ions from the viewpoint of suppressing the influence on the characteristics of the chromium-free sealing film.
  • an ammonium salt derived from ammonium ions contained in the chemical conversion treatment liquid may remain on the chromium-free sealing film.
  • Organic film is a film formed on the surface of the chromium-free sealing film and containing an organic resin as a main component.
  • the organic resin constituting the organic film may be any organic resin usually used for surface treatment of galvanized steel sheets, and may be appropriately selected from, for example, urethane resin, fluororesin, acrylic resin, polyester resin and the like. Can be done.
  • the organic film containing these organic resins can enhance the corrosion resistance and processability of the coated steel sheet.
  • the organic resin is preferably a urethane resin or a polyester resin, and more preferably a urethane resin.
  • the urethane resin usually has a structural unit derived from an isocyanate compound and a structural unit derived from a polyol compound.
  • Examples of the structural unit derived from the isocyanate compound include a structural unit derived from an aliphatic diisocyanate and a structural unit derived from an alicyclic diisocyanate.
  • Examples of the aliphatic diisocyanate include phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate.
  • Examples of the alicyclic diisocyanate include cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate.
  • Examples of the structural unit derived from the above-mentioned polyol compound include a structural unit derived from a polyolefin polyol.
  • Examples of the polyolefin polyols include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols and polybutadiene polyols.
  • the organic film is one or more compounds selected from the group consisting of an oxide of a valve metal, a hydroxide of a valve metal, or a fluoride of a valve metal (hereinafter, also simply referred to as "valve metal compound").
  • valve metal compound a compound selected from the group consisting of an oxide of a valve metal, a hydroxide of a valve metal, or a fluoride of a valve metal (hereinafter, also simply referred to as "valve metal compound”).
  • Etc. may be included.
  • the valve metal compound can impart an excellent barrier action to the organic film while reducing the environmental load.
  • the valve metal is a metal whose oxide exhibits high insulation resistance. Examples of the valve metal include one kind or two or more kinds of metals selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W. A known valve metal compound may be used.
  • soluble fluoride of valve metal in the organic film, it is possible to impart a self-repairing action to the organic film.
  • Fluoride of the valve metal dissolves in the moisture in the atmosphere and then reprecipitates as a sparingly soluble oxide or hydroxide on the surface of the plated steel sheet exposed from the film defect part, and the film defect part is formed. Can be filled.
  • the organic film may further contain a soluble or sparingly soluble metal phosphate or a composite phosphate in addition to the soluble fluoride of the valve metal.
  • Soluble phosphate elutes from the organic film into the film defect and reacts with the metal of the plated steel plate to form an insoluble phosphate, which can complement the self-healing action of the soluble fluoride of valve metal. can.
  • the poorly soluble phosphate can be dispersed in the organic film to improve the film strength.
  • the film thickness of the organic film is preferably 3.0 ⁇ m or more.
  • the film thickness of the organic film is 3.0 ⁇ m or more, it becomes difficult for the corrosive factor permeating the organic film to reach the plating layer, and the corrosion resistance of the coated steel sheet can be sufficiently enhanced.
  • the upper limit of the film thickness of the organic film is not particularly limited, it can be 15 ⁇ m.
  • the organic film may be a colored film containing an organic pigment or the like, but from the viewpoint of further enhancing the visibility of the black appearance of the phosphate-treated layer and further enhancing the design of the coated steel sheet. , It is preferable that it is a clear film.
  • coated steel sheet can be used for various purposes.
  • the coated steel sheet has a sufficiently blackened appearance, and has sufficiently improved corrosion resistance and adhesion of the processed portion, so that it can be suitably used as an exterior building material such as a roof of a building. can.
  • the coated steel sheet may be a flat plate or a processed product processed into various shapes.
  • the above-mentioned coated steel sheet includes a step of preparing a plated steel sheet having a zinc-based plating layer, a step of forming the phosphate-treated layer, a step of forming the chrome-free sealing film, and the above-mentioned organic. It can be produced by a method including a step of forming a system film.
  • Step of preparing a plated steel sheet In the step of preparing the above-mentioned plated steel sheet, the above-mentioned steel sheet is used as a base steel sheet, and the above-mentioned galvanized steel sheet is prepared. In this step, a plated steel sheet that has already been produced may be prepared, or the base steel sheet is subjected to zinc-based plating by a known method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method, and the plated steel sheet is subjected to zinc-based plating. May be produced.
  • a known method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method
  • Step of Forming Phosphate Treatment Layer In the step of forming the phosphate treatment layer, a phosphate treatment liquid is applied so as to be in contact with the zinc-based plating layer of the prepared plated steel plate, and the zinc-based plating is performed. Phosphate crystals are deposited on the surface of the layer.
  • the phosphate treatment liquid is a treatment liquid containing Ni or Co and phosphate ions.
  • the phosphate treatment solution can be prepared by dissolving phosphate or phosphoric acid and a metal salt capable of generating Ni or Co ions in an aqueous solvent.
  • Examples of the above phosphate include magnesium phosphate, manganese phosphate, zinc phosphate, iron phosphate, zinc iron phosphate, zinc phosphate calcium and the like.
  • the concentration of phosphate ions in the phosphate treatment solution is 0.03. It is preferably mol / L or more and 0.5 mol / L or less.
  • the concentration of Ni or Co ions in the phosphate treatment solution is the total adhesion of Ni and Co when the adhesion amount of the phosphate treatment layer is 2.0 g / m 2 or more and 7.0 g / m 2 or less. The amount may be adjusted to be 20 mg / m 2 or more and 100 mg / m 2 or less.
  • the phosphate treatment solution further contains a polyamine-based organic inhibitor containing an aliphatic polyamine containing polyethylamine, polyethyleneimine, polyetheramine, polyaminoacrylate and the like, and an aromatic polyamine containing polyaniline and the like. May be good.
  • the polyamine-based organic inhibitor can precipitate the crystal particles of phosphate at appropriate intervals and can make the crystal particles of phosphate finer.
  • the number average molecular weight of the polyamine-based organic inhibitor is preferably 200 or more and 30,000 or less. Further, from the viewpoint of appropriately adjusting the amount of precipitated phosphate crystals, the concentration of the polyamine-based organic inhibitor in the phosphate treatment liquid is preferably 0.01% by mass or more and 5% by mass or less.
  • the phosphate treatment solution may further contain nitrate ions. Nitrate ions promote the precipitation of phosphate.
  • the concentration of nitrate ions in the phosphate treatment solution is preferably 0.01 mol / L or more and 1.0 mol / L or less.
  • the phosphate treatment solution may further contain fluoride.
  • fluoride include sodium fluoride, potassium fluoride, sodium hydrogen fluoride and the like.
  • concentration of fluoride in the phosphate treatment liquid is preferably 0.001 mol / L or more and 0.5 mol / L or less.
  • the method for applying the phosphate treatment liquid is not particularly limited, and may be appropriately selected from known methods for applying the phosphate treatment liquid to the surface of the plating layer.
  • Examples of the above-mentioned applying method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping pulling method, and the like.
  • the phosphate treatment liquid may be applied so that the amount of the phosphate treatment layer applied is 2.0 g / m 2 or more and 7.0 g / m 2 or less.
  • the temperature of the phosphate treatment liquid at the time of application is preferably 40 ° C. or higher and 80 ° C. or lower.
  • a phosphate treatment solution heated to 40 ° C. or higher and 80 ° C. or lower is used, a large number of fine phosphate crystals can be stably precipitated in a short time.
  • the surface of the galvanized steel sheet may be adjusted with a known surface conditioner before the phosphate treatment liquid is applied.
  • Step of Forming Chrome-Free Sealing Film In the step of forming the chrome-free sealing film, an oxidase of Group 4 metal, a salt of Group 1 metal or its salt, and ammonium so as to be in contact with the formed phosphate-treated layer. A chemical conversion treatment solution containing ions and having a pH of 7.0 or more and 9.0 or less is applied and dried to form a chrome-free sealing film on the surface of the phosphate-treated layer.
  • the above-mentioned chemical conversion treatment liquid is a chemical conversion treatment liquid containing the above-mentioned acid acid salt of the Group 4 metal and the Group 1 metal or a salt thereof, and the pH of which is adjusted to 7.0 or more and 9.0 or less by ammonium ions.
  • the pH of the chemical conversion treatment liquid is preferably 7.2 or more and 8.5 or less, and more preferably 7.3 or more and 8.0 or less.
  • the content of the above-mentioned Group 4 metal oxynate and Group 1 metal or a salt thereof is not particularly limited.
  • the concentration of the Group 4 metal atom in the chemical conversion treatment liquid is preferably 5 g / L or more and 40 g / L or less, and more preferably 5 g / L or more and 35 g / L or less.
  • the concentration of the Group 1 metal atom in the chemical conversion treatment liquid is preferably 0.2 g / L or more.
  • the amount of the Group 1 metal or a salt thereof in the chemical conversion treatment liquid is such that the Group 1 metal atom is 0.5 parts by mass or more and 21 parts by mass or less with respect to 100 parts by mass of the Group 4 metal atom. It is also preferable that the molar ratio of the group 1 metal atom to the group 4 metal atom is 0.02 or more and 0.8 or less.
  • the chemical conversion treatment liquid contains oxides, hydroxides or fluorides of V, Mo, P, Ti or Si in order to further enhance the corrosion resistance of the coated steel sheet in a situation where salt water such as seawater is applied. You may be.
  • the method for applying the chemical conversion treatment liquid is not particularly limited, and may be appropriately selected from known methods such as a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dipping pulling method.
  • Step of Forming Organic Film In the step of forming the organic film, the organic film treatment liquid containing the above-mentioned organic resin is applied and dried so as to be in contact with the formed chrome-free sealing film. An organic film is formed on the surface of the chrome-free sealing film.
  • a molten Zn-0.1 mass% Al plating layer (plating adhesion amount 200 g / m 2 ) was formed on the surface of ordinary steel having a plate thickness of 0.6 mm to obtain a plated steel sheet 3.
  • a molten Zn-6% by mass Al-3% by mass Mg plating layer (plating adhesion amount 140 g / m 2 ) was formed on the surface of ordinary steel having a plate thickness of 0.6 mm to obtain a plated steel sheet 4.
  • chrome-free sealing film Zirconium zirconium in an amount that has a Zr concentration of 5 g / L as an oxidate of a Group 4 metal, and sodium diphosphate in an amount that has a Na concentration of 0.5 g / L as a salt of a Group 1 metal.
  • a chemical conversion treatment liquid for forming a chrome-free sealing film containing (a salt of a group 1 metal) and ammonia in an amount such that the pH of the aqueous solution was 7.5 was prepared.
  • the chemical conversion treatment liquid was applied to the surface of the plated steel sheet 1 on which the phosphate-treated layer was formed, and dried in an oven at 200 ° C. to form a chrome-free sealing film.
  • the amount of the chemical conversion treatment liquid applied was adjusted so that the amount of the chromium-free sealing film adhered was 10 mg / m 2 .
  • the coated steel sheet 4 and the coated steel sheet 5 were formed in the same manner as the coated steel sheet 3 except that the content of ammonia in the chemical conversion treatment solution was changed so that the pH of the chemical conversion treatment solution was 7.1 and 8.9, respectively. Obtained.
  • a coated steel sheet 6 was obtained in the same manner as the coated steel sheet 3 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
  • the type of Group 4 metal oxyate acid salt contained in the chemical conversion treatment liquid was changed to titanium ammonium fluoride (group 4 metal oxyate acid salt) having a Ti concentration of 2 g / L, and the pH of the chemical conversion treatment liquid was changed.
  • a coated steel plate 7 was obtained in the same manner as the coated steel plate 3 except that the content of ammonia in the chemical conversion treatment liquid was adjusted so as to be 7.1.
  • a coated steel sheet 8 was obtained in the same manner as the coated steel sheet 3 except that the type of the organic resin contained in the organic film treatment liquid was changed to an acrylic resin (Boncoat CG-8400 manufactured by DIC Corporation).
  • the coated steel plate 11 was obtained in the same manner as the coated steel plate 3 except that the plated steel plate was changed to the plated steel plate 2.
  • a coated steel sheet 12 was obtained in the same manner as the coated steel sheet 11 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
  • the coated steel sheet 13 was obtained in the same manner as the coated steel sheet 3 except that the plated steel sheet was changed to the plated steel sheet 3.
  • the type of organic resin contained in the organic film treatment liquid is changed to acrylic resin (Boncoat CG-8400 manufactured by DIC), and the organic film treatment liquid has a film thickness of 2.0 ⁇ m.
  • a coated steel sheet 14 was obtained in the same manner as the coated steel sheet 13 except that the coating amount of was changed.
  • the coated steel sheet 15 was obtained in the same manner as the coated steel sheet 3 except that the plated steel sheet was changed to the plated steel sheet 4 and the coating amount of the organic film treatment liquid was changed so that the film thickness of the organic film was 6.0 ⁇ m. rice field.
  • the type of the oxychloride of the Group 4 metal contained in the chemical conversion treatment liquid was changed to titanium ammonium fluoride in an amount such that the Ti concentration was 2 g / L, and the pH of the chemical conversion treatment liquid was changed to 7.1.
  • a coated steel sheet 16 was obtained in the same manner as the coated steel sheet 15 except that the content of ammonia in the treatment liquid was adjusted.
  • a coated steel sheet 17 was obtained in the same manner as the coated steel sheet 15 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
  • Ni and Ni in the phosphate treatment solution so that the total adhesion of Ni and Co in the phosphate treatment layer is 11 mg / m 2 , 18 mg / m 2 , 0 mg / m 2 and 110 mg / m 2 .
  • the coated steel sheets 18 to 21 were obtained in the same manner as in the production of the coated steel sheet 1 except that the total content of Co was changed.
  • the immersion time in the phosphate treatment solution was changed so that the adhesion amount of the phosphate treatment layer was 1.7 g / m 2 and 7.5 g / m 2 , and in either case, the phosphate treatment layer was used.
  • the coated steel plate 22 was used in the same manner as the coated steel plate 1, except that the total content of Ni and Co in the phosphate treatment liquid was changed so that the total adhesion amount of Ni and Co was 62 mg / m 2 , the coated steel plate 22 was used. And a coated steel plate 23 was obtained.
  • a coated steel sheet 24 was obtained in the same manner as the coated steel sheet 3 except that the chemical conversion treatment liquid did not contain a group 1 metal salt.
  • the coated steel sheet 25 and the coated steel sheet 26 were formed in the same manner as the coated steel sheet 3 except that the content of ammonia in the chemical conversion treatment solution was changed so that the pH of the chemical conversion treatment solution was 6.5 and 10.6, respectively. Obtained.
  • a coated steel sheet 27 was obtained in the same manner as the coated steel sheet 3 except that an organic film was not formed.
  • a coated steel sheet 28 was obtained in the same manner as the coated steel sheet 3 except that the chemical conversion treatment liquid did not contain the oxygen acid salt of the Group 4 metal.
  • a coated steel sheet 29 was obtained in the same manner as the coated steel sheet 3 except that the phosphate-treated layer and the chromium-free sealing were not formed.
  • the plated steel sheet was changed to the plated steel sheet 4, and the coated steel sheet 30 was obtained in the same manner as the coated steel sheet 13 except that the phosphate-treated layer and the chrome-free sealing were not formed.
  • Tables 1 and 2 show the adhered amounts of the plated steel plate and the phosphate-treated layer, the total adhered amount of Ni and Co in the phosphate-treated layer, and the chrome-free sealing of the coated steel plates 1 to 30.
  • Types of Group 4 metals that make up Group 4 metal oxyphosphates types of Group 1 metals that form salts of Group 1 metals, pH of chemical conversion treatment solutions, types of organic resins that make up organic films, and their film thicknesses. Is shown.
  • Evaluation Results Tables 3 and 4 show the evaluation results of corrosion resistance, brightness, and adhesion to the processed portion of the coated steel sheets 1 to 30.
  • the total adhesion amount of the steel sheet, the zinc-based plating layer, and Ni and Co is 20 mg / m 2 or more and 100 mg / m 2 or less, and the adhesion amount of the treated layer is 2.
  • a phosphate-treated layer having a pH of 0.0 g / m 2 or more and 7.0 g / m 2 or less, a chromium-free sealing film containing an oxidate of a Group 4 metal and a Group 1 metal or a salt thereof, and an organic film.
  • the coated steel sheets 1 to 17 arranged in this order had a brightness (L *) of 55 or less, and had high corrosion resistance and adhesion to the processed portion.
  • the total adhesion amount of Ni and Co in the phosphate-treated layer is 30 mg / m 2 or more and 80 mg / m 2 or less.
  • the surface brightness of the painted steel sheet was lower, and the corrosion resistance was higher. This is because when the total amount of Ni and Co adhered to the phosphate-treated layer is 30 mg / m 2 or more, the surface brightness of the coated steel plate becomes lower because Ni and Co are sufficiently precipitated, and the phosphate treatment is performed.
  • the total adhesion of Ni and Co in the layer was 80 mg / m 2 or less, it is considered that the corrosion resistance of the coated steel plate was higher because the precipitation of Ni and Co was difficult to inhibit the precipitation of phosphate crystals. ..
  • the chrome-free sealing film contains Zr oxygenate as the oxygen acid salt of the Group 4 metal.
  • the brightness of the surface of the coated steel sheet was lower than that when the chrome-free sealing film contained Ti oxidate as the oxidate of Group 4 metal. It is considered that this is because the pH of the chrome-free sealing treatment liquid is low, so that the phosphate film or Ni substitution layer on the surface is slightly removed, and the brightness of the surface of the coated steel sheet becomes lower.
  • the adhesion amount of the phosphate-treated layer is 2.5 g / m 2 or more and 7.0 g / m 2 or less
  • the surface of the coated steel sheet is surfaced.
  • the brightness was lower. This is because when the amount of the phosphate-treated layer adhered is 2.5 g / m 2 or more and 7.0 g / m 2 or less, the amount of the phosphate film adhered is small and the surface brightness of the coated steel sheet becomes lower. It is thought that it was.
  • the coated steel sheet 3 when the total adhesion amount of Ni and Co in the phosphate-treated layer is less than 20 mg / m 2 , the coated steel sheet The brightness of the surface was higher than 55. It is considered that this is because when the total adhesion amount of Ni and Co in the phosphate treatment layer was less than 20 mg / m 2 , the brightness of the surface of the coated steel sheet did not decrease because the precipitation amount of Ni or Co was small. Be done.
  • the adhesion amount of the phosphate-treated layer is less than 2.0 g / m 2
  • the brightness of the surface of the coated steel sheet is higher than 55. rice field. It is probable that when the adhesion amount of the phosphate-treated layer was less than 2.0 g / m 2 , the brightness of the surface of the coated steel sheet did not decrease because the adhesion amount of the phosphate film was small.
  • the chromium-free sealing film does not contain the Group 1 metal or a salt thereof, the corrosion resistance of the coated steel sheet and the adhesion to the processed portion are deteriorated. This is because if the chromium-free sealing film does not contain a Group 1 metal or a salt thereof, the amount of hydroxyl groups in the chemical conversion treatment liquid is insufficient, so that the corrosion resistance of the coated steel sheet does not easily increase, and the organic film peels off, resulting in the processed portion of the coated steel sheet. It is probable that it was difficult to increase the adhesion.
  • the coated steel sheet 3 does not have an organic film, the corrosion resistance and the corrosion resistance of the coated steel sheet are lowered.
  • the corrosion resistance of the coated steel sheet is lowered.
  • the coated steel sheet 3 and the coated steel sheet 29 and the comparison between the coated steel sheet 15 and the coated steel sheet 30 if the coated steel sheet does not have the phosphate-treated layer and the chrome-free sealing film, it is coated. Corrosion resistance, lightness and adhesion to the processed part of the steel sheet were not all desired.
  • the coated steel sheet of the present invention is suitably used for, for example, various electronic devices, household electric appliances, medical devices, automobile bodies, vehicle-mounted products, building materials, and the like.
  • the coated steel sheet of the present invention has excellent designability because of its low lightness, and also has excellent corrosion resistance and adhesion to the processed portion, so that it can be suitably used as a building material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Le but de la présente invention est de fournir : une tôle d'acier revêtue qui comporte un revêtement d'étanchéité sans chrome et un revêtement organique, qui a un aspect suffisamment noir et qui possède une résistance à la corrosion et une adhérence suffisamment élevées au niveau d'une partie traitée ; et un procédé de fabrication d'une telle tôle d'acier revêtue. La présente invention, afin d'atteindre l'objectif, porte sur une tôle d'acier revêtue comprenant, séquentiellement disposées dans celle-ci : une tôle d'acier ; une couche de placage de zinc ; une couche traitée au phosphate qui est déposée à hauteur de 2,02 à 7,0 g/m2 et dans laquelle la quantité déposée totale de Ni et Co va de 202 à 100 mg/m2 ; un revêtement d'étanchéité sans chrome contenant un oxoate d'un métal du groupe 4, et un métal du groupe 1 ou un sel de celui-ci ; et un revêtement organique. La luminosité (L*) de la surface de la tôle d'acier revêtue est inférieure ou égale à 55.
PCT/JP2020/032350 2020-08-27 2020-08-27 Tôle d'acier revêtue et procédé de fabrication de tôle d'acier revêtue Ceased WO2022044195A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005126811A (ja) * 2003-10-01 2005-05-19 Nisshin Steel Co Ltd 耐食性，塗装性，接着性に優れた亜鉛系めっき鋼板
JP2014510837A (ja) * 2011-02-08 2014-05-01 日本パーカライジング株式会社 ジルコニウム酸化物で前処理された亜鉛表面の腐食性能を改善するためのプロセス及び組成物
WO2017002805A1 (fr) * 2015-07-02 2017-01-05 新日鐵住金株式会社 Tôle d'acier revêtue de noir
WO2019187945A1 (fr) * 2018-03-26 2019-10-03 日新製鋼株式会社 Liquide de traitement chimique et tôle d'acier chimiquement traitée
JP2020152986A (ja) * 2019-03-22 2020-09-24 日鉄日新製鋼株式会社 塗装鋼板および塗装鋼板の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005126811A (ja) * 2003-10-01 2005-05-19 Nisshin Steel Co Ltd 耐食性，塗装性，接着性に優れた亜鉛系めっき鋼板
JP2014510837A (ja) * 2011-02-08 2014-05-01 日本パーカライジング株式会社 ジルコニウム酸化物で前処理された亜鉛表面の腐食性能を改善するためのプロセス及び組成物
WO2017002805A1 (fr) * 2015-07-02 2017-01-05 新日鐵住金株式会社 Tôle d'acier revêtue de noir
WO2019187945A1 (fr) * 2018-03-26 2019-10-03 日新製鋼株式会社 Liquide de traitement chimique et tôle d'acier chimiquement traitée
JP2020152986A (ja) * 2019-03-22 2020-09-24 日鉄日新製鋼株式会社 塗装鋼板および塗装鋼板の製造方法

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