WO2022091481A1 - 缶用鋼板およびその製造方法 - Google Patents

缶用鋼板およびその製造方法 Download PDF

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WO2022091481A1
WO2022091481A1 PCT/JP2021/024578 JP2021024578W WO2022091481A1 WO 2022091481 A1 WO2022091481 A1 WO 2022091481A1 JP 2021024578 W JP2021024578 W JP 2021024578W WO 2022091481 A1 WO2022091481 A1 WO 2022091481A1
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steel sheet
chromium
silica
particle size
average particle
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PCT/JP2021/024578
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English (en)
French (fr)
Japanese (ja)
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祐介 中川
勇人 川村
洋一郎 山中
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Ｊｆｅスチール株式会社
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Priority to JP2021553151A priority Critical patent/JP7239014B2/ja
Priority to KR1020237011209A priority patent/KR20230061477A/ko
Priority to CN202180071412.2A priority patent/CN116438332A/zh
Publication of WO2022091481A1 publication Critical patent/WO2022091481A1/ja

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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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • 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
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

Definitions

  • the present invention relates to a steel sheet for cans and a method for manufacturing the same.
  • Patent Documents 1 and 2 have "a metal chromium layer and a chromium hydrated oxide layer on the surface of the steel sheet in this order from the steel sheet side", and further, the metal chromium layer is a steel sheet for cans having "granular protrusions”. Is disclosed.
  • the conventional steel sheets for cans disclosed in Patent Documents 1 and 2 have good weldability, for example.
  • chromium is hard and has a high coefficient of friction.
  • problems are likely to occur, for example, in the can manufacturing process.
  • the surface of the steel sheet for cans is in contact with some object (the surface of other steel sheets for cans, rolls of production lines, tools during processing, etc.), they may not slip or get caught in each other. be. That is, the slidability may be insufficient.
  • an object of the present invention is to provide a steel sheet for cans having excellent weldability and slidability and a method for manufacturing the same.
  • the surface of the steel plate has a metallic chromium layer and a chromium hydrated oxide layer in this order from the steel plate side, and the amount of the metallic chromium layer adhered is 50 to 150 mg / m 2 , and the chromium hydration.
  • the adhesion amount of the oxide layer in terms of chromium is 3 to 15 mg / m 2
  • the metal chromium layer includes a flat plate-shaped base and granular protrusions provided on the base, and is the same as the granular protrusions.
  • the average particle size D1 is 20 to 200 nm, the number density of the granular protrusions is 10 pieces / ⁇ m 2 or more, the chromium hydrated oxide layer contains silica, and the chromium hydrated oxide layer is contained.
  • the content of the silica in the above is 0.1 to 45 mg / m 2 in terms of SiO 2 , and is a steel plate for cans.
  • a method for producing a steel plate for a can which contains silica and the content of the colloidal silica in the second aqueous solution is 0.10 g / L or more in terms of SiO 2 .
  • FIG. 1 is a cross-sectional view schematically showing an example of a steel plate for a can. As shown in FIG. 1, it has a steel plate 2.
  • the steel sheet for can 1 further has a metal chromium layer 3 and a chromium hydrated oxide layer 4 on the surface of the steel sheet 2 in this order from the steel plate 2 side.
  • the metal chromium layer 3 includes a flat plate-shaped base portion 3a that covers the steel plate 2 and granular protrusions 3b provided on the base portion 3a.
  • the chromium hydrated oxide layer 4 is arranged on the metal chromium layer 3 so as to follow the shape of the granular protrusions 3b.
  • the type of steel sheet is not particularly limited. Usually, a steel plate used as a container material (for example, a low carbon steel plate or an extremely low carbon steel plate) can be used.
  • the manufacturing method and material of the steel sheet are not particularly limited. It is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling from the normal steel piece manufacturing process.
  • a metal chromium layer is arranged on the surface of the steel sheet described above.
  • Metallic chromium suppresses surface exposure of the steel sheet and improves corrosion resistance.
  • Adhesion amount The amount of the metal chromium layer adhered is 50 mg / m 2 or more, preferably 60 mg / m 2 or more, and more preferably 70 mg / m 2 or more because the corrosion resistance of the steel sheet for cans is excellent.
  • the adhesion amount is the adhesion amount per one side of the steel sheet (hereinafter, the same applies).
  • the amount of metallic chromium is too large, the high melting point metallic chromium covers the entire surface of the steel sheet, and the welding strength is significantly reduced and dust is generated significantly during welding, which may deteriorate the weldability.
  • the amount of the metal chromium layer adhered is 150 mg / m 2 or less, preferably 140 mg / m 2 or less, and more preferably 130 mg / m 2 or less because the weldability of the steel sheet for cans is more excellent.
  • the amount of adhesion of the metallic chromium layer and the amount of adhesion of the chromium hydrated oxide layer described later in terms of chromium are measured as follows. First, the amount of chromium (total amount of chromium) is measured for a steel sheet for cans on which a metallic chromium layer and a chromium hydrated oxide layer are formed, using a fluorescent X-ray apparatus. Next, the steel sheet for cans is subjected to an alkali treatment by immersing it in 7.5 N-NaOH at 90 ° C.
  • (alkali-soluble chromium amount) (total chromium amount)-(chromium amount after alkali treatment) is calculated, and the alkali-soluble chromium amount is used as the chromium-equivalent adhesion amount of the chromium hydrated oxide layer.
  • Such a metallic chromium layer includes a flat plate-shaped base and granular protrusions provided on the base. Next, each of these parts included in the metallic chromium layer will be described in detail.
  • the base of the metal chromium layer mainly covers the surface of the steel sheet to improve corrosion resistance.
  • the base of the metal chromium layer has a sufficient thickness so that when the steel plates for cans inevitably come into contact with each other during handling, the granular protrusions provided on the surface layer destroy the base and the steel plates are not exposed. Is preferable.
  • the amount of adhesion of the base of the metal chromium layer is preferably 30 mg / m 2 or more, and more preferably 40 mg / m 2 or more because the corrosion resistance of the steel sheet for cans is excellent.
  • the granular protrusions of the metal chromium layer are formed on the surface of the above-mentioned base portion, and reduce the contact resistance between the steel plates for cans to improve the weldability.
  • the estimation mechanism for reducing contact resistance is described below. Since the chromium hydrated oxide layer coated on the metallic chromium layer is a non-conductor film, it has a higher electrical resistance than metallic chromium and becomes an inhibitory factor for welding.
  • the granular protrusions When granular protrusions are formed on the surface of the base of the metal chromium layer, the granular protrusions destroy the chromium hydrated oxide layer due to the surface pressure at the time of contact between the steel plates for cans during welding, and the current-carrying point of the welding current. , And the contact resistance is greatly reduced.
  • the average particle size D1 of the granular protrusions of the metal chromium layer is 20 nm or more, preferably 40 nm or more, and more preferably 60 nm or more, because the weldability of the steel sheet for cans is excellent.
  • the average particle size D1 of the granular protrusions of the metal chromium layer is 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, further preferably 80 nm or less, still more preferably 70 nm, because the surface appearance of the steel sheet for cans is excellent.
  • the following are particularly preferred. It is considered that this is because the particle size of the granular protrusions is reduced, so that the absorption of light on the short wavelength side is suppressed and the scattering of reflected light is suppressed.
  • the number density of the granular protrusions of the metal chromium layer is 10 pieces / ⁇ m 2 or more, preferably 15 pieces / ⁇ m 2 or more, more preferably 20 pieces / ⁇ m 2 or more, and further preferably 30 pieces / ⁇ m 2 or more.
  • 50 pieces / ⁇ m 2 or more is particularly preferable, and 100 pieces / ⁇ m 2 or more is most preferable.
  • the number density of the granular protrusions of the metal chromium layer is preferably 10,000 pieces / ⁇ m 2 or less, more preferably 5,000 pieces / ⁇ m 2 or less, and 1, It is more preferably 000 pieces / ⁇ m 2 or less, and particularly preferably 800 pieces / ⁇ m 2 or less.
  • the particle size and the number density of the granular protrusions of the metallic chromium layer are determined as follows. First, carbon vapor deposition is performed on the surface of a steel sheet for cans on which a metallic chromium layer and a chromium hydrated oxide layer are formed to prepare an observation sample. Then, a photograph is taken with a scanning electron microscope (SEM) at a magnification of 20,000. The photograph taken is binarized using software (trade name: ImageJ) and image analysis is performed. Calculate back from the area occupied by the granular protrusions and convert to a perfect circle to obtain the particle size and number density. The average particle size D1 and the number density are the averages of the five fields of view.
  • SEM scanning electron microscope
  • Chromium hydrated oxide layer Chromium hydrate precipitates on the surface of the steel sheet at the same time as metallic chromium, improving corrosion resistance.
  • Chromium hydrated oxides include, for example, chromium oxides and chromium hydroxides.
  • the adhesion amount of the chromium hydrated oxide layer in terms of chromium is 3 mg / m 2 or more, preferably 4 mg / m 2 or more.
  • the adhesion amount of the chromium hydrated oxide layer in terms of chromium is 15 mg / m 2 or less, preferably 12 mg / m 2 or less, and 10 mg / m 2 or less, because the weldability of the steel sheet for cans is excellent. Is more preferable.
  • the method for measuring the amount of chromium-equivalent adhesion of the chromium hydrated oxide layer is as described above.
  • the chromium hydrated oxide layer contains silica (silicon oxide) inside or on the surface thereof.
  • Silica which is a hard fine particle, is present in the chromium hydrated oxide layer, which is the outermost layer of the steel sheet for cans, and when it comes into contact with the object, the wear of the metal chromium layer and the chromium hydrated oxide layer is reduced, or The coefficient of friction is reduced. As a result, it is presumed that the above effect can be obtained.
  • the silica content in the chromium hydrated oxide layer is 0.1 mg / m 2 in terms of SiO 2 , and 0.3 mg / m 2 or more.
  • 1.0 mg / m 2 or more is more preferable, and 1.5 mg / m 2 or more is further preferable.
  • the silica content in the chromium hydrated oxide layer is 45 mg / m 2 or less in terms of SiO 2 .
  • the silica content (SiO 2 equivalent) in the chromium hydrated oxide layer is preferably 30 mg / m 2 or less, more preferably 25 mg / m 2 or less, and 10 mg / m 2 or less because the weldability is more excellent. More preferably, 1.6 mg / m 2 or less is particularly preferable.
  • the silica content (SiO 2 equivalent) in the chromium hydrated oxide layer is determined as follows. First, a certain amount of colloidal silica having a known concentration is dropped on a filter paper and then sufficiently dried to prepare a standard sample. By measuring the Si intensity of the prepared standard samples using a fluorescent X-ray apparatus, a calibration curve showing the relationship between the Si intensity and the amount of SiO 2 is prepared. Next, the Si intensity of the chromium hydrated oxide layer is measured using a fluorescent X-ray apparatus, and the amount of SiO 2 is determined with reference to the prepared calibration curve. The determined amount of SiO 2 is defined as the silica content (converted to SiO 2 ) in the chromium hydrated oxide layer.
  • the average particle size D2 of silica is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, because the slidability of the steel sheet for cans is more excellent.
  • the average particle size D2 of silica is preferably 200 nm or less, more preferably 180 nm or less, and even more preferably 160 nm or less.
  • the average particle size D2 of silica contained in the chromium hydrated oxide layer is determined as follows. The surface of the chromium hydrated oxide layer is observed at a magnification of 20,000 using an SEM (scanning electron microscope) to obtain an SEM image. Si is analyzed by element mapping using an EDX (energy dispersive X-ray analysis) device attached to the SEM, and silica in the obtained SEM image is identified. For the specified silica, the particle size is determined in terms of a perfect circle using software (trade name: ImageJ). The average particle size D2 is the average of 5 fields of view.
  • colloidal silica is used as a raw material in the production of steel sheets for cans, and this colloidal silica serves as silica for the chromium hydrated oxide layer.
  • the average particle size of colloidal silica used as a raw material may be regarded as the average particle size D2 of the silica of the chromium hydrated oxide layer.
  • the ratio D1 / D2 (hereinafter, also referred to as “particle size ratio D1 / D2”) between the average particle size D1 of the granular protrusions of metallic chromium and the average particle size D2 of silica is preferably 0.2 or more, and is 0.4. The above is more preferable, and 0.6 or more is further preferable.
  • the particle size ratio D1 / D2 is in this range, the effect of improving the slidability is easily maintained over time, and the slidability is more excellent.
  • the reason is presumed as follows. First, since silica is present in the chromium hydrated oxide layer, which is the outermost layer of the steel sheet for cans, it is generally easily desorbed by being rubbed in contact with an object. However, a recess is formed between the granular protrusions of the metallic chromium layer, and when silica is contained in the recess, the silica is difficult to be detached. Moreover, even if it is detached, it is easy to enter the recess again. Therefore, the effect of improving the slidability of silica is likely to be maintained. That is, it has excellent silica retention. When the particle size ratio D1 / D2 is within the above range, good silica retention is exhibited and excellent slidability is easily maintained.
  • the silica in the recess is in a state where it is easy to come into contact with the object (first contact with the object). That is, it is preferable that the granular protrusions are not too large with respect to the size of silica. Therefore, the particle size ratio D1 / D2 is preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.5 or less, and particularly preferably 3.0 or less. Within this range, the slidability of the steel sheet for cans is more excellent.
  • the steel plate is subjected to the first treatment (cathode electrolysis treatment C1, anodic electrolysis treatment A1 and cathode electrolysis treatment C2) using the first aqueous solution containing a hexavalent chromium compound and a fluorine-containing compound.
  • a second treatment immersion treatment or cathode electrolysis treatment C3 is performed using the second aqueous solution.
  • the second aqueous solution is an aqueous solution containing a certain amount of colloidal silica and having a small amount of Cr.
  • the chromium hydrated oxide layer is generated by the first treatment, and then colloidal silica (silica) is dispersed inside or on the surface of the chromium hydrated oxide layer by the second treatment. Be done. That is, the colloidal silica contained in the second aqueous solution becomes the silica of the chromium hydrated oxide layer.
  • the amount of each precipitation can be controlled by the conditions of each treatment.
  • the cathode electrolytic treatment C1, the anodic electrolytic treatment A1 and the cathode electrolytic treatment C2 are applied to the steel sheet in this order using the first aqueous solution.
  • the first aqueous solution contains at least a hexavalent chromium compound and a fluorine-containing compound.
  • hexavalent chromium compound examples include chromium trioxide (CrO 3 ); dichromate such as potassium dichromate (K 2 Cr 2 O 7 ); and chromate such as potassium dichromate (K 2 CrO 4 ). ; Etc. can be mentioned.
  • Fluorine-containing compounds include, for example, hydrofluoric acid (HF), potassium fluoride (KF), sodium fluoride (NaF), hydrofluoric acid (H2 SiF 6 ) and / or salts thereof.
  • Examples of the salt of sodium fluorosilicate include sodium silica (Na 2 SiF 6 ), potassium fluorosilicate (K 2 SiF 6 ), ammonium silica fluoride ((NH 4 ) 2 SiF 6 ) and the like.
  • the amount of Cr is preferably 0.50 mol / L or more, more preferably 0.80 mol / L or more.
  • the amount of Cr is preferably 3.00 mol / L or less, more preferably 2.50 mol / L or less.
  • the amount of F is preferably 0.020 mol / L or more, more preferably 0.080 mol / L or more.
  • the amount of F is preferably 0.480 mol / L or less, more preferably 0.400 mol / L or less.
  • the first aqueous solution may further contain sulfuric acid.
  • Sulfuric acid may be a sulfate salt such as sodium sulfate, calcium sulfate, and ammonium sulfate in whole or in part.
  • the fluorine-containing compound and sulfuric acid in the aqueous solution exist in a dissociated state into fluoride ions, sulfate ions and hydrogen sulfate ions. These act as catalysts involved in the reduction reaction and oxidation reaction of hexavalent chromium ions present in the aqueous solution, which proceed in the cathode electrolysis treatment and the anodic electrolysis treatment.
  • the amount of chromium-equivalent adhesion of the chromium hydrated oxide layer of the obtained steel sheet for cans can be reduced. It is considered that this is because the amount of chromium oxide produced decreases as the amount of anion increases.
  • the SO4-2 amount in the first aqueous solution is preferably 0.0001 mol / L or more, more preferably 0.0003 mol / L or more, and 0.0010 mol / L or more. More preferred. On the other hand, the amount of SO 4-2 is preferably 0.1000 mol / L or less, more preferably 0.0500 mol / L or less.
  • the liquid temperature of the first aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher. On the other hand, the liquid temperature is preferably 80 ° C. or lower, more preferably 60 ° C. or lower.
  • Cathode electrolysis treatment C1 precipitates metallic chromium and chromium hydrated oxide.
  • the electric quantity density (product of the current density and the energization time) of the cathode electrolytic treatment C1 is preferably 15 C / dm 2 or more, more preferably 20 C / dm 2 or more, and 25 C. / Dm 2 or more is more preferable.
  • the electric energy density of the cathode electrolysis treatment C1 is preferably 50 C / dm 2 or less, more preferably 45 C / dm 2 or less, and further preferably 35 C / dm 2 or less.
  • the current density (unit: A / dm 2 ) and energization time (unit: sec.) Of the cathode electrolysis treatment C1 are appropriately set from the above-mentioned electric quantity density.
  • Anode electrolysis treatment A1 dissolves the metallic chromium precipitated in the cathode electrolysis treatment C1 to form a site where granular protrusions of the metallic chromium layer are generated in the cathode electrolysis treatment C2.
  • the dissolution in the anode electrolysis treatment A1 is too strong or too weak, the number of generated sites decreases, the number density of the granular protrusions decreases, or the dissolution progresses unevenly and the distribution of the granular protrusions varies. It may occur or the thickness of the base of the metal chromium layer may be reduced.
  • the electric quantity density (product of current density and energization time) of the anode electrolysis treatment A1 is preferably 0.1 C / dm 2 or more, more preferably 0.3 C / dm 2 or more, and 0.3 C / dm. More than dm 2 is more preferred.
  • the electric energy density of the anode electrolysis treatment A1 is preferably less than 5.0 C / dm 2 , more preferably 3.0 C / dm 2 or less, and further preferably 2.0 C / dm 2 or less.
  • the current density (unit: A / dm 2 ) and energization time (unit: sec.) Of the anode electrolysis treatment A1 are appropriately set from the above-mentioned electric quantity density.
  • the cathode electrolysis treatment precipitates metallic chromium and chromium hydrated oxide.
  • the cathode electrolysis treatment C2 generates granular protrusions of the metal chromium layer starting from the above-mentioned generation site. At this time, if the electric energy density is too high, the granular protrusions of the metallic chromium layer may grow rapidly and the particle size may become coarse.
  • the current density of the cathode electrolysis treatment C2 is preferably less than 60.0 A / dm 2 , more preferably less than 50.0 A / dm 2 , and further preferably less than 40.0 A / dm 2 .
  • the current density of the cathode electrolysis treatment C2 is preferably 10 A / dm 2 or more, and more preferably more than 15.0 A / dm 2 .
  • the electric energy density (product of current density and energization time) of the cathode electrolysis treatment C2 is preferably less than 30.0 C / dm 2 and more preferably 25.0 C / dm 2 or less.
  • the electric energy density of the cathode electrolysis treatment C2 is preferably 1.0 C / dm 2 or more, and more preferably 2.0 C / dm 2 or more.
  • the energization time (unit: sec.) Of the cathode electrolysis treatment C2 is appropriately set from the above-mentioned electric energy density.
  • the cathode electrolysis treatment C1, the anode electrolysis treatment A1 and the cathode electrolysis treatment C2 do not have to be continuous electrolysis treatment. That is, in industrial production, it may be an intermittent electrolysis treatment in which a non-energized immersion time is inevitably present by electrolyzing the electrodes separately. In the case of intermittent electrolysis treatment, it is preferable that the total electric quantity density is within the above range.
  • the steel sheet that has undergone the first treatment is subjected to a dipping treatment or a cathode electrolysis treatment C3 using a second aqueous solution containing colloidal silica.
  • silica adheres to the inside or the surface of the chromium hydrated oxide layer produced by the first treatment.
  • the second aqueous solution contains colloidal silica.
  • the colloidal silica is not particularly limited, but colloidal silica in which the dispersion medium is water is preferable from the viewpoint of stability, and specific examples thereof include the Snowtex series manufactured by Nissan Chemical Industries, Ltd.
  • the average particle size of colloidal silica contained in the second aqueous solution can be regarded as the average particle size D2 of the silica of the chromium hydrated oxide layer.
  • the average particle size of colloidal silica is less than 10 nm, it is calculated from the specific surface area obtained by the BET method.
  • the specific surface area is measured by the BET method using nitrogen gas in accordance with JIS Z 8830: 2013. In the case of 10 to 100 nm, it is calculated from the specific surface area obtained by the Sears method.
  • the Sears method is a method for determining the specific surface area by titration using sodium hydroxide, which is described in Analytical Chemistry, Vol. 28, No. 12, December 1956, pp. 1981-1983. be. If it exceeds 100 nm, it is determined by using a laser diffraction method. More specifically, the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction method is defined as the average particle size.
  • the content of colloidal silica in the second aqueous solution is 0.10 g / L or more, preferably 0.20 g / L or more, and more preferably 0.30 g / L or more in terms of SiO 2 .
  • the upper limit is not particularly limited.
  • the content of colloidal silica in the second aqueous solution is preferably 40 g / L or less, more preferably 30 g / L or less, still more preferably 20 g / L or less in terms of SiO 2 .
  • the present invention is not limited to these, and can be appropriately adjusted according to the desired silica content.
  • the second aqueous solution is preferably different from the first aqueous solution in order to stably disperse colloidal silica in water. Therefore, the amount of Cr in the second aqueous solution is preferably less than 0.50 mol / L, more preferably 0.45 mol / L or less, and even more preferably 0.40 mol / L or less.
  • a second aqueous solution may be prepared.
  • the cathode electrolysis treatment C3 is carried out instead of the dipping treatment.
  • colloidal silica may be added to the water (rinse solution) used for the washing to prepare a second aqueous solution.
  • the second treatment is not the cathode electrolysis treatment C3 but the immersion treatment.
  • the liquid temperature of the second aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher.
  • the upper limit is not particularly limited.
  • the liquid temperature of the second aqueous solution is preferably 80 ° C. or lower, more preferably 60 ° C. or lower.
  • the present invention is not limited to these, and can be appropriately adjusted according to the desired silica content.
  • the immersion time is preferably 0.20 seconds or longer, more preferably 0.80 seconds or longer, still more preferably 1.20 seconds or longer. ..
  • the upper limit is not particularly limited.
  • the immersion time is preferably 10.00 seconds or less, more preferably 8.00 seconds or less, still more preferably 6.00 seconds or less.
  • the present invention is not limited to these, and can be appropriately adjusted according to the desired silica content.
  • Cathode electrolysis treatment C3 Using the steel sheet that has undergone the first treatment as a cathode, an electrolytic treatment is carried out in a second aqueous solution containing a hexavalent chromium compound in the same manner as the above-mentioned cathode electrolytic treatment C1 and cathode electrolytic treatment C2. As a result, silica adheres to the chromium hydrated oxide layer, and for example, the amount of the chromium hydrated oxide layer can be increased.
  • the electrolytic conditions (electricity density, etc.) of the cathode electrolytic treatment C3 are not particularly limited from the viewpoint of the silica content in the chromium hydrated oxide layer, but by adjusting this, the chromium hydrated oxide layer adheres. You can control the amount.
  • the electric energy density (product of current density and energization time) of the cathode electrolysis treatment C3 is preferably 5 C / dm 2 or more, and more preferably 10 C / dm 2 or more.
  • the electric energy density of the cathode electrolysis treatment C3 is preferably 30 C / dm 2 or less, and more preferably 20 C / dm 2 or less.
  • the current density (unit: A / dm 2 ) and energization time (unit: sec.) Of the cathode electrolysis treatment C3 are appropriately set from the above-mentioned electric quantity density.
  • ⁇ Making steel sheets for cans> A steel sheet manufactured with a plate thickness of 0.20 mm (furnishing degree: T5CA, surface roughness Ra: 0.25 ⁇ m) was subjected to normal degreasing and pickling.
  • the first treatment and the second treatment were carried out on this steel sheet using the aqueous solution shown in Table 1 below. More specifically, first, the aqueous solution A is circulated in a flow cell by a pump at an equivalent rate of 100 mpm, a lead electrode is used, and the first treatment (cathode electrolysis treatment C1, anodic electrolysis treatment A1 and cathode) is performed under the conditions shown in Table 2 below. Electrolytic treatment C2) was performed.
  • Comparative Example 3 the anode electrolysis treatment A1 and the cathode electrolysis treatment C2 were not performed (“ ⁇ ” is described in the corresponding column in Table 2 below). Then, using any of the aqueous solutions B1 to G, the second treatment (immersion treatment or cathode electrolysis treatment C3) was performed under the conditions shown in Table 2 below (the treatment column of the one not performed in Table 2 below). "-" Is described). In this way, a steel plate for cans was produced. The prepared steel sheet for cans was washed with water and dried at room temperature using a blower.
  • the results are shown in Table 2 below.
  • the average particle size D2 and the particle size ratio D1 / D2 of silica are also shown in Table 2 below.
  • the silica average particle size D2 (see Table 2 below) of the produced steel sheet for cans was the same as the average particle size of colloidal silica used as a raw material (see Table 1 below).
  • ⁇ Sliding property 1 The coefficient of static friction was measured on the surface (target surface) of the produced steel sheet for cans by an inclination method based on JIS P 8147: 2010. More specifically, a sample cut out from a steel plate for a can was placed on a table with the target surface as the table side. A weight of 150 g was placed on the surface of the sample opposite to the target surface, the table was tilted, the static friction force was calculated from the angle of the table at the time when the sample started to move, and the static friction coefficient was obtained. From the obtained static friction coefficient, the slidability was evaluated according to the following criteria. If it is " ⁇ ", " ⁇ " or " ⁇ ", it can be evaluated as having excellent slidability.
  • ⁇ Static friction coefficient less than 0.25 ⁇ : Static friction coefficient 0.25 or more and less than 0.30 ⁇ : Static friction coefficient 0.30 or more and less than 0.45 ⁇ : Static friction coefficient 0.45 or more and less than 0.55 ⁇ : Static friction coefficient 0 .55 or more
  • ⁇ Dynamic friction coefficient less than 0.20 ⁇ : Dynamic friction coefficient 0.20 or more and less than 0.25 ⁇ : Dynamic friction coefficient 0.25 or more and less than 0.30 ⁇ : Dynamic friction coefficient 0.30 or more and less than 0.45 ⁇ : Dynamic friction coefficient 0 .45 or more
  • Comparative Example 1 is an example in which the aqueous solution B1 containing no colloidal silica was used as the second aqueous solution, but the chromium hydroxide layer did not contain silica and the slidability was insufficient.
  • Invention Example 1 in which the immersion treatment was carried out as the second treatment is more chromium hydrated oxide than Invention Example 2 in which the cathode electrolysis treatment C3 was carried out as the second treatment.
  • the amount of layer adhesion was small, and the weldability was better.
  • Invention Example 1 and Invention Example 5 were equally good in slidability and weldability.
  • Comparative Example 2 is an example in which the aqueous solution E1 having a low colloidal silica content was used as the second aqueous solution, but the silica content in the chromium hydroxide layer was as low as less than 0.1 mg / m 2 , and sliding. The sex was insufficient.
  • Invention Example 1 and Invention Example 7 were equally good in slidability and weldability.
  • Invention Example 8 having a silica content of 1.5 mg / m 2 in the chromium hydroxide layer has an invention example having a silica content of 1.4 mg / m 2 .
  • the slidability was better than that of 1.
  • the average particle size D2 of silica is as large as 220 nm, and the silica content is as high as 45.6 mg / m 2 . Therefore, the weldability was insufficient.
  • Invention Example 15 and Invention Example 16 had good slidability and weldability as in Invention Example 9 and Invention Example 10.
  • Invention Examples 18 to 20 in which the particle size ratio D1 / D2 is in the range of 0.6 to 3.0 are compared with Invention Example 17, Invention Example 21 and Invention Example 22 which do not satisfy this. Therefore, the evaluation result of the slidability 3 was good.

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62146295A (ja) * 1985-12-21 1987-06-30 Nippon Steel Corp 金属の表面処理方法
JPH0431036B2 (ko) * 1986-09-12 1992-05-25
JPH0941193A (ja) * 1995-07-28 1997-02-10 Kawasaki Steel Corp 潤滑性および耐食性に優れたクロメート処理亜鉛系めっき鋼板、およびその製造方法

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JP3048177B2 (ja) * 1990-12-13 2000-06-05 日本化薬株式会社 マイクロカプセルの製造方法
ES2846953T3 (es) 2015-12-11 2021-07-30 Jfe Steel Corp Lámina de acero para latas y método de producción de láminas de acero para latas
US10753005B2 (en) 2015-12-11 2020-08-25 Jfe Steel Corporation Steel sheet for cans and production method for steel sheet for cans

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62146295A (ja) * 1985-12-21 1987-06-30 Nippon Steel Corp 金属の表面処理方法
JPH0431036B2 (ko) * 1986-09-12 1992-05-25
JPH0941193A (ja) * 1995-07-28 1997-02-10 Kawasaki Steel Corp 潤滑性および耐食性に優れたクロメート処理亜鉛系めっき鋼板、およびその製造方法

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