WO2022085721A1 - Ｚｎ系めっき鋼板 - Google Patents

Ｚｎ系めっき鋼板 Download PDF

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Publication number
WO2022085721A1
WO2022085721A1 PCT/JP2021/038767 JP2021038767W WO2022085721A1 WO 2022085721 A1 WO2022085721 A1 WO 2022085721A1 JP 2021038767 W JP2021038767 W JP 2021038767W WO 2022085721 A1 WO2022085721 A1 WO 2022085721A1
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Prior art keywords
region
plating layer
chemical conversion
steel sheet
conversion treatment
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Application number
PCT/JP2021/038767
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English (en)
French (fr)
Japanese (ja)
Inventor
哲也 鳥羽
邦彦 東新
敦司 森下
Original Assignee
日本製鉄株式会社
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Application filed by 日本製鉄株式会社 filed Critical 日本製鉄株式会社
Priority to JP2022503921A priority Critical patent/JP7047993B1/ja
Priority to KR1020237011851A priority patent/KR102626695B1/ko
Priority to CN202180070204.0A priority patent/CN116406430B/zh
Publication of WO2022085721A1 publication Critical patent/WO2022085721A1/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/18—Alloys based on aluminium with copper as the next major constituent with zinc
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • 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 Zn-based plated steel sheet.
  • This application claims priority based on Japanese Patent Application No. 2020-176149 filed in Japan on October 20, 2020, the contents of which are incorporated herein by reference.
  • Zn-based plated steel sheet is the most used plated steel sheet with good corrosion resistance.
  • Zn-based galvanized steel sheets are used in various manufacturing industries such as automobiles, home appliances, and building materials. Among them, the amount of plating to which Al is added has been increasing in recent years because of its high corrosion resistance.
  • Patent Document 1 describes a molten Zn-Al-Mg-Si plated steel sheet. Since the appearance of this plated steel sheet has a satin finish, it is also characterized by its excellent appearance.
  • the present invention has been made in view of the above circumstances, and in a Zn-based plated steel sheet containing Al, even when the plated surface is partially or wholly blackened, the blackening is not noticeable and the metal appearance is reduced. It is an object of the present invention to provide a Zn-based plated steel sheet which can maintain the above-mentioned properties and has improved corrosion resistance and weather resistance.
  • the present inventors have diligently studied, and by incorporating a pigment in the chemical conversion treatment layer, the blackened portion on the surface of the plating layer is made inconspicuous, and the metallic appearance of the surface of the plating layer is improved. I found that I could not damage it.
  • the present invention adopts the following configuration.
  • a chromate-free chemical conversion treatment layer having an adhesion amount of 0.1 to 15 g / m 2 per side, which is arranged on the Zn-based plating layer, is provided.
  • the chemical conversion treatment layer contains 20% by mass or more of a resin, 1 to 20% by mass of silica particles having an average particle size of 5 to 200 nm, and a pigment containing one or more of Cu, Co or Fe.
  • Is contained When the appearance is evaluated in the CIE1976 (L * , a * , b * ) color space, b * is -30 or more and -2 or less, and the 60 degree mirror gloss G s (60 °) specified in JIS Z 8741: 1997. ) Is 50 to 200, and is a Zn-based galvanized steel sheet showing a metallic appearance.
  • System plated steel plate wherein the pigment is one or more of copper (II) phthalocyanine, cobalt (II) phthalocyanine, copper sulfate, cobalt sulfate, iron sulfate or iron oxide.
  • the mixing ratio of the silica particles and the pigment in the chemical conversion treatment layer is the Si conversion amount [Si] of the silica particles and the Cu conversion amount [Cu], Co conversion amount [Co] of the pigment. [1] or [2], wherein [Si] / ([Cu] + [Co] + [Fe]) is in the range of 1 to 200 when expressed as an Fe conversion amount [Fe].
  • the resin in the chemical conversion treatment layer contains any one or more of a polyolefin resin, a fluororesin, an acrylic resin, a urethane resin, a polyester resin, an epoxy resin, and a phenol resin, [1] to The Zn-based plated steel sheet according to any one of [5].
  • the Zn-based plating layer contains Al: 4% by mass or more and 22% by mass or less, Mg: 1% by mass or more and 10% by mass or less, and the balance is Zn and impurities in an average composition [1].
  • the Zn-based plating layer is further characterized by containing 0.0001 to 2% by mass in total of any one or more of Ni, Sb, and Pb in an average composition [1].
  • a patterned portion and a non-patterned portion arranged so as to have a predetermined shape are formed on the Zn-based plating layer.
  • the patterned portion and the non-patterned portion include one or two of a first region and a second region determined by any of the following determination methods 1 to 5, respectively. Any one of [1] to [9], wherein the absolute value of the difference between the area ratio of the first region in the pattern portion and the area ratio of the first region in the non-pattern portion is 30% or more.
  • [Determination method 1] Virtual grid lines are drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and in each of the plurality of regions partitioned by the virtual grid lines, the inside of a circle having a diameter of 0.5 mm centered on the center of gravity of each region is formed.
  • the measurement area A is used, and the L * value in each measurement area A is measured.
  • the reference L * value is used as the region where the L * value is equal to or greater than the reference L * value.
  • One area, the area less than the standard L * value is defined as the second area.
  • [Determination method 2] Virtual grid lines are drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and in each of the plurality of regions partitioned by the virtual grid lines, the inside of a circle having a diameter of 0.5 mm centered on the center of gravity of each region is formed.
  • the measurement area A is used, and the L * value in each measurement area A is measured.
  • the area where the L * value is 45 or more is defined as the first area, and the area where the L * value is less than 45 is defined as the second area.
  • [Determination method 3] Virtual grid lines are drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and the arithmetic mean height Sa2 is measured in each of the plurality of regions partitioned by the virtual grid lines.
  • the region where the obtained arithmetic mean height Sa2 is 1 ⁇ m or more is defined as the first region, and the region where the obtained arithmetic mean height Sa2 is less than 1 ⁇ m is defined as the second region.
  • the region having an orientation ratio of 3.5 or more is referred to as a first region, and the region having an orientation ratio of less than 3.5 is referred to as a second region.
  • Virtual grid lines are drawn on the surface of the Zn-based plating layer at 1 mm intervals, and then a circle S centered on the center of gravity point G of each region is drawn for each of a plurality of regions partitioned by the virtual grid lines.
  • the diameter R of the circle S is set so that the total length of the surface boundary lines of the Zn-based plating layer contained inside the circle S is 10 mm.
  • the average value of the maximum diameter Rmax and the minimum diameter Rmin among the diameters R of the circles S in a plurality of regions is defined as the reference diameter Rave, and the region having the circle S in which the diameter R is less than the reference diameter Rave is defined as the first region.
  • the region where R has a circle S having a reference diameter Rave or more is defined as a second region.
  • a Zn-based plated steel sheet containing Al blackening occurs even when the plated surface is partially or wholly blackened due to oxidation of Al contained in the plating layer. It is possible to provide a Zn-based plated steel sheet which can maintain a metallic appearance inconspicuously and has improved corrosion resistance and weather resistance.
  • the present inventors have found that by incorporating a pigment into the chemical conversion treatment layer and coloring the chemical conversion treatment layer in blue, the blackened portion generated on the surface of the plating layer becomes inconspicuous. However, if the blue color is too dark, it becomes difficult to visually recognize the metallic appearance of the surface of the plating layer. It was also found that the visibility of the blackened portion and the visibility of the metal appearance change depending on whether the incident light is reflected on the surface of the plating layer or the incident light is reflected on the surface of the chemical conversion treatment layer. ..
  • the b * value when evaluated in the CIE1976 (L * , a * , b * ) color space and the 60-degree mirror gloss G s (60 °) specified in JIS Z 8741: 1997 were obtained. It has been found that by controlling the plating layer so as to be within a predetermined range, the blackened portion generated on the surface of the plating layer is made inconspicuous and the appearance of the metal can be visually recognized. In addition, by controlling the b * value and the 60-degree mirror gloss G s (60 °), even if an arbitrary shape such as a character is represented on the surface of the plating layer, the arbitrary shape can be easily seen. I found it.
  • the Zn-based plated steel plate of the embodiment of the present invention includes a steel plate, a Zn-based plating layer containing 0.05 to 60% by mass of Al and Zn arranged on at least one side of the steel plate, and Zn-based plating.
  • the pigment is one or more of copper (II) phthalocyanine, cobalt (II) phthalocyanine, copper sulfate, cobalt sulfate, iron sulfate or iron oxide. Is preferable.
  • the mixing ratio of the silica particles and the pigment in the chemical conversion treatment layer is the Si conversion amount [Si] of the silica particles and the Cu conversion amount [Cu] and Co conversion of the pigment.
  • Si conversion amount [Si] of the silica particles and the Cu conversion amount [Cu] and Co conversion of the pigment When expressed as an amount [Co] or an Fe-converted amount [Fe], [Si] / ([Cu] + [Co] + [Fe]) is preferably in the range of 1 to 200.
  • the units of Si-converted amount, Cu-converted amount, Co-converted amount, and Fe-converted amount are "g / m 2 ".
  • the arithmetic average roughness Ra of the Zn-based plated layer is 0.5 to 2.0 ⁇ m, and the arithmetic average height Sa of the chemical conversion treatment layer is 5 nm to 100 nm. Is preferable.
  • the material of the steel sheet used as the base of the Zn-based plating layer is not particularly limited.
  • general steel or the like can be used without particular limitation, Al killed steel or some high alloy steel can also be applied, and the shape is not particularly limited.
  • the Zn-based plating layer preferably contains 0.05 to 60% by mass of Al and Zn, and more preferably contains 0.05 to 60% by mass of Al, and the balance is made of Zn and impurities. ..
  • the Zn-based plating layer may contain 40% by mass or more of Zn.
  • the Zn-based plating layer of the present embodiment may contain Al: 4 to 22% by mass and Mg: 1 to 10% by mass in an average composition, and may be composed of Zn and impurities as the balance. Further, the Zn-based plating layer may contain Si: 0.0001 to 2% by mass in an average composition.
  • the Al content is in the range of 4 to 22% by mass. Al may be contained in order to ensure corrosion resistance. When the Al content in the Zn-based plating layer is 4% by mass or more, the effect of improving the corrosion resistance is further enhanced. When the Al content is 22% by mass or less, the effect of improving corrosion resistance and weather resistance can be easily ensured while maintaining the metal appearance.
  • the Mg content is in the range of 1 to 10% by mass. Mg may be contained in order to improve corrosion resistance. When the Mg content in the Zn-based plating layer is 1% by mass or more, the effect of improving the corrosion resistance is further enhanced. When the Mg content is 10% by mass or less, the generation of dross in the plating bath can be suppressed, and the adhesion of dross to the plating can suppress the occurrence of places where the plating is not normally formed, resulting in a decrease in corrosion resistance. It can be suppressed.
  • the Mg content may be 0%. That is, the Zn-based plating layer of the Zn-based plated steel sheet of the present embodiment is not limited to the Zn—Al—Mg-based hot-dip plating layer, and may be a Zn-Al-based hot-dip plating layer.
  • the Zn-based plating layer may contain Si in the range of 0.0001 to 2% by mass. Since Si may improve the adhesion of the Zn-based plating layer, Si may be contained. Since the effect of improving the adhesion is exhibited by containing 0.0001% by mass or more, preferably 0.001% or more, more preferably 0.01% or more of Si, the content of Si is 0.0001% by mass or more. It is preferable to let it. On the other hand, even if Si is contained in an amount of more than 2% by mass, the effect of improving the plating adhesion is saturated, so the content of Si is set to 2% by mass or less. From the viewpoint of plating adhesion, the Si content may be in the range of 0.001 to 1% by mass or 0.01 to 0.8% by mass.
  • the Zn-based plating layer may contain one or more of Ni, Sb, and Pb in a total amount of 0.0001 to 2% by mass, preferably 0.001 to 2% by mass, in terms of average composition. By containing these elements, the corrosion resistance can be further improved.
  • the rest of the chemical components of the Zn-based plating layer are zinc (Zn) and impurities.
  • Impurities include those that are inevitably contained in zinc and other bullions, and those that are contained by melting steel in a plating bath.
  • the average composition of the Zn-based plating layer can be measured by the following method. First, the chemical conversion treatment layer is removed with a coating film stripping agent that does not erode the plating (for example, Neo River SP-751 manufactured by Sansai Kako Co., Ltd.). If a surface coating film is present on the chemical conversion treatment layer, the surface coating film is also removed. Then, it can be obtained by dissolving the Zn-based plating layer with hydrochloric acid containing an inhibitor (for example, Hiviron manufactured by Sugimura Chemical Industrial Co., Ltd.) and subjecting the obtained solution to inductively coupled plasma (ICP) emission spectroscopic analysis.
  • ICP inductively coupled plasma
  • the surface of the Zn-based plating layer has any one or two or more elements of Co, Fe, and Ni.
  • Co, Fe, and Ni are attached to the surface of the Zn-based plating layer by performing Co treatment, Fe treatment, or Ni treatment after the formation of the Zn-based plating layer.
  • these elements are present on the surface of the Zn-based plating layer, blackening resistance can be improved.
  • Co, Fe or Ni is present on the surface of the Zn-based plating layer in the form of a compound.
  • the chemical conversion treatment layer of the present embodiment contains 20% by mass or more of a resin, 1 to 20% by mass of silica particles having an average particle size of 5 to 200 nm, and one or more of Cu, Co or Fe. Contains pigments.
  • the chemical conversion treatment layer of the present embodiment is a film obtained by applying an aqueous composition containing a resin, silica particles, and a pigment to a Zn-based plating layer formed on a steel sheet and drying it.
  • the resin contained in the chemical conversion treatment layer may be a general resin, and examples thereof include a polyolefin resin, a fluororesin, an acrylic resin, a urethane resin, a polyester resin, an epoxy resin, and a phenol resin.
  • These resins may be water-soluble resins, or may be resins (water-dispersible resins) that are originally water-insoluble but can be finely dispersed in water such as emulsions and suspensions.
  • resins including resins that are originally water-insoluble but can be finely dispersed in water such as emulsions and suspensions are called resins.
  • the polyolefin resin is not particularly limited, and for example, ethylene and an unsaturated carboxylic acid such as methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid are radically polymerized under high temperature and high pressure, and then ammonia or amine.
  • an unsaturated carboxylic acid such as methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid are radically polymerized under high temperature and high pressure, and then ammonia or amine.
  • examples thereof include compounds obtained by neutralizing with a metal compound such as KOH, NaOH, LiOH or an ammonia or an amine compound containing the above metal compound and dispersing in water.
  • the fluororesin is not particularly limited, and examples thereof include a homopolymer or a copolymer of a fluoroolefin.
  • a copolymer a copolymer of a fluoroolefin and a fluoroolefin-containing monomer other than the fluoroolefin and / or a monomer having no fluorine atom can be mentioned.
  • the acrylic resin is not particularly limited, and for example, unsaturated monomers such as styrene, alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylates, and alkoxysilane (meth) acrylates can be used. Examples thereof include those obtained by radical polymerization using a polymerization initiator in an aqueous solution.
  • the polymerization initiator is not particularly limited, and for example, persulfates such as potassium persulfate and ammonium persulfate, and azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile can be used.
  • the urethane resin is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylolethane, and trimethylolpropane.
  • examples thereof include those obtained by reacting polyhydric alcohols with diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate, further extending the chain with diamine or the like, and dispersing in water.
  • the polyester resin is not particularly limited, and for example, ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane and the like.
  • Polyhydric alcohols and polybasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, sebacic acid, maleic anhydride, itaconic acid, fumaric acid, and hymic anhydride are dehydrated and condensed. Examples thereof include those obtained by neutralizing with ammonia, an amine compound, or the like and dispersing in water.
  • the epoxy resin is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, resorcin type epoxy resin, novolak.
  • a high acid value acrylic resin obtained by reacting an epoxy resin such as a type epoxy resin with an amine compound such as diethanolamine or N-methylethanolamine and neutralizing it with an organic acid or an inorganic acid or in the presence of the above epoxy resin. Is subjected to radical polymerization, neutralized with an ammonia, an amine compound, or the like, and dispersed in water.
  • the phenol resin is not particularly limited, and for example, phenol such as methylolated phenol resin obtained by addition-reacting formaldehyde with aromatics such as phenol, resorcin, cresol, bisphenol A, and paraxylylene dimethyl ether.
  • phenol such as methylolated phenol resin obtained by addition-reacting formaldehyde with aromatics such as phenol, resorcin, cresol, bisphenol A, and paraxylylene dimethyl ether.
  • examples thereof include those obtained by reacting a resin with an amine compound such as diethanolamine and N-methylethanolamine and neutralizing it with an organic acid or an inorganic acid.
  • the resin is contained in the chemical conversion treatment layer in a proportion of 20% by mass or more. By setting the resin content to 20% by mass or more, the chemical conversion treatment layer itself does not become brittle, and the Zn-based plating layer can be stably coated.
  • the chemical conversion treatment layer may contain components other than the resin such as Nb compound and phosphoric acid compound together with the resin, silica particles and pigment, and the content of the resin may be the balance of these components.
  • Silica particles are added to improve the corrosion resistance of the chemical conversion treatment layer.
  • the silica particles preferably have an average particle size in the range of 5 to 200 nm.
  • Silica particles are contained in the chemical conversion treatment layer in a proportion of 1 to 20% by mass. By setting the content of the silica particles to 1% by mass or more, the effect of improving the corrosion resistance can be obtained. Further, by setting the content of the silica particles to 20% by mass or less, the chemical conversion treatment layer itself does not become brittle, and the Zn-based plating layer can be stably coated.
  • the average particle size of the silica particles is large.
  • the lower limit is 5 nm or more.
  • the chemical conversion treatment layer may become cloudy and the metallic appearance of the Zn-based plating layer may be impaired.
  • the content of the silica particles is more preferably 3 to 15% by mass in the chemical conversion treatment layer from the viewpoint of maintaining both the corrosion resistance and the strength of the chemical conversion treatment layer.
  • an inorganic pigment such as silica particles since an inorganic pigment such as silica particles has a small particle size, it may exist in the chemical conversion treatment layer in the form of secondary particles having a particle size larger than the primary particle size.
  • the particle size of these secondary particles is hereinafter referred to as "secondary particle size".
  • the silica particles in the present embodiment may be a mixture of primary particles and secondary particles, and even if primary particles and secondary particles are mixed, the average particle size is in the range of 5 to 200 nm. All you need is.
  • the average particle size of the silica particles is more preferably 5 to 150 nm from the viewpoint of maintaining high permeability of the chemical conversion treatment layer.
  • the average particle size of silica in the chemical conversion treatment layer is measured by the following method.
  • a thin film sample of a chemical conversion treatment layer is prepared by a microtome method so that a cross section perpendicular to the rolling direction of the steel sheet of the present invention can be observed.
  • a 200 kV field emission transmission electron microscope (FE-TEM) was used in a region of 20 ⁇ m ⁇ t ⁇ m of the obtained thin film sample (a region having a thickness of 20 ⁇ m in the direction parallel to the plate width direction and a thickness of t ⁇ m in the plate thickness direction). Observe at least 5 areas at a magnification of 100,000 times.
  • the circle-equivalent diameters of all the silica particles in the observation region are calculated, and the circle-equivalent diameters are used as the particle diameters of the respective silica particles, and the average particle diameter is obtained by averaging them.
  • Circle equivalent diameter 2 ⁇ (S / ⁇ )... Equation 1
  • S is the area of the silica particles
  • ⁇ is the pi.
  • the content of silica particles in the chemical conversion treatment layer is measured by the following method. First, apart from the target sample, a plurality of comparative samples having a chemical conversion treatment layer having a known silica particle content were prepared, and the surfaces thereof were measured by a fluorescent X-ray apparatus, and the detection intensity of Si and silica obtained were measured. A calibration curve is drawn from the relationship of the particle content. Next, the target sample is measured with a fluorescent X-ray device under the same conditions as the comparative sample, and the content of silica particles is determined from the obtained Si detection intensity using the above calibration curve.
  • the average particle size in the state of water-dispersed silica before being dispersed in the paint is maintained even in the chemical conversion treatment layer, that value may be used.
  • titania particles, alumina particles, zirconia particles and the like may be contained in addition to the silica particles.
  • the chemical conversion treatment layer contains a pigment containing one or more Cu, Co or Fe.
  • the pigment may contain one kind of Cu, Co or Fe, or may contain two or more kinds of pigments.
  • the chemical conversion treatment layer may contain one kind of pigment containing one kind or two or more kinds of Cu, Co or Fe, or two or more kinds of pigments.
  • the pigment include copper (II) phthalocyanine, cobalt (II) phthalocyanine, copper sulfate, cobalt sulfate, iron sulfate or iron oxide.
  • the content of the pigment in the chemical conversion treatment layer is preferably in the range of 0.1 to 10% by mass.
  • the blackened portion on the surface of the Zn-based plating layer can be made inconspicuous.
  • the metallic appearance of the Zn-based plating layer is not impaired.
  • the content of the pigment is more preferably 0.1 to 5% by mass, still more preferably 0.1 to 3% by mass, from the viewpoint of maintaining the appearance of the metal.
  • the content of the pigment in the chemical conversion treatment layer is measured by the following method.
  • a thin film sample of a chemical conversion treatment layer is prepared by a microtome method so that a cross section perpendicular to the rolling direction of the Zn-based plated steel sheet of the present embodiment can be observed.
  • a 200 kV field emission transmission electron microscope (FE-TEM) was used in a region of 20 ⁇ m ⁇ t ⁇ m of the obtained thin film sample (a region having 20 ⁇ m in the direction parallel to the plate width direction and t ⁇ m in the plate thickness direction). At least 5 regions are observed at a magnification of 100,000 times, and element mapping is performed using an energy dispersive X-ray analyzer (EDS or EDX).
  • EDS energy dispersive X-ray analyzer
  • the area ratio of the region where Cu, Co or Fe exists is obtained.
  • the area ratio of the region where Cu, Co or Fe is present in a plurality of comparative samples having a chemical conversion treatment layer having a known pigment content is obtained, and the relationship with the pigment content is obtained.
  • the pigment colors the chemical conversion treatment layer blue to make the blackened portion on the surface of the Zn-based plating layer less noticeable, but if the chemical conversion treatment layer contains a pigment, the corrosion resistance of the chemical conversion treatment layer may decrease. .. Therefore, in order to prevent deterioration of the corrosion resistance of the chemical conversion treatment layer, it is preferable to optimize the mixing ratio of the silica particles and the pigment in the chemical conversion treatment layer of the present embodiment. That is, the mixing ratio (mass ratio) of the silica particles and the pigment in the chemical conversion treatment layer is the Si conversion amount [Si] (g / m 2 ) of the silica particles and the Cu conversion amount [Cu] (g / m) of the pigment.
  • [Si] / [Fe] is preferably in the range of 1 to 200.
  • [Si] / [Cu], [Si] / [Co] or [Si] / [Fe] are more preferably 10 to 150 from the viewpoint of preventing deterioration of appearance and maintaining both corrosion resistance.
  • [Si] / ([Cu] + [Co] + [Fe]) is in the range of 1 to 200.
  • the chemical conversion treatment layer may further contain either one or both of the Nb compound and the phosphoric acid compound.
  • the corrosion resistance of the Zn-based plating layer is improved.
  • niobium-containing compound As the Nb compound, a conventionally known niobium-containing compound can be used, and examples thereof include niobium oxide, niobium acid and salts thereof, fluoroniobate, fluorooxoniobate, and the like. Of these, niobium oxide is preferably used from the viewpoint of improving corrosion resistance.
  • Examples of the phosphoric acid compound include phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid and salts thereof; aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphon.
  • Phosphoric acids such as acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and salts thereof; organic phosphoric acids such as phytic acid and salts thereof can be mentioned.
  • the cation species of salts are not particularly limited, and examples thereof include Cu, Co, Fe, Mn, Sn, V, Mg, Ba, Al, Ca, Sr, Nb, Y, Ni and Zn. These may be used alone or in combination of two or more.
  • the Nb compound and the phosphoric acid compound are preferably contained in the chemical conversion treatment layer in a proportion of 0.5 to 30% by mass in total. If the content of the Nb compound or the phosphoric acid compound is 0.5% by mass or more, the effect of improving the corrosion resistance can be obtained, and if the content of the Nb compound or the phosphoric acid compound is 30% by mass or less, the chemical conversion treatment layer is brittle. However, the Zn-based plating layer can be stably coated.
  • the content of Nb compound and phosphoric acid compound in the chemical conversion treatment layer is measured by the following method. First, apart from the target sample, a plurality of comparative samples having a chemical conversion-treated layer having a known content of Nb compound or phosphoric acid compound were prepared, and the surfaces thereof were measured by a fluorescent X-ray device to obtain Nb or the like. A calibration line is drawn from the relationship between the detection intensity of P and the content of Nb compound and phosphoric acid compound. Next, the target sample is measured with a fluorescent X-ray device under the same conditions as the comparative sample, and the content of the Nb compound or the phosphoric acid compound is determined from the obtained Si detection intensity using the above calibration curve.
  • the amount of the chemical conversion treatment layer adhered to one side of the Zn-based plating layer is 0.1 to 15 g / m 2 .
  • the adhesion amount is 0.1 g / m 2 or more, the adhesion amount of the chemical conversion treatment layer is sufficient, the blackened portion on the surface of the Zn-based plating layer can be made inconspicuous, and the corrosion resistance of the Zn-based plating layer is further improved. Can be improved.
  • the adhesion amount is 15 g / m 2 or less, even if the pigment is contained in the chemical conversion treatment layer, the reflection of light on the surface of the chemical conversion treatment layer is reduced, and the metallic appearance of the surface of the Zn-based plating layer is improved. It is visible.
  • a more preferable adhesion amount is 0.2 to 2 g / m 2 .
  • the chemical conversion treatment layer may further contain at least one cross-linking agent selected from the group consisting of a silane coupling agent, a cross-linking zirconium compound and a cross-linking titanium compound. These may be used alone or in combination of two or more.
  • the adhesion between the Zn-based plating layer and the chemical conversion treatment layer is further improved. ..
  • the silane coupling agent is not particularly limited, and is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, and ⁇ -aminopropyltrimethoxysilane sold by Shin-Etsu Chemical Industry, Nippon Unicar, Chisso, Toshiba Silicone, and the like.
  • ⁇ -Aminopropylethoxysilane N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacry Loxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 2-( 3,4-Epoxycyclohexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) -(a
  • the crosslinkable zirconium compound is not particularly limited as long as it is a zirconium-containing compound having a plurality of functional groups capable of reacting with a carboxyl group or a hydroxyl group, but a compound soluble in water or an organic solvent is preferable, and the compound is water-soluble. More preferably, it is a zirconium compound. Examples of such a compound include zirconylammonium carbonate.
  • the crosslinkable titanium compound is not particularly limited as long as it is a titanium-containing compound having a plurality of functional groups capable of reacting with a carboxyl group or a hydroxyl group, but dipropoxy-bis (triethanol aminato) titanium and dipropoxy-bis (diethanol aminato).
  • the above-mentioned cross-linking agent may be used alone or in combination of two or more.
  • At least one cross-linking agent selected from the group consisting of the silane coupling agent, the cross-linking zirconium compound and the cross-linking titanium compound shall contain 0.1 to 50% by mass with respect to 100% by mass of the solid content of the resin. Is preferable. If the content of the cross-linking agent is less than 0.1% by mass, the effect of improving the adhesion may not be obtained, and if the content of the cross-linking agent exceeds 50% by mass, the stability of the aqueous composition becomes low. May decrease.
  • the chemical conversion treatment layer may further contain at least one cross-linking agent selected from the group consisting of an amino resin, a polyisocyanate compound, a block thereof, an epoxy compound and a carbodiimide compound. These cross-linking agents may be used alone or in combination of two or more.
  • the cross-linking density is increased and the barrier property of the chemical conversion treatment layer is improved. , Corrosion resistance is further improved.
  • the amino resin is not particularly limited, and examples thereof include melamine resin, benzoguanamine resin, urea resin, and glycoluril resin.
  • the polyisocyanate compound is not particularly limited, and examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and tolylene diisocyanate.
  • the blocked product is a blocked product of the polyisocyanate compound.
  • the epoxy compound is not particularly limited as long as it is a compound having a plurality of oxylan rings, and is, for example, adipinoic acid diglycidyl ester, phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, sorbitan polyglucidyl ether, pentaerythritol polyglycidyl ether.
  • Glycerin polyglycidyl ether trimethylpropane polyglycidyl ether, neopentyl glycol polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylenelen glycol diglycidyl ether, polypropylenelen glycol diglycidyl ether, 2,2-bis -(4'-Glysidyloxyphenyl) propane, tris (2,3-epoxypropyl) isocyanurate, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and the like can be mentioned.
  • an isocyanate-terminated polycarbodiimide is synthesized by a condensation reaction involving decarbonation of a diisocyanate compound such as an aromatic diisocyanate, an aliphatic diisocyanate, or an alicyclic diisocyanate, and then the reactivity with an isocyanate group is further increased.
  • a diisocyanate compound such as an aromatic diisocyanate, an aliphatic diisocyanate, or an alicyclic diisocyanate
  • examples thereof include compounds to which a hydrophilic segment having a functional group is added.
  • At least one cross-linking agent selected from the group consisting of the amino resin, the polyisocyanate compound, a block thereof, an epoxy compound and a carbodiimide compound contains 0.1 to 50% by mass with respect to 100% by mass of the solid content of the resin. It is preferable to do so. If the content of the cross-linking agent is less than 0.1% by mass, the effect of improving the corrosion resistance may not be obtained, and if the content of the cross-linking agent exceeds 50% by mass, the chemical conversion treatment layer becomes brittle and the corrosion resistance becomes poor. May decrease.
  • the chemical conversion treatment layer further contains at least one selected from the group consisting of vanadium compounds, tungsten compounds and molybdenum compounds. These may be used alone or in combination of two or more.
  • the corrosion resistance of the chemical conversion treatment layer is improved by containing at least one selected from the group consisting of the vanadium compound, the tungsten compound and the molybdenum compound.
  • the vanadium compound is not particularly limited, and conventionally known vanadium-containing compounds can be used. Limbanadium salt and the like can be mentioned.
  • the tungsten compound is not particularly limited, and conventionally known tungsten-containing compounds can be used.
  • tungstic acid and tungstic acid such as ammonium tungstate and sodium tungstate, tungstic acid and ammonium phosphotungstate and the like can be used. Examples thereof include phosphotungstate.
  • the molybdenum compound is not particularly limited, and a conventionally known molybdenum-containing compound can be used, for example, a molybdate salt or the like can be used.
  • the molybdate is not limited in its skeleton and degree of condensation, and examples thereof include orthomolybdate, paramolybdate, and metamolybdate. Further, it contains all salts such as a simple salt and a double salt, and examples of the double salt include molybdate phosphate and the like.
  • At least one selected from the group consisting of the vanadium compound, the tungsten compound and the molybdenum compound contains 0.01 to 20% by mass with respect to 100% by mass of the solid content of the resin. If the content of at least one selected from the group consisting of the vanadium compound, the tungsten compound and the molybdenum compound is less than 0.01% by mass, the effect of improving the corrosion resistance may not be obtained, and the vanadium compound and the tungsten compound may not be obtained. If the content of at least one selected from the group consisting of the molybdenum compound and the molybdenum compound exceeds 20% by mass, the chemical conversion layer may become brittle and the corrosion resistance may decrease.
  • the chemical conversion treatment layer may further contain a polyphenol compound.
  • the polyphenol compound is a compound having two or more phenolic hydroxyl groups bonded to a benzene ring or a condensate thereof.
  • the compound having two or more phenolic hydroxyl groups bonded to the benzene ring include gallic acid, pyrogallol, and catechol.
  • the condensate of the compound having two or more phenolic hydroxyl groups bonded to the benzene ring is not particularly limited, and examples thereof include a polyphenol compound generally called tannic acid, which is widely distributed in the plant kingdom. Tannic acid is a general term for aromatic compounds having a complex structure having a large number of phenolic hydroxyl groups that are widely distributed in the plant kingdom.
  • the tannic acid may be hydrolyzable tannic acid or condensed tannic acid.
  • the tannin acid is not particularly limited, and examples thereof include hamameli tannin, kaki tannin, chatan nin, quintuple tannin, eclipse tannin, milovalantinin, dividibitannin, algarovira tannin, baronia tannin, and catechin tannin. ..
  • tannin acid examples include commercially available products such as “tannin acid extract A”, “B tannin acid”, “N tannin acid”, “technical tannin acid”, “purified tannin acid”, and “Hi tannin acid”.
  • “F tannin acid”, “local tannin acid” all manufactured by Dainippon Pharmaceutical Co., Ltd.
  • “tannin acid: AL” manufactured by Fuji Chemical Industry Co., Ltd.
  • the above polyphenol compound may be used alone or in combination of two or more.
  • the polyphenol compound is preferably contained in an amount of 0.1 to 50% by mass with respect to 100% by mass of the solid content of the resin. If the content of the polyphenol compound is less than 0.1% by mass, the effect of improving corrosion resistance may not be obtained, and if the content of the polyphenol compound exceeds 50% by mass, the stability of the aqueous composition is lowered. May be done.
  • the chemical conversion treatment layer may further contain a solid lubricant.
  • the lubricity of the chemical conversion treatment layer is improved, workability during press molding is improved, flaws are prevented by dies and handling, and wear scratches are prevented during transport of molded products and coils. effective.
  • the solid lubricant is not particularly limited, and examples thereof include known fluorine-based, hydrocarbon-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based, and inorganic-based lubricants.
  • a lubricating additive for improving workability it is recommended to select a substance that exists on the surface of the chemical conversion treatment layer rather than being dispersed in the chemical conversion treatment layer on which the added lubricant is formed. It is necessary from the viewpoint of reducing the friction between the surface of the molded product and the mold and maximizing the lubrication effect.
  • the surface friction coefficient is high and the chemical conversion treatment layer is easily destroyed, and the powdery substance is peeled and deposited, resulting in poor appearance and processability called a powdering phenomenon.
  • a powdering phenomenon causes a drop.
  • the substance existing on the surface of the chemical conversion treatment layer a substance that is incompatible with the resin and has a small surface energy is selected.
  • polyolefin wax because the coefficient of dynamic friction on the surface is lowered, the workability is greatly improved, and the corrosion resistance after processing is also improved.
  • this wax include hydrocarbon waxes such as paraffin, microcrystallin and polyethylene.
  • the melting point of the wax is more preferably 70 to 160 ° C. because the film temperature rises due to the heat of deformation and friction of the material. If the melting point of the wax is less than 70 ° C., it may soften and melt during processing and may not exhibit excellent properties as a solid lubricant. Further, if the melting point of the wax exceeds 160 ° C., hard particles are present on the surface and the frictional characteristics are deteriorated, so that a high degree of molding processability may not be obtained.
  • the particle size of these waxes is more preferably 0.1 to 5 ⁇ m. If the particle size of the wax exceeds 5 ⁇ m, the distribution of the solidified wax may be uneven, or the wax may fall off from the chemical conversion treatment layer. Further, when the particle size of the wax is less than 0.1 ⁇ m, the processability may be insufficient.
  • the solid lubricant is preferably contained in an amount of 0.1 to 30% by mass with respect to 100% by mass of the solid content of the resin.
  • the content of the solid lubricant is less than 0.1%, the effect of improving workability is small, and when the content of the solid lubricant exceeds 30%, the corrosion resistance may decrease.
  • the chemical conversion treatment layer is obtained by applying an aqueous composition containing components such as a resin, silica particles, a blue organic pigment, an Nb compound, and a phosphoric acid compound to the surface of a Zn-based plating layer and drying it.
  • a solvent may be used in the aqueous composition in order to improve the film-forming property and form a more uniform and smooth film.
  • the solvent is not particularly limited as long as it is generally used for paints, and examples thereof include alcohol-based, ketone-based, ester-based, and ether-based hydrophilic solvents from the viewpoint of leveling.
  • the coating method of the aqueous composition used for forming the chemical conversion treatment layer is to apply the aqueous composition to the surface of the Zn-based plating layer to form a film.
  • the coating method is not particularly limited, and generally used roll coats, air sprays, airless sprays, dipping and the like can be appropriately adopted.
  • any method such as hot air, induction heating, near infrared ray, far infrared ray, etc. may be used, or may be used in combination.
  • the heating temperature of the object to be coated is 50 to 250 ° C, preferably 70 to 220 ° C. If the heating temperature is less than 50 ° C., the evaporation rate of water is slow and sufficient film forming property cannot be obtained, so that the corrosion resistance may decrease. On the other hand, if the heating temperature exceeds 250 ° C., thermal decomposition of the resin occurs, the corrosion resistance is lowered, and the appearance is deteriorated due to yellowing or the like. When heat-drying after coating, the drying time is preferably 1 second to 5 minutes. Further, if the resin is cured by an electron beam or ultraviolet rays, it may be cured by these irradiations or may be used in combination with heat drying.
  • the arithmetic average roughness Ra of the Zn-based plating layer is 0.5 to 2.0 ⁇ m, and the arithmetic average height Sa of the chemical conversion treatment layer is 5 nm to 100 nm.
  • the arithmetic mean roughness Ra of the Zn-based plating layer is 2.0 ⁇ m or less, the metallic appearance of the Zn-based plating layer can be maintained high.
  • Ra exceeds 2.0 ⁇ m the light that hits the surface of the Zn-based plating layer tends to be diffusely reflected, and the appearance of the metal tends to deteriorate.
  • the arithmetic average height Sa of the chemical conversion treatment layer is 100 nm or less, the transparency of the chemical conversion treatment layer can be maintained.
  • the arithmetic average roughness Ra of the Zn-based plating layer and the arithmetic average height Sa of the chemical conversion treatment layer are each equal to or less than the upper limit, the metallic appearance of the Zn-based plating layer can be maintained. Further, even if the arithmetic average roughness Ra of the Zn-based plating layer and the arithmetic average height Sa of the chemical conversion treatment layer are each less than the lower limit, the effect of maintaining the metal appearance and permeability is saturated, so the respective lower limit values are set.
  • the arithmetic mean roughness Ra of the Zn-based plating layer is measured and calculated by a 3D laser microscope (manufactured by KEYENCE CORPORATION).
  • the height Z is measured at a measurement interval of 50 ⁇ m using a 20x standard lens.
  • the number of measurement points is preferably 100.
  • the arithmetic average roughness Ra is calculated from the following equation 2 using the obtained height Z100 points as the number of measurement points and the height Z1 to the height Z100.
  • Zave is the average of 100 points of height Z.
  • the arithmetic average height Sa of the chemical conversion treatment layer is measured and calculated by the following method.
  • the surface of a sample cut out from a Zn-based plated steel sheet to a predetermined size is gold-deposited to a thickness of 50 nm, the gold-deposited sample is embedded in a resin, and the sample is polished so that the cross section in the plate thickness direction is exposed.
  • the cross section of the sample is observed with a scanning electron microscope at a magnification of 5000 times, and the line roughness of the gold-deposited layer when observed from the direction perpendicular to the cross section is calculated.
  • the arithmetic mean height Sa of the chemical conversion treatment layer is obtained by converting the obtained line roughness into a surface roughness difference.
  • the gold vapor deposition is carried out to clarify the boundary between the chemical conversion treatment layer and the resin, and the thickness of the gold vapor deposition layer is negligible as compared with the chemical conversion treatment layer. It can be substituted as the arithmetic mean height Sa of the surface of the treated layer.
  • the chemical conversion treatment layer is formed on the surface of the Zn-based plating layer without interposing another film or the like. Further, in order to obtain a more beautiful metallic appearance, it is preferable not to provide another colored film, a low-permeability film, or the like on the chemically treated layer.
  • L * 1 be obtained at this time, and in the above plane, light is incident on the surface of the chemical conversion treatment layer from an angle of 120 ° from the surface of the chemical conversion treatment layer, and the light reflected on the surface of the chemical conversion treatment layer is emitted.
  • L * obtained when light is received from the surface of the chemical conversion treatment layer at an angle of 135 ° is L * 2 , it is preferable to satisfy L * 1 / L * 2 ⁇ 2. It has been found that this feature is a peculiar property of a Zn-based plated steel sheet having a metallic luster even with a chemical conversion treatment layer and, as a result, having a metallic appearance.
  • the appearance of the Zn-based plated steel sheet of the present embodiment is that b * is -30 or more and -2 or less when evaluated in the CIE1976 (L * , a * , b * ) color space, and JIS.
  • the 60-degree mirror surface gloss G s (60 °) specified in Z 8741: 1997 is 50 to 200, and indicates a metallic appearance.
  • the reasons for limiting b * and the 60-degree mirror surface gloss G s (60 °) will be described.
  • the predetermined 60-degree mirror gloss Gs (60 °) and b * should be used in order to have excellent blackening resistance while visually recognizing the metallic appearance of the Zn-based plating layer. It is presumed that this is because the b * value fluctuates in the direction of increasing during blackening.
  • b * when evaluated in the CIE1976 (L * , a * , b * ) color space is less than -30, the blue color of the surface of the Zn-based plated steel sheet becomes dark and the metallic appearance of the Zn-based plated layer becomes invisible. Further, when b * exceeds -2, the blue color becomes lighter, the blackened portion on the surface of the Zn-based plating layer becomes conspicuous, and the appearance deteriorates. Therefore, b * is in the range of -30 or more and -2 or less.
  • the lower limit of b * is preferably -22, more preferably -15, from the viewpoint of maintaining the appearance of the metal.
  • the upper limit of b * is preferably ⁇ 3.5, more preferably ⁇ 5, from the viewpoint of preventing blackening.
  • L * is 85 or less when evaluated in the CIE1976 (L * , a * , b * ) color space. ..
  • L * is more preferably 80 or less, and further preferably 75 or less, from the viewpoint of making blackening less noticeable.
  • the appearance in the present invention means the appearance of the Zn-based plated steel sheet when viewed from the Zn-based plated layer side arranged on at least one side of the steel sheet.
  • a patterned portion and a non-patterned portion arranged so as to have a predetermined shape may be formed.
  • the pattern portion is preferably arranged so as to have a shape of any one of a straight line portion, a curved portion, a dot portion, a figure, a number, a symbol, a pattern or a character, or a combination of two or more of them. ..
  • the non-patterned portion is an area other than the patterned portion. Further, the shape of the pattern portion is acceptable as long as it can be recognized as a whole even if a part is missing such as missing dots. Further, the non-patterned portion may have a shape that borders the boundary of the patterned portion.
  • any one of a straight line part, a curved line part, a dot part, a figure, a number, a symbol, a pattern or a character, or a combination of two or more of them is arranged is arranged on the surface of the Zn-based plating layer. These areas can be used as the pattern part, and the other areas can be used as the non-pattern part.
  • the boundary between the patterned portion and the non-patterned portion can be grasped with the naked eye.
  • the boundary between the patterned portion and the non-patterned portion may be grasped from a magnified image by an optical microscope or a magnifying glass.
  • the pattern portion may be formed in a size that allows the presence of the pattern portion to be discernible with the naked eye, under a magnifying glass, or under a microscope.
  • the non-patterned portion is a region that occupies most of the Zn-based plating layer (the surface of the Zn-based plating layer), and the pattern portion may be arranged in the non-patterned portion.
  • the pattern portion is arranged in a predetermined shape in the non-pattern portion.
  • the pattern part is a straight line part, a curved part, a figure, a dot part, a figure, a number, a symbol, a pattern or a character, or a combination of two or more of them in a non-pattern part.
  • the pattern part By adjusting the shape of the pattern part, one of straight lines, curved lines, figures, dots, figures, numbers, symbols, patterns or letters or two of them can be placed on the surface of the Zn-based plating layer.
  • a shape that combines the above is revealed.
  • a character string composed of a pattern portion, a number string, a symbol, a mark, a diagram, a design drawing, a combination thereof, or the like appears on the surface of the Zn-based plating layer.
  • This shape is a shape intentionally or artificially formed by a manufacturing method described later, and is not a naturally formed shape.
  • the patterned portion and the non-patterned portion are regions formed on the surface of the Zn-based plating layer, and the patterned portion and the non-patterned portion include one of the first region and the second region, respectively. Includes seeds or two.
  • the pattern portion and the non-pattern portion include one or two of the first region and the second region determined by any one of the following determination methods 1 to 5, respectively, and the first region in the pattern portion.
  • the absolute value of the difference between the area ratio of the above and the area ratio of the first region in the non-patterned portion is 30% or more.
  • the difference between the area ratio of the first region in the pattern portion and the area ratio of the first region in the non-patterned portion is 30% or more in absolute value
  • the patterned portion and the non-patterned portion can be distinguished.
  • the difference in the area ratio is less than 30%, the difference between the area ratio of the first region in the pattern portion and the area ratio of the first region in the non-patterned portion is small, and the appearances of the patterned portion and the non-patterned portion are similar. It has a nice appearance and it becomes difficult to identify the pattern part.
  • the larger the difference in area ratio, the better, and the difference in area ratio is more preferably 40% or more, and the difference in area ratio is more preferably 60% or more.
  • the area ratio of each of the first region and the second region can be obtained.
  • the pattern portion looks relatively white or a color close to white as compared with the case where the surface integral of the first region is 70% or less.
  • the pattern portion looks relatively satin-like.
  • the surface integral of the first region is less than 30%, the pattern portion appears to have a relatively metallic luster. As described above, the appearance of the pattern portion depends on the surface integral of the first region.
  • the area ratio of each of the first region and the second region can be obtained. Similar to the patterned portion, the appearance of the non-patterned portion depends on the surface integral of the first region.
  • the pattern portion and the non-pattern portion can be distinguished. Become.
  • the difference in the area ratio is less than 30%, the difference between the area ratio of the first region in the pattern portion and the area ratio of the first region in the non-patterned portion is small, and the appearances of the patterned portion and the non-patterned portion are similar. It has a nice appearance and it becomes difficult to identify the pattern part.
  • the larger the difference in area ratio the better, more preferably 40% or more, and even more preferably 60% or more.
  • Determination method 1 In the determination method 1, virtual grid lines are drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and each of the plurality of regions partitioned by the virtual grid lines has a diameter of 0.5 mm centered on the center of gravity of each region.
  • the inside of the circle is defined as the measurement area A, and the L * value in each measurement area A is measured.
  • the region where the L * value is equal to or greater than the reference L * value is the first.
  • One area, the area less than the standard L * value is defined as the second area.
  • Determination method 2 In the determination method 2, virtual grid lines are drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and each of the plurality of regions partitioned by the virtual grid lines has a diameter of 0.5 mm centered on the center of gravity of each region.
  • the inside of the circle is defined as the measurement region A, the L * value in each measurement region A is measured, the region where the L * value is 45 or more is defined as the first region, and the region where the L * value is less than 45 is defined as the second region.
  • Determination method 3 In the determination method 3, virtual grid lines are drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and the arithmetic mean height Sa2 is measured in each of the plurality of regions partitioned by the virtual grid lines. The region where the obtained arithmetic mean height Sa2 is 1 ⁇ m or more is defined as the first region, and the region where the obtained arithmetic mean height Sa2 is less than 1 ⁇ m is defined as the second region. The arithmetic average height Sa2 is measured using a 3D laser microscope (manufactured by KEYENCE CORPORATION).
  • a 20x standard lens is used to measure the height Z in each of the plurality of regions partitioned by the virtual grid lines at a measurement interval of 50 ⁇ m.
  • 100 measurement points are obtained in the region.
  • the arithmetic mean height Sa2 is calculated by the following formula 3.
  • Zave is the average of 100 points of height Z.
  • Determination method 4 In the determination method 4, virtual grid lines are drawn on the surface of the Zn-based plating layer at 1 mm intervals or 10 mm intervals, and X-rays are incident on each of a plurality of regions partitioned by the virtual grid lines by an X-ray diffraction method for each region.
  • the diffraction peak intensity I 0002 of the (0002) plane of the Zn phase and the diffraction peak intensity I 10-11 of the (10-11) plane of the Zn phase were measured, and the intensity ratio (I 0002 / I 10- ) thereof was measured.
  • 11 is the orientation ratio.
  • the region having an orientation ratio of 3.5 or more is referred to as a first region, and the region having an orientation ratio of less than 3.5 is referred to as a second region.
  • Determination method 5 In the determination method 5, virtual grid lines are drawn on the surface of the Zn-based plating layer at 1 mm intervals, and then a circle S centered on the center of gravity point G of each region is drawn for each of a plurality of regions partitioned by the virtual grid lines. ..
  • the diameter R of the circle S is set so that the total length of the surface boundary lines of the Zn-based plating layer contained inside the circle S is 10 mm.
  • the average value of the maximum diameter Rmax and the minimum diameter Rmin among the diameters R of the circles S in a plurality of regions is defined as the reference diameter Rave, and the region having the circle S in which the diameter R is less than the reference diameter Rave is defined as the first region.
  • the region where R has a circle S having a reference diameter Rave or more is defined as a second region.
  • the pattern portion and the non-pattern portion in which the first region and the second region are specified by the determination method 1 or 2 are formed after the Zn-based plating layer is formed.
  • the patterned portion and the non-patterned portion are formed by adhering an acidic solution to the surface of the Zn-based plating layer at 60 to 200 ° C. More specifically, it is advisable to prepare an acidic solution and attach it to the surface of the Zn-based plating layer by printing means.
  • a general printing method such as a printing method using various plates (gravure printing, flexographic printing, offset printing, silk printing, etc.), an inkjet method, and the like can be applied.
  • the very surface of the Zn-based plating layer melts, and the surface of the Zn-based plating layer changes from the state of being plated.
  • the appearance of the portion to which the acidic solution is attached changes in comparison with the portion to which the acidic solution does not adhere. In this way, it is presumed that the difference between the area ratio of the first region in the patterned portion and the area ratio of the first region in the non-patterned portion becomes large, and the patterned portion and the non-patterned portion can be distinguished.
  • the adhesion range of the acidic solution may be a region corresponding to the pattern portion or a region corresponding to the non-pattern portion.
  • an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid as the acidic solution.
  • the acid concentration in the acidic solution is preferably 0.1 to 10% by mass.
  • the temperature of the steel sheet when the acidic solution is attached is preferably 60 to 200 ° C, preferably 50 to 80 ° C.
  • the surface temperature of the Zn-based plating layer when the acidic solution is attached is less than 60 ° C., it takes time to form the patterned portion or the non-patterned portion, which is not preferable. If the surface temperature of the Zn-based plating layer exceeds 200 ° C., It is not preferable because the acidic solution volatilizes immediately and it becomes impossible to form a patterned portion or a non-patterned portion.
  • the pattern portion and the non-pattern portion in which the first region and the second region are specified by the determination method 3 are formed after the Zn-based plating layer is formed.
  • the patterned portion and the non-patterned portion are formed by pressing a roll having a partially increased surface roughness against the surface of the Zn-based plating layer and transferring the surface shape of the roll to the Zn-based plating layer.
  • the roughness of the portion corresponding to the pattern portion on the roll surface is made larger than that of other portions, so that the surface roughness is large. It is possible to form a pattern portion containing a large amount of one region.
  • a roll may be used in which the roughness of the portion corresponding to the pattern portion is made smaller than that of the other portion.
  • the roughness of the roll surface (arithmetic mean height Sa2 ( ⁇ m)) is set to 0.6 to 3.0 ⁇ m, preferably 1.2 to 3.0 ⁇ m, in the range of roughness at the portion where the roughness is increased.
  • the range of roughness at the portion where the roughness is lowered is preferably 0.05 to 1.0 ⁇ m, preferably 0.05 to 0.8 ⁇ m. It is preferable to perform the transfer in the range where the surface temperature of the Zn-based plating layer is in the range of 100 to 300 ° C.
  • the difference between the roughness in the place where the roughness is high and the roughness in the place where the roughness is low is more than 0.2 ⁇ m, preferably 0.3 ⁇ m or more at the arithmetic mean height Sa2.
  • the difference in roughness becomes small, it becomes difficult to distinguish between the patterned portion and the non-patterned portion.
  • the patterned portion and the non-patterned portion specified by the determination method 4 are formed by locally spraying a non-oxidizing gas onto the molten metal with a gas nozzle on the steel sheet immediately after being pulled up from the hot-dip plating bath.
  • a non-oxidizing gas nitrogen or argon may be used.
  • the optimum temperature range differs depending on the composition, it is preferable to spray the non-oxidizing gas when the temperature of the molten metal is in the range of (final solidification temperature ⁇ 5) ° C. to (final solidification temperature + 5) ° C. Further, the temperature of the non-oxidizing gas shall be lower than the final solidification temperature.
  • the cooling rate of the molten metal increases at the location where the non-oxidizing gas is sprayed, which increases the orientation rate of the Zn-based plating layer after solidification.
  • the cooling rate of the molten metal is lowered, and as a result, the orientation ratio of the Zn-based plating layer after solidification is lowered. Therefore, by adjusting the spraying range of the non-oxidizing gas, it becomes possible to intentionally or arbitrarily adjust the appearance points of the region having a high orientation ratio and the region having a low orientation ratio.
  • the shapes of the patterned portion and the non-patterned portion can be arbitrarily adjusted, and the patterned portion and the non-patterned portion can be identified. Since the lower the temperature of the sprayed gas, the higher the orientation rate, the orientation rate can be adjusted by the temperature of the sprayed gas.
  • the gas temperature is preferably lower than the final solidification temperature, and for example, the gas temperature may be adjusted to 25 to 250 ° C.
  • the formation of the patterned portion and the non-patterned portion specified by the determination method 5 is performed by locally applying a non-oxidizing gas having a temperature equal to or higher than the final solidification temperature of plating to the molten metal on the steel sheet immediately after being pulled up from the hot-dip plating bath. It is done by spraying on the target.
  • a non-oxidizing gas nitrogen or argon may be used.
  • the optimum temperature range differs depending on the composition, it is preferable to spray the non-oxidizing gas when the temperature of the molten metal is in the range of (final solidification temperature ⁇ 5) ° C. to (final solidification temperature + 5) ° C.
  • the temperature of the non-oxidizing gas is preferably set to be equal to or higher than the final solidification temperature.
  • a non-oxidizing gas having a gas temperature equal to or higher than the final solidification temperature when the temperature of the molten metal is 330 to 340 ° C.
  • the spray amount and range of the non-oxidizing gas the size of the boundary or grain boundary appearing on the surface can be arbitrarily adjusted.
  • the pattern portion and the non-pattern portion can be distinguished. Since the formed patterned portion and non-patterned portion are not formed by printing or painting, the durability is high. Further, since the patterned portion and the non-patterned portion are not formed by printing or painting, there is no influence on the corrosion resistance of the Zn-based plating layer. Therefore, the Zn-based plated steel sheet of the present embodiment has excellent corrosion resistance.
  • the pattern part can be intentionally or artificially shaped, any one of a straight part, a curved part, a dot part, a figure, a number, a symbol, a pattern or a character, or two or more of them can be used.
  • the pattern portion can be arranged so as to have a combined shape.
  • various designs, trademarks, and other identification marks can be displayed on the surface of the Zn-based plating layer without printing or painting, and the identification and design of the source of the steel sheet can be improved. ..
  • the pattern unit can add information necessary for process control, inventory control, etc., and arbitrary information requested by the consumer to the hot-dip galvanized steel sheet. This can also contribute to improving the productivity of Zn-based plated steel sheets.
  • the chemical conversion treatment layer containing the pigment is formed on the Zn-based plated layer on which the pattern portion is formed, so that the visibility of the pattern portion can be further improved. can.
  • a cold-rolled steel sheet having a thickness of 1 mm was prepared, immersed in a plating bath having each composition, and the plating adhesion amount was adjusted to 80 g / m 2 on one side by N 2 wiping.
  • Table 1 shows the plating composition of the obtained Zn-based plated steel sheet.
  • the pattern portion and the non-pattern portion include one or two of the first region and the second region determined by any of the determination methods 1 to 5, respectively, and the area ratio of the first region in the pattern portion.
  • the absolute value of the difference from the area ratio of the first region in the non-patterned portion was 40%.
  • a hydrochloric acid solution is attached to a rubber plate having a convex or concave portion of a square pattern with a side of 50 mm, and this rubber plate is pressed against the surface of the Zn-based plating layer to attach an acidic solution to the steel plate, resulting in a square pattern. Formed a part.
  • the surface temperature of the Zn-based plating layer of the hot-dip galvanized steel sheet when the acidic solution was attached was in the range of 60 to 200 ° C.
  • the non-patterned portion was defined as a portion other than the square patterned portion.
  • ⁇ Pattern 2> With the surface temperature of the Zn-based plating layer set to 100 to 300 ° C., a roll having a square pattern with a side of 50 mm was pressed against the surface of the Zn-based plating layer to form a pattern portion. The part of the square pattern was used as the pattern part, and the part other than the square pattern was used as the non-pattern part. Based on the determination method 3, virtual grid lines were drawn on the surface of the Zn-based plating layer at intervals of 0.5 mm, and the arithmetic mean height Sa2 was measured in each of the plurality of regions partitioned by the virtual grid lines.
  • Example 71 This Zn-based plated steel sheet was designated as Example 71.
  • the part of the square pattern was used as the pattern part, and the part other than the square pattern was used as the non-pattern part. Then, based on the determination method 5, virtual grid lines are drawn on the surface of the Zn-based plating layer at 1 mm intervals, and then, for each of a plurality of regions partitioned by the virtual grid lines, a circle centered on the center of gravity point G of each region. I drew S.
  • the diameter R of the circle S was set so that the total length of the surface boundary lines of the Zn-based plating layer contained inside the circle S was 10 mm.
  • the average value of the maximum diameter Rmax and the minimum diameter Rmin among the diameters R of the circles S in a plurality of regions is defined as the reference diameter Rave, and the region having the circle S in which the diameter R is less than the reference diameter Rave is defined as the first region.
  • the region where R has a circle S having a reference diameter Rave or more was defined as the second region.
  • the Zn-based plated steel sheets were designated as Examples 73 and 74.
  • the arithmetic average roughness Ra of the Zn-based plating layer was measured using a 3D laser microscope (manufactured by KEYENCE CORPORATION).
  • the height Z in each of the plurality of regions partitioned by the virtual grid lines was measured at a measurement interval of 50 ⁇ m using a 20x standard lens. Measurements were made on a grid, and 100 measurement points were obtained in the area.
  • the arithmetic mean roughness Ra was calculated using the above-mentioned equation 2 with the obtained height Z100 points as height Z1 to height Z100. Zave is the average of 100 points of height Z.
  • various aqueous resins (urethane resin, polyester resin, polyolefin resin, epoxy resin, acrylic resin, phenol resin, fluororesin), silica particles, niobium oxide, Sodium phosphate, various pigments (copper sulfate, cobalt sulfate, iron sulfate, Cu phthalocyanine (copper (II) phthalocyanine), Co phthalocyanine (cobalt (II) phthalocyanine), iron oxide, carbon black, quinacridone red, bismus vanadium, titanium oxide ) Is applied with a bar coater to a dry adhesion amount of 1.5 g / m 2 , dried in a hot air drying furnace at a plate temperature of 150 ° C., and then cooled with water to make it chromate-free. A chemical treatment layer was formed. The contents of niobium oxide and sodium phosphate
  • Tables 4A to 5B show the composition of the chemical conversion treatment layer and the like.
  • the drying temperature was set to be out of the range of 50 to 250 ° C., or the drying time was set to be out of the range of 1 second to 5 minutes.
  • the arithmetic mean height Sa of the chemical conversion treatment layer was obtained by the following method.
  • the surface of a sample cut out from a Zn-based plated steel sheet to a predetermined size was gold-deposited to a thickness of 50 nm, the gold-deposited sample was embedded in a resin, and the sample was polished so that the cross section in the plate thickness direction was exposed.
  • the cross section of the sample was observed at a magnification of 5000 times using a scanning electron microscope, and the roughness of the gold-deposited layer when observed from the direction perpendicular to the cross section was calculated to obtain the arithmetic mean height Sa of the chemical conversion layer. rice field.
  • Gold vapor deposition was carried out to clarify the boundary between the chemical conversion treatment layer and the resin. Since the thickness of the gold-deposited layer is negligible as compared with the chemical conversion-treated layer, the arithmetic average height of the gold-deposited layer was replaced with the arithmetic average height Sa on the surface of the chemical conversion-treated layer.
  • L * value L * was measured using a spectrocolorimeter (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.). When L * is 75 or less, it is “AAA”, when L * is more than 75 and 80 or less, it is “AA”, when L * is more than 80 and 85 or less, it is “A”, and when L * is more than 85. Was set to “B”. The results are shown in Tables 5A and 5B.
  • the metallic luster was evaluated using a multi-angle spectrophotometer (MAT12 manufactured by X-rite). In a plane orthogonal to the surface of the chemical conversion treatment layer, light is incident on the surface of the chemical conversion treatment layer from an angle of 60 ° from the surface of the chemical conversion treatment layer, and the light reflected on the surface of the chemical conversion treatment layer is reflected on the surface of the chemical conversion treatment layer.
  • L * 1 be L * obtained when light is received at an angle of 135 °, and light is incident from the surface of the chemical conversion treatment layer toward the surface of the chemical conversion treatment layer from an angle of 120 ° on the above plane to perform the chemical conversion treatment.
  • L * 1 / L * 2 When L * obtained when the light reflected on the surface of the layer is received from the surface of the chemical conversion treatment layer at an angle of 135 ° is L * 2 , L * 1 / L * 2 of 3 or more is defined as "AA”. , L * 1 / L * 2 is 2 or more and less than 3, "A”, and L * 1 / L * 2 is less than 2, "B”. The results are shown in Tables 5A and 5B.
  • the blackening resistance was evaluated by the color difference ⁇ E * ab from the color change of the surface of the Zn-plated layer before and after the test when the Zn-based plated steel sheet was allowed to stand at 70 ° C. and 80% RH for 12 days at high temperature and high humidity.
  • the color difference is expressed by the following equation 4 when the chromaticity index in the L * a * b * color system is a * and b * and the lightness index is L * .
  • ⁇ a * is the difference between the Zn-based plating layer a * before the test and the Zn-based plating layer a * after the test
  • ⁇ b * is the difference between the Zn-based plating layer b * before the test and the test. It is the difference from b * of the subsequent Zn-based plating layer
  • ⁇ L * is the difference between L * of the Zn-based plating layer before the test and L * of the Zn-based plating layer after the test.
  • the residual rate of the chemical conversion treatment layer is 90% or more 3: The residual rate of the chemical conversion treatment layer is 50 to less than 90% 2: The residual rate of the chemical conversion treatment layer is 30 to less than 50% 1: The residual rate of the chemical conversion treatment layer is 30 %Less than
  • the Zn-based plated steel sheets of Examples 1 to 74 all have a chemical conversion treatment layer satisfying the scope of the present invention, and have blackening resistance, corrosion resistance, metal appearance, and weather resistance. Was good. Further, the Zn-based plated steel sheets of Examples 14 to 16 using a phenol resin, a polyolefin resin, a fluororesin or an acrylic resin as the resin contained in the chemical conversion treatment layer were particularly excellent in weather resistance. Further, in Examples 70 to 74 in which the pattern portion was formed on the plating layer, the blackening resistance, the corrosion resistance, the metal appearance, and the weather resistance were good, and the visibility of the pattern portion was significantly improved.
  • Comparative Example 1 since the resin was not contained in the chemical conversion treatment layer, the chemical conversion treatment layer itself became very brittle, and various evaluation tests could not be carried out.
  • Comparative Example 2 since it did not contain silica particles, the corrosion resistance was lowered.
  • Comparative Example 3 since the content of silica particles was as high as 30%, the chemical conversion treatment layer itself became very brittle, and various evaluation tests could not be carried out.
  • Comparative Example 4 since the chemical conversion treatment layer did not contain a pigment, the blackening resistance was reduced.
  • Comparative Example 5 the drying conditions at the time of forming the chemical conversion treatment layer were out of the preferable range, and the b * of the chemical conversion treatment layer was out of the range of ⁇ 30 to ⁇ 2, so that the metal appearance was insufficient.
  • Comparative Example 6 since the drying conditions at the time of forming the chemical conversion treatment layer were out of the preferable range, the 60 degree mirror gloss Gs (60 °) on the surface of the chemical conversion treatment layer was out of the range of 50 to 200, so that the metal appearance was poor. It was inadequate.
  • Comparative Example 7 since the diameter of the silica particles was 450 nm, the metal appearance was insufficient.
  • Comparative Examples 8 to 11 did not contain a pigment containing Cu, Co or Fe, and had insufficient blackening resistance.
  • the present invention in a Zn-based plated steel sheet containing Al, blackening occurs even when the plated surface is partially or wholly blackened due to oxidation of Al contained in the plating layer.
  • the present invention has high industrial applicability because it is possible to provide a Zn-based plated steel sheet that can maintain a metallic appearance inconspicuously and has improved corrosion resistance and weather resistance.

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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0994916A (ja) * 1995-10-03 1997-04-08 Kawasaki Steel Corp 有機複合被覆鋼板
WO2013065354A1 (ja) * 2011-10-31 2013-05-10 新日鐵住金株式会社 メタリック調外観を有するクロメートフリープレコート金属板およびその製造に用いる水系塗料組成物
WO2016208621A1 (ja) * 2015-06-25 2016-12-29 新日鐵住金株式会社 塗装鋼板
WO2019225764A1 (ja) * 2018-05-25 2019-11-28 日本製鉄株式会社 表面処理鋼板

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4546884B2 (ja) * 2004-07-07 2010-09-22 新日本製鐵株式会社 加工部耐食性に優れる表面処理めっき鋼板
TWI519678B (zh) * 2013-11-20 2016-02-01 Nippon Steel & Sumitomo Metal Corp Galvanized steel sheet with excellent blackening resistance and corrosion resistance and its manufacturing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0994916A (ja) * 1995-10-03 1997-04-08 Kawasaki Steel Corp 有機複合被覆鋼板
WO2013065354A1 (ja) * 2011-10-31 2013-05-10 新日鐵住金株式会社 メタリック調外観を有するクロメートフリープレコート金属板およびその製造に用いる水系塗料組成物
WO2016208621A1 (ja) * 2015-06-25 2016-12-29 新日鐵住金株式会社 塗装鋼板
WO2019225764A1 (ja) * 2018-05-25 2019-11-28 日本製鉄株式会社 表面処理鋼板

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