Classifications

• • 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
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • 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
• • 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
  • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/56—Electroplating: Baths therefor from solutions of alloys
  • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/48—After-treatment of electroplated surfaces
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/48—After-treatment of electroplated surfaces
  • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
• • 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
• • 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
  • C25D7/0614—Strips or 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
  • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Definitions

• the present disclosure relates to a surface-treated steel sheet, in particular, a surface-treated steel sheet with excellent sulfide staining resistance after painting, adhesion to the paint layer in wet environments, and appearance.
• the surface-treated steel sheet of the present disclosure can be suitably used in containers such as cans.
• the present disclosure also relates to a method of producing the surface-treated steel sheet.
• a Sn plating steel sheet (tinplate), one type of surface-treated steel sheet, is widely used as material for various metal cans such as beverage cans, food cans, pails, and 18-liter cans because of its excellent corrosion resistance, weldability, workability, bright and beautiful appearance, and ease of production.
• Sn plating steel sheets used for these applications are required to have excellent adhesion to paint along with excellent resistance (sulfide staining resistance) to discoloration (sulfide staining) caused by the reaction between sulfur and Sn from the can contents (especially protein). Therefore, it is common for Sn plating steel sheets to be subjected to chromating treatment to improve the paint adhesion property and sulfide staining resistance.
• Chromating treatment is one type of surface treatment using a coating solution containing a chromium compound, such as chromic acid or chromate.
• a chromium compound such as chromic acid or chromate.
• a metal Cr layer and an Cr oxide layer are formed on the surface of the steel sheet by cathodic electrolysis in an electrolytic solution containing a hexavalent chromium compound, as described in Patent Literature (PTL) 1 to 3.
• PTL 5 proposes a method of forming a surface treatment layer composed of a metal Cr layer and a Cr oxide layer on the surface of a Sn plating steel sheet by performing cathodic electrolysis in an electrolytic solution containing trivalent chromium ions.
• the surface-treated steel sheet proposed in PTL 4 can be formed without performing chromate treatment.
• the surface-treated steel sheet has excellent sulfide staining resistance and paint layer adhesion.
• the paint layer adhesion was evaluated under mild conditions compared to the actual environment of a can.
• the surface-treated steel sheet proposed in PTL 4 has insufficient adhesion to paint (hereinafter referred to as "paint secondary adhesion" (coating secondary adhesion)) in wet environments, which represent more severe conditions.
• a surface treatment layer can be formed without using hexavalent chromium.
• the surface-treated steel sheet obtained by the above method has excellent paint secondary adhesion and sulfide staining resistance under severe conditions similar to the actual environment of a can.
• the surface-treated steel sheet produced by the method proposed in PTL 5 has a poor appearance because the original bright and beautiful metallic luster of the tinplate is lost.
• a surface-treated steel sheet that uses no hexavalent chromium and that combines excellent sulfide staining resistance, paint secondary adhesion, and appearance can be provided.
• the surface-treated steel sheet of the present disclosure can be suitably used as a material for containers and the like.
• a surface-treated steel sheet in an embodiment of the present disclosure includes, on at least one side of the steel sheet, a Ni-containing layer and a coating layer disposed on the Ni-containing layer, the coating layer containing at least one of Zr oxide and Ti oxide.
• the water contact angle be 50° or less, and that the total atomic ratio of K, Na, Mg, and Ca adsorbed on a surface of the steel sheet to all elements be 5.0 % or less. The following is a description of each of the above constituent elements of the surface-treated steel sheet.
• any steel sheet can be used as the above steel sheet without any particular limitation, but a steel sheet for cans is preferred.
• a steel sheet for cans is preferred.
• an ultra low carbon steel sheet or low carbon steel sheet can be used as the steel sheet.
• the method of producing the steel sheet is not limited, and a steel sheet produced by any method may be used, but it typically suffices to use a cold-rolled steel sheet.
• the cold-rolled steel sheet can be produced by general production processes, for example, hot rolling, pickling, cold rolling, annealing, and temper rolling.
• the chemical composition of the steel sheet is not limited, but the steel sheet may contain C, Mn, Cr, P, S, Si, Cu, Ni, Mo, Al, and unavoidable impurities to the extent that the effects of the scope of the present disclosure are not impaired.
• a steel sheet with the chemical composition specified in ASTM A623M-09, for example, can be suitably used as the steel sheet.
• the Ni-containing layer need only be provided on at least one side of the steel sheet but may be provided on both sides.
• the Ni-containing layer need only cover at least a portion of the steel sheet but may cover the entire side on which the Ni-containing layer is provided.
• the Ni-containing layer may be a continuous layer or a discontinuous layer.
• the discontinuous layer is, for example, a layer with an island-like structure.
• any layer that contains nickel can be used.
• a Ni layer and a Ni alloy layer can be used.
• the case of a Ni alloy layer resulting from diffusion annealing treatment after Ni plating is also considered a Ni alloy layer.
• the Ni alloy layer is, for example, a Ni-Fe alloy layer.
• the Ni-containing layer is preferably a Ni-based plating layer.
• the "Ni-based plating layer” is defined as a plating layer with a Ni content of 50 mass% or more.
• the Ni-based plating layer is a Ni plating layer or a plating layer consisting of Ni-based alloy.
• the Ni-based plating layer may be a dispersion plating layer (composite plating layer) in which solid fine particles are dispersed in Ni or a Ni-based alloy as a matrix.
• the fine particles may be either inorganic fine particles or organic fine particles.
• the organic fine particles include, for example, fine particles made of resin. Any resin can be used as the resin, but fluororesin is preferably used, and polytetrafluoroethylene (PTFE) is more preferably used.
• PTFE polytetrafluoroethylene
• the inorganic fine particles fine particles made of any inorganic material can be used without any limitation.
• the inorganic material may, for example, be a metal (including alloys), a compound, or other single substance.
• fine particles including at least one selected from the group consisting of oxides, nitrides, and carbides are preferably used, and fine particles of metal oxides are preferably used.
• the metal oxides include aluminum oxide, chromium oxide, titanium oxide, and zinc oxide.
• the particle size of the fine particles used in the dispersion plating is not limited, and particles of any size can be used.
• the diameter of the fine particles preferably does not exceed the thickness of the dispersion plating layer as the Ni-containing layer.
• the diameter of the fine particles is preferably 1 nm or more, more preferably 10 nm or more.
• the diameter of the fine particles is preferably 50 ⁇ m or less, more preferably 1000 nm or less.
• the Ni coating weight in the Ni-containing layer is not limited and can be any amount. However, from the perspective of further improving the appearance and corrosion resistance of the surface-treated steel sheet, the Ni coating weight is preferably set to 20.0 g/m 2 or less per side of the steel sheet. From the same perspective, the Ni coating weight is preferably set to 0.1 g/m 2 or more and more preferably to 0.2 g/m 2 or more. From the perspective of further improving workability, the Ni coating weight is even more preferably set to 1.0 g/m 2 or more.
• the Ni coating weight of the Ni-containing layer is measured by a calibration curve method using X-ray fluorescence.
• a plurality of steel sheets with known Ni coating weight are prepared, the X-ray fluorescence intensity derived from Ni is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the Ni coating weight is linearly approximated to yield a calibration curve.
• the X-ray fluorescence intensity derived from Ni in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the Ni coating weight of the Ni-containing layer.
• the method of forming the Ni-containing layer is not limited, and any method, such as electroplating, can be used.
• the Ni-Fe alloy layer can be formed by forming a Ni layer on the steel sheet surface, by electroplating or another such method, and then annealing.
• the surface side of the Ni-containing layer may contain Ni oxide or may contain no Ni oxide at all. However, from the perspective of further improving the paint secondary adhesion and sulfide staining resistance, the surface side of the Ni-containing layer preferably does not contain Ni oxide. Although Ni oxide can be formed by dissolved oxygen contained in water used in water washing after Ni plating, the Ni oxide contained in the Ni-containing layer is preferably removed by the below-described pretreatment or the like.
• a coating layer containing at least one of Zr oxide and Ti oxide exists on the Ni-containing layer.
• the inclusion of at least one of Zr oxide and Ti oxide in the coating layer is necessary to obtain excellent sulfide staining resistance, paint secondary adhesion, and appearance.
• the total coating weight of the Zr oxide and Ti oxide is preferably 0.3 mg/m 2 or more, more preferably 0.4 mg/m 2 or more, and even more preferably 0.5 mg/m 2 or more, per side of the steel sheet in terms of the amount of metal Zr and amount of metal Ti.
• No upper limit is placed on the total coating weight of Zr oxide and Ti oxide in the coating layer either. However, if the total coating weight of Zr oxide and Ti oxide is excessively high, the appearance may be impaired and the paint secondary adhesion may be compromised due to cohesion failure of the coating layer.
• the total coating weight of the Zr oxide and Ti oxide is preferably 50.0 mg/m 2 or less, more preferably 45.0 mg/m 2 or less, and even more preferably 40.0 mg/m 2 or less, per side of the steel sheet in terms of the amount of metal Zr and amount of metal Ti.
• the value yielded by conversion to the amount of metal Zr is used as the coating weight of Zr oxide
• the value yielded by conversion to the amount of metal Ti is used as the coating weight of Ti oxide.
• the coating weight of Zr oxide in the coating layer is measured by a calibration curve method using X-ray fluorescence.
• a plurality of steel sheets with known Zr coating weight are prepared, the X-ray fluorescence intensity derived from Zr is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the coating weight as metal Zr is linearly approximated to yield a calibration curve.
• the X-ray fluorescence intensity derived from Zr in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of Zr oxide in the coating layer in terms of metal Zr.
• the coating weight of Ti oxide in the coating layer is also measured by a calibration curve method using X-ray fluorescence.
• a calibration curve method using X-ray fluorescence First, a plurality of steel sheets with known Ti coating weight are prepared, the X-ray fluorescence intensity derived from Ti is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the coating weight as metal Ti is linearly approximated to yield a calibration curve.
• the X-ray fluorescence intensity derived from Ti in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of Ti oxide in the coating layer in terms of metal Ti.
• the coating layer may contain P from the perspective of further improving sulfide staining resistance.
• the coating weight of P is preferably 50.0 mg/m 2 or less per side of the steel sheet, since paint secondary adhesion may be impaired due to cohesion failure of the coating layer.
• No lower limit is placed on the coating weight of P in the coating layer, and the coating weight of P may, for example, be 0.0 mg/m 2 , i.e., no P whatsoever may be contained.
• the coating weight of P in the coating layer is measured by a calibration curve method using X-ray fluorescence.
• a plurality of steel sheets with known P coating weight are prepared, the X-ray fluorescence intensity derived from P is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the P coating weight is linearly approximated to yield a calibration curve.
• the X-ray fluorescence intensity derived from P in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of P in the coating layer.
• the coating layer may contain Mn from the perspective of further improving sulfide staining resistance.
• the coating weight of Mn is preferably 50.0 mg/m 2 or less per side of the steel sheet, since paint secondary adhesion may be impaired due to cohesion failure of the coating layer.
• No lower limit is placed on the coating weight of Mn in the coating layer, and the coating weight of Mn may, for example, be 0.0 mg/m 2 , i.e., no Mn whatsoever may be contained.
• the coating weight of Mn in the coating layer is measured by a calibration curve method using X-ray fluorescence.
• a plurality of steel sheets with known Mn coating weight are prepared, the X-ray fluorescence intensity derived from Mn is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the Mn coating weight is linearly approximated to yield a calibration curve.
• the X-ray fluorescence intensity derived from Mn in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of Mn in the coating layer.
• the aforementioned coating layer may contain Ni. No upper limit is placed on the Ni content in the coating layer.
• the coating layer need not contain Ni, i.e., the content may be 0.0 mg/m 2 .
• the aforementioned coating layer may contain C. No upper limit is placed on the C content in the coating layer.
• the coating layer need not contain C, i.e., the content may be 0.0 mg/m 2 .
• the aforementioned coating layer may contain elements other than Zr, Ti, O, Ni, Mn, P and C, along with the below-described K, Na, Mg, and Ca.
• Elements other than those described above include metallic impurities such as Cu, Zn, and Fe, and elements such as S, N, F, Cl, Br, and Si, contained in the aqueous solution used in the coating formation process described below.
• an excessive presence of elements other than Zr, Ti, O, Ni, Mn, P, C, K, Na, Mg, and Ca may reduce sulfide staining resistance or adhesion.
• the total content of elements other than Zr, Ti, O, Ni, Mn, P, C, K, Na, Mg, and Ca in the coating layer is preferably 30 % or less, and more preferably 20 % or less, in atomic ratio.
• the coating layer need not contain elements other than Zr, Ti, O, Ni, Mn, P, C, K, Na, Mg, and Ca, i.e., the content may be 0 % in atomic ratio.
• the content of the above elements can be measured by XPS (X-ray photoelectron spectroscopy).
• the water contact angle on the surface-treated steel sheet be 50° or less.
• the water contact angle is preferably set to 48° or less, and even more preferably to 45° or less. No lower limit is placed on the water contact angle, and the water contact angle may be 0°, because a lower contact angle is preferable from the perspective of improving adhesion.
• the water contact angle may be 5° or more, or 8° or more.
• the surface of the surface-treated steel sheet in the present disclosure i.e., the surface of the coating layer containing at least one of Zr oxide and Ti oxide
• the water contact angle does not change significantly after heat treatment equivalent to paint baking. It is assumed that such thermal stability of the surface state also contributes to improved adhesion. Therefore, the water contact angle on the surface-treated steel sheet after heat treatment equivalent to painting is also preferably 50° or less, more preferably 48° or less, and even more preferably 45° or less. No lower limit is placed on the water contact angle of the surface-treated steel sheet after heat treatment equivalent to painting, and the water contact angle may be 0°, but the water contact angle may be 5° or more, or 8° or more.
• the conditions of the heat treatment equivalent to painting are set to a maximum temperature of 200 °C and a holding time at the maximum temperature of 10 minutes.
• the water contact angle measured by the method described in the Examples after vaporizing the painted oil by the heat treatment equivalent to painting is taken as the water contact angle of the surface-treated steel sheet after painting with oil.
• the surface-treated steel sheet of the present disclosure is stable with respect to heat treatment. Therefore, if the water contact angle measured after the aforementioned heat treatment and the atomic ratio of the adsorbed elements described below satisfy the conditions of the present disclosure, the surface-treated steel sheet before the aforementioned heat treatment is also considered to achieve the effects of the present disclosure.
• additives such as rust inhibitors contained in the painted oil may remain on the surface of the surface-treated steel sheet after heat treatment equivalent to painting, the amount thereof is so small that it does not affect the above-described water contact angle and atomic ratio of adsorbed elements.
• a high degree of hydrophilicity is developed by the action of the minute irregularities on the surface of the coating layer formed in the surface conditioning process described below, allowing a paint to penetrate into the fine irregularities and form firm mechanical bonds at the interface between the paint layer and the surface treated steel sheet by the anchor effect, thereby maintaining high adhesion even under wet conditions.
• the surface-treated steel sheet of the present disclosure has high hydrophilicity, with a water contact angle of 50° or less, and the surface is chemically active. Therefore, cations of elements such as K, Na, Mg, and Ca are easily adsorbed on the surface of the surface-treated steel sheet. We discovered that simply setting the water contact angle to 50° or less does not achieve the intended adhesion, due to the effect of the adsorbed cations. By reducing the amount of the cations adsorbed on the surface of the surface-treated steel sheet, the present disclosure improves adhesion to the resin and achieves excellent paint secondary adhesion, while also exhibiting firm barrier properties against sulfur penetration, thus achieving excellent sulfide staining resistance.
• the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet to all elements is 5.0 % or less, preferably 3.0 % or less, and more preferably 1.0 % or less.
• the total atomic ratio can be measured by XPS. In the measurement, it suffices to determine the atomic ratios of K, Na, Mg, and Ca to all elements from the integrated intensity of the narrow spectra of K2p, Nals, Ca2p, and Mgls at the top surface of the surface-treated steel sheet, using the relative sensitivity factor method.
• measurement can be made by the method described in the Examples.
• the atomic ratio measured by the method described in the Examples after vaporizing the painted oil by the heat treatment equivalent to painting is taken as the atomic ratio of the elements adsorbed to the surface-treated steel sheet after painting with oil.
• a surface-treated steel sheet with the aforementioned characteristics can be produced by the method described below.
• a method of producing a surface-treated steel sheet in an embodiment of the present disclosure is a method of producing a surface-treated steel sheet that includes, on at least one side of the steel sheet, a Ni-containing layer and a coating layer disposed on the Ni-containing layer, and the method includes the following processes (1) to (3). Each process is described below.
• the surface of a steel sheet having a Ni-containing layer on at least one side is treated with an aqueous solution containing at least one of Zr ions and Ti ions to form a coating layer on the Ni-containing layer.
• the formed coating layer is a coating layer containing at least one of Zr oxide and Ti oxide.
• the treatment with an aqueous solution is not limited and may be performed by any method.
• the treatment can, for example, be performed by electrolysis.
• the steel sheet with the Ni-containing layer is preferably subjected to cathodic electrolysis in the aqueous solution.
• Conventional equipment used for chromating treatment or the like can be used as is for the cathodic electrolysis. Therefore, from the perspective of equipment cost reduction, the coating layer is preferably formed by cathodic electrolysis.
• the method of preparing the aqueous solution is not limited.
• the aqueous solution can be prepared by dissolving one or both of a Zr-containing compound as a Zr ion source and a Ti-containing compound as a Ti ion source in water. Distilled water or deionized water can be used as the water, but these examples are not limiting, and any water can be used.
• Zr salts such as ZrF 4 or Zr complexes such as H 2 ZrF 6 and K 2 ZrF 6 are preferably used as the Zr-containing compound.
• Zr ions become Zr oxide and form a coating.
• Ti salts such as TiF 4 or Ti complexes such as H 2 TiF 6 and K 2 TiF 6 are preferably used as the Ti-containing compound.
• Ti ions become Ti oxide and form a coating.
• the aqueous solution may further contain at least one selected from the group consisting of fluorine ions, nitrate ions, ammonium ions, phosphate ions, Mn ions, and sulfate ions.
• the treatment can be performed in a short time, from several seconds to several tens of seconds, which is extremely advantageous from an industrial standpoint.
• the aqueous solution therefore preferably contains both nitrate ions and ammonium ions in addition to at least one of Zr ions and Ti ions.
• the unit of ionic concentration "ppm" refers to parts per million unless otherwise specified.
• the aqueous solution contains Zr ions
• the concentration is preferably set to 100 ppm or more.
• the concentration is preferably set to 4000 ppm or less.
• the aqueous solution contains Ti ions
• no lower limit is placed on the concentration of the Ti ions, but the concentration is preferably set to 100 ppm or more.
• the concentration is preferably set to 4000 ppm or less.
• the aqueous solution contains fluorine ions
• the concentration is preferably set to 120 ppm or more.
• No upper limit is placed on the concentration of the fluorine ions either, but the concentration is preferably set to 4000 ppm or less.
• the aqueous solution contains phosphate ions
• no lower limit is placed on the concentration of the phosphate ions, but the concentration is preferably set to 50 ppm or more.
• No upper limit is placed on the concentration of the phosphate ions either, but the concentration is preferably set to 5000 ppm or less.
• the aqueous solution contains Mn ions
• the concentration is preferably set to 50 ppm or more.
• No upper limit is placed on the concentration of the Mn ions either, but the concentration is preferably set to 5000 ppm or less.
• the aqueous solution contains ammonium ions
• no lower limit is placed on the concentration of the ammonium ions, and the concentration may be 0 ppm.
• No upper limit is placed on the concentration of the ammonium ions either, but the concentration is preferably set to 20000 ppm or less.
• the aqueous solution contains nitrate ions
• no lower limit is placed on the concentration of the nitrate ions, and the concentration may be 0 ppm.
• No upper limit is placed on the concentration of the nitrate ions either, but the concentration is preferably set to 20000 ppm or less.
• the aqueous solution contains sulfate ions
• no lower limit is placed on the concentration of the sulfate ions
• the concentration may be 0 ppm.
• No upper limit is placed on the concentration of the sulfate ions either, but the concentration is preferably set to 20000 ppm or less.
• No upper limit is placed on the temperature of the aqueous solution during cathodic electrolysis, but the temperature is preferably set to 50 °C or lower, for example.
• Cathodic electrolysis at temperatures of 50 °C or lower enables the formation of a dense, uniform coating microstructure constituted by very fine particles.
• the temperature of the aqueous solution is preferably set to 10 °C or higher, for example.
• the efficiency of coating formation can be increased.
• the temperature of the aqueous solution is 10 °C or higher, cooling of the solution is not necessary even when the outside temperature is high, such as during the summer, which is economical.
• No lower limit is placed on the pH of the aqueous solution, but the pH is preferably set to 3 or higher. If the pH is 3 or higher, the formation efficiency of Zr oxide or Ti oxide can be further improved.
• No upper limit is placed on the pH of the aqueous solution either, but the pH is preferably set to 5 or less. A pH of 5 or less prevents the formation of large amounts of precipitation in the aqueous solution and can achieve good continuous productivity.
• Nitric acid, ammonia water, or the like, for example, may be added to the aqueous solution for the purpose of adjusting pH and improving electrolytic efficiency.
• the current density for cathodic electrolysis is, for example, preferably set to 0.05 A/dm 2 or higher, more preferably 1 A/dm 2 or higher. If the current density is 0.05 A/dm 2 or higher, the formation efficiency of Zr oxide or Ti oxide is improved. As a result, a more stable coating layer containing Zr oxide or Ti oxide can be generated, further improving sulfide staining resistance and anti-yellowing property.
• No upper limit is placed on the current density during cathodic electrolysis, but the current density is, for example, preferably set to 50 A/dm 2 or less, more preferably 10 A/dm 2 or less. If the current density is 50 A/dm 2 or less, the efficiency of generating Zr oxides or Ti oxides can be made appropriate, and the generation of coarse Zr oxide or Ti oxide with poor adhesion can be suppressed.
• the current pattern in the aforementioned cathodic electrolysis may be continuous current passage or intermittent current passage.
• the relationship between the aqueous solution and the steel sheet during the aforementioned cathodic electrolysis is not limited, and the solution may be relatively stationary or moving.
• cathodic electrolysis is preferably conducted while the steel sheet and the aqueous solution are moved relative to each other.
• cathodic electrolysis can be performed continuously while passing a steel sheet through a treatment tank housing an aqueous solution containing at least one of Zr ions and Ti ions, so that the steel sheet and the aqueous solution are moved relative to each other.
• the relative flow speed between the aqueous solution and the steel sheet is preferably 50 m/min or more. If the relative flow speed is 50 m/min or more, the pH of the steel sheet surface where hydrogen is generated together with current passage can be made more uniform, effectively suppressing the formation of coarse Zr oxide or Ti oxide. No upper limit is placed on the relative flow speed.
• the mechanism by which the surface conditioning process can fix the coating layer in a highly hydrophilic state is not clear but is thought to be as follows.
• the surface of the coating layer is slightly etched, forming minute irregularities on the surface of the coating layer.
• the action of these minute irregularities results in a high degree of hydrophilicity.
• This hydrophilicity is different from the hydrophilicity resulting from the presence of hydrophilic functional groups, such as OH groups, and is due to the physical structure provided by the surface roughness, which also has excellent stability with respect to heat.
• the steel sheet after the surface conditioning process is subjected to water washing at least once.
• Water washing removes any residual aqueous solution from the surface of the steel sheet.
• the water washing is not limited and may be performed by any method.
• a water washing tank can be installed downstream from the tank for coating formation, and the steel sheet after the coating formation process can be continuously immersed in water. Water washing may also be performed by spraying water on the steel sheet after the coating formation process.
• the number of times the water washing is performed is not limited and may be one or more. However, to avoid an excessively large number of water washing tanks, the number of times water washing is performed is preferably five or less. In the case of performing water washing treatment two or more times, each water washing may be performed in the same or a different manner.
• water with an electrical conductivity of 100 ⁇ S/m or less at least in the last water washing of the water washing process. This reduces the amount of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet and thereby improves adhesion.
• Water with an electrical conductivity of 100 ⁇ S/m or less can be produced by any method.
• the water with an electrical conductivity of 100 ⁇ S/m or less may, for example, be reverse osmosis water, ion-exchanged water, or distilled water.
• the electrical conductivity of the water used for water washing can be measured using a conductivity meter.
• any water can be used for the water washing other than the last water washing, since the above-described effect can be obtained by using water with an electrical conductivity of 100 ⁇ S/m or less for the last water washing.
• Water with an electrical conductivity of 100 ⁇ S/m or less may also be used for water washing other than the last water washing.
• water with an electrical conductivity of 100 ⁇ S/m or less is preferably used only for the last water washing, with normal water such as tap water or industrial water being used for water washing other than the last water washing.
• the electrical conductivity of the water used for the last water washing is preferably set to 50 ⁇ S/m or less, more preferably 30 ⁇ S/m or less.
• no lower limit is placed on the electrical conductivity, and the electrical conductivity may be 0 ⁇ S/m.
• the electrical conductivity is preferably set to 1 ⁇ S/m or more.
• the water washing time is preferably 0.1 seconds or longer, more preferably 0.2 seconds or longer.
• No upper limit is placed on the water washing time per water washing treatment either, but in the case of production on a continuous line, the water washing time is preferably 10 seconds or less, more preferably 8 seconds or less, because a longer water washing time reduces the line speed and lowers productivity.
• surface-treated steel sheets were produced by the following procedures, and their properties were evaluated.
• the present disclosure is not, however, limited to the following examples.
• Ni-Fe alloy layer was formed as the Ni-containing layer. That is, after forming the Ni plating layer by the above-described method, a Ni-Fe alloy layer was formed by annealing.
• the surface of the pretreated steel sheet with the Ni-containing layer formed thereon was treated with an aqueous solution to form a coating layer on the Ni-containing layer.
• an aqueous solution with the composition illustrated in Table 1 was used as the aqueous solution, and the coating layer was formed by performing cathodic electrolysis in the aqueous solution.
• the temperature of the aqueous solution was set to 35 °C, and the pH was adjusted to be between 3 and 5.
• the Zr coating weight and Ti coating weight were controlled by adjusting the electrical density.
• Zirconium fluoride (ZrF 4 ) was used as the Zr-containing compound and titanium fluoride (TiF 4 ) as the Ti-containing compound.
• the aqueous solution was prepared by adjusting the concentration of each ion through use of additional compounds other than the Zr-containing compound and the Ti-containing compound for the aqueous solution to have the compositions illustrated in Table 1.
• surface conditioning was performed under the set of conditions illustrated in Tables 2 and 3. Specifically, at the end of the coating formation process, the steel sheet having the aqueous solution adhering to its surface was squeezed with a wringer roll to adjust the amount of aqueous solution present on the surface of the coating layer to the amounts listed in Tables 2 and 3. The amount of aqueous solution was measured by a moisture meter using a filter-type infrared absorption method, as described above. The steel sheets were then held for the holding time illustrated in Tables 2 and 3. In other words, the aqueous solution used in the surface conditioning process is the same as that used in the aforementioned coating formation process.
• the coating weight of Zr oxide, the coating weight of Ti oxide, the P coating weight, and the Mn coating weight in the coating layer were measured for each of the obtained surface-treated steel sheets.
• the measurements were performed by the above-described calibration curve method using X-ray fluorescence.
• the measurement results are listed in Tables 4 and 5.
• the coating weight for Zr oxide and Ti oxide are listed as the amount of metal Zr and amount of metal Ti, respectively.
• the water contact angle was measured using an automatic contact angle meter, model CA-VP, produced by Kyowa Interface Science Co., Ltd.
• the surface temperature of the surface treated steel sheet was 20 °C ⁇ 1 °C, and distilled water at 20 °C ⁇ 1°C was used.
• a 2 ⁇ l drop of distilled water was dropped onto the surface of the surface-treated steel sheet, and the contact angle was measured 1 second later by the ⁇ /2 method.
• the arithmetic mean value of the contact angles of 5 drops was used as the water contact angle.
• the contact angle was also measured after the surface-treated steel sheet was subjected to heat treatment at 200 °C for 10 minutes.
• the measurement conditions were the same as above.
• the contact angle values were substantially the same before and after heat treatment for the surface-treated steel sheets meeting the conditions of the present disclosure.
• some of the surface-treated steel sheets that did not meet the conditions of the present disclosure exhibited significant changes in contact angle values due to heat treatment.
• the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet to all elements was measured by XPS. No sputtering was performed in the measurements. From the integrated intensity of the narrow spectra of K2p, Nals, Ca2p, and Mgls at the top surface of the sample, the detected atomic ratios to all elements were quantified using the relative sensitivity factor method and calculated as (K atomic ratio + Na atomic ratio + Ca atomic ratio + Mg atomic ratio).
• the scanning X-ray photoelectron spectrometer PHI X-tool produced by ULVAC-PHI, was used, with the X-ray source being a monochrome AlK ⁇ beam, the voltage being 15 kV, the beam diameter being 100 ⁇ m ⁇ , and the take-off angle being 45°.
• a commercial epoxy resin paint for cans was applied at a dry mass of 60 mg/dm 2 , subsequently baked at 200 °C for 10 minutes, and then left at room temperature for 24 hours. The resulting steel sheet was then cut to a predetermined size.
• the resulting aqueous solution was poured into a pressure-resistant, heat-resistant container made of Teflon ® (Teflon is a registered trademark in Japan, other countries, or both).
• Teflon is a registered trademark in Japan, other countries, or both.
• the steel sheet cut to the predetermined size was immersed in the aqueous solution, and the lid of the container was closed and sealed.
• the sealed container was subjected to retort treatment at a temperature of 131 °C for 60 minutes.
• the sulfide staining resistance was evaluated based on the appearance of the steel sheet after the retort treatment. No change whatsoever in the appearance before and after the test was evaluated as "1”, the occurrence of blackening in 10 % by area or less was evaluated as “2”, the occurrence of blackening in 20 % or less by area and more than 10 % by area was evaluated as "3”, and the occurrence of blackening in more than 20 % by area was evaluated as "4".
• a rating of 1 to 3 indicates excellent sulfide staining resistance in practical use and was thus considered passing.
• the surface of the resulting surface-treated steel sheet was coated with an epoxy phenolic paint and baked at 210 °C for 10 minutes to produce a prepainted steel sheet.
• the coating weight of the paint was 50 mg/dm 2 .
• Two prepainted steel sheets made under the same conditions were stacked so that the coated surfaces faced each other with a nylon adhesive film therebetween and were then pressure bonded under a set of conditions including a pressure of 2.94 ⁇ 10 5 Pa, a temperature of 190 °C, and a pressure bonding time of 30 seconds.
• the bonded steel sheets were then divided into 5 mm wide test pieces.
• the divided test pieces were immersed for 168 hours in a 55 °C test solution consisting of a mixed aqueous solution containing 1.5 mass% citric acid and 1.5 mass% common salt. After immersion and subsequent washing and drying, the two steel sheets of the divided test pieces were pulled apart in a tensile tester, and the tensile strength at the time of separation was measured.
• the average of three test pieces was evaluated at the following four levels. For practical purposes, a result of 1 to 3 can be evaluated as excellent paint secondary adhesion.
• Table 1 Aqueous solution Composition (ppm) Zr 4+ Ti 4+ Mn 4+ PO 4 3- F NO 3 3- NH 4 + A 3000 - - - 4000 - - B 1500 - - - 2000 3000 2000 C 2000 - - 950 2000 1600 1000 D 2000 - - 950 2000 7000 2500 E 2000 2000 - 950 2000 7000 2500 F - 1500 - - 2000 3000 2000 G - 2000 - 950 2000 1600 1000 H - 2000 - 950 2000 7000 2500 I 2000 2000 2000 950 2000 7000 2500

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