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
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
• • 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
  • 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
  • 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
  • C23C22/368—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 magnesium cations
• • 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
  • C23C22/78—Pretreatment of the material to be coated
• • 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
  • 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
  • C25D5/10—Electroplating with more than one layer of the same or of different metals
  • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
• • 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
  • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
• • 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
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
• • 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
  • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
• • 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
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/30—Electroplating: Baths therefor from solutions of tin
• • 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
  • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

Definitions

• the present invention relates to a steel plate for containers used for DI cans, food cans, beverage cans, etc., and particularly to a steel plate for containers coated with a treatment liquid not containing Cr.
• a tin-plated steel plate conventionally referred to as “blink” As a steel plate for containers (surface-treated steel plate for cans), a tin-plated steel plate conventionally referred to as “blink” has been widely used.
• the surface of the tin-plated surface is usually obtained by immersing the steel plate in an aqueous solution containing a hexavalent chromium compound such as dichromic acid, or by performing a chromate treatment such as performing an electrolytic treatment in this solution.
• a chromate film is formed on the surface. Formation of the chromate film prevents oxidation of the tin plating surface, which is likely to occur during long-term storage, and suppresses deterioration of the appearance (yellowing).
• Patent Document 1 discloses a steel plate for containers provided with a base Ni layer, a Sn plating layer, a chemical conversion treatment layer containing tin oxide and tin phosphate, and a Zr-containing coating layer on the steel plate surface.
• Patent Document 2 a surface treatment layer containing one or more of Sn, Ni, Fe, Cr, and hydrated Cr oxide, Ti or Zr or a compound thereof, a phosphoric acid compound, and organosilicon A steel sheet for a laminate container provided with a film made of an organic resin containing a compound is disclosed.
• the present invention provides a steel plate for containers that exhibits excellent appearance characteristics and excellent paint adhesion and anti-sulfur blackening resistance after high-temperature retort treatment without containing Cr in the film. With the goal.
• the present inventors provide a coating containing a predetermined amount of tin oxide and a predetermined amount of Zr, Ti, and P on a steel plate with a tin plating layer.
• a desired effect can be obtained. That is, the present inventors have found that the above problem is solved by the following configuration.
• a steel plate for containers, The coating contains tin oxide, and Zr, Ti and P; The amount of electricity required for the reduction of the tin oxide is 0.20 to 3.50 mC / cm 2 , The metal zirconium content in the film is 1.0 ⁇ 40.0 mg / m 2, the metal titanium amount 0.01 mg / m 2 Ultra 2.50 mg / m less than 2, the amount of phosphorus is 0.10 ⁇ 10.00 mg / m 2. Steel plate for containers.
• the amount of phosphorus present in the region from the outermost surface opposite to the steel plate side of the coating to the middle portion of the depth corresponding to 1 ⁇ 2 of the total thickness is 70% or more of the total phosphorus content in the coating.
• a steel plate for containers having a coated film The coating contains tin oxide, and Zr, Ti and P; The amount of electricity required for the reduction of the tin oxide is 0.20 to 3.50 mC / cm 2 , The metal zirconium content in the film is 1.0 ⁇ 40.0 mg / m 2, the metal titanium content is 0.01 mg / m 2 Ultra 2.50 mg / m less than 2, the amount of phosphorus is 0.10 ⁇ 10.00 mg / m 2 and A steel plate for containers in which zirconium oxyacetate or zirconium acetate is used as a source of the Zr ions. (6) The steel plate for containers according to (2), wherein the film is formed by cathodic electro
• the present invention it is possible to provide a steel plate for containers that exhibits excellent appearance characteristics, excellent paint adhesion and high resistance to sulfurization blackening after high-temperature retort treatment without containing Cr in the film.
• a tin-plated steel sheet (steel-plated steel sheet) has a coating containing a predetermined amount of tin oxide and a predetermined amount of Zr, Ti, and P.
• a predetermined amount of tin oxide and a predetermined amount of Zr, Ti, and P.
• Cr is not used, it is excellent in external appearance characteristics, and is excellent in paint adhesion after high-temperature retort and resistance to sulfur blackening.
• a good paint after a high temperature retort which has been difficult to achieve in the past, by further containing a predetermined amount of tin oxide, a predetermined amount of Zr, and a small amount of Ti in a film containing a predetermined amount of P. It has been found that adhesion and sulfur blackening resistance can be imparted. Furthermore, when a fluorine-free compound (zirconium compound) such as zirconium oxyacetate or zirconium acetate is used in the treatment liquid, the deposited film has a higher level of adhesion, and the paint adhesion after high temperature retort is the same as above. And extremely excellent performance in sulfur blackening resistance.
• the Ti compound deposited in the film has a large specific surface area and a needle-like shape, and the adhesion between the coating film and the film by the anchor effect of the compound
• the effect of the present invention is synergistically improved by suppressing the diffusion of moisture at a high temperature at the interface between the coating film and the film, and forming a complex compound with Zr in the film. Etc. are considered.
• the steel plate for containers of the present invention has a steel plate with a tin plating layer and a film disposed on the surface on the tin plating layer side of the steel plate with a tin plating layer.
• coat are explained in full detail. First, the aspect of the steel plate with a tin plating layer is explained in full detail.
• the steel sheet with a tin plating layer has a tin plating layer that covers at least a part of the surface of the steel sheet and the steel sheet.
• the type of the steel plate in the steel plate with the tin plating layer is not particularly limited, and a steel plate (for example, a low carbon steel plate or an extremely low carbon steel plate) that is usually used as a container material can be used.
• the manufacturing method and material of the steel plate are not particularly restricted, and the steel plate is manufactured through a normal slab manufacturing process through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling.
• a steel sheet having a nickel (Ni) -containing layer formed on the surface thereof may be used, and a tin plating layer may be formed on the Ni-containing layer.
• Ni-containing layer only needs to contain nickel, and examples thereof include a Ni plating layer and a Ni—Fe alloy layer.
• the method for applying the Ni-containing layer to the steel plate is not particularly limited, and examples thereof include known methods such as electroplating.
• the Ni diffusion layer is coordinated to form a Ni—Fe alloy layer by annealing after applying Ni on the steel sheet surface by electroplating or the like. Can do.
• the amount of Ni in the Ni-containing layer is not particularly limited, and is preferably 50 to 2000 mg / m 2 in terms of metallic Ni per side. If it is in the above-mentioned range, it is more excellent in resistance to sulfur blackening and is advantageous in terms of cost.
• the steel plate with a tin plating layer has a tin plating layer on the steel plate surface.
• the tin plating layer only needs to be provided on at least one side of the steel plate, and may be provided on both sides.
• the Sn adhesion amount per one surface of the steel sheet in the tin plating layer is preferably 0.1 to 15.0 g / m 2 .
• the Sn adhesion amount is within the above range, the outer appearance characteristics and corrosion resistance of the steel plate for containers are excellent.
• 0.2 to 15.0 g / m 2 is preferable from the viewpoint that these characteristics are more excellent, and 1.0 to 15.0 g / m 2 is further preferable from the viewpoint of better workability.
• the Sn adhesion amount can be measured by surface analysis by a coulometric method or fluorescent X-ray.
• fluorescent X-rays a calibration curve relating to the amount of metallic Sn is specified in advance using an Sn adhesion amount sample with a known amount of metallic Sn, and the amount of metallic Sn is relatively identified using the calibration curve.
• the tin plating layer is a layer covering at least a part on the surface of the steel plate, and may be a continuous layer or a discontinuous island shape.
• the tin plating layer is a tin plating layer obtained by plating tin, or by heating and melting tin by reflow treatment that is energized and heated after tin plating, and the tin plating bottom layer (tin plating / base metal interface) is Fe- A tin plating layer in which a part of the Sn alloy layer is formed is also included.
• tin plating layer tin plating is performed on a steel sheet having a Ni-containing layer on the surface, and further tin is heated and melted by reflow treatment, etc., and the tin plating bottom layer (tin plating / base metal interface)
• a tin plating layer in which a Fe—Sn—Ni alloy, a Fe—Sn alloy layer or the like is partially formed is included.
• a known method for example, an electroplating method or a method of plating by immersing in molten Sn
• a phenol sulfonate tin plating bath, a methane sulfonate tin plating bath, or a halogen-based tin plating bath is used, and Sn is applied to the surface of the steel sheet so that the adhesion amount per side becomes a predetermined amount (for example, 2.8 g / m 2 ).
• a reflow treatment is performed at a temperature equal to or higher than the melting point of Sn (231.9 ° C.), and a tin plating layer in which an Fe—Sn alloy layer is formed as the lowermost layer of the tin single plating layer can be manufactured.
• a tin plating layer can be produced.
• the steel sheet has a Ni-containing layer on its surface
• a tin plating layer is formed on the Ni-containing layer and reflow treatment is performed.
• -Sn-Ni alloy layer, Fe-Sn alloy layer and the like are formed.
• membrane is arrange
• the coating contains tin oxide and Zr, Ti and P as its components. First, each component will be described in detail below, and then the method for forming the film will be described in detail.
• the coating contains tin oxide, and its content is 0.20 to 3.50 mC / cm 2 as the amount of electricity required for reduction. Within this range, the sulfur blackening resistance is excellent.
• the amount of electricity is preferably 0.30 mC / cm 2 or more, and more preferably 0.70 to 1.80 mC / cm 2 in terms of more excellent characteristics. If the quantity of electricity required for reduction of the tin oxide is less than 0.20mC / cm 2, and, if it exceeds 3.50mC / cm 2, the appearance characteristics of the vessel steel plate, paint adhesion, or sulfurization blackening poor .
• the amount of electricity required for the reduction of tin oxide is a constant current of 0.05 mA / cm 2 in a 0.001 mol / L hydrobromic acid aqueous solution from which dissolved oxygen has been removed by means such as bubbling of nitrogen gas. It can be obtained from the potential-time curve obtained by cathodic electrolysis of the steel plate for containers of the invention.
• the coating contains Zr (zirconium), Ti (titanium) and P (phosphorus). More specifically, the film contains Zr (zirconium element), and the amount of metal zirconium (the amount of metal Zr in the film) is 1.0 to 40.0 g / m 2 . When the amount of metal zirconium is within the above range, the container steel plate is excellent in appearance characteristics, paint adhesion, and resistance to sulfur blackening.
• the metal zirconium content is preferably 2.5 ⁇ 40mg / m 2, 2.5 and more preferably from ⁇ 18.0mg / m 2, 4.0 ⁇ 12.0mg / m 2 is more preferable.
• the film contains Ti (titanium element), and the amount of metal titanium (the amount of metal Ti in the film) is more than 0.01 mg / m 2 and less than 2.50 mg / m 2 . If the amount of metal titanium is within the above range, the paint adhesion and sulfur blackening resistance are excellent. Furthermore, in terms of appearance characteristics more excellent, Ti adhesion amount is preferably from 1.50 mg / m 2 or less, more preferably less than 1.00 mg / m 2, more preferably 0.05 ⁇ 0.90mg / m 2. In addition, when the amount of metal titanium is 0.01 mg / m 2 or less, paint adhesion or sulfide blackening resistance is poor. When the amount of metal titanium is 2.50 mg / m 2 or more, the appearance has an interference color, and the appearance characteristics are inferior, or the sulfide blackening resistance is inferior.
• the coating contains P (phosphorus element), and the phosphorus content (P content in the coating) is 0.10 to 10.00 mg / m 2 .
• P is necessary to maintain paint adhesion. If the amount of phosphorus is in the above range, the steel sheet for containers is excellent in appearance characteristics, paint adhesion, and resistance to sulfur blackening. Among them, in terms of sulfidation blackening more excellent, phosphorus content is preferably 1.00 ⁇ 10.00mg / m 2, more preferably 1.00 ⁇ 5.00mg / m 2. Note that when phosphorus content is less than 0.10 mg / m 2, and in the case of 10.00 mg / m 2 greater, poor paint adhesion or sulfidation blackening.
• the amount of metallic zirconium, the amount of metallic titanium, and the amount of phosphorus described above can be measured by surface analysis using fluorescent X-rays.
• membrane is contained as zirconium compounds, such as a zirconium oxide, a zirconium hydroxide, a zirconium fluoride, a zirconium phosphate, or these composite compounds, for example.
• the said metal zirconium amount means the Zr conversion amount of these zirconium compounds.
• Ti in the film is contained as a titanium compound such as titanium phosphate, titanium hydrated oxide, or a composite compound thereof.
• the amount of metallic titanium means the Ti equivalent amount of these titanium compounds.
• P in the film is, for example, phosphoric acid such as iron phosphate, nickel phosphate, tin phosphate, zirconium phosphate, or a composite compound thereof formed by reacting with the base (steel plate, tin plating layer). Included as a compound.
• the atomic ratio (Ti / Zr) of Ti and Zr on the outermost surface of the film is 0.1 to 0.4, and P and Zr In which the atomic ratio (P / Zr) is 0.7 to 1.4. If it is this aspect, the coating-material adhesiveness of a steel plate for containers and sulfide blackening-proof are more excellent.
• the atomic ratio is obtained by analyzing the peaks of Zr3d, Ti3d, and P2p by XPS analysis.
• XPS analysis include the following conditions.
• Equipment: AXIS-HS, Shimadzu / KRATOS X-ray source: Monochrome AlK ⁇ ray (hv 14866.6 eV)
• the amount of phosphorus present in the region from the outermost surface of the film (the outermost surface opposite to the steel plate side) to the middle part of the depth corresponding to 1/2 of the entire thickness of the film A mode in which (P amount) is 70% or more of the total phosphorus amount (P amount existing in a region up to a depth corresponding to the entire thickness) is mentioned.
• P amount 70% or more of the total phosphorus amount (P amount existing in a region up to a depth corresponding to the entire thickness)
• it is 80% or more, an upper limit in particular is not restrict
• the network structure of a phosphoric acid component is located in the outermost surface vicinity of a membrane
• a method for identifying the intermediate portion for example, when analyzed by XPS, from the position where the Zr intensity is first recognized (Ar sputtering start position (time)) to the position where the Zr intensity disappears by Ar sputtering (time) Is a region up to a depth corresponding to the entire thickness of the film, and a half of the sputtering time corresponds to the middle part of the film.
• XPS analysis include the following conditions.
• Measurement area Hybrid mode 250 ⁇ 500 ( ⁇ m)
• the method for forming the film described above is not particularly limited as long as it can form a film containing a predetermined amount of tin oxide and a predetermined amount of Zr, Ti, and P.
• a method comprising a step (2) of immersing a steel plate in a treatment solution containing ions or subjecting the immersed steel plate to cathodic electrolysis treatment is preferred.
• step (1) and step (2) will be described in detail.
• Step (1) is a step of subjecting the steel plate with a tin plating layer to cathodic electrolysis in an alkaline aqueous solution (particularly, an aqueous sodium carbonate solution).
• an alkaline aqueous solution particularly, an aqueous sodium carbonate solution.
• the surface of the tin-plated layer is oxidized to form tin oxide.
• unnecessary tin oxide can be removed and the amount of tin oxide can be adjusted.
• tin oxide is also formed when a steel sheet is processed using a treatment liquid containing Ti ions, Zr ions, and phosphate ions, but the amount of tin oxide after film formation is within a predetermined range.
• a treatment liquid containing Ti ions, Zr ions, and phosphate ions but the amount of tin oxide after film formation is within a predetermined range.
• Examples of the solution used for the cathodic electrolysis include an alkaline aqueous solution (for example, an aqueous sodium carbonate solution).
• concentration of the alkali component (for example, sodium carbonate) in the alkaline aqueous solution is not particularly limited, but is preferably 5 to 15 g / L, more preferably 8 to 12 g / L from the viewpoint that removal of tin oxide proceeds more efficiently. preferable.
• the liquid temperature of the alkaline aqueous solution during the cathodic electrolysis is not particularly limited, but is preferably 40 to 60 ° C. in terms of more excellent appearance characteristics.
• the electrolysis conditions (current density, electrolysis time) of the cathodic electrolysis are appropriately adjusted so as to obtain a tin oxide showing the amount of electricity required for the desired reduction described above.
• Step (2) is a step of forming a film containing predetermined amounts of Zr, Ti, and P. This is a step of immersing a steel plate in a treatment solution containing Ti ions, Zr ions, and phosphate ions (immersion treatment), or subjecting the immersed steel plate to cathodic electrolysis.
• Cathodic electrolytic treatment is preferable because a uniform film can be obtained at a higher speed than immersion treatment.
• the treatment liquid to be used examples include liquids containing Zr ions, Ti ions, and phosphate ions.
• Zr compounds that do not contain fluorine atoms such as those containing fluorozirconic acid, hexafluorozirconic acid, ammonium hexafluorozirconate, potassium hexafluorozirconate, zirconic hydrofluoric acid, and the like.
• the Ti ion supply source only needs to contain Ti element, and examples thereof include fluorinated titanic acid, ammonium fluorinated titanate, potassium fluorinated titanate, potassium titanate, and calcium titanate.
• the phosphate ion supply source only needs to contain element P, and examples thereof include orthophosphoric acid, sodium phosphate, sodium hydrogen phosphate, primary aluminum phosphate, primary magnesium phosphate, primary calcium phosphate, and the like. .
• the concentration of each ion in the treatment liquid is not particularly limited as long as a desired amount of film can be obtained.
• the Zr ion concentration in the treatment liquid is preferably 0.30 to 5.0 g / l
• the Ti ion concentration is preferably 0.001 to 2 g / l, in view of easy control of the adhesion amount.
• the (PO 4 3 ⁇ ) ion concentration is preferably 0.01 to 5.0 g / l.
• Water is usually used as the solvent in the treatment liquid, but an organic solvent may be used in combination.
• the pH of the treatment liquid is not particularly limited as long as it is appropriately controlled from the deposition efficiency of Zr, Ti and P, but is preferably pH 2.0 to 5.0. Within this range, the treatment time can be shortened and the stability of the treatment liquid is excellent.
• a known acid component for example, phosphoric acid, sulfuric acid
• alkali component for example, sodium hydroxide, aqueous ammonia
• the treatment liquid may contain a surfactant such as sodium lauryl sulfate or acetylene glycol as necessary. Further, from the viewpoint of the stability of the adhesion behavior over time, the treatment liquid may contain a condensed phosphate such as pyrophosphate.
• the temperature of the treatment liquid at the time of carrying out the treatment is preferably 20 to 80 ° C., more preferably 40 to 60 ° C. from the viewpoint of excellent film formation efficiency and tissue uniformity and low cost.
• the electrolysis current density at the time of carrying out the cathodic electrolysis treatment is preferably a low current density from the viewpoint of better appearance characteristics and resistance to sulfur blackening, and more specifically 0.05 to 7 A / dm 2. Is preferable, and 0.5 to 5 A / dm 2 is more preferable.
• the energization time of the cathodic electrolysis treatment is preferably 0.1 to 5 seconds from the viewpoint that a decrease in the adhesion amount can be further suppressed and a film can be stably formed, and a decrease in the characteristics of the formed film can be further suppressed. 0.3 to 2 seconds is more preferable.
• the electric density at the time of cathodic electrolysis is preferably 0.20 to 3.50 C / dm 2 and more preferably 0.40 to 2.00 C / dm 2 from the viewpoint of more excellent appearance characteristics.
• it in order to cope with the more severe antisulfurization blackening with a retort time of 3 hours or more, it contains a predetermined amount of tin oxide and a predetermined amount of Zr, Ti, and P, and further, predetermined Ti and Zr And the atomic ratio (Ti / Zr) of P and the atomic ratio of P and Zr (P / Zr) can be formed, and the electric density is 0.40 to 1.50 C / dm 2. preferable.
• the water-washing process and / or drying of the obtained steel plate may be performed as needed.
• it does not specifically limit about the temperature and system in the case of drying For example, a normal dryer and an electric furnace drying system are applicable.
• temperature in the case of a drying process 100 degrees C or less is preferable. If it is in the said range, the oxidation of a film
• the lower limit is not particularly limited, but is usually about room temperature.
• the steel plate for containers obtained by the above treatment is used for manufacturing various containers such as DI cans, food cans and beverage cans.
• a steel plate with a tin plating layer was produced by the following two methods [(K-1) and (K-2)].
• K-1) Electrolytic degreasing and pickling were performed on a steel plate (T4 original plate) having a plate thickness of 0.22 mm, and then tin plating with a Sn adhesion amount per one side shown in Table 3 was performed. Subsequently, a reflow treatment was performed at a temperature equal to or higher than the melting point of Sn to form a Sn layer on the Fe—Sn alloy layer and its upper layer, thereby manufacturing a steel plate with a tin plating layer.
• K-2 A steel plate (T4 original plate) having a thickness of 0.22 mm is electrolytically degreased and a nickel plating layer is formed with a Ni adhesion amount per one side shown in Table 3 using a Watt bath, and then a 10 vol.% H 2 +90 vol.% N 2 atmosphere
• An Fe—Ni alloy layer (Ni-containing layer) (shown in Ni deposition amount in Table 3) was formed by annealing at 700 ° C. and allowing nickel plating to diffuse and penetrate. Subsequently, the steel sheet having the Ni-containing layer as the surface layer was subjected to tin plating with an Sn adhesion amount per one side shown in Table 3 using a tin plating bath.
• a reflow treatment was performed at a temperature equal to or higher than the melting point of Sn to form a discontinuous Sn layer on the Fe—Ni—Sn alloy layer and its upper layer, and a steel plate with a tin plating layer was manufactured.
• the component amount (mg / m 2 ) in each layer in Table 3 was measured using fluorescent X-rays (manufactured by Rigaku Corporation).
• Sn adhesion amount and Ni adhesion amount mean the adhesion amount per one surface of a steel plate.
• Ti / Zr (atomic ratio)” and “P / Zr (atomic ratio)” in Table 3 are atomic ratios of Ti and Zr on the outermost surface of the film (the outermost surface opposite to the steel plate side). (Ti / Zr) and the atomic ratio of P and Zr (P / Zr).
• “P abundance ratio” in Table 3 is a region from the outermost surface on the opposite side to the steel plate side of the coating to the middle portion of the depth corresponding to 1 ⁇ 2 of the total thickness of the coating with respect to the total phosphorus content in the coating The ratio (%) of the amount of phosphorus in.
• P existence ratio The ratio of the integrated value (P intensity) from the position where the Zr intensity is initially recognized to the intermediate portion to the integrated value (P intensity) from the position where the Zr intensity is initially recognized to the position where the Zr intensity disappears.
• P existence ratio The ratio of the integrated value (P intensity) from the position where the Zr intensity is initially recognized to the intermediate portion to the integrated value (P intensity) from the position where the Zr intensity is initially recognized to the position where the Zr intensity disappears.
• amount of tin oxide (mC / cm 2 ) is 0.001 mol / L hydrobromic acid aqueous solution degassed by nitrogen bubbling with respect to the steel plate obtained above. A constant current cathodic electrolysis of 05 mA / cm 2 was performed, and the amount of electricity required for reduction was determined from the obtained potential-time curve.
• sulfurization blackening resistance 1 indicates the evaluation result of discoloration of the above ⁇ sulfuration blackening resistance 1>.
• 1> shows the tape peeling evaluation
• sulfurization blackening resistance 2 shows the evaluation result of discoloration of the above ⁇ sulfuration blackening resistance 2>.
• the steel plate for containers of the present invention was excellent in paint adhesion, resistance to sulfur blackening, and appearance characteristics. Further, from Examples 7, 8, 9, 17, and 19, the atomic ratio of Ti and Zr (Ti / Zr) and the atomic ratio of P and Zr (P When / Zr) is within the predetermined range, it was confirmed that the paint adhesion and the resistance to sulfur blackening were more excellent. Moreover, from Example 18, when P presence rate was more than predetermined value, it was confirmed that sulfide blackening-proof is more excellent. Further, from Examples 10, 16, and 19, it was confirmed that the appearance characteristics were more excellent when the amount of metal titanium was small (particularly, less than 1.0 mg / m 2 ).
• the film shown in Comparative Example 1 can achieve a predetermined effect, but contains Cr. Further, as shown in Comparative Examples 2 to 11, when any of the amount of electricity required for reduction of tin oxide, the amount of metal zirconium in the coating, the amount of metal titanium, or the amount of phosphorus is outside the predetermined range, the paint adhesion -It was confirmed that it was inferior to at least one of sulfur blackening resistance and appearance characteristics.

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