WO2018225739A1 - 缶用鋼板およびその製造方法 - Google Patents
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- WO2018225739A1 WO2018225739A1 PCT/JP2018/021570 JP2018021570W WO2018225739A1 WO 2018225739 A1 WO2018225739 A1 WO 2018225739A1 JP 2018021570 W JP2018021570 W JP 2018021570W WO 2018225739 A1 WO2018225739 A1 WO 2018225739A1
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- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- 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
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- 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
- C23C22/37—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 hexavalent chromium compounds
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- 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
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- 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
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- 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
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- 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
- C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
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- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- 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
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- 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
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- 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
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- C25D7/00—Electroplating characterised by the article coated
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- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
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- 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
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
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- 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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
Definitions
- the present invention relates to a steel plate for cans and a manufacturing method thereof.
- Cans which are containers applied to beverages and foods, are used all over the world because the contents can be stored for a long time.
- the can is drawn, ironed, pulled and bent on a metal plate, and the can bottom and can body are integrally formed, and then wrapped with an upper lid.
- It can be broadly divided into a three-piece can that is formed by winding a can body welded by a seam method and both ends thereof with a lid.
- TFS may be inferior in weldability as compared with tinplate.
- the reason for this is that the surface chromium hydrated oxide layer undergoes a dehydration condensation reaction due to baking after coating or heat treatment after laminating the organic resin film, thereby increasing the contact resistance.
- the baking treatment after painting is at a higher temperature than the heat treatment after laminating the organic resin film, so that the weldability tends to be inferior. Therefore, the current TFS enables welding by mechanically polishing and removing the chromium hydrated oxide layer immediately before welding.
- problems such as the risk that the metal powder after polishing is mixed into the contents, an increase in maintenance load such as cleaning of the can-making apparatus, and the risk of fire occurrence due to the metal powder.
- Patent Documents 1 and 2 propose a technique for welding TFS without polishing.
- an object of the present invention is to provide a steel plate for cans excellent in weldability and a method for producing the same.
- the present inventors have found that the weldability of the steel plate for cans is improved by densifying the granular protrusions of the metal chromium layer, and the present invention has been completed. It was.
- a metal chromium layer and a chromium hydrated oxide layer are provided on the surface of the steel plate in this order from the steel plate side, and the adhesion amount of the metal chromium layer is 50 to 200 mg / m 2.
- the oxide layer has a chromium equivalent deposition amount of 3 to 30 mg / m 2
- the metal chromium layer is provided on a base having a thickness of 7.0 nm or more, and the base has a maximum particle size of 200 nm.
- a steel plate for cans comprising: a granular projection having a number density per unit area of 30 / ⁇ m 2 or more.
- the step of performing the treatment 1 comprising the cathodic electrolysis treatment C1 on the steel sheet using the aqueous solution, and the anodic electrolysis on the steel plate subjected to the cathodic electrolysis treatment C1 using the aqueous solution.
- the process of performing the process 2 which consists of the process A1 and the cathodic electrolysis process C2 after the said anodic electrolysis process A1 two times or more.
- the current density of the anodic electrolytic treatment A1 is 0.1 A / dm 2 or more and less than 5.0 A / dm 2
- the electric density of the anodic electrolytic treatment A1 is more than 0.3 C / dm 2 and more than 5.0 C / dm 2.
- a steel plate for cans excellent in weldability and a method for producing the same can be provided.
- FIG. 1 is a cross-sectional view schematically showing an example of a steel plate for cans according to the present invention.
- the steel plate 1 for cans has a steel plate 2.
- the steel plate for cans 1 further has a metal chromium layer 3 and a chromium hydrated oxide layer 4 in order from the steel plate 2 side on the surface of the steel plate 2.
- the metal chromium layer 3 includes a base portion 3a that covers the steel plate 2 and a granular protrusion 3b that is provided on the base portion 3a.
- the thickness of the base 3a is 7.0 nm or more.
- the granular protrusions 3b have a maximum particle size of 200 nm or less and a number density per unit area of 30 pieces / ⁇ m 2 or more.
- the adhesion amount of the metal chromium layer 3 including the base portion 3a and the granular protrusion 3b is 50 to 200 mg / m 2 .
- the chromium hydrated oxide layer 4 is disposed on the metal chromium layer 3 so as to follow the shape of the granular protrusion 3b.
- the chromium equivalent amount of the hydrated chromium oxide layer 4 is 3 to 30 mg / m 2 .
- the amount of adhesion is the amount of adhesion per one side of the steel sheet.
- the kind of steel plate is not particularly limited. Usually, a steel plate (for example, a low carbon steel plate or an ultra low carbon steel plate) used as a container material can be used.
- the manufacturing method and material of the steel plate are not particularly limited. It is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, temper rolling and the like from a normal billet manufacturing process.
- the steel plate for cans of this invention has a metal chromium layer on the surface of the steel plate mentioned above.
- the role of metallic chromium in general TFS is to improve the corrosion resistance by suppressing the surface exposure of the steel sheet as the material. If the amount of metal chromium is too small, exposure of the steel sheet is unavoidable, and the corrosion resistance may deteriorate.
- the adhesion amount of the metal chromium layer is 50 mg / m 2 or more, and from the reason that the corrosion resistance is more excellent, 60 mg / m 2 or more is preferable, and 65 mg / m 2 or more is more.
- 70 mg / m 2 or more is more preferable.
- the adhesion amount of the metal chromium layer is 200 mg / m 2 or less, and from the reason that the weldability is more excellent, 180 mg / m 2 or less is preferable, and 160 mg / m 2 or less. Is more preferable.
- the adhesion amount of the metal chromium layer and the adhesion amount in terms of chromium of the chromium hydrated oxide layer described later are measured as follows. First, about the steel plate for cans in which the metal chromium layer and the chromium hydrated oxide layer are formed, a chromium amount (total chromium amount) is measured using a fluorescent X-ray apparatus. Next, the steel plate for cans is subjected to an alkali treatment in which the steel plate for cans is immersed in 6.5N-NaOH at 90 ° C.
- the amount of chromium (the amount of chromium after alkali treatment) is measured using an X-ray fluorescence apparatus. .
- the amount of chromium after alkali treatment is defined as the amount of deposited metal chromium layer.
- (alkali-soluble chromium amount) (total chromium amount) ⁇ (chromium amount after alkali treatment) is calculated, and the alkali-soluble chromium amount is defined as the amount of deposited chromium equivalent of the chromium hydrated oxide layer.
- Such a metal chromium layer includes a base and granular protrusions provided on the base. Next, each of these parts included in the metal chromium layer will be described in detail.
- the base of the metal chromium layer mainly serves to cover the steel plate surface and improve the corrosion resistance.
- the base of the metal chromium layer in the present invention inevitably breaks the base due to the granular protrusions provided on the surface layer when the steel plates for cans inevitably contact each other during handling. Therefore, it is necessary to ensure a sufficient uniform thickness so that the steel plate is not exposed.
- the present inventors conducted a rubbing test between steel plates for cans and investigated rust resistance. As a result, it was found that if the thickness of the base portion of the metal chromium layer is 7.0 nm or more, the rust resistance is excellent. That is, the thickness of the base portion of the metal chromium layer is 7.0 nm or more because the rust resistance of the steel plate for cans is excellent, and 9.0 nm or more is preferable because the rust resistance is more excellent. 0.0 nm or more is more preferable.
- the upper limit of the thickness of the base part of a metal chromium layer is not specifically limited, For example, it is 20.0 nm or less, and 15.0 nm or less is preferable.
- the thickness of the base portion of the metal chromium layer is measured as follows. First, a cross-sectional sample of a steel plate for a can on which a metal chromium layer and a chromium hydrated oxide layer are formed is produced by a focused ion beam (FIB) method and observed at 20,000 times with a scanning transmission electron microscope (TEM). To do.
- FIB focused ion beam
- TEM scanning transmission electron microscope
- the adhesion amount of the base of the metallic chromium layer 10 mg / m 2 or more preferably, 30 mg / m 2 or more preferably, 40 mg / m 2 or more is more preferable.
- the granular protrusions of the metal chromium layer are formed on the surface of the base described above, and mainly play the role of reducing the contact resistance between the steel plates for cans and improving the weldability.
- the presumed mechanism for reducing the contact resistance is described below. Since the chromium hydrated oxide layer coated on the metal chromium layer is a non-conductive film, it has an electric resistance higher than that of metal chromium, and becomes an inhibiting factor for welding.
- the granular protrusions When granular protrusions are formed on the surface of the base of the metallic chromium layer, the granular protrusions destroy the chromium hydrated oxide layer due to the contact pressure between the steel plates for cans during welding, and the welding current conduction point As a result, the contact resistance is greatly reduced.
- the energization point during welding decreases, and the contact resistance cannot be lowered, resulting in poor weldability.
- the contact resistance can be lowered even when the chromium hydrated oxide layer as the insulating layer is thick.
- paint adhesion, corrosion resistance under coating, weldability, etc. can be realized with an excellent balance.
- the number density per unit area of the granular projections is 30 / ⁇ m 2 or more because the weldability of the steel plate for cans is excellent, and 200 / ⁇ m 2 or more is preferable because the weldability is more excellent. 1,000 / [mu] m 2 or more, and still more preferably 1,000 / [mu] m 2 greater.
- the upper limit of the number density per unit area of the granular protrusions may affect the color tone and the like if the number density per unit area is too high, and the surface appearance of the steel plate for cans is 10,000. / ⁇ m 2 or less is preferable, and 5,000 / ⁇ m 2 or less is more preferable.
- the present inventors have found that if the maximum particle size of the granular protrusions of the metal chrome layer is too large, the color tone of the steel plate for cans is affected, resulting in a brown pattern and a poor surface appearance. This is because the granular protrusions absorb light on the short wavelength side (blue), and the reflected light attenuates to exhibit a reddish brown color; the granular protrusions scatter the reflected light, and the whole The reason for this is considered to be darker due to a decrease in typical reflectance.
- the maximum particle size of the granular protrusions of the metal chromium layer is set to 200 nm or less.
- the surface appearance of the steel plate for cans is excellent. This is considered to be because the absorption of light on the short wavelength side is suppressed or the scattering of reflected light is suppressed by reducing the diameter of the granular protrusions.
- the maximum particle size of the granular protrusions of the metal chromium layer is preferably 150 nm or less, more preferably 100 nm or less, and still more preferably 80 nm or less.
- the lower limit of the maximum particle size is not particularly limited, but is preferably 10 nm or more, for example.
- the particle size and the number density per unit area of the granular protrusions of the metal chromium layer are measured as follows. First, carbon deposition was performed on the surface of the steel plate for cans on which the metal chromium layer and the chromium hydrated oxide layer were formed, and a sample for observation was prepared by the extraction replica method. Thereafter, the sample was observed with a scanning transmission electron microscope (TEM).
- TEM scanning transmission electron microscope
- the photograph is taken at a magnification of 1,000, and the photographed image is binarized using software (trade name: ImageJ) and subjected to image analysis, so that the particle size is calculated as a perfect circle by calculating back from the area occupied by the granular protrusions. And the number density per unit area is obtained.
- the maximum particle size is the maximum particle size in the observation field of view taken at 20,000 times and 5 fields, and the number density per unit area is the average of 5 fields.
- Chromium hydrated oxide layer On the surface of the steel plate, the hydrated chromium oxide precipitates simultaneously with the metallic chromium and plays a role mainly in improving the corrosion resistance. Chromium hydrated oxides improve both post-coating corrosion resistance such as undercoat corrosion resistance and paint adhesion. From the reason for ensuring the corrosion resistance and paint adhesion of the steel plate for cans, the chromium equivalent amount of the chromium hydrated oxide layer is 3 mg / m 2 or more, and from the reason that the corrosion resistance and paint adhesion are more excellent, 10 mg / M 2 or more is preferable, and more than 15 mg / m 2 is more preferable.
- chromium hydrated oxide has poor electrical conductivity compared to metallic chromium, and if the amount is too large, it becomes excessive resistance during welding, causing various welding defects such as blowholes due to generation of dust and splash and overfusion welding. This may cause poor weldability of the steel plate for cans.
- the chromium equivalent amount of the hydrated chromium oxide layer is 30 mg / m 2 or less because the weldability of the steel plate for cans is excellent, and 25 mg / m 2 because the weldability is more excellent. The following is preferable, and 20 mg / m 2 or less is more preferable.
- the method for measuring the chromium equivalent amount of the hydrated chromium oxide layer is as described above.
- the method for producing a steel plate for cans of the present invention uses the aqueous solution containing a hexavalent chromium compound, a fluorine-containing compound, and sulfuric acid, as described above.
- a method for producing a steel plate for cans which is a method for producing a steel plate for cans, wherein the steel plate is subjected to a treatment 1 comprising a cathode electrolysis treatment C1 using the aqueous solution, and the cathode electrolysis treatment C1 is applied.
- a method for producing a steel plate for a can comprising: a step of subjecting a steel plate to treatment 2 consisting of anodic electrolysis A1 and cathodic electrolysis C2 after anodic electrolysis A1 using the aqueous solution twice or more.
- chromium chromium hydrated oxide which is an intermediate product of metal chromium, is formed on the surface.
- This chromium hydrated oxide dissolves non-uniformly by being subjected to electrolytic treatment intermittently or being immersed for a long time in an aqueous solution of a hexavalent chromium compound. A granular projection is formed.
- the metal chrome is frequently dissolved over the entire surface of the steel sheet, and becomes the starting point of the granular protrusions formed of the metal chrome formed by the subsequent cathodic electrolysis.
- the base portion of the metal chromium layer is deposited by the cathode electrolysis treatment C1 before the anodic electrolysis treatment A1, and the granular protrusion of the metal chrome layer is deposited by the cathodic electrolysis treatment C2 after the anodic electrolysis treatment A1.
- the amount of each precipitation can be controlled by the electrolysis conditions in each electrolysis process.
- the aqueous solution and each electrolytic treatment used in the production method of the present invention will be described in detail.
- the aqueous solution used in the production method of the present invention contains a hexavalent chromium compound, a fluorine-containing compound, and sulfuric acid.
- the fluorine-containing compound and sulfuric acid in the aqueous solution exist in a state dissociated into fluoride ions, sulfate ions and hydrogen sulfate ions. Since these act as catalysts involved in the reduction and oxidation reactions of hexavalent chromium ions present in aqueous solutions that proceed in cathodic and anodic electrolysis, they are generally added as an auxiliary to the chromium plating bath.
- the aqueous solution used for the electrolytic treatment contains a fluorine-containing compound and sulfuric acid, it is possible to reduce the amount of chromium equivalent deposited on the chromium hydrated oxide layer of the steel plate for cans obtained. The reason for this is not clear, but it is thought that the amount of oxide produced decreases as the amount of anions during the electrolytic treatment increases.
- the cathodic electrolysis C1 the anodic electrolysis A1
- the cathodic electrolysis C2 it is preferable to use only one type of aqueous solution.
- the hexavalent chromium compound contained in the aqueous solution is not particularly limited.
- the content of the hexavalent chromium compound in the aqueous solution is preferably 0.14 to 3.00 mol / L, and more preferably 0.30 to 2.50 mol / L as the Cr amount.
- the fluorine-containing compound contained in the aqueous solution is not particularly limited, for example, hydrofluoric acid (HF), potassium fluoride (KF), sodium fluoride (NaF), silicic hydrofluoric acid (H 2 SiF 6) And / or a salt thereof.
- the salt of silicohydrofluoric acid include sodium silicofluoride (Na 2 SiF 6 ), potassium silicofluoride (K 2 SiF 6 ), and ammonium silicofluoride ((NH 4 ) 2 SiF 6 ).
- the content of the fluorine-containing compound in the aqueous solution is preferably 0.02 to 0.48 mol / L, more preferably 0.08 to 0.40 mol / L as the F amount.
- the content of sulfuric acid (H 2 SO 4 ) in the aqueous solution is preferably 0.0001 to 0.1000 mol / L, more preferably 0.0003 to 0.0500 mol / L as the amount of SO 4 2 ⁇ , 0.0010 More preferable is 0.0500 mol / L.
- Sulfuric acid improves the electrolytic efficiency of adhesion of the metal chromium layer by using it together with the fluorine-containing compound.
- the content of sulfuric acid in the aqueous solution is within the above range, the size of the granular protrusions of the metal chromium layer deposited in the cathodic electrolysis process C2 can be easily controlled within an appropriate range.
- the sulfuric acid also affects the formation of the generation site of the granular protrusion of the metal chromium layer in the anodic electrolytic treatment.
- the granular protrusions of the metal chromium layer are less likely to be excessively fine or coarse, and an appropriate number density is more easily obtained.
- the temperature of the aqueous solution in each electrolytic treatment is preferably 20 to 80 ° C, more preferably 40 to 60 ° C.
- ⁇ Cathode electrolysis treatment C1 (treatment 1)>
- metallic chromium and chromium hydrated oxide are deposited.
- the electric quantity density (product of current density and energization time) of the cathode electrolytic treatment C1 is 20 -50 C / dm 2 is preferable, and 25-45 C / dm 2 is more preferable.
- the current density (unit: A / dm 2 ) and the energization time (unit: sec.) Are appropriately set from the above-described electric quantity density.
- the cathode electrolytic treatment C1 may not be a continuous electrolytic treatment. That is, the cathodic electrolysis treatment C1 may be an intermittent electrolysis treatment in which an electroless immersion time inevitably exists by performing electrolysis by dividing into a plurality of electrodes in industrial production. In the case of intermittent electrolytic treatment, the total electric density is preferably within the above range.
- the anodic electrolysis A1 plays a role of dissolving the metal chromium deposited in the cathodic electrolysis C1 and forming a generation site of granular protrusions of the metal chrome layer in the cathodic electrolysis C2.
- the generation sites decrease and the number density per unit area of the granular protrusions decreases, or the dissolution progresses unevenly and the distribution of the granular protrusions varies. May occur or the thickness of the base of the metal chromium layer may be reduced to less than 7.0 nm.
- the corrosion resistance and the like may be adversely affected. This is presumably because a part of the metal chromium layer is dissolved more than necessary, and a generation site where the thickness of the base portion of the metal chromium layer is locally less than 7.0 nm is formed.
- the metal chromium layer formed by the cathodic electrolysis C1 and the first anodic electrolysis A1 is mainly the base.
- the current density of the anodic electrolysis A1 (the anodic electrolysis A1 is performed twice or more, and the current density for each round) is to form a metal chromium layer having granular protrusions in the subsequent cathodic electrolysis C2.
- it is adjusted suitably and it is preferable to set it as 0.1 A / dm ⁇ 2 > or more and less than 5.0 A / dm ⁇ 2 >.
- current density is 0.1 A / dm 2 or more, generating sites of granular protrusions are sufficiently formed, in cathodic electrolysis treatment C2 after the granular projections are sufficiently generated, and made uniform easily distributed Therefore, it is preferable.
- the current density is less than 5.0 A / dm 2 , the rust resistance and the under-coating corrosion resistance are improved, which is preferable. This is because the amount of metallic chromium dissolved in one anodic electrolytic treatment is not inadvertently increased, and the generation site of granular protrusions does not become too large, so that the thickness of the base portion of the metallic chromium layer is locally reduced. Presumed to be suppressed.
- electric charge density of the anodic electrolysis treatment A1 is less than 0.3 C / dm 2 super 5.0C / dm 2 is preferred, 0.3 C / dm 2 super 3.0C / dm 2 and more preferably less, 0.3 C / dm 2 ultra 2.0 C / dm 2 or less is more preferable.
- Electric quantity density is the product of current density and energization time. The energization time (unit: sec.) Is appropriately set from the current density (unit: A / dm 2 ) and the electric quantity density (unit: C / dm 2 ).
- the anodic electrolytic treatment A1 may not be a continuous electrolytic treatment. That is, the anodic electrolytic treatment A1 may be an intermittent electrolytic treatment in which an electroless immersion time inevitably exists by performing electrolysis by dividing into a plurality of electrodes in industrial production. In the case of intermittent electrolytic treatment, the total electric density is preferably within the above range.
- ⁇ Cathode electrolysis treatment C2> As described above, in the cathode electrolytic treatment, metallic chromium and chromium hydrated oxide are deposited. In particular, in the cathodic electrolytic treatment C2, the granular protrusions of the metal chromium layer are generated starting from the generation site described above. At this time, if the current density and electric quantity density are too large, the granular protrusions of the metal chromium layer may grow rapidly and the particle size may become coarse.
- current density of the cathode electrolytic treatment C2 is preferably less than 60.0A / dm 2, less than 50.0 A / dm 2 Is more preferable and less than 40.0 A / dm 2 is even more preferable.
- the lower limit is not particularly limited, but is preferably 10.0A / dm 2 or more, 15.0A / dm 2 greater is more preferable.
- the electric quantity density of the cathodic electrolysis process C2 (the cathodic electrolysis process C2 is performed twice or more, and the electric quantity density per time) is preferably less than 30.0 C / dm 2.
- the energization time (unit: sec.) Is appropriately set from the above current density and electric quantity density.
- the cathode electrolytic treatment C2 may not be a continuous electrolytic treatment. That is, the cathodic electrolysis process C2 may be an intermittent electrolysis process in which an electroless immersion time inevitably exists by performing electrolysis by dividing into a plurality of electrodes in industrial production. In the case of intermittent electrolytic treatment, the total electric density is preferably within the above range.
- the process 2 which consists of the anodic electrolysis process A1 and the cathodic electrolysis process C2 is performed twice or more with respect to the steel plate in which the cathodic electrolysis process C1 was performed.
- the number of treatments 2 is preferably 3 times or more, more preferably 5 times or more, and still more preferably 7 times or more.
- the granular protrusions of the metal chromium layer can be formed more uniformly and with high density. For this reason, even when the adhesion amount of the chromium hydrated oxide layer is increased in order to improve the corrosion resistance and the like, the uniform and high-density granular protrusions exert the effect of increasing the number of contacts during welding, and the contact resistance By reducing, weldability becomes good.
- the upper limit of the number of treatments 2 is not particularly limited, but it is preferable not to repeat excessively from the viewpoint of controlling the thickness of the base of the metal chromium layer formed by the cathodic electrolysis treatment C1 to an appropriate range. 30 times or less, preferably 20 times or less.
- a post-treatment may be performed after the treatment 2 including the anodic electrolysis treatment A1 and the cathodic electrolysis treatment C2.
- Immersion treatment or cathodic electrolysis treatment may be performed. Even if such post-treatment is performed, the thickness of the base portion of the metal chromium layer, and the particle size and number density of the granular protrusions are not affected.
- the hexavalent chromium compounds contained in the aqueous solution used for post-treatment is not particularly limited, for example, chromium trioxide (CrO 3); dichromates such as potassium dichromate (K 2 Cr 2 O 7) ; And chromates such as potassium chromate (K 2 CrO 4 ).
- treatment 1 consisting of cathodic electrolysis C1 and treatment 2 consisting of anodic electrolysis A1 and cathodic electrolysis C2 were performed in this order using aqueous solutions A to D.
- the number of times of processing 2 is two times or more, in some comparative examples, the number of times of processing 2 is only one.
- the aqueous solution E was used to perform a post treatment (cathodic electrolysis treatment or immersion treatment).
- the current density and the electric density shown in Table 2 below are values per each time.
- the first cathodic electrolysis C2 is performed at a current density of 30.0 A / dm 2 and an electric density of 15.0 C / dm 2 .
- the second cathodic electrolysis C2 was performed under the conditions of current density: 30.0 A / dm 2 and electric density: 15.0 C / dm 2 .
- Rust Resistance 1 Rust Resistance Test after Scraping of Steel Sheet >> Rust resistance was evaluated by conducting a rust resistance test after rubbing the steel sheet. That is, two samples were cut out from the produced steel plate for cans, one sample (30 mm ⁇ 60 mm) was fixed to a rubbing tester to be an evaluation sample, and the other sample (10 mm square) was fixed to the head, and 1 kgf / With a surface pressure of cm 2 , the rubbing speed was 1 reciprocation 1 second, and the length of 60 mm was 10 strokes. Thereafter, the sample for evaluation was aged for 7 days in a constant temperature and humidity chamber with an air temperature of 40 ° C. and a relative humidity of 80%.
- the rusting area ratio of the scratched part was confirmed by image analysis from a photograph observed at low magnification with an optical microscope, and evaluated according to the following criteria. Practically, if “ ⁇ ”, “ ⁇ ” or “ ⁇ ”, it can be evaluated as having excellent rust resistance.
- ⁇ Rust area ratio less than 1%
- ⁇ Rust area ratio from 1% to less than 2%
- ⁇ Rust area ratio from 2% to less than 5%
- Rust Resistance 2 Storage Rust Test >> Twenty 100 mm ⁇ 100 mm samples were cut out from the produced steel plate for cans, overlapped, packed in rust-proof paper, sandwiched and fixed with a plywood plate, and then kept in a constant temperature and humidity chamber with a temperature of 30 ° C. and a relative humidity of 85%. Aged for 2 months. Then, the area ratio (rust area ratio) of rust generated on the overlapping surface was confirmed and evaluated according to the following criteria. Practically, if “ ⁇ ”, “ ⁇ ” or “ ⁇ ”, it can be evaluated as having excellent rust resistance.
- ⁇ No rusting ⁇ : Very little rusting to less than 0.1% rust area ratio ⁇ : Rust area ratio 0.1% or more and less than 0.3% ⁇ : Rust area ratio 0.3% or more and 0.5% Less than ⁇ : Rust area ratio 0.5% or more
- Corrosion width 0.2 mm or less Corrosion width 0.2 to 0.3 mm or less
- the steel sheets for cans of Examples 1 to 44 are excellent in weldability, and further have rust resistance, corrosion resistance under the coating film, and paint adhesion (primary and secondary). Was also good.
- the steel plates for cans of Comparative Examples 1 to 3 have insufficient weldability, and further, either rust resistance or paint adhesion may be insufficient.
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Abstract
Description
近年は、金属クロム層およびクロム水和酸化物層を有する電解クロメート処理鋼板(以下、ティンフリースチール(TFS)ともいう)が、ぶりきよりも安価で、塗料密着性に優れることから、適用範囲が拡大しつつある。
洗浄廃液およびCO2の低減という環境対応の観点から、塗装およびその後の焼付け処理を省略できる代替技術として、PET(ポリエチレンテレフタレート)などの有機樹脂フィルムをラミネートした鋼板を使用した缶が注目されている。この点でも、有機樹脂フィルムとの密着性に優れるTFSの適用範囲は、今後も拡大すると予想される。
そのため、現状のTFSは、溶接直前にクロム水和酸化物層を機械的に研磨して除去することで溶接を可能としている。
しかし、工業的な生産においては、研磨後の金属粉が内容物に混入するリスク、製缶装置の清掃などメンテナンス負荷の増加、金属粉による火災発生のリスク等の問題も多い。
この技術によれば、金属クロムからなる粒状突起が、溶接時に、表層の溶接阻害因子であるクロム水和酸化物層を破壊することにより、接触抵抗が低減し、溶接性が改善することが期待される。
しかしながら、本発明者らが、特許文献1および2に具体的に記載された缶用鋼板を検討した結果、溶接性が不十分である場合があった。
[1]鋼板の表面に、上記鋼板側から順に、金属クロム層およびクロム水和酸化物層を有し、上記金属クロム層の付着量が、50~200mg/m2であり、上記クロム水和酸化物層のクロム換算の付着量が、3~30mg/m2であり、上記金属クロム層が、厚さが7.0nm以上である基部と、上記基部上に設けられ、最大粒径が200nm以下であり、単位面積あたりの個数密度が30個/μm2以上である粒状突起と、を含む、缶用鋼板。
[2]上記クロム水和酸化物層のクロム換算の付着量が、15mg/m2超30mg/m2以下である、上記[1]に記載の缶用鋼板。
[3]上記粒状突起の単位面積あたりの個数密度が200個/μm2以上である、上記[1]または[2]に記載の缶用鋼板。
[4]六価クロム化合物、フッ素含有化合物、および、硫酸を含有する水溶液を用いて、上記[1]~[3]のいずれかに記載の缶用鋼板を得る、缶用鋼板の製造方法であって、鋼板に対して、上記水溶液を用いて、陰極電解処理C1からなる処理1を施す工程と、上記陰極電解処理C1が施された上記鋼板に対して、上記水溶液を用いて、陽極電解処理A1および上記陽極電解処理A1後の陰極電解処理C2からなる処理2を2回以上施す工程と、を備える缶用鋼板の製造方法。
[5]上記陽極電解処理A1の電流密度が0.1A/dm2以上5.0A/dm2未満であり、上記陽極電解処理A1の電気量密度が0.3C/dm2超5.0C/dm2未満であり、上記陰極電解処理C2の電流密度が60.0A/dm2未満であり、上記陰極電解処理C2の電気量密度が30.0C/dm2未満である、上記[4]に記載の缶用鋼板の製造方法。
[6]上記陰極電解処理C1、上記陽極電解処理A1および上記陰極電解処理C2に、1種類の上記水溶液を用いる、上記[4]または[5]に記載の缶用鋼板の製造方法。
図1は、本発明の缶用鋼板の一例を模式的に示す断面図である。
図1に示すように、缶用鋼板1は、鋼板2を有する。缶用鋼板1は、更に、鋼板2の表面に、鋼板2側から順に、金属クロム層3およびクロム水和酸化物層4を有する。
金属クロム層3は、鋼板2を覆う基部3aと、基部3a上に設けられた粒状突起3bとを含む。基部3aの厚さは7.0nm以上である。粒状突起3bは、最大粒径が200nm以下であり、単位面積あたりの個数密度が30個/μm2以上である。基部3aおよび粒状突起3bを含む金属クロム層3の付着量は、50~200mg/m2である。
クロム水和酸化物層4は、粒状突起3bの形状に追従するように、金属クロム層3上に配置されている。クロム水和酸化物層4のクロム換算の付着量は、3~30mg/m2である。
付着量は鋼板片面当たりの付着量である。
以下、本発明の各構成について、より詳細に説明する。
鋼板の種類は特に限定されない。通常、容器材料として使用される鋼板(例えば、低炭素鋼板、極低炭素鋼板)を用いることができる。この鋼板の製造方法、材質なども特に限定されない。通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。
本発明の缶用鋼板は、上述した鋼板の表面に、金属クロム層を有する。
一般的なTFSにおける金属クロムの役割は、素材となる鋼板の表面露出を抑えて耐食性を向上させることにある。金属クロム量が少なすぎると、鋼板の露出が避けられず、耐食性が劣化する場合がある。
缶用鋼板の耐食性が優れるという理由から、金属クロム層の付着量は、50mg/m2以上であり、耐食性がより優れるという理由から、60mg/m2以上が好ましく、65mg/m2以上がより好ましく、70mg/m2以上が更に好ましい。
缶用鋼板の溶接性が優れるという理由から、金属クロム層の付着量は、200mg/m2以下であり、溶接性がより優れるという理由から、180mg/m2以下が好ましく、160mg/m2以下がより好ましい。
金属クロム層の付着量、および、後述するクロム水和酸化物層のクロム換算の付着量は、次のようにして測定する。
まず、金属クロム層およびクロム水和酸化物層を形成させた缶用鋼板について、蛍光X線装置を用いて、クロム量(全クロム量)を測定する。次いで、缶用鋼板を、90℃の6.5N-NaOH中に10分間浸漬させるアルカリ処理を行なってから、再び、蛍光X線装置を用いて、クロム量(アルカリ処理後クロム量)を測定する。アルカリ処理後クロム量を、金属クロム層の付着量とする。
次に、(アルカリ可溶性クロム量)=(全クロム量)-(アルカリ処理後クロム量)を計算し、アルカリ可溶性クロム量を、クロム水和酸化物層のクロム換算の付着量とする。
次に、金属クロム層が含むこれらの各部について、詳細に説明する。
金属クロム層の基部は、主に、鋼板表面を被覆し、耐食性を向上させる役割を担う。
本発明における金属クロム層の基部は、一般的にTFSに要求される耐食性に加えて、ハンドリング時に不可避的に缶用鋼板どうしが接触した際に、表層に設けられた粒状突起が基部を破壊して鋼板が露出しないように、均一な厚みを十分に確保していることを要する。
一方、金属クロム層の基部の厚さの上限は、特に限定されないが、例えば、20.0nm以下であり、15.0nm以下が好ましい。
金属クロム層の基部の厚さは、次のようにして測定する。
まず、金属クロム層およびクロム水和酸化物層を形成させた缶用鋼板の断面サンプルを、集束イオンビーム(FIB)法で作製し、走査透過電子顕微鏡(TEM)で20,000倍にて観察する。次いで、明視野像での断面形状観察で、粒状突起がなく基部のみが存在する部分に注目し、エネルギー分散型X線分光法(EDX)によるライン分析で、クロムおよび鉄の強度曲線(横軸:距離、縦軸:強度)から基部の厚さを求める。このとき、より詳細には、クロムの強度曲線において、強度が最大値の20%である点を最表層として、鉄の強度曲線とのクロス点を鉄との境界点として、2点間の距離を基部の厚さとする。
金属クロム層の粒状突起は、上述した基部の表面に形成されており、主として、缶用鋼板どうしの接触抵抗を低下させて溶接性を向上させる役割を担う。接触抵抗が低下する推定のメカニズムを以下に記述する。
金属クロム層の上に被覆されるクロム水和酸化物層は、不導体皮膜であるため、金属クロムよりも電気抵抗が大きく、溶接の阻害因子になる。金属クロム層の基部の表面に粒状突起を形成させると、溶接する際の缶用鋼板どうしの接触時の面圧により、粒状突起がクロム水和酸化物層を破壊して、溶接電流の通電点になり、接触抵抗が大幅に低下する。
缶用鋼板の表面外観がより優れるという理由から、金属クロム層の粒状突起の最大粒径は、150nm以下が好ましく、100nm以下がより好ましく、80nm以下が更に好ましい。
最大粒径の下限は、特に限定されないが、例えば、10nm以上が好ましい。
金属クロム層の粒状突起の粒径および単位面積あたりの個数密度は、次のようにして測定する。
まず、金属クロム層およびクロム水和酸化物層を形成させた缶用鋼板の表面に、カーボン蒸着を行ない、抽出レプリカ法によって観察用サンプルを作製し、その後、走査透過電子顕微鏡(TEM)で20,000倍にて写真を撮影し、撮影した写真をソフトウェア(商品名:ImageJ)を用いて二値化して画像解析を行なうことで、粒状突起の占める面積から逆算し、真円換算として粒径および単位面積あたりの個数密度を求める。最大粒径は20,000倍で5視野撮影した観察視野での最大の粒径とし、単位面積あたりの個数密度は5視野の平均とする。
鋼板の表面において、クロム水和酸化物は、金属クロムと同時に析出し、主に耐食性を向上させる役割を担う。また、クロム水和酸化物は、塗膜下耐食性などの塗装後耐食性と塗料密着性とを共に向上させる。缶用鋼板の耐食性および塗料密着性を確保する理由から、クロム水和酸化物層のクロム換算の付着量は、3mg/m2以上であり、耐食性および塗料密着性がより優れるという理由から、10mg/m2以上が好ましく、15mg/m2超がより好ましい。
このため、クロム水和酸化物層のクロム換算の付着量は、缶用鋼板の溶接性が優れるという理由から、30mg/m2以下であり、溶接性がより優れるという理由から、25mg/m2以下が好ましく、20mg/m2以下がより好ましい。
次に、本発明の缶用鋼板の製造方法を説明する。
本発明の缶用鋼板の製造方法(以下、単に「本発明の製造方法」ともいう)は、六価クロム化合物、フッ素含有化合物、および、硫酸を含有する水溶液を用いて、上述した本発明の缶用鋼板を得る、缶用鋼板の製造方法であって、鋼板に対して、上記水溶液を用いて、陰極電解処理C1からなる処理1を施す工程と、上記陰極電解処理C1が施された上記鋼板に対して、上記水溶液を用いて、陽極電解処理A1および上記陽極電解処理A1後の陰極電解処理C2からなる処理2を2回以上施す工程と、を備える缶用鋼板の製造方法である。
以下、本発明の製造方法に用いる水溶液および各電解処理について、詳細に説明する。
本発明の製造方法に用いる水溶液は、六価クロム化合物、フッ素含有化合物、および、硫酸を含有する。
水溶液中に含まれる六価クロム化合物としては、特に限定されないが、例えば、三酸化クロム(CrO3);二クロム酸カリウム(K2Cr2O7)などの二クロム酸塩;クロム酸カリウム(K2CrO4)などのクロム酸塩;等が挙げられる。
水溶液中の六価クロム化合物の含有量は、Cr量として、0.14~3.00mol/Lが好ましく、0.30~2.50mol/Lがより好ましい。
水溶液中に含まれるフッ素含有化合物としては、特に限定されないが、例えば、フッ化水素酸(HF)、フッ化カリウム(KF)、フッ化ナトリウム(NaF)、ケイフッ化水素酸(H2SiF6)および/またはその塩などが挙げられる。ケイフッ化水素酸の塩としては、例えば、ケイフッ化ナトリウム(Na2SiF6)、ケイフッ化カリウム(K2SiF6)、ケイフッ化アンモニウム((NH4)2SiF6)などが挙げられる。
水溶液中のフッ素含有化合物の含有量は、F量として、0.02~0.48mol/Lが好ましく、0.08~0.40mol/Lがより好ましい。
水溶液中の硫酸(H2SO4)の含有量は、SO4 2-量として、0.0001~0.1000mol/Lが好ましく、0.0003~0.0500mol/Lがより好ましく、0.0010~0.0500mol/Lが更に好ましい。
更に、硫酸は、陽極電解処理における金属クロム層の粒状突起の発生サイトの形成にも影響する。水溶液中の硫酸の含有量が上記範囲内にあることにより、金属クロム層の粒状突起が過度に微細または粗大になりにくくなり、適正な個数密度がより得られやすい。
陰極電解処理C1では、金属クロムおよびクロム水和酸化物を析出させる。
このとき、適切な析出量とする観点、および、金属クロム層の基部の適切な厚さを確保する観点から、陰極電解処理C1の電気量密度(電流密度と通電時間との積)は、20~50C/dm2が好ましく、25~45C/dm2がより好ましい。
電流密度(単位:A/dm2)および通電時間(単位:sec.)は、上記の電気量密度から、適宜設定される。
陽極電解処理A1は、陰極電解処理C1で析出した金属クロムを溶解させて、陰極電解処理C2における金属クロム層の粒状突起の発生サイトを形成する役割を担う。
このとき、陽極電解処理A1での溶解が強すぎると、発生サイトが減少して粒状突起の単位面積あたりの個数密度が減少したり、不均一に溶解が進行して粒状突起の分布にばらつきが生じたり、金属クロム層の基部の厚さが減少して7.0nmを下回ったりする場合がある。
また、陽極電解処理A1の電流密度が高すぎると、耐食性等に悪影響を及ぼす場合がある。これは、金属クロム層の一部を必要以上に溶解し、局所的に金属クロム層の基部の厚さが7.0nmを下回る発生サイトが形成されるためと推定される。
電流密度が0.1A/dm2以上であることにより、粒状突起の発生サイトが十分に形成され、後の陰極電解処理C2において、粒状突起が十分に生成し、かつ、均一に分布しやすくなるため、好ましい。
また、電流密度が5.0A/dm2未満であることにより、耐錆性および塗膜下耐食性が良好となるため、好ましい。これは、1回の陽極電解処理で溶解する金属クロムが不用意に多くならず、粒状突起の発生サイトが大きくなりすぎないため、局所的に金属クロム層の基部の厚さが薄くなることが抑制されるためと推定される。
通電時間(単位:sec.)は、上記の電流密度(単位:A/dm2)および電気量密度(単位:C/dm2)から、適宜設定される。
上述したように、陰極電解処理では、金属クロムおよびクロム水和酸化物を析出させる。とりわけ、陰極電解処理C2では、上述した発生サイトを起点として、金属クロム層の粒状突起を生成させる。このとき、電流密度および電気量密度が大きすぎると、金属クロム層の粒状突起が急激に成長し、粒径が粗大となる場合がある。
以上の観点から、陰極電解処理C2の電流密度(陰極電解処理C2は2回以上行なわれるので、各回あたりの電流密度)は、60.0A/dm2未満が好ましく、50.0A/dm2未満がより好ましく、40.0A/dm2未満が更に好ましい。下限は、特に限定されないが、10.0A/dm2以上が好ましく、15.0A/dm2超がより好ましい。
同様の理由から、陰極電解処理C2の電気量密度(陰極電解処理C2は2回以上行なわれるので、各回あたりの電気量密度)は、30.0C/dm2未満が好ましく、25.0C/dm2以下がより好ましく、7.0C/dm2以下が更に好ましい。下限は、特に限定されないが、1.0C/dm2以上が好ましく、2.0C/dm2以上がより好ましい。
通電時間(単位:sec.)は、上記の電流密度および電気量密度から、適宜設定される。
本発明の製造方法においては、陰極電解処理C1が施された鋼板に対して、陽極電解処理A1および陰極電解処理C2からなる処理2を2回以上施す。
上記処理2の回数は、3回以上が好ましく、5回以上がより好ましく、7回以上が更に好ましい。上記処理2を繰り返し行なうことにより、金属クロム層の粒状突起の発生サイトの形成(陽極電解処理A1)と、金属クロム層の粒状突起の形成(陰極電解処理C2)とを繰り返すことになるため、金属クロム層の粒状突起をより均一で高密度に形成できる。このため、耐食性等を向上させるためにクロム水和酸化物層の付着量を多くした場合においても、均一で高密度の粒状突起が溶接時の接点の数を増大させる作用を発揮し、接触抵抗を低減することによって溶接性が良好となる。
上記処理2の回数の上限は、特に限定されないが、陰極電解処理C1で形成される金属クロム層の基部の厚さを適切な範囲に制御する観点から、過度に繰り返さないことが好ましく、例えば、30回以下であり、20回以下が好ましい。
陽極電解処理A1および陰極電解処理C2からなる処理2の後、後処理をしてもよい。
例えば、塗料密着性および塗膜下耐食性の確保の観点から、クロム水和酸化物層の量のコントロールおよび改質などを目的として、六価クロム化合物を含む水溶液を用いて、鋼板に対して、浸漬処理または陰極電解処理を施してもよい。
このような後処理を行なっても、金属クロム層の基部の厚さ、ならびに、粒状突起の粒径および個数密度には、影響を及ぼさない。
0.22mmの板厚で製造した調質度T4CAの鋼板に対して、通常の脱脂および酸洗を施し、次いで、下記表1に示す水溶液を流動セルでポンプにより100mpm相当で循環させ、鉛電極を使用し、下記表2に示す条件で電解処理を施して、TFSである缶用鋼板を作製した。作製後の缶用鋼板は、水洗し、ブロアを用いて室温で乾燥した。
例えば、下記表2に示す実施例1(処理2の回数:2)では、1回目の陰極電解処理C2を、電流密度:30.0A/dm2、電気量密度:15.0C/dm2の条件で行ない、2回目の陰極電解処理C2を、電流密度:30.0A/dm2、電気量密度:15.0C/dm2の条件で行なった。
作製した缶用鋼板について、金属クロム層(金属Cr層)の付着量、および、クロム水和酸化物層(Cr水和酸化物層)のクロム換算の付着量(下記表3では単に「付着量」と表記)を測定した。測定方法は、上述したとおりである。結果を下記表3に示す。
作製した缶用鋼板の金属Cr層について、基部の厚さ、ならびに、粒状突起の最大粒径および単位面積あたりの個数密度を測定した。測定方法は、上述したとおりである。結果を下記表3に示す。
作製した缶用鋼板について、以下の評価を行なった。評価結果は下記表3に示す。
鋼板擦過後耐錆性試験を行なうことにより耐錆性を評価した。すなわち、作製した缶用鋼板からサンプルを2つ切り出し、一方のサンプル(30mm×60mm)をラビングテスターに固定して評価用サンプルとし、他方のサンプル(10mm四方)をヘッドに固定して、1kgf/cm2の面圧で、擦過速度1往復1秒とし、60mm長さを10ストロークさせた。その後、評価用サンプルを、気温40℃、相対湿度80%の恒温恒湿庫内で7日間経時させた。その後、光学顕微鏡で低倍観察した写真から画像解析により、擦過部の発錆面積率を確認し、下記基準で評価した。実用上、「◎◎」、「◎」または「○」であれば、耐錆性に優れるものとして評価できる。
◎◎:発錆面積率1%未満
◎:発錆面積率1%以上2%未満
○:発錆面積率2%以上5%未満
△:発錆面積率5%以上10%未満
×:発錆面積率10%以上、または、擦過部以外からの発錆
作製した缶用鋼板から100mm×100mmのサンプルを20枚切り出し、重ね合わせて、防錆紙に梱包し、ベニヤ板で挟み込んで固定した後、気温30℃、相対湿度85%の恒温恒湿庫内で2か月間経時させた。その後、重ね合わせ面で発生した錆の面積率(錆面積率)を確認し、下記基準で評価した。実用上、「◎◎」、「◎」または「○」であれば、耐錆性に優れるものとして評価できる。
◎◎:発錆なし
◎:発錆ごくわずか~錆面積率0.1%未満
○:錆面積率0.1%以上0.3%未満
△:錆面積率0.3%以上0.5%未満
×:錆面積率0.5%以上
作製した缶用鋼板について、旧JIS Z 8730(1980)において規定されるハンター式色差測定に基づいて、L値を測定し、下記基準で評価した。実用上、「◎◎」、「◎」または「○」であれば、表面外観に優れるものとして評価できる。
◎◎:L値65以上
◎:L値60以上、65未満
○:L値55以上、60未満
△:L値50以上、55未満
×:L値50未満
作製した缶用鋼板について、210℃×10分間の熱処理を2回行なった後、接触抵抗を測定した。より詳細には、缶用鋼板のサンプルを、バッチ炉中で加熱(到達板温210℃で10分間保持)を行ない、熱処理後のサンプルを重ね合わせた。次いで、DR型1質量%Cr-Cu電極を先端径が6mm、曲率R40mmとして加工し、この電極で、重ね合わせたサンプルを挟み込んで、加圧力1kgf/cm2として15秒保持した後、10Aの通電を行ない、板-板間の接触抵抗を測定した。10点測定し、平均値を接触抵抗値とし、下記基準で評価した。実用上、「◎◎◎」、「◎◎」、「◎」または「○」であれば、溶接性に優れるものとして評価できる。
◎◎◎:接触抵抗20μΩ以下
◎◎:接触抵抗20μΩ超、100μΩ以下
◎:接触抵抗100μΩ超、300μΩ以下
○:接触抵抗300μΩ超、500μΩ以下
△:接触抵抗500μΩ超、1000μΩ以下
×:接触抵抗1000μΩ超
作製した缶用鋼板について、エポキシ-フェノール樹脂を塗布し、210℃×10分間の熱処理を2回行なった。その後、鋼板まで達する深さの切り傷を1mm間隔で碁盤目状に入れ、テープで剥離して、剥離状況を観察した。剥離面積率を下記基準にて評価した。実用上、「◎◎」、「◎」または「○」であれば、一次塗料密着性に優れるものとして評価できる。
◎◎:剥離面積率0%
◎:剥離面積率0%超、2%以下
○:剥離面積率2%超、5%以下
△:剥離面積率5%超、30%以下
×:剥離面積率30%超
作製した缶用鋼板について、エポキシ-フェノール樹脂を塗布し、210℃×10分間の熱処理を2回行なった。その後、鋼板まで達する深さの切り傷を1mm間隔で碁盤目状に入れ、125℃×30分間のレトルト処理を行ない、乾燥後にテープで剥離して、剥離状況を観察した。剥離面積率を下記基準にて評価した。実用上、「◎◎」、「◎」または「○」であれば、二次塗料密着性に優れるものとして評価できる。
◎◎:剥離面積率0%
◎:剥離面積率0%超、2%以下
○:剥離面積率2%超、5%以下
△:剥離面積率5%超、30%以下
×:剥離面積率30%超
作製した缶用鋼板について、エポキシ-フェノール樹脂を塗布し、210℃で10分間の熱処理を2回行なった。鋼板まで達する深さのクロスカットを入れ、1.5%クエン酸-1.5%NaCl混合液からなる45℃の試験液に、72時間浸漬した。浸漬後、洗浄し、乾燥後、テープ剥離を行なった。クロスカットの交差部から10mm以内の4箇所について剥離巾(カット部から広がる左右の合計巾)を測定し、4箇所の平均値を求めた。剥離巾の平均値を、塗膜下の腐食巾とみなし、下記基準にて評価した。実用上、「◎◎」、「◎」または「○」であれば、塗膜下耐食性に優れるものとして評価できる。
◎◎:腐食巾0.2mm以下
◎:腐食巾0.2超0.3mm以下
○:腐食巾0.3超0.4mm以下
△:腐食巾0.4超0.5mm以下
×:腐食巾0.5mm超
2:鋼板
3:金属クロム層
3a:基部
3b:粒状突起
4:クロム水和酸化物層
Claims (6)
- 鋼板の表面に、前記鋼板側から順に、金属クロム層およびクロム水和酸化物層を有し、
前記金属クロム層の付着量が、50~200mg/m2であり、
前記クロム水和酸化物層のクロム換算の付着量が、3~30mg/m2であり、
前記金属クロム層が、厚さが7.0nm以上である基部と、前記基部上に設けられ、最大粒径が200nm以下であり、単位面積あたりの個数密度が30個/μm2以上である粒状突起と、を含む、缶用鋼板。 - 前記クロム水和酸化物層のクロム換算の付着量が、15mg/m2超30mg/m2以下である、請求項1に記載の缶用鋼板。
- 前記粒状突起の単位面積あたりの個数密度が200個/μm2以上である、請求項1または2に記載の缶用鋼板。
- 六価クロム化合物、フッ素含有化合物、および、硫酸を含有する水溶液を用いて、請求項1~3のいずれか1項に記載の缶用鋼板を得る、缶用鋼板の製造方法であって、
鋼板に対して、前記水溶液を用いて、陰極電解処理C1からなる処理1を施す工程と、
前記陰極電解処理C1が施された前記鋼板に対して、前記水溶液を用いて、陽極電解処理A1および前記陽極電解処理A1後の陰極電解処理C2からなる処理2を2回以上施す工程と、を備える缶用鋼板の製造方法。 - 前記陽極電解処理A1の電流密度が0.1A/dm2以上5.0A/dm2未満であり、
前記陽極電解処理A1の電気量密度が0.3C/dm2超5.0C/dm2未満であり、
前記陰極電解処理C2の電流密度が60.0A/dm2未満であり、
前記陰極電解処理C2の電気量密度が30.0C/dm2未満である、請求項4に記載の缶用鋼板の製造方法。 - 前記陰極電解処理C1、前記陽極電解処理A1および前記陰極電解処理C2に、1種類の前記水溶液を用いる、請求項4または5に記載の缶用鋼板の製造方法。
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JP2020117748A (ja) * | 2019-01-22 | 2020-08-06 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
WO2022163073A1 (ja) | 2021-01-27 | 2022-08-04 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
WO2023112467A1 (ja) | 2021-12-14 | 2023-06-22 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
JPWO2023127237A1 (ja) * | 2021-12-28 | 2023-07-06 |
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BR112018011442A2 (ja) * | 2015-12-11 | 2018-11-27 | Jfe Steel Corporation | A steel-for-can board and a manufacturing method for the same |
WO2018225726A1 (ja) * | 2017-06-09 | 2018-12-13 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
WO2023127236A1 (ja) * | 2021-12-28 | 2023-07-06 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
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- 2018-06-05 MX MX2019014692A patent/MX2019014692A/es unknown
- 2018-06-05 KR KR1020197035721A patent/KR102313040B1/ko active IP Right Grant
- 2018-06-05 EP EP18812947.2A patent/EP3620553B1/en active Active
- 2018-06-05 ES ES18812947T patent/ES2950567T3/es active Active
- 2018-06-05 US US16/619,234 patent/US10968528B2/en active Active
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JP2020117748A (ja) * | 2019-01-22 | 2020-08-06 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
JP7056594B2 (ja) | 2019-01-22 | 2022-04-19 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
WO2022163073A1 (ja) | 2021-01-27 | 2022-08-04 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
JPWO2022163073A1 (ja) * | 2021-01-27 | 2022-08-04 | ||
JP7239055B2 (ja) | 2021-01-27 | 2023-03-14 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
KR20230121871A (ko) | 2021-01-27 | 2023-08-21 | 제이에프이 스틸 가부시키가이샤 | 캔용 강판 및 그 제조 방법 |
EP4269660A4 (en) * | 2021-01-27 | 2024-07-10 | Jfe Steel Corp | CAN STEEL SHEET AND METHOD FOR MANUFACTURING SAME |
WO2023112467A1 (ja) | 2021-12-14 | 2023-06-22 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
KR20240089713A (ko) | 2021-12-14 | 2024-06-20 | 제이에프이 스틸 가부시키가이샤 | 캔용 강판 및 그 제조 방법 |
JPWO2023127237A1 (ja) * | 2021-12-28 | 2023-07-06 | ||
WO2023127237A1 (ja) * | 2021-12-28 | 2023-07-06 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
JP7416323B2 (ja) | 2021-12-28 | 2024-01-17 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
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AU2018280968B2 (en) | 2021-01-21 |
EP3620553A4 (en) | 2020-06-24 |
TW201903170A (zh) | 2019-01-16 |
JP6648835B2 (ja) | 2020-02-14 |
KR20190141247A (ko) | 2019-12-23 |
CA3064731C (en) | 2022-02-15 |
EP3620553A1 (en) | 2020-03-11 |
EP3620553B1 (en) | 2023-05-10 |
PH12019550287A1 (en) | 2020-07-13 |
TWI676692B (zh) | 2019-11-11 |
MY192632A (en) | 2022-08-29 |
US20200149179A1 (en) | 2020-05-14 |
CN110709537A (zh) | 2020-01-17 |
KR102313040B1 (ko) | 2021-10-14 |
CN110709537B (zh) | 2021-08-06 |
ES2950567T3 (es) | 2023-10-11 |
BR112019025647A2 (pt) | 2020-08-25 |
CA3064731A1 (en) | 2018-12-13 |
MX2019014692A (es) | 2020-02-07 |
AU2018280968A1 (en) | 2019-12-05 |
US10968528B2 (en) | 2021-04-06 |
JPWO2018225739A1 (ja) | 2019-06-27 |
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