WO2016121276A1 - 表面処理鋼板、金属容器及び表面処理鋼板の製造方法 - Google Patents
表面処理鋼板、金属容器及び表面処理鋼板の製造方法 Download PDFInfo
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- WO2016121276A1 WO2016121276A1 PCT/JP2015/085947 JP2015085947W WO2016121276A1 WO 2016121276 A1 WO2016121276 A1 WO 2016121276A1 JP 2015085947 W JP2015085947 W JP 2015085947W WO 2016121276 A1 WO2016121276 A1 WO 2016121276A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
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- 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
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- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Definitions
- the present invention relates to a surface-treated steel sheet, a metal container, and a method for producing the surface-treated steel sheet.
- Patent Document 1 discloses a non-chromium surface treatment technique for forming a metal oxygen compound film containing aluminum on the surface of a base material by cathodic electrolysis using an electrolytic treatment liquid containing aluminum ions. ing.
- the surface-treated steel sheet obtained by the conventional technique described in Patent Document 1 sometimes has poor corrosion resistance when used in a food can, etc., compared to a surface-treated steel sheet having a chromate-treated surface.
- An object of the present invention is to provide a surface-treated steel sheet having excellent corrosion resistance.
- the present inventors form a phosphoric acid compound layer containing tin phosphate on a tin-plated steel sheet, and form an aluminum oxygen compound layer containing an aluminum oxygen compound as a main component on the phosphoric acid compound layer.
- the above object can be achieved by adjusting the content ratio of tin oxide and tin phosphate contained in the aluminum oxygen compound layer, and the present invention has been completed.
- a tin-plated steel sheet obtained by performing tin plating on a steel sheet, a phosphate compound layer containing tin phosphate formed on the tin-plated steel sheet, and the phosphate compound layer
- An aluminum oxygen compound layer mainly composed of an aluminum oxygen compound, and a 3d 5/2 spectrum of tin in the aluminum oxygen compound layer measured using an X-ray photoelectron spectrometer.
- a surface-treated steel sheet in which the ratio of the integral value of the profile derived from tin oxide (tin oxide / tin phosphate) to the integral value of the profile derived from tin phosphate is 6.9 or more.
- the aluminum oxygen compound layer preferably contains aluminum phosphate.
- the total amount of phosphorus contained in each layer formed on the tin-plated steel sheet is preferably 0.5 to 20 mg / m 2 .
- the aluminum content in the aluminum oxygen compound layer is preferably 5 to 15 mg / m 2 .
- it is preferable that the aluminum oxygen compound layer does not substantially contain fluorine.
- the tin-plated steel sheet comprises the steel sheet and a tin-plated layer formed on the tin alloy layer, and a total tin amount of the tin alloy layer and the tin-plated layer is It is preferable to consist of a tin plating layer of 1.0 g / m 2 or more.
- the metal container which consists of said surface-treated steel plate is provided. Moreover, according to this invention, a metal container provided with the said surface-treated steel plate and the coating layer which has as a main component the organic material formed on the said aluminum oxygen compound layer of the said surface-treated steel plate is provided.
- An aluminum oxygen compound layer forming step of forming an aluminum oxygen compound layer by electrolytic treatment using an electrolytic treatment solution containing aluminum is provided.
- the phosphoric acid compound layer is formed by performing the cathodic electrolysis treatment after performing the anodic electrolysis treatment on the tin-plated steel sheet. .
- the aluminum oxygen compound layer forming step it is preferable to use a treatment liquid having a phosphoric acid content of 0.55 g / L or less as the amount of phosphorus.
- a phosphate compound layer and an aluminum oxygen compound layer are formed on a tin-plated steel sheet, and the aluminum oxide compound layer has a tin oxide / tin phosphate ratio of 6.9 or more.
- a surface-treated steel sheet having excellent corrosion resistance can be provided by the action of phosphates such as tin oxide and tin phosphate contained in the oxygen compound layer.
- TEM transmission electron microscope
- FIG. 1 is a cross-sectional view showing a configuration of a surface-treated steel sheet 1 according to an embodiment of the present invention.
- the surface-treated steel sheet 1 of the present embodiment is obtained by subjecting a tin-plated steel sheet 10 formed by forming a tin-plated layer 12 on a steel sheet 11 to electrolytic treatment in an electrolytic treatment solution containing phosphate ions.
- the phosphoric acid compound layer 20 is formed on the tin-plated steel sheet 10 while dissolving a part of the tin plating layer 12, and then further subjected to an electrolytic treatment in an electrolytic treatment solution containing Al ions.
- An aluminum oxygen compound layer 30 is formed on 20 while dissolving a part of the phosphate compound layer 20.
- the surface-treated steel sheet 1 of the present embodiment is not particularly limited, but can be used as a member such as a can container or a can lid, for example.
- the surface-treated steel sheet 1 is used as a member such as a can container or a can lid, the surface-treated steel sheet 1 is used as it is (for non-coating applications in which a coating layer is not formed on the surface), and an uncoated can container or can
- a cover layer made of an organic material may be formed on the aluminum oxygen compound layer 30 of the surface-treated steel sheet 1 and then formed into a can container or a lid. .
- the tin-plated steel sheet 10 that is the base material of the surface-treated steel sheet 1 of the present invention is obtained by performing tin plating on the steel sheet 11 and forming a tin-plated layer 12 on the steel sheet 11.
- the steel plate 11 for performing the tin plating is not particularly limited as long as it is excellent in drawing workability, drawing ironing workability, workability of drawing and bending back work (DTR), for example, Further, a hot-rolled steel sheet based on an aluminum killed steel continuous cast material, a cold-rolled steel sheet obtained by cold rolling these hot-rolled steel sheets, or the like can be used.
- a nickel plating layer is formed on the above-described steel plate, and this is heated and thermally diffused to form a nickel-iron alloy layer between the steel plate and the nickel plating layer. By doing so, a nickel-plated steel sheet with improved corrosion resistance may be used. Further, when the nickel plating layer is formed in a granular shape, the adhesion of the coating layer can be enhanced by the anchor effect.
- the method for applying tin plating to the steel plate 11 is not particularly limited, and examples thereof include a method using a known ferrostan bath, halogen bath, sulfuric acid bath, or the like.
- the method of performing nickel plating is not particularly limited, and a known Watt bath made of nickel sulfate and nickel chloride can be used.
- a bath composition made of nickel sulfate and ammonium sulfate is used. Is preferred.
- the tin-plated steel sheet 10 obtained by performing tin plating in this way is subjected to a rapid cooling process (reflow process) after being heated to a temperature higher than the melting temperature of tin, whereby the steel sheet 11 and tin A tin-iron alloy layer may be formed between the plating layer 12 and the plating layer 12.
- the obtained tin-plated steel sheet 10 has a tin-iron alloy layer and a tin-plated layer 12 formed in this order on the steel sheet 11, and has corrosion resistance. improves.
- a nickel plating layer is present on the base, a tin-nickel or tin-nickel-iron alloy can also be formed between the steel plate 11 and the tin plating layer 12 by this reflow process.
- the oxide film layer made of SnO x tends to reduce the adhesion of the phosphoric acid compound layer 20 formed on the tin-plated steel sheet 10 when the film amount is too large, while the tin-plated steel sheet when the film amount is too small. Since 10 tends to be blackened easily, it is desirable to adjust to an appropriate film amount. Therefore, in this embodiment, you may perform the process which removes a part or all of the oxide film layer of a surface, and adjusts the film quantity of an oxide film layer with respect to the tin plating steel plate 10.
- an aqueous carbonate carbonate solution such as sodium carbonate or sodium hydrogencarbonate is used for the tin-plated steel sheet 10 under the conditions of a current density of 0.5 to 20 A / dm 2 and an energization time of 0.1 to 1.0 seconds.
- You may perform the process which removes the oxide film layer of the surface of the tin-plated steel plate 10 by performing at least one of a cathodic electrolysis process and an anodic electrolysis process.
- the oxide film layer may be removed using an acidic aqueous solution such as hydrochloric acid.
- the time for immersing the tin-plated steel sheet 10 in the acidic aqueous solution is preferably 2 seconds or less.
- the oxide film layer made of SnO x can be efficiently removed while suppressing the dissolution of the metal tin portion of the tin-plated layer 12.
- the thickness of the tin plating layer 12 formed on the steel plate 11 is not particularly limited, and may be appropriately selected according to the intended use of the surface-treated steel plate 1 to be manufactured.
- the tin amount is preferably 1.0 g / m 2.
- the above is more preferably 1.0 to 15 g / m 2 .
- the thickness of the nickel plating layer is not particularly limited, and the thickness of the nickel plating layer is preferably 0.01 to 15 g / m 2 in terms of nickel amount.
- the average particle diameter of the granular nickel is preferably 0.01 to 0.7 ⁇ m.
- the total thickness of the tin-plated steel sheet 10 is not particularly limited and may be appropriately selected depending on the intended use of the surface-treated steel sheet 1 to be manufactured, but is preferably 0.07 to 0.4 mm.
- the phosphoric acid compound layer 20 is a layer containing tin phosphate, and the above-described tin-plated steel sheet 10 is immersed in an electrolytic treatment solution containing phosphate ions, and is subjected to cathodic electrolysis using the tin-plated steel sheet 10 as a cathode. Is formed.
- the tin-plated steel sheet 10 immersed in an electrolytic treatment solution containing phosphate ions is caused to flow from the tin-plated steel sheet 10 to the tin as shown in the left diagram in FIG. Dissolves to generate divalent tin ions (Sn 2+ ).
- FIG. 2 is a conceptual diagram showing how the phosphoric acid compound layer 20 and the aluminum oxygen compound layer 30 are formed on the tin-plated steel sheet 10.
- a state in which cathodic electrolytic treatment using an electrolytic treatment solution containing phosphate ions is performed on the tin plating layer 12 of the tin-plated steel sheet 10 is shown. Further, in the middle of FIG. In FIG. 2, showing how performed on Sn 3 (PO 4) 2 which is formed as a phosphate compound layer 20, a cathode electrolytic treatment to form an aluminum oxygen compounds layer 30.
- Sn 3 (PO 4) 2 which is formed as a phosphate compound layer 20
- a cathode electrolytic treatment to form an aluminum oxygen compounds layer 30 In the right figure in FIG.
- tin ions Sn 2+ generated from the tin-plated steel sheet 10 react with phosphate ions PO 4 3 ⁇ in the electrolytic treatment solution, and Sn 3 (PO 4 ) 2 etc.
- the tin phosphate is deposited on the tin-plated steel sheet 10.
- tin ions Sn 2+ generated from the tin-plated steel sheet 10 are deposited on the tin-plated steel sheet 10 as tin oxide (SnO x ).
- the phosphoric acid in the aqueous solution is composed of a primary phosphate ion (H 2 PO 4 ⁇ ), a secondary phosphate ion (HPO 4 2 ⁇ ), and a tertiary phosphate ion (PO 4 3 ) depending on the pH of the aqueous solution.
- - and ionization equilibrium is known to vary in)
- ionization equilibrium more pH of the aqueous solution is low primary phosphate ion H 2 PO 4 - inclination towards the increased presence rate
- the pH of the aqueous solution The higher the ionization equilibrium is, the higher the abundance of the tertiary phosphate ion PO 4 3 ⁇ increases.
- the tin-plated steel sheet 10 when the tin-plated steel sheet 10 is subjected to cathodic electrolysis with an electrolytic treatment solution containing phosphate ions, the oxidation formed on the surface of the tin-plated layer 12 as shown in the left diagram of FIG.
- the pH is adjusted in a range in which the abundance of secondary phosphate ions in the electrolytic treatment liquid increases.
- tin phosphate such as Sn 3 (PO 4 ) 2 is formed by the reaction of ions with tin ions.
- the tin phosphate obtained in this way is partially dissolved to form aluminum phosphate when the aluminum oxygen compound layer 30 is formed by electrolytic treatment, as will be described later.
- anodic electrolytic treatment using an electrolytic treatment solution containing phosphate ions is performed on the tin-plated steel sheet 10 before performing the above-described cathodic electrolytic treatment. You may go. Thereby, the oxide film layer formed on the surface of the tin-plated steel sheet 10 by anodic electrolysis is appropriately removed, and then the tin-plated layer 12 of the tin-plated steel sheet 10 is easily dissolved by anodic electrolysis. Formation of the phosphoric acid compound layer 20 becomes easy.
- the surface-treated steel sheet 1 obtained by forming the phosphoric acid compound layer 20 containing tin phosphate by the above-described cathodic electrolysis treatment is obtained when the coating layer 40 made of an organic material is formed on the surface.
- the adhesion of the coating layer 40 is excellent. That is, when the aluminum oxygen compound layer 30 is directly formed on the surface-treated steel sheet 1, when the coating layer 40 is formed by baking coating or the like, the oxide film that covers the tin-plated layer 12 of the surface-treated steel sheet 1 by the heat of baking A layer grows, and the aluminum oxygen compound layer 30 and the covering layer 40 may peel from the oxide film layer.
- the phosphoric acid compound layer 20 described above it is possible to suppress the growth of the oxide film layer that covers the tin plating layer 12 when forming the coating layer 40, and as a result, the surface of the surface-treated steel sheet 1.
- the adhesiveness of the coating layer 40 to be formed can be improved.
- the surface-treated steel sheet 1 obtained improves the corrosion resistance by forming the phosphate compound layer 20 containing tin phosphate by the cathodic electrolysis described above. That is, the present inventors perform cathodic electrolysis treatment on the tin-plated steel sheet 10 so that the second phosphate ions react with the tin ions to form tin phosphate, as described above. It is found that the chemical bonding state and surface form of tin phosphate formed by diphosphate ions are difficult to dissolve in the electrolytic treatment solution used when the aluminum oxygen compound layer 30 described later is formed by electrolytic treatment. The corrosion resistance of the surface-treated steel sheet 1 can be improved.
- the surface-treated steel sheet 1 to be obtained has sufficient corrosion resistance even when the coating layer 40 mainly composed of an organic material is not formed on the surface, and as a metal container for non-coating applications in which the coating layer 40 is not formed. Can also be suitably used.
- both the phosphate compound layer 20 and the aluminum oxygen compound layer 30 may contain tin phosphate and aluminum phosphate.
- FIG. 6 is a cross-sectional photograph of the phosphate compound layer 20 and the aluminum oxygen compound layer 30 of the surface-treated steel sheet obtained in the example of the present invention, and the results of quantitative analysis by EDS at each point.
- both the phosphate compound layer 20 and the aluminum oxygen compound layer 30 contain tin phosphate and aluminum phosphate. It was confirmed that this was sometimes the case.
- the electrolytic treatment liquid for forming the phosphate compound layer 20 includes phosphoric acid (H 3 PO 4 ), sodium dihydrogen phosphate (NaH 2 PO) as compounds for generating phosphate ions in the electrolytic treatment liquid. 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), phosphorous acid (H 3 PO 3 ) and the like can be used. These phosphoric acids and phosphates may be used alone or in combination, and among them, a mixture of phosphoric acid and sodium dihydrogen phosphate precipitates tin phosphate well as the phosphoric acid compound layer 20. This is preferable.
- the concentration of phosphate ions in the electrolytic treatment solution is not particularly limited, but is preferably 5 to 200 g / L in terms of phosphorus amount.
- concentration of phosphate ions in the electrolytic treatment liquid is preferably 5 to 200 g / L in terms of phosphorus amount.
- the pH of the electrolytic treatment solution is not particularly limited, but is preferably 1-7. If the pH is less than 1, the formed tin phosphate tends to be dissolved. On the other hand, if the pH is more than 7, the dissolution of the oxide film layer on the surface of the tin-plated steel sheet 10 becomes insufficient, and it is difficult to form the phosphate compound layer 20 in the portion where many oxide film layers remain. There is a possibility that the homogeneous phosphoric acid compound layer 20 cannot be formed on the steel plate 10.
- the current density at the time of performing the anodic electrolysis treatment or the cathodic electrolysis treatment is not particularly limited, but is preferably 1 to 30 A / dm 2 .
- the phosphate compound layer 20 can be satisfactorily formed on the tin-plated steel sheet 10.
- the counter electrode plate installed on the tin-plated steel plate 10 does not dissolve in the electrolytic treatment solution during the electrolysis treatment.
- a titanium plate coated with iridium oxide or a titanium plate coated with platinum is preferable because it is difficult to dissolve in the electrolytic treatment solution.
- the energization time for performing the anodic electrolysis treatment or the cathodic electrolysis treatment is not particularly limited, but is preferably 0.15 to 3.0 seconds, and more preferably 0.15 to 1.0 seconds. As described above, when the anodic electrolysis is performed after the cathodic electrolysis, it is preferable that the energization time of the cathodic electrolysis and the energization time of the anodic electrolysis are substantially the same.
- the energization time and the number of cycles of energization stop when performing anodic electrolysis after anodic electrolysis or cathodic electrolysis are preferably 1 to 10 times, and the energization time so that the phosphorus content in the phosphoric acid compound layer 20 is appropriate.
- An appropriate content of phosphorus in the phosphoric acid compound layer 20 is preferably 0.5 to 20 mg / m 2 , more preferably 0.5 to 5.0 mg / m 2 , and particularly preferably 0.7 to 4. 0 mg / m 2 .
- the tin-plated steel sheet 10 on which the phosphoric acid compound layer 20 is formed is washed with water as appropriate, and then subjected to electrolytic treatment in an electrolytic treatment liquid containing Al ions, so that aluminum is formed on the phosphoric acid compound layer 20.
- An oxygen compound is deposited to form the aluminum oxygen compound layer 30.
- the electrolytic treatment method may be either anodic electrolytic treatment or cathodic electrolytic treatment. However, from the viewpoint that the aluminum oxygen compound layer 30 can be satisfactorily formed, the cathodic electrolytic treatment is preferable.
- the content of Al ions in the electrolytic treatment solution for forming the aluminum oxygen compound layer 30 can be appropriately selected according to the coating amount of the aluminum oxygen compound layer 30 to be formed. And preferably 0.5 to 10 g / l, more preferably 1 to 5 g / l.
- the stability of the electrolytic treatment liquid can be improved and the deposition efficiency of the aluminum oxygen compound can be improved.
- nitrate ions may be added to the electrolytic treatment solution used for forming the aluminum oxygen compound layer 30.
- the content of nitrate ions in the electrolytic treatment liquid is preferably 11,500 to 25,000 ppm by weight.
- the electrolytic treatment liquid used for forming the aluminum oxygen compound layer 30 does not contain F ions.
- the electrolytic treatment liquid used for forming the aluminum oxygen compound layer 30 it is possible to form a dense aluminum oxygen compound layer 30 with a small particle size by not containing F ions. Corrosion resistance can be improved.
- F ions are contained in the electrolytic treatment solution, SnF 2 is formed, which is taken in by the aluminum oxygen compound layer 30, thereby reducing sulfur blackening resistance and corrosion resistance.
- the said electrolytic treatment liquid should just contain F ion substantially, and may contain F ion as long as it is the amount of impurities. That is, since F atoms are slightly contained in industrial water or the like, F ions derived from such F atoms may be mixed in the electrolytic treatment solution.
- F ions in the electrolytic treatment liquid there are F ions forming complex ions with metals, free F ions, etc., and the total amount of these F ions is preferably If it is 50 ppm by weight or less, more preferably 20 ppm or less, and even more preferably 5 ppm or less, the amount of F ions contained in the electrolytic treatment liquid is about the amount of impurities, and the electrolytic treatment liquid substantially contains F ions. It can be judged that it is not.
- examples of the method for measuring the contents of F ions and nitrate ions in the electrolytic treatment solution include a method of measuring by quantitative analysis by ion chromatography.
- the electrolytic treatment solution for forming the aluminum oxygen compound layer 30 includes at least one of organic acids (citric acid, lactic acid, tartaric acid, glycolic acid, etc.), polyacrylic acid, polyitaconic acid, and phenol resin.
- organic acids citric acid, lactic acid, tartaric acid, glycolic acid, etc.
- polyacrylic acid polyitaconic acid
- phenol resin phenol resin
- the above additives may be added.
- an organic material can be contained in the formed aluminum oxygen compound layer 30 by appropriately adding these additives alone or in combination to the electrolytic treatment liquid.
- the adhesion of the coating layer 40 formed on the top can be improved.
- the electrolytic treatment liquid for forming the aluminum oxygen compound layer 30 it is desirable to adjust the content of phosphate ions, and the content of phosphate ions in the electrolytic treatment liquid is the amount of phosphorus, preferably 0. 0.55 g / L or less, more preferably 0.33 g / L or less, and still more preferably 0.11 g / L.
- the aluminum oxygen compound layer 30 when the aluminum oxygen compound layer 30 is formed by electrolytic treatment, tin phosphate and the like are dissolved from the phosphate compound layer 20 in the electrolytic treatment liquid used for forming the aluminum oxygen compound layer 30. Then, phosphate ions are generated. If the amount of generated phosphate ions is too large, the phosphate ions bind to Al ions and precipitate as aluminum phosphate in the electrolytic treatment liquid. As a result, in the electrolytic treatment liquid, the aluminum oxygen compound layer The amount of Al ions used for forming 30 decreases, and the formation efficiency of the aluminum oxygen compound layer 30 decreases. Further, the aluminum phosphate compound precipitated in the electrolytic treatment solution causes the formed aluminum oxygen compound layer 30 to become non-uniform and mottled, and there is no problem in quality, but the appearance quality tends to deteriorate. .
- the content of phosphate ions in the electrolytic treatment liquid for forming the aluminum oxygen compound layer 30 is in the above range, the formed aluminum oxygen compound layer 30 becomes uniform, and the surface treatment to be obtained The appearance quality of the steel plate 1 is improved.
- the aluminum oxygen compound layer 30 is formed by electrolytic treatment, it is preferable to use an intermittent electrolysis system in which a cycle of energization and deenergization is repeated.
- the total energization time (energization and deenergization of the base material) is used.
- the total energization time when the cycle is repeated a plurality of times is preferably 1.5 seconds or less, more preferably 1 second or less.
- the number of cycles of energization and deenergization is preferably 1 to 10 times, and may be adjusted along with the energization time so that the aluminum content in the aluminum oxygen compound layer 30 is appropriate.
- Suitable aluminum content of the aluminum oxygen compound layer 30 is preferably 3 ⁇ 40mg / m 2, more preferably 5 ⁇ 15mg / m 2, particularly preferably 5.1 ⁇ 10.6mg / m 2 .
- any counter electrode may be used as long as it does not dissolve in the electrolytic treatment solution while the electrolytic treatment is being performed.
- a titanium plate coated with iridium oxide or a titanium plate coated with platinum is preferred because it has a small overvoltage and is difficult to dissolve in an electrolytic treatment solution.
- the aluminum oxygen compound layer 30 formed as described above is mainly composed of aluminum oxide or the like, but also includes aluminum hydroxide and phosphate.
- the phosphate include aluminum phosphate and an oxygen compound containing phosphoric acid (Al (PO 4 ) y O z and the like).
- This phosphate is an aluminum oxygen compound as described below.
- tin phosphate A part of tin phosphate is dissolved, and phosphate ions such as aluminum phosphate and phosphate such as oxygen compound containing phosphoric acid are precipitated. Further, in the formation of the aluminum oxygen compound layer, tin ions Sn 2+ are generated in the electrolytic treatment solution by dissolution of the phosphate compound layer 20 or dissolution of exposed portions of the tin plating that is not coated with the phosphate compound. In addition to tin phosphate, a part of tin oxide (SnO x ) is contained in the aluminum oxygen compound layer 30.
- the tin-plated steel sheet 10 is heated by the heat during baking.
- the growth of the oxide film layer can be suppressed, and as a result, the adhesion of the coating layer 40 formed on the surface of the surface-treated steel sheet 1 can be improved.
- the phosphate compound layer 20 obtained by the cathodic electrolysis treatment is mainly formed by the reaction of the second phosphate ion with the tin ion to form tin phosphate.
- the chemical bonding state and surface form of tin phosphate formed by the second phosphate ions are difficult to dissolve in the electrolytic treatment solution used when the aluminum oxygen compound layer 30 is formed by electrolytic treatment.
- fever at the time of baking can be suppressed, As a result, the adhesiveness of the coating layer 40 formed in the surface of the surface treatment steel plate 1 improves.
- the tin phosphate coating changes in quality over time, and initially the increase in the oxide film in the painting and baking process can be suppressed, but gradually becomes weaker, It is considered that the adhesion with the coating layer 40 is lowered.
- the aluminum oxygen compound layer 30 was obtained by integrating an integral value of a profile derived from tin phosphate (spectral intensity was integrated by binding energy) when a 3d 5/2 spectrum of tin was measured using an X-ray photoelectron spectrometer.
- the ratio of the integral value of the profile derived from tin oxide to (value) (tin oxide / tin phosphate) is 6.9 or more.
- the peak of the profile derived from tin phosphate is seen around 489.0 eV
- the peak of the profile derived from tin oxide is seen around 487.5 eV.
- the peak around 485.0 eV is considered to be derived from metallic tin.
- FIG. 3 is a graph showing a spectrum obtained by measuring the aluminum oxygen compound layer 30 with an X-ray photoelectron spectrometer for the surface-treated steel sheet 1 of Example 6 described later, and the vertical axis shows the spectrum intensity. The horizontal axis indicates the binding energy (eV).
- the surface-treated steel sheet 1 obtained has excellent corrosion resistance and excellent adhesion of the coating layer 40 formed on the surface. It can be.
- the content of aluminum in the aluminum oxygen compound layer 30 is preferably 5 ⁇ 15mg / m 2, more preferably 5.1 ⁇ 10.6mg / m 2. If the aluminum content in the aluminum oxygen compound layer 30 is too small, an oxide film layer on the surface of the tin-plated steel sheet 10 increases due to heat during baking when the coating layer 40 made of an organic material is formed by baking. Thereby, it exists in the tendency for the aluminum oxygen compound layer 30 and the coating layer 40 to peel easily from an oxide film layer. On the other hand, if the aluminum content in the aluminum oxygen compound layer 30 is too large, the aluminum oxygen compound layer 30 may become brittle and cause cohesive failure.
- the aluminum oxygen compound layer 30 contains phosphate, but the content ratio (P / P) of the phosphorus amount (mol / m 2 ) to the aluminum amount (mol / m 2 ) in the aluminum oxygen compound layer 30 (P / Al) is preferably 0.06 to 0.35, more preferably 0.07 to 0.27.
- the content ratio (P / Al) is less than 0.06, an oxide film layer on the surface of the tin-plated steel sheet 10 grows by heat during baking when the coating layer 40 made of an organic material is formed by baking coating.
- the aluminum oxygen compound layer 30 and the covering layer 40 tend to be easily peeled off from the oxide film layer.
- the content ratio (P / Al) is more than 0.35, the formed aluminum oxygen compound layer 30 becomes non-uniform and mottles are generated. There is a tendency.
- the surface-treated steel sheet 1 of the present embodiment is obtained.
- the total amount of phosphorus contained in each layer (tin plating layer 12, phosphate compound layer 20 and aluminum oxygen compound layer 30) formed on the steel sheet 11 is preferably 0.5. It is ⁇ 10 mg / m 2 , more preferably 0.7 to 2.5 mg / m 2 . If the total amount of phosphorus contained in each layer is too small, an oxide film layer of the tin-plated steel sheet 10 grows due to heat during baking when the coating layer 40 made of an organic material is formed by baking, thereby oxidizing. The aluminum oxygen compound layer 30 and the coating layer 40 tend to be easily peeled from the film layer.
- the total amount of phosphorus contained in each layer is too large, the content ratio of tin phosphate in the phosphate compound layer 20 increases, and this tin phosphate acts as an insulator, so that the aluminum oxygen compound layer 30 is formed.
- the aluminum oxygen compound is deposited non-uniformly, and the aluminum oxygen compound layer 30 is formed with mottle and there is no problem in quality, but the appearance quality tends to deteriorate.
- a method for measuring the total amount of phosphorus contained in each layer formed on the steel plate 11 for example, a method of quantitatively analyzing the obtained surface-treated steel plate 1 using a fluorescent X-ray analyzer. Is mentioned.
- the surface-treated steel sheet 1 of this embodiment is not specifically limited, It can be used as members, such as a can container and a can lid.
- the surface-treated steel sheet 1 is used as a member such as a can container or a can lid, the surface-treated steel sheet 1 is used as it is (used for non-coating applications in which the coating layer 40 is not formed on the surface).
- thermoplasticity examples thereof include a resin and a thermosetting resin.
- Thermoplastic resins include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic ester copolymers, olefin resin films such as ionomers, and polyesters such as polyethylene terephthalate and polybutylene terephthalate.
- a film, an unstretched film such as a polyvinyl chloride film or a polyvinylidene chloride film or a biaxially stretched film, or a polyamide film such as nylon 6, nylon 6, 6, nylon 11, or nylon 12 can be used.
- non-oriented polyethylene terephthalate obtained by copolymerizing isophthalic acid is particularly preferable.
- the organic material for comprising such a coating layer 40 may be used independently, and different organic materials may be blended and used.
- the thermosetting resin epoxy-phenol resin, polyester resin, or the like can be used.
- thermoplastic resin When the thermoplastic resin is coated as the coating layer 40, it may be a single-layer resin layer or a multilayer resin layer formed by coextrusion or the like.
- a polyester resin having a composition with excellent adhesion is selected for the base layer, that is, the surface-treated steel sheet 1 side, and content resistance, that is, extraction resistance and flavor component non-adsorption on the surface layer This is advantageous because a polyester resin having a composition excellent in properties can be selected.
- Examples of multilayer polyester resin layers are shown as surface layer / lower layer, polyethylene terephthalate / polyethylene terephthalate / isophthalate, polyethylene terephthalate / polyethylene / cyclohexylene dimethylene / terephthalate, polyethylene terephthalate / isolated with low isophthalate content.
- Polyethylene terephthalate / isophthalate having a high phthalate / isophthalate content polyethylene terephthalate / isophthalate / [blend of polyethylene terephthalate / isophthalate and polybutylene terephthalate / adipate] and the like are of course not limited thereto.
- the thickness ratio of the surface layer to the lower layer is preferably in the range of 5:95 to 95: 5.
- the coating layer 40 has a resin compounding agent known per se, for example, an antiblocking agent such as amorphous silica, an inorganic filler, various antistatic agents, a lubricant, an antioxidant (for example, tocophenol), and an ultraviolet absorber. Etc. can be blended according to a known formulation.
- an antiblocking agent such as amorphous silica, an inorganic filler, various antistatic agents, a lubricant, an antioxidant (for example, tocophenol), and an ultraviolet absorber.
- Etc. can be blended according to a known formulation.
- the thickness of the coating layer 40 formed on the surface-treated steel sheet 1 obtained according to the present invention is desirably 3 to 50 ⁇ m, particularly 5 to 40 ⁇ m in general with a thermoplastic resin coating.
- the later thickness is preferably in the range of 1 to 50 ⁇ m, particularly 3 to 30 ⁇ m. When the thickness is less than the above range, the corrosion resistance becomes insufficient, and when the thickness exceeds the above range, a problem is likely to occur in terms of workability.
- the thermal adhesion of the polyester resin to the surface-treated steel sheet 1 is performed by the amount of heat that the molten resin layer has and the amount of heat that the surface-treated steel sheet 1 has.
- the heating temperature of the surface-treated steel sheet 1 is generally 90 ° C. to 290 ° C., particularly 100 ° C. to 230 ° C., while the laminating roll temperature is suitably 10 ° C. to 150 ° C.
- the covering layer 40 formed on the surface-treated steel sheet 1 can also be formed by thermally bonding a polyester resin film previously formed by a T-die method or an inflation film-forming method to the surface-treated steel sheet 1. .
- an unstretched film formed by a cast molding method in which the extruded film is rapidly cooled can be used, and this film is biaxially stretched sequentially or simultaneously at the stretching temperature, and the stretched film is heat-set. It is also possible to use a biaxially stretched film produced by the above method.
- the surface-treated steel sheet 1 of the present invention can be formed into a can container by forming a coating layer 40 on the surface to obtain an organic material-coated steel sheet, and then processing this.
- a can container For example, the seamless can 5 (two piece can) shown to FIG. 4 (A) and the three-piece can 5a (welding can) shown to FIG. 4 (B) are mentioned.
- the body 51 and the upper lid 52 constituting the seamless can 5 and the body 51a, the upper lid 52a and the lower lid 53 constituting the three-piece can 5a are all formed by forming the coating layer 40 on the surface-treated steel sheet 1 of the present embodiment.
- An organic material-coated steel sheet is formed.
- FIGS. 4 (A) and 4 (B) are drawn, drawn / re-squeezed, and bent and stretched by drawing / re-drawing (stretching) so that coating layer 40 is on the inner surface side of the can. ), Can be produced by subjecting to conventionally known means such as bending / stretching / ironing by drawing / redrawing or drawing / ironing.
- the coating layer 40 is thermoplastic by an extrusion coating method. It is particularly preferable that it is made of a resin coating. That is, since the organic material-coated steel sheet is excellent in work adhesion, it is possible to provide a seamless can having excellent corrosion resistance and excellent corrosion resistance even when subjected to severe processing.
- the surface-treated steel sheet 1 of the present invention can be manufactured by forming a coating layer 40 on the surface to obtain an organic material-coated steel sheet, and then processing this to produce a can lid.
- the can lid is not particularly limited, and examples thereof include a flat lid, a stay-on-tab type easy open can lid, and a full open type easy open can lid.
- phosphate ion concentration or Al ion concentration was measured using an ICP emission spectrometer (ICPE-9000, manufactured by Shimadzu Corporation), and the F ion concentration was measured using an ion chromatograph (made by Dionex, DX-500). And nitrate ion concentration was measured.
- pH was measured using the pH meter (made by Horiba Ltd.).
- Measuring device JPS-9200 manufactured by JEOL Ltd.
- Excitation X-ray source MgK ⁇ voltage 12 kV, current 25 mA Measurement diameter: 3mm diameter Photoelectron extraction angle: 90 ° (0 ° with respect to the normal of the sample)
- Analysis software SpecSurf (ver. 1.7.3.9) manufactured by JEOL Ltd.
- Waveform separation conditions Waveform separation with tin oxide binding energy 487.5 eV, tin phosphate binding energy 489.1 eV, metallic tin binding energy 485.4 eV
- paint adhesion evaluation was performed about all the Examples and comparative examples which are mentioned later. 3 points: As a result of visual judgment, peeling of the paint was not recognized. 2 points: As a result of visual judgment, peeling of the paint was recognized at an area ratio of 1/5 or less. 1 point: As a result of visual determination, peeling of the paint was recognized at an area ratio exceeding 1/5. In the paint adhesion evaluation, when the evaluation was 2 points or more according to the above criteria, it was determined that the surface-treated steel sheet 1 had sufficient paint adhesion when used as a food can application.
- the surface-treated steel sheet 1 was heat-treated at a temperature of 205 ° C. for 30 minutes, and the amount of tin oxide film layer formed on the surface of the tin-plated steel sheet 10 before and after the heat treatment was measured.
- the amount of the oxide film layer was evaluated by the amount of electricity required to remove the oxide film layer by electrochemical reduction.
- a 1 / 1000N hydrogen bromide solution was used as the electrolytic solution, and electrolysis was performed under a current density of 25 ⁇ A / cm 2 .
- Evaluation of the growth of the oxide film layer is to calculate the value obtained by dividing the amount of the oxide film layer after the heat treatment by the amount of the oxide film layer before the heat treatment (the oxide film layer after the heat treatment / the oxide film layer before the heat treatment). It was evaluated that the larger the value, the easier the oxide film layer grows by heat treatment. The evaluation of the growth of the oxide film layer was performed for all examples and comparative examples described later.
- ⁇ The oxide film layer after heat treatment / the oxide film layer before heat treatment was 1.2 or less.
- X The oxide film layer after the heat treatment / the oxide film layer before the heat treatment exceeded 1.4.
- Model solution An aqueous solution in which NaCl and citric acid were dissolved at 1.5% by weight, respectively, and then opened, and the degree of corrosion of the test piece was visually observed and evaluated according to the following criteria.
- corrosion resistance evaluation (model liquid) was performed about all the Examples and comparative examples which are mentioned later. 3 points: As a result of visual judgment, the degree of corrosion was clearly small as compared with Comparative Example 2. 2 points: As a result of visual judgment, the degree of corrosion was comparable to that of Comparative Example 2. 1 point: As a result of visual judgment, the degree of corrosion was clearly greater than that of Comparative Example 2.
- the corrosion resistance evaluation model solution
- Model solution An aqueous solution in which 1% by weight of acetic acid and 10% by weight of sucrose (sucrose) are dissolved. Thereafter, the can is opened, and the Sn amount of the test piece after 10 days in a 37 ° C. environment is measured by fluorescent X-ray.
- Example 1 First, a low carbon cold-rolled steel plate (plate thickness: 0.225 mm) was prepared as the steel plate 11.
- the prepared steel sheet was degreased by performing cathodic electrolytic treatment at 60 ° C. for 10 seconds using an aqueous solution of an alkaline degreasing agent (Nippon Quaker Chemical Co., Ltd., Formula 618-TK2).
- an alkaline degreasing agent Naippon Quaker Chemical Co., Ltd., Formula 618-TK2
- the degreased steel sheet was washed with tap water and then pickled by dipping it in a pickling agent (5% by volume aqueous solution of sulfuric acid) at room temperature for 5 seconds.
- Electrolytic treatment solution pH 1.3 aqueous solution in which phosphorous acid is dissolved at a concentration of 10 g / L (treatment solution A in Table 1)
- Electrolytic solution temperature 40 ° C
- Current density 3 A / dm 2
- Total energization time 0.5 seconds (energization time 0.5 seconds, 1 cycle)
- the electrolytic processing liquid used for formation of the phosphoric acid compound layer 20 was analyzed. The results are shown in Table 1.
- Table 1 the concentration (g / L) of phosphorus atoms calculated according to the concentration of the dissolved phosphate compound is also shown.
- the electrolytic treatment solution shown as treatment solution A in Table 1 was used to form the phosphoric acid compound layer 20.
- the treatment liquid B was used for Examples 2 and 3 described later, and the treatment liquid C was used for Examples 4 to 6 and Comparative Example 2 described later.
- Table 2 shows the conditions for the electrolytic treatment when the phosphoric acid compound layer 20 was formed on the tin-plated steel sheet 10.
- the tin-plated steel sheet 10 on which the phosphoric acid compound layer 20 was formed was washed with water, and then immersed in the electrolytic treatment solution under the following conditions, and the electrolytic treatment solution was stirred and disposed at a distance of 17 mm between the electrodes.
- the aluminum oxygen compound layer 30 was formed by performing cathodic electrolysis using the iridium oxide-coated titanium plate as an anode.
- the surface-treated steel sheet 1 in which the phosphoric acid compound layer 20 and the aluminum oxygen compound layer 30 were formed in this order on the tin-plated steel sheet 10 was obtained by washing with running water and drying.
- the electrolytic processing liquid used for formation of the aluminum oxygen compound layer 30 was analyzed according to the method mentioned above.
- Electrolytic treatment solution Aluminum nitrate is dissolved as an Al compound to have an Al ion concentration of 1500 ppm by weight, an nitrate ion concentration of 15,000 ppm by weight, and an F ion concentration of 0 ppm by weight (pH 3.0).
- the surface-treated steel sheet 1 was subjected to a heat treatment at a temperature of 190 ° C. for 10 minutes, and then an epoxy phenol-based paint was applied so that the coating thickness after baking and drying was 70 mg / dm 2.
- the organic material covering steel plate which formed the coating layer 40 on the surface treatment steel plate 1 was obtained.
- the obtained organic material-coated steel sheet was subjected to paint adhesion evaluation, corrosion resistance evaluation (model solution), and evaluation of growth of the oxide film layer in accordance with the above-described methods. The results are shown in Table 3.
- Example 2 When the phosphoric acid compound layer 20 is formed on the tin-plated steel sheet 10, an aqueous solution of pH 1.8 in which phosphoric acid is dissolved at a concentration of 30 g / L and disodium phosphate is dissolved at a concentration of 30 g / L as an electrolytic treatment solution ( A surface-treated steel sheet 1 and an organic material-coated steel sheet were prepared and evaluated in the same manner as in Example 1 except that the treatment liquid B) in Table 1 was used. The results are shown in Table 3.
- Example 3 Example 2 except that the energization time of the electrolytic treatment when forming the phosphoric acid compound layer 20 was 0.3 seconds and the energization time of the electrolytic treatment when forming the aluminum oxygen compound layer 30 was 0.15 seconds.
- the surface-treated steel sheet 1 and the organic material-coated steel sheet were produced in the same manner as described above and evaluated in the same manner.
- Example 4 When forming the phosphoric acid compound layer 20 on the tin-plated steel sheet 10, the pH of 2.4 was obtained by dissolving phosphoric acid as an electrolytic treatment solution at a concentration of 10 g / L and sodium dihydrogen phosphate at a concentration of 30 g / L.
- Example 5 When forming the phosphoric acid compound layer 20 on the tin-plated steel sheet 10, the surface-treated steel sheet 1 and the organic material-coated steel sheet were prepared in the same manner as in Example 4 except that the treatment liquid C shown in Table 1 was used as the electrolytic treatment liquid. It produced and evaluated similarly. The results are shown in Table 3. In addition, about Example 5, the spectrum obtained when the tin compound in the aluminum oxygen compound layer 30 was measured and the tin compound in the aluminum oxygen compound layer 30 was measured using an X-ray photoelectron spectrometer. Is shown in FIG.
- Example 6 When forming the phosphoric acid compound layer 20 on the tin-plated steel sheet 10, the anodic electrolysis treatment was performed under the same conditions except that the reverse polarity treatment (anodic electrolysis treatment) was performed before the cathodic electrolysis treatment described above. Went. Otherwise, the surface-treated steel sheet 1 and the organic material-coated steel sheet were produced in the same manner as in Example 5 and evaluated in the same manner. The results are shown in Table 3. In addition, about Example 6, the spectrum obtained when the tin compound in the aluminum oxygen compound layer 30 was measured and the tin compound in the aluminum oxygen compound layer 30 was measured using an X-ray photoelectron spectrometer. FIG. 5B shows a TEM image and a quantitative analysis result obtained by cross-sectional observation of the surface-treated steel sheet.
- Example 7 shows the current density of the electrolytic treatment when forming the phosphoric acid compound layer 20 on the tin-plated steel sheet 10, and the current density, current application time and cycle number of the electrolytic treatment when forming the aluminum oxygen compound layer 30.
- the surface-treated steel sheet 1 and the organic material-coated steel sheet were produced in the same manner as in Example 6 except that the evaluation was made in the same manner as in Example 6 and evaluated in the same manner.
- the tin oxide film formed in the tin plating surface was removed by being immersed in hydrochloric acid aqueous solution as a pretreatment. The results are shown in Table 3.
- Comparative Example 1 About the tin-plated steel sheet 10 produced in Example 1, after forming the phosphoric acid compound layer 20, without forming the aluminum oxygen compound layer 30, the paint adhesion evaluation, the evaluation of the growth of the oxide film layer, and the corrosion resistance evaluation (model) Liquid). The results are shown in Table 3.
- Comparative Example 2 By forming the aluminum oxygen compound layer 30 directly on the tin-plated steel sheet 10 in the same manner as in Example 1 without forming the phosphate compound layer 20 for the tin-plated steel sheet 10 produced in Example 1. A surface-treated steel sheet was obtained. The obtained surface-treated steel sheet was subjected to paint adhesion evaluation, oxide film layer growth evaluation and corrosion resistance evaluation (model solution). The results are shown in Table 3.
- the phosphoric acid compound layer 20 was formed by subjecting the tin-plated steel sheet 10 to cathodic electrolysis, and the aluminum oxygen compound layer 30 was formed on the phosphoric acid compound layer 20 in Examples 1 to 7 shows good results of coating adhesion evaluation, evaluation of oxide film layer growth and corrosion resistance evaluation (model solution), excellent corrosion resistance and adhesion of the coating layer 40, metal containers used for a long period of time, etc. It was confirmed that it was suitable for the use.
- Comparative Example 1 in which the aluminum oxygen compound layer 30 was not formed had a poor evaluation result of the growth of the oxide film layer, thereby causing the coating layer to grow due to the growth of the oxide film layer. It is considered that the adhesiveness of 40 may be lowered. Further, in Comparative Example 2 in which the aluminum oxygen compound layer 30 was formed directly on the tin-plated steel sheet 10 without forming the phosphoric acid compound layer 20, the results of paint adhesion evaluation and evaluation of growth of the oxide film layer were As compared with the examples, both were bad and it was confirmed that the adhesion of the coating layer 40 was inferior.
- Example 8 When the tin plating layer 12 is formed, the total energization time is set to 7.5 seconds, the tin amount of the tin plating layer 12 is set to 11.2 g / m 2 , electrolytic treatment for forming the phosphate compound layer, and formation of the aluminum oxygen compound layer A surface-treated steel sheet 1 was produced in the same manner as in Example 1 except that the electrolytic treatment was performed under the conditions shown in Table 2. The obtained surface-treated steel sheet 1 was subjected to tin removal evaluation (model solution) according to the method described above. The results are shown in Table 4.
- Comparative Example 3 In forming the tin plating layer 12, the total energization time is 7.5 seconds, the tin amount of the tin plating layer 12 is 11.2 g / m 2, and the aluminum oxygen compound is formed without forming the phosphate compound layer 20.
- a surface-treated steel sheet was produced in the same manner as in Example 1 except that the electrolytic treatment for layer formation was changed to the conditions shown in Table 2. The obtained surface-treated steel sheet was subjected to tin removal evaluation (model solution) in the same manner as in Example 14. The results are shown in Table 4.
- Reference Example 1 When the tin plating layer 12 was formed, the total energization time was set to 7.5 seconds, the tin amount of the tin plating layer 12 was set to 11.2 g / m 2 , and the tin-plated steel sheet 10 was produced. Thereafter, chromium hydroxide was formed on the surface of the tin-plated steel sheet 10 by electrolytic treatment to produce a surface-treated steel sheet. The obtained surface-treated steel sheet was subjected to tin removal evaluation (model solution) in the same manner as in Example 14. The results are shown in Table 4. Reference Example 1 corresponds to a product of surface-treated steel sheet that is currently commercially available.
- the phosphoric acid compound layer 20 was formed by subjecting the tin-plated steel sheet 10 to cathodic electrolysis, and the aluminum oxygen compound layer 30 was formed on the phosphoric acid compound layer 20 in Example 8.
- the amount of remaining Sn is the amount of remaining Sn equal to or greater than that of Reference Example 1, which is a current product, and the aluminum oxygen compound layer 30 is directly formed on the tin-plated steel sheet 10 without forming the phosphate compound layer 20.
- the surface-treated steel sheet 1 of Example 8 obtained by forming only the phosphate compound layer 20 and the aluminum oxygen compound layer 30 on the tin-plated steel sheet 10 does not have the coating layer 40. Even in the unpainted state, the amount of residual Sn was large, so that it was confirmed that it was excellent in corrosion resistance and sulfur blackening resistance and suitable for applications such as metal containers used without coating.
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Abstract
Description
してなる表面処理鋼板において、アルミニウム酸素化合物層に含有される酸化錫及びリン酸錫の含有比を調整することにより、上記目的を達成できることを見出し、本発明を完成させるに至った。
本発明の表面処理鋼板において、前記錫めっき鋼板上に形成された各層に含まれるリンの合計量が0.5~20mg/m2であることが好ましい。
本発明の表面処理鋼板において、前記アルミニウム酸素化合物層におけるアルミニウムの含有量が5~15mg/m2であることが好ましい。
本発明の表面処理鋼板において、前記アルミニウム酸素化合物層は、実質的にフッ素を含まないことが好ましい。
本発明の表面処理鋼板において、前記錫めっき鋼板は、前記鋼板と、前記錫合金層上に形成された錫めっき層と、からなり、前記錫合金層と前記錫めっき層の合計の錫量が1.0g/m2以上の錫めっき層とからなることが好ましい。
また、本発明によれば、前記表面処理鋼板と、前記表面処理鋼板の前記アルミニウム酸素化合物層上に形成された有機材料を主成分とする被覆層と、を備える金属容器が提供される。
本発明の製造方法において、前記アルミニウム酸素化合物層形成工程において、前記電解処理液として、リン酸の含有量がリン量で0.55g/L以下である処理液を用いることが好ましい。
本発明の表面処理鋼板1の基材となる錫めっき鋼板10は、鋼板11に対して錫めっきを施し、鋼板11上に錫めっき層12を形成することにより得られる。
リン酸化合物層20は、リン酸錫を含有する層であり、上述した錫めっき鋼板10を、リン酸イオンを含む電解処理液に浸漬させ、錫めっき鋼板10を陰極とした陰極電解処理を施すことにより形成される。
図6は本発明の実施例で得られた表面処理鋼板のリン酸化合物層20及びアルミニウム酸素化合物層30の断面写真および各点におけるEDSによる定量分析の結果である。上述の通り、リン酸化合物層20とアルミニウム酸素化合物層30の境界は明確でなく、またリン酸化合物層20及びアルミニウム酸素化合物層30のいずれにも、リン酸錫及びリン酸アルミニウムが含有される場合もあることが確認された。
本実施形態では、リン酸化合物層20を形成した錫めっき鋼板10について、適宜水洗を行った後、Alイオンを含む電解処理液中で電解処理を行うことで、リン酸化合物層20上にアルミニウム酸素化合物を析出させてアルミニウム酸素化合物層30を形成する。電解処理の方法としては、陽極電解処理及び陰極電解処理のいずれでもよいが、良好にアルミニウム酸素化合物層30を形成できるという観点より、陰極電解処理が好ましい。
本実施形態の表面処理鋼板1は、特に限定されないが、缶容器や缶蓋などの部材として用いることができる。表面処理鋼板1を缶容器や缶蓋などの部材として用いる場合には、表面処理鋼板1をそのまま用いて(表面に被覆層40を形成しない無塗装用途で用いて)、無塗装の缶容器や缶蓋として成形してもよいし、表面処理鋼板1のアルミニウム酸素化合物層30上に有機材料からなる被覆層40を形成してから缶容器や缶蓋などに成形してもよい。被覆層40を構成する有機材料としては、特に限定されず、表面処理鋼板1の用途(たとえば、特定の内容物を充填する缶容器などの用途)に応じて適宜選択すればよいが、熱可塑性樹脂や、熱硬化性樹脂などを挙げることができる。
熱硬化性樹脂としては、エポキシ-フェノール樹脂、ポリエステル樹脂等を用いることができる。
多層ポリエステル樹脂層の例を示すと、表層/下層として表示して、ポリエチレンテレフタレート/ポリエチレンテレフタレート・イソフタレート、ポリエチレンテレフタレート/ポリエチレン・シクロへキシレンジメチレン・テレフタレート、イソフタレート含有量の少ないポリエチレンテレフタレート・イソフタレート/イソフタレート含有量の多いポリエチレンテレフタレート・イソフタレート、ポリエチレンテレフタレート・イソフタレート/[ポリエチレンテレフタレート・イソフタレートとポリブチレンテレフタレート・アジペートとのブレンド物]等であるが、勿論上記の例に限定されない。表層:下層の厚み比は、5:95~95:5の範囲にあるのが望ましい。
また、表面処理鋼板1上に形成する被覆層40は、T-ダイ法やインフレーション製膜法で予め製膜されたポリエステル樹脂フィルムを表面処理鋼板1に熱接着させることによっても形成することができる。フィルムとしては、押し出したフィルムを急冷した、キャスト成形法による未延伸フィルムを用いることもでき、また、このフィルムを延伸温度で、逐次或いは同時二軸延伸し、延伸後のフィルムを熱固定することにより製造された二軸延伸フィルムを用いることもできる。
また、絞り・再絞りによる曲げ伸ばし加工(ストレッチ加工)、絞り・再絞りによる曲げ伸ばし・しごき加工等の高度な加工が施されるシームレス缶5においては、被覆層40が押出コート法による熱可塑性樹脂被覆から成るものであることが特に好ましい。
すなわち、かかる有機材料被覆鋼板は、加工密着性に優れていることから、過酷な加工に賦された場合にも被覆の密着性に優れ、優れた耐食性を有するシームレス缶を提供することができる。
なお、各特性の評価方法は、以下のとおりである。
電解処理液について、ICP発光分析装置(島津製作所社製、ICPE-9000)を用いてリン酸イオン濃度又はAlイオン濃度を、イオンクロマトグラフ(ダイオネクス社製、DX-500)を用いてFイオン濃度及び硝酸イオン濃度を測定した。また、上記電解処理液について、pHメーター(堀場製作所社製)を用いてpHを測定した。
表面処理鋼板1について、蛍光X線分析装置(リガク社製、ZSX100e)を用いて、鋼板11上に形成された各層に含まれるリン量及びアルミニウム量をmg/m2の単位で測定した。また、得られた測定値を、mol/m2の単位に換算して、アルミニウム量(mol/m2)に対するリン量(mol/m2)の含有比(P/Al)を算出した。なお、リン量及びアルミニウム量の測定及びP/Alの算出は、後述する全ての実施例及び比較例について行った。
表面処理鋼板1について、下記条件にてX線光電子分光装置を用いて錫の3d5/2のスペクトルを測定することで、アルミニウム酸素化合物層30における、リン酸錫に由来するプロファイルの積分値に対する、酸化錫に由来するプロファイルの積分値の比(酸化錫/リン酸錫)を求めた。なお、アルミニウム酸素化合物層30中の錫化合物の測定及び上記比(酸化錫/リン酸錫)の算出は、後述する実施例6についてのみ行った。得られた錫の3d5/2のスペクトルをソフトウェアにて波形分離を行い、解析した。
測定装置:日本電子株式会社製 JPS-9200
励起X線源:MgKα 電圧12kV,電流25mA
測定径:直径3mm
光電子取り出し角:90°(試料の法線に対し0°)
解析ソフト:日本電子株式会社製 SpecSurf(ver.1.7.3.9)
波形分離条件:酸化錫の結合エネルギー487.5eV、リン酸錫の結合エネルギー489.1eV、金属錫の結合エネルギー485.4eVとして波形分離
表面処理鋼板1について、カーボン蒸着を施した後、更にFIB装置内で炭素を約1μmデポジションし、マイクロサンプリング法によってサンプルを切り出し、銅製の支持台上に固定した。その後、FIB加工により断面TEM試料を作製し、TEM観察および各点におけるEDS分析を行い、定量分析を行った。
<FIB>日立製作所製 FB-2000C型 集束イオンビーム装置 加速電圧40kV
<TEM>日本電子製 JEM-2010F型 電界放射形透過電子顕微鏡 加速電圧200kV
<EDS>ノーラン製 UTW型Si(Li)半導体検出器 分析領域 1nm
なお、表面処理鋼板の断面観察および定量分析は、後述する実施例6についてのみ行った。
<塗料密着性評価>
表面処理鋼板1に被覆層40を形成してなる有機材料被覆鋼板について、温度125℃で30分間のレトルト処理を行った後、5mm間隔で鋼板11に達する深さの碁盤目を入れ、テープで剥離し、剥離の程度を目視にて観察し、以下の基準で評価した。なお、塗料密着性評価は、後述する全ての実施例及び比較例について行った。
3点:目視で判定した結果、塗料の剥離が認められなかった。
2点:目視で判定した結果、塗料の剥離が1/5以下の面積率で認められた。
1点:目視で判定した結果、塗料の剥離が1/5を超える面積率で認められた。
なお、塗料密着性評価においては、上記基準で評価が2点以上である場合に、表面処理鋼板1を、飲食缶用途として用いた際に十分な塗料密着性を有するものであると判断した。
表面処理鋼板1について、温度205℃で30分間の熱処理を行い、熱処理前後における、錫めっき鋼板10の表面に形成された錫の酸化膜層の量をそれぞれ測定した。なお、酸化膜層の量は、酸化膜層を電気化学的還元により除去するのに要した電気量で評価した。電解液には1/1000Nの臭化水素溶液を用い、電流密度25μA/cm2の条件で電解を行った。酸化膜層の成長の評価は、熱処理後の酸化膜層の量を、熱処理前の酸化膜層の量で除した値(熱処理後の酸化膜層/熱処理前の酸化膜層)を算出することで行い、値が大きいほど熱処理により酸化膜層が成長し易いと評価した。なお、酸化膜層の成長の評価は、後述する全ての実施例及び比較例について行った。
○:熱処理後の酸化膜層/熱処理前の酸化膜層が1.2以下であった。
△:熱処理後の酸化膜層/熱処理前の酸化膜層が1.2を越え1.4以下であった。
×:熱処理後の酸化膜層/熱処理前の酸化膜層が1.4を越えた。
表面処理鋼板1に被覆層40を形成してなる有機材料被覆鋼板を、40mm角に切断した後、切断面を3mm幅テープで保護することで試験片を作製した。次いで、作製した試験片に対して、カッターを用いて鋼板に達する深さのクロスカット傷をつけて、クロスカットの交点部分が張出し加工部の頂点になるように、エリクセン試験機(コーティングテスター社製)により3mmの張り出し加工を行った。そして、張り出し加工を行った試験片を密封容器に入れ、下記モデル液を充填した後、90℃の環境下で24時間保管した。
モデル液:NaCl及びクエン酸をそれぞれ1.5重量%で溶解させた水溶液
その後開缶し、試験片の腐食の程度を目視にて観察し、以下の基準で評価した。なお、耐食性評価(モデル液)は、後述する全ての実施例及び比較例について行った。
3点:目視で判定した結果、比較例2と比較して明らかに腐食の程度が小さかった。
2点:目視で判定した結果、比較例2と比較して腐食の程度が同等であった。
1点:目視で判定した結果、比較例2と比較して明らかに腐食の程度が大きかった。
なお、耐食性評価(モデル液)においては、上記基準で評価が2点以上である場合に、表面処理鋼板1を、飲食缶用途として用いた際に十分な耐食性を有するものであると判断した。
表面処理鋼板1を、直径49mmの円盤に切断した後、切断面を3mm幅テープで保護することで試験片を作製し、作製した試験片のSn量を蛍光X線にて測定した。次いで、試験片を密封容器に入れ、下記モデル液を充填した後、37℃環境下で10日間保管した。
モデル液:酢酸1重量%及びショ糖(スクロース)10重量%を溶解させた水溶液
その後開缶し、37℃環境下で10日間の継時後の試験片のSn量を、蛍光X線にて測定し、以下の式を用いて、残存Sn量%を算出した。
残存Sn量(%)=(経時前Sn量-経時後Sn量)/経時前Sn量×100
なお、残存Sn量%が参考例1と同等もしくはそれ以上の場合に、飲食缶用途として用いた際に十分な脱錫性を有するものであると判断した。なお、脱錫性評価(モデル液)は、後述する実施例14、比較例8及び参考例1について行った。
まず、鋼板11として低炭素冷延鋼板(板厚0.225mm)を準備した。
浴温:40℃
電流密度:10A/dm2
陽極材料:市販の99.999%金属錫
トータル通電時間:5秒(通電時間1秒、停止時間0.5秒を1サイクルとした際における、サイクル数5回)
電解処理液:亜リン酸を濃度10g/Lで溶解させたpH1.3の水溶液(表1の処理液A)
電解処理液の温度:40℃
電流密度:3A/dm2
トータル通電時間:0.5秒(通電時間0.5秒、サイクル数1回)
電解処理液:Al化合物として硝酸アルミニウムを溶解させ、Alイオン濃度1,500重量ppm、硝酸イオン濃度15,000重量ppmとし、Fイオン濃度が0重量ppmであるpH3.0の水溶液(表1の処理液E)
電解処理液の温度:40℃
電流密度:4A/dm2
トータル通電時間:0.3秒(通電時間0.3秒、サイクル数1回)
錫めっき鋼板10上にリン酸化合物層20を形成する際において、電解処理液としてリン酸を濃度30g/Lで、リン酸二ナトリウムを濃度30g/Lでそれぞれ溶解させたpH1.8の水溶液(表1の処理液B)を用いた以外は、実施例1と同様にして表面処理鋼板1及び有機材料被覆鋼板を作製し、同様に評価を行った。結果を表3に示す。
リン酸化合物層20を形成する際の電解処理の通電時間を0.3秒とし、アルミニウム酸素化合物層30を形成する際の電解処理の通電時間を0.15秒とした以外は、実施例2と同様にして表面処理鋼板1及び有機材料被覆鋼板を作製し、同様に評価を行った。
錫めっき鋼板10上にリン酸化合物層20を形成する際において、電解処理液としてリン酸を濃度10g/Lで、リン酸二水素ナトリウムを濃度30g/Lでそれぞれ溶解させたpH 2.4の水溶液(表1の処理液C)を用い、また、アルミニウム酸素化合物層30を形成する際の電解処理の通電時間を0.15秒に変更した以外は、実施例1と同様にして表面処理鋼板1及び有機材料被覆鋼板を作製し、同様に評価を行った。結果を表3に示す。
錫めっき鋼板10上にリン酸化合物層20を形成する際において、電解処理液として表1の処理液Cを用いた以外は、実施例4と同様にして表面処理鋼板1及び有機材料被覆鋼板を作製し、同様に評価を行った。結果を表3に示す。なお、実施例5については、アルミニウム酸素化合物層30中の錫化合物の測定を行い、X線光電子分光装置を用いてアルミニウム酸素化合物層30中の錫化合物の測定を行った際に得られたスペクトルを図5(A)に示した。
錫めっき鋼板10上にリン酸化合物層20を形成する際において、上述した陰極電解処理を行う前に、極性のみ逆転した処理(陽極電解処理)を行った以外は同様の条件にて陽極電解処理を行った。それ以外は、実施例5と同様にして表面処理鋼板1及び有機材料被覆鋼板を作製し、同様に評価を行った。結果を表3に示す。なお、実施例6については、アルミニウム酸素化合物層30中の錫化合物の測定を行い、X線光電子分光装置を用いてアルミニウム酸素化合物層30中の錫化合物の測定を行った際に得られたスペクトルを図5(B)、表面処理鋼板の断面観察により得られたTEM像および定量分析結果を図8にそれぞれ示した。
錫めっき鋼板10上にリン酸化合物層20を形成する際の電解処理の電流密度、また、アルミニウム酸素化合物層30を形成する際の電解処理の電流密度、通電時間およびサイクル数を表2のように変更した以外は、実施例6と同様にして表面処理鋼板1及び有機材料被覆鋼板を作製し、同様に評価を行った。なお、リン酸化合物層20を形成する前に、前処理として塩酸水溶液中に浸漬することにより、錫めっき表面に形成された錫酸化膜の除去を行った。結果を表3に示す。
実施例1で作製した錫めっき鋼板10について、リン酸化合物層20を形成した後、アルミニウム酸素化合物層30を形成することなく、塗料密着性評価、酸化膜層の成長の評価及び耐食性評価(モデル液)を行った。結果を表3に示す。
実施例1で作製した錫めっき鋼板10について、リン酸化合物層20を形成することなく、錫めっき鋼板10上に、直接、実施例1と同様の方法でアルミニウム酸素化合物層30を形成することで表面処理鋼板を得た。そして、得られた表面処理鋼板について、塗料密着性評価、酸化膜層の成長の評価及び耐食性評価(モデル液)を行った。結果を表3に示す。
表3に示すように、錫めっき鋼板10に対して陰極電解処理を施すことでリン酸化合物層20を形成し、このリン酸化合物層20上にアルミニウム酸素化合物層30を形成した実施例1~7は、塗料密着性評価、酸化膜層の成長の評価及び耐食性評価(モデル液)の結果がいずれも良好であり、耐食性及び被覆層40の密着性に優れ、長期にわたって使用される金属容器等の用途に好適であることが確認された。
錫めっき層12を形成する際において、トータル通電時間を7.5秒として、錫めっき層12の錫量を11.2g/m2とし、リン酸化合物層形成の電解処理、アルミニウム酸素化合物層形成の電解処理を表2に示す条件とした以外は、実施例1と同様にして、表面処理鋼板1を作製した。得られた表面処理鋼板1について、上述した方法にしたがって、脱錫性評価(モデル液)を行った。結果を表4に示す。
錫めっき層12を形成する際において、トータル通電時間を7.5秒として、錫めっき層12の錫量を11.2g/m2とし、リン酸化合物層20を形成することなく、アルミニウム酸素化合物層形成の電解処理を表2に示す条件とした以外は、実施例1と同様にして、表面処理鋼板を作製した。得られた表面処理鋼板について、実施例14と同様に脱錫性評価(モデル液)を行った。結果を表4に示す。
錫めっき層12を形成する際において、トータル通電時間を7.5秒として、錫めっき層12の錫量を11.2g/m2とし、錫めっき鋼板10を作製した。その後、錫めっき鋼板10の表面に、電解処理によってクロム水酸化物を形成し、表面処理鋼板を作製した。得られた表面処理鋼板について、実施例14と同様に脱錫性評価(モデル液)を行った。結果を表4に示す。なお、参考例1は現行市販されている表面処理鋼板の生産品に相当する。
表4に示すように、錫めっき鋼板10に対して陰極電解処理を施すことでリン酸化合物層20を形成し、このリン酸化合物層20上にアルミニウム酸素化合物層30を形成した実施例8の残存Sn量は、現行の生産品である参考例1と同等以上の残存Sn量であり、さらにリン酸化合物層20を形成することなく、錫めっき鋼板10上に、直接、アルミニウム酸素化合物層30を形成した比較例3と比較して多かった。このことから、このことから、錫めっき鋼板10上に、リン酸化合物層20及びアルミニウム酸素化合物層30のみを形成して得られた実施例8の表面処理鋼板1は、被覆層40を有しない無塗装の状態でも、残存Sn量が多いことから、耐食性及び耐硫化黒変性に優れ、無塗装で使用される金属容器等の用途にも好適であることが確認された。
10…錫めっき鋼板
11…鋼板
12…錫めっき層
20…リン酸化合物層
30…アルミニウム酸素化合物層
40…被覆層
Claims (11)
- 鋼板上に錫めっきを施してなる錫めっき鋼板と、
前記錫めっき鋼板上に形成された、リン酸錫を含有するリン酸化合物層と、
前記リン酸化合物層上に形成された、アルミニウム酸素化合物を主成分とするアルミニウム酸素化合物層と、を備え、
前記アルミニウム酸素化合物層における、X線光電子分光装置を用いて錫の3d5/2のスペクトルを測定した際の、リン酸錫に由来するプロファイルの積分値に対する、酸化錫に由来するプロファイルの積分値の比(酸化錫/リン酸錫)が6.9以上である表面処理鋼板。 - 前記アルミニウム酸素化合物層は、リン酸アルミニウムを含有する請求項1に記載の表面処理鋼板。
- 前記錫めっき鋼板上に形成された各層に含まれるリンの合計量が0.5~20mg/m2である請求項1又は2に記載の表面処理鋼板。
- 前記アルミニウム酸素化合物層におけるアルミニウムの含有量が3~40mg/m2である請求項1~3の何れか一項に記載の表面処理鋼板。
- 前記アルミニウム酸素化合物層は、実質的にフッ素を含まない請求項1~4の何れか一項に記載の表面処理鋼板。
- 前記錫めっき鋼板は、前記鋼板と、前記鋼板上に形成された錫合金層と、前記錫合金層上に形成された錫めっき層と、からなり、前記錫合金層と前記錫めっき層の合計の錫量が1.0g/m2以上の錫めっき層とからなる請求項1~5の何れか一項に記載の表面処理鋼板。
- 請求項1~6の何れか一項に記載の表面処理鋼板からなる金属容器。
- 請求項1~6の何れか一項に記載の表面処理鋼板と、
前記アルミニウム酸素化合物層上に形成された有機材料を主成分とする被覆層と、を備える金属容器。 - 鋼板上に錫めっきを施してなる錫めっき鋼板上に、陰極電解処理を行うことによりリン酸化合物層を形成するリン酸化合物層形成工程と、
前記リン酸化合物層上に、アルミニウムを含む電解処理液を用いた電解処理によりアルミニウム酸素化合物層を形成するアルミニウム酸素化合物層形成工程と、を有する表面処理鋼板の製造方法。 - 前記リン酸化合物層形成工程において、前記錫めっき鋼板上に、陽極電解処理を行った後に、前記陰極電解処理を行うことにより前記リン酸化合物層を形成する請求項9に記載の表面処理鋼板の製造方法。
- 前記アルミニウム酸素化合物層形成工程において、前記電解処理液として、リン酸の含有量がリン量で0.55g/L以下である処理液を用いる請求項9又は10に記載の表面処理鋼板の製造方法。
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EP20192629.2A EP3786319B1 (en) | 2015-01-26 | 2015-12-24 | Method for producing surface-treated steel plate |
US15/546,624 US20180010259A1 (en) | 2015-01-26 | 2015-12-24 | Surface-treated steel sheet, metal container, and method for producing surface-treated steel sheet |
CN201580074640.XA CN107208300B (zh) | 2015-01-26 | 2015-12-24 | 表面处理钢板、金属容器及表面处理钢板的制造方法 |
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WO2021261155A1 (ja) * | 2020-06-26 | 2021-12-30 | 東洋鋼鈑株式会社 | 表面処理鋼板、金属容器および表面処理鋼板の製造方法 |
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