WO2021124510A1 - Sn系めっき鋼板 - Google Patents
Sn系めっき鋼板 Download PDFInfo
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- WO2021124510A1 WO2021124510A1 PCT/JP2019/049820 JP2019049820W WO2021124510A1 WO 2021124510 A1 WO2021124510 A1 WO 2021124510A1 JP 2019049820 W JP2019049820 W JP 2019049820W WO 2021124510 A1 WO2021124510 A1 WO 2021124510A1
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- film layer
- steel sheet
- metal
- oxide
- zirconium oxide
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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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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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
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
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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
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
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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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- 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
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated 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
- 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 Sn-based plated steel sheet.
- Tin (Sn) -based plated steel sheets are well known as "tinplate” and are widely used for cans such as beverage cans and food cans. This is because Sn is a beautiful metal that is safe for the human body.
- This Sn-based plated steel sheet is mainly manufactured by an electroplating method. This is because the electroplating method is more advantageous than the hot-dip plating method in order to control the amount of Sn, which is a relatively expensive metal, to the minimum necessary amount.
- the Sn-based plated steel sheet is subjected to chromate treatment (electrolytic treatment, dipping treatment, etc.) using a hexavalent chromium salt solution after plating or heat-melting treatment after plating to impart a beautiful metallic luster.
- a chromate film is often applied on the Sn-based plating layer.
- the effects of this chromate film are to prevent yellowing of the appearance by suppressing oxidation of the surface of the Sn-based plating layer, and to prevent deterioration of coating film adhesion due to cohesive destruction of tin oxide when used after painting. Improvement of sulfide blackening resistance, etc.
- the Sn-based galvanized steel sheet without a chromate film has a yellowing appearance due to the growth of tin oxide, a decrease in coating film adhesion, and a decrease in sulfurization blackening resistance.
- Patent Document 1 proposes a tin-based galvanized steel sheet in which a chemical conversion film containing P and Si is formed by a treatment using a chemical conversion treatment liquid containing a phosphate ion and a silane coupling agent. There is.
- Patent Document 2 a tin-plated steel sheet having a chemical conversion-treated film containing Al and P, at least one selected from Ni, Co, and Cu, and a reaction product layer with a silane coupling agent. Has been proposed.
- Patent Document 3 proposes a method for producing a Sn-plated steel sheet, which is obtained by multi-layer plating Zn on Sn plating and then heating until the Zn single plating layer substantially disappears.
- Patent Document 4 a steel sheet for a container having a Zr film formed on a surface treatment layer containing Sn is proposed, and in Patent Document 5 below, a steel sheet for a container having a Zr compound film layer is proposed.
- Patent Document 6 proposes a steel sheet for a container having a base Ni layer, an island-shaped Sn plating layer, a chemical conversion treatment layer containing tin oxide and tin phosphate, and a Zr-containing film layer.
- Patent Document 7 proposes a steel sheet for a container having a tin oxide and a film containing Zr, Ti, and P on the surface of the tin-plated layer. Patent Document 7 also proposes that in forming a film, alternating electrolysis in which cathode electrolysis treatment and anodic electrolysis treatment are alternately performed may be performed.
- Japanese Unexamined Patent Publication No. 2004-060052 Japanese Unexamined Patent Publication No. 2011-174172 JP-A-63-290292 JP-A-2007-284789 Japanese Unexamined Patent Publication No. 2010-013728 Japanese Unexamined Patent Publication No. 2009-249691 International Publication No. 2015/001598
- Patent Documents 1 to 7 cannot sufficiently suppress the growth of tin oxide over time, resulting in yellowing resistance and coating adhesion. There was room for improvement in black denaturation resistance.
- the present invention has been made in view of the above problems, and an object of the present invention is excellent in yellowing resistance, coating film adhesion, and sulfide blackening resistance without performing conventional chromate treatment.
- the present invention is to provide Sn-based galvanized steel sheets.
- a metal Sn terms contained per side 0.10 g / m 2 or more 15.00 g / m 2 or less
- the coating layer contains zirconium oxide and manganese oxide, the zirconium oxide in the coating layer
- the content of the substance is 0.20 mg / m 2 or more and 50.00 mg / m 2 or less per side in terms of metal Zr, and the content of the manganese oxide in the film layer in terms of metal Mn is as described above.
- the content of zirconium oxide in terms of metal Zr is 0.01 times or more and 0.50 times or less on a mass basis, and is present as the manganese oxide in the depth direction element analysis by X-ray photoelectron spectroscopy.
- the depth position A where the element concentration of Mn is maximum is located on the surface side of the film layer and the depth is higher than the depth position B where the element concentration of Zr existing as the zirconium oxide is maximum.
- a Sn-based plated steel plate in which the distance between the vertical position A and the deep position B in the depth direction is 2 nm or more.
- the mass of the zirconium oxide in the depth direction elemental analysis by the X-ray photoelectron spectroscopy is the mass of the manganese oxide in the depth direction elemental analysis by the X-ray photoelectron spectroscopy.
- the Sn-based plated steel sheet according to (1) which is 0.01 times or less of the above.
- the content of the zirconium oxide in the film layer is 1.00 mg / m 2 or more and 30.00 mg / m 2 or less per side in terms of metal Zr, according to (1) to (3).
- the content of the zirconium oxide in the film layer is 2.00 mg / m 2 or more and 10.00 mg / m 2 or less per side in terms of metal Zr, according to (1) to (4).
- the metal Mn-equivalent content of the manganese oxide in the film layer is 0.05 times or more and 0.40 times or less on a mass basis with respect to the metal Zr-equivalent content of the zirconium oxide.
- the metal Mn-equivalent content of the manganese oxide in the film layer is 0.10 times or more and 0.20 times or less on a mass basis with respect to the metal Zr-equivalent content of the zirconium oxide.
- process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended purpose of the process is achieved. Included in the term.
- steel plate means a base steel plate (so-called plating base plate) to be formed with a Sn-based plating layer and a coating layer.
- the present invention described below relates to a Sn-based galvanized steel sheet widely used for cans such as food cans and beverage cans. More specifically, the present invention relates to a Sn-based plated steel sheet that is more excellent in yellowing resistance, coating film adhesion, and sulfurization blackening resistance without performing conventional chromate treatment.
- FIG. 1 is an explanatory view schematically showing an example of the structure of the Sn-based plated steel sheet according to the present embodiment.
- the Sn-based plated steel sheet 1 includes a steel sheet (base steel sheet) 10 and a Sn-based plated layer 20 located on at least one surface of the steel sheet 10. It has a film layer 30 located on the Sn-based plating layer 20.
- the coating layer 30 contains a zirconium oxide and manganese oxide ,
- the content of zirconium oxide in the film layer 30 is 0.20 mg / m 2 or more and 50.00 mg / m 2 or less per side in terms of metal Zr, and the metal Mn of the manganese oxide in the film layer 30.
- the converted content is 0.01 times or more and 0.50 times or less on a mass basis with respect to the content of zirconium oxide in terms of metal Zr.
- the depth position A where the element concentration of Mn existing as an oxide is maximum is located closer to the surface side of the film layer than the depth position B where the element concentration of Zr existing as a zirconium oxide is maximum.
- the distance in the depth direction between the depth position A and the depth position B is 2 nm or more.
- the steel sheet 10 used as the base material of the Sn-based plated steel sheet 1 according to the present embodiment is not particularly specified, and is arbitrary as long as it is a steel sheet used for a general Sn-based plated steel sheet for containers. Things can be used. Examples of such a steel sheet 10 include low carbon steel and ultra-low carbon steel.
- Sn-based plating layer 20 At least one surface of the steel sheet 10 as described above is subjected to Sn-based plating to form a Sn-based plating layer 20.
- the Sn-based plating layer 20 improves the corrosion resistance of the steel sheet 10.
- the term "Sn-based plating layer" as used herein refers not only to plating with metal Sn, but also to an alloy of metal Sn and metal Fe, metal Ni, and at least one of trace elements and impurities other than metal Sn. The included Sn-based plating layer is also included.
- Sn content per one side the amount of metal Sn as (i.e. metal Sn equivalent amount), it is 0.10 g / m 2 or more 15.00 g / m 2 or less.
- the Sn content per side is preferably 1.0 g / m 2 or more in terms of the amount of metal Sn.
- the content of the Sn-based plating layer 20 per side exceeds 15.00 g / m 2 in terms of the amount of metal Sn, the effect of improving the corrosion resistance by the metal Sn is sufficient, and further increase is preferable from the economical point of view. Absent. In addition, the adhesion of the coating film tends to decrease.
- the Sn content per side is preferably 13.00 g / m 2 or less in terms of the amount of metal Sn.
- the amount of metal Sn in the Sn-based plating layer was measured by, for example, the electrolytic method or the fluorescent X-ray method described in JIS G 3303. Let it be a value.
- the amount of metal Sn in the Sn-based plating layer can be determined by the following method. Prepare a test piece without a film layer. The test piece was immersed in 10% nitric acid to dissolve the Sn-based plating layer, and Sn in the obtained solution was subjected to ICP emission spectrometry (high-frequency inductively coupled plasma emission spectroscopy), for example, as an apparatus as an Agilent.
- ICP emission spectrometry high-frequency inductively coupled plasma emission spectroscopy
- the amount of metal Sn can be determined based on the intensity signal obtained by the analysis, the calibration curve prepared from the solution having a known concentration, and the formation area of the Sn-based plating layer of the test piece.
- the amount of metal Sn can be determined by a calibration curve method using GDS (glow discharge emission spectroscopy), and the method is, for example, as follows. is there.
- the relationship between the intensity signal of metal Sn and the sputter rate in the reference sample is obtained in advance by GDS, and a calibration curve is prepared. Based on this calibration curve, the amount of metal Sn can be obtained from the intensity signal and the sputtering rate of the test piece whose metal Sn amount is unknown.
- the Sn-based plating layer is made of Fe because the intensity signal of Zr becomes 1/2 of the maximum value of the intensity signal of Zr when the Sn-based plated steel sheet is analyzed in the depth direction from the surface. It is defined as the part up to the depth where the intensity signal becomes 1/2 of the maximum value of the intensity signal of Fe. From the viewpoint of measurement accuracy and speed, measurement by the fluorescent X-ray method is industrially preferable.
- a film layer 30 containing a zirconium oxide and a manganese oxide is formed on the Sn-based plating layer 20.
- the Sn-based plated steel sheet 1 according to the present embodiment has a film layer 30 on the surface of the Sn-based plated layer 20 in which the above-mentioned zirconium oxide and manganese oxide coexist in a quantitative relationship described later. It is possible to further improve yellowing resistance, coating adhesion, and blackening resistance to sulfurization. It should be noted that the film layer containing only zirconium oxide or manganese oxide cannot sufficiently improve yellowing resistance, coating film adhesion, and sulfurization blackening resistance. The reason for this is not clear, but the detailed investigation by the present inventors considers it as follows.
- Tin oxide is present on the surface of the conventional Sn-based plating layer, and as the amount of tin oxide increases with time, yellowing resistance and coating adhesion are reduced, and sulfide blackening resistance is also reduced. To do.
- the rate of increase of tin oxide with time tends to be suppressed by the barrier property of the zirconium oxide layer itself.
- the film layer containing the zirconium oxide is an inhomogeneous film containing the tin oxide, oxygen and sulfur permeate through the fine cracks existing in the brittle tin oxide and Sn. It reaches the system plating surface, and tin oxide and tin sulfide gradually increase.
- the coating layer 30 containing both zirconium oxide and manganese oxide is present on the surface of the Sn-based plating layer 20, the tin oxide contained in the coating layer 30 is reduced by the manganese oxide and the tin oxide is reduced. Decreases. Further, when the manganese oxide becomes an oxide having a higher oxidation number, a film having a high barrier property is formed, the permeation of oxygen and sulfur is suppressed, and the production of tin oxide and tin sulfide is reduced. As a result, yellowing resistance and coating film adhesion are improved, and sulfurization blackening resistance is also improved.
- a zirconium oxide having a metal Zr amount of 0.20 mg / m 2 or more and 50.00 mg / m 2 or less per side is required in the film layer 30.
- the content of the zirconium oxide is less than 0.20 mg / m 2 in terms of the amount of metal Zr, the barrier property of the zirconium oxide is insufficient, and yellowing resistance, coating adhesion, and black sulfide resistance are deteriorated. Does not improve.
- the content of zirconium oxide per one side, a metal Zr content is preferably at 1.00 mg / m 2 or more, more preferably 2.00 mg / m 2 or more.
- a metal Zr content is preferably at 30.00mg / m 2 or less, and more preferably 10.00 mg / m 2 or less.
- the content of manganese oxide in terms of metal Mn in the film layer 30 is 0.01 in terms of mass with respect to the content of zirconium oxide in terms of metal Zr. It is necessary that it is more than double and 0.50 times or less.
- the amount of manganese oxide per side is less than 1/100 of the metal Zr content of zirconium oxide, the reduction of tin oxide contained in the film and manganese Further oxidation of the oxide is insufficient, and yellowing resistance, coating adhesion, and sulfide blackening resistance cannot be sufficiently improved.
- the metal Mn-equivalent content of manganese oxide in the film layer 30 is preferably 0.05 times or more, preferably 0.10 times or more, based on the mass, with respect to the metal Zr-equivalent content of zirconium oxide. Is more preferable.
- the metal Mn-equivalent content of manganese oxide in the film layer 30 is preferably 0.40 times or less, preferably 0.20 times or less, based on the mass, with respect to the metal Zr-equivalent content of zirconium oxide. Is more preferable.
- the manganese oxide is concentrated on the surface side of the film layer 30 (that is, the concentration of manganese oxide near the surface of the film layer 30 is higher than that of the Sn-based plating layer 20 of the film layer 30. It is necessary that the concentration is higher than the manganese oxide concentration near the interface of.
- the barrier effect of the manganese oxide is sufficiently exhibited, so that the yellowing resistance, the sulfurization resistance and the blackening resistance, and the corrosion resistance after painting are further improved. Further, since the amount of manganese oxide at the interface between the film layer 30 and the Sn-based plating layer 20 is small, the adhesion to the coating film is further improved.
- the element concentration of Mn existing as a manganese oxide is the maximum.
- Depth position A (in other words, the position where the detection intensity of Mn element is maximum) is the depth position B where the element concentration of Zr existing as zirconium oxide is maximum (in other words, the detection intensity of Zr element is maximum). It is necessary that the film layer 30 is located on the surface side of the film layer 30 and the distance between the depth position A and the depth position B in the depth direction is 2 nm or more.
- FIG. 2 is a diagram showing an example of the element concentration profile in the thickness direction (depth direction) of the Sn-based plating layer 20 and the coating layer 30 of the Sn-based plated steel sheet 1 according to the present embodiment.
- the element concentration profile shown in FIG. 2 measures the distribution of the element concentration from the surface of the film layer 30 to the surface of the steel sheet 10 through the Sn-based plating layer 20 by analysis in the depth direction of XPS.
- the position where the “sputter depth” on the horizontal axis is 0 is the surface of the film layer 30.
- the value of "sputter depth" in FIG. 2 is synonymous with "depth position".
- the depth position A is the position where the sputter depth is 0 nm
- the depth position B is the position where the sputter depth is 4.0 nm.
- the depth position A is located on the surface of the film layer 30 (the upper surface of the film layer 30 in FIG. 1)
- the depth position B is the film layer 30. It is located at a location 4 nm away from the surface of the film layer 30 in the depth direction (in FIG. 1, a location 4 nm downward from the upper surface of the film layer 30). That is, in the example shown in FIG. 2, the distance between the depth directions A and B is 4 nm.
- the manganese oxide is present in a larger amount than the zirconium oxide on the mass basis.
- the fact that the depth positions are separated from the depth directions A and B by 2 nm or more means that the manganese oxide is thicker than the zirconium oxide on the surface side of the film layer 30. Therefore, the manganese oxide concentrated on the surface of the film layer 30 becomes an oxide having a higher oxidation number, so that the film has a high barrier property.
- the film made of manganese oxide suppresses the permeation of oxygen and sulfur, the formation of tin oxide and tin sulfide in the Sn-based plating layer is suppressed. Therefore, the yellowing resistance and the coating film adhesion of the Sn-based plating layer are improved, and the sulfurization blackening resistance is also improved.
- the depth position A where the element concentration of Mn existing as a manganese oxide is maximum is 4 nm or more more than the depth position B where the element concentration of Zr existing as a zirconium oxide is maximum, and the surface of the film layer. It is preferably located on the side.
- these depth positions are separated by 4 nm or more, the concentration of manganese oxide on the surface of the film layer 30 becomes more remarkable, and the film made of manganese oxide exerts a further barrier function.
- the upper limit value of the separation distance at the depth position is not particularly specified, and the farther the distance is, the more preferable the upper limit value is, but the actual upper limit value is about 15 nm.
- the distribution of zirconium oxide and manganese oxide in the film layer 30 can be specified and quantified by analyzing the film layer 30 from the surface side by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the zirconium oxide in the film layer 30 is 3.0 eV or more and 4.0 eV or less on the higher energy side than the peak position of the binding energy of the metal Zr in the element concentration profile obtained by X-ray photoelectron spectroscopy. It is identified based on the peak of the binding energy of Zr3d5 / 2 at a distant position.
- the manganese oxide in the film layer 30 exists at a distance of 1.5 eV or more and 3.5 eV or less on the high energy side of the peak position of the binding energy of the metal Mn in the element concentration profile obtained by X-ray photoelectron spectroscopy. It is specified based on the peak of the binding energy of Mn 2p3 / 2.
- the Zr 3d2 / 5 and Mn 2p3 / 2 represent the energy levels of electrons in Zr or Mn, and for example, P.I. It is interpreted in the same way as the representation of the energy level of the electron in Sn described in 83.
- the film layer 30 may contain a zirconium oxide, a manganese oxide, or a compound other than the oxide having another structure.
- a film layer 30 in which a zirconium oxide and a manganese oxide coexist is present on the surface of the Sn-based plated layer 20 containing a metal Sn. You can see that there is.
- the film layer 30 containing the zirconium oxide and the manganese oxide may be in a mixed state of both or in a solid solution of the oxide, and its existence state does not matter. Further, there is no problem even if any element such as Fe, Ni, Cr, Ca, Na, Mg, Al, Si and the like is contained in the film layer 30.
- the content of zirconium oxide (amount of metal Zr) and the content of manganese oxide (amount of metal Mn) are determined by the Sn-based plated steel sheet 1 according to the present embodiment, for example, hydrofluoric acid and sulfuric acid. It is dissolved by immersing it in an acidic solution, and the obtained solution is used as a value measured by chemical analysis such as inductively coupled plasma (ICP) emission spectrometry.
- the zirconium oxide content (metal Zr amount) and the manganese oxide content (metal Mn amount) in the film layer 30 may be determined by fluorescent X-ray measurement. From the viewpoint of measurement accuracy and speed, measurement by the fluorescent X-ray method is industrially preferable.
- the Sn-based plated steel sheet 1 has a film layer 30 containing a predetermined amount of zirconium oxide and manganese oxide on the Sn-based plated layer 20. Then, the content of the manganese oxide in the film layer 20 is within a predetermined range with respect to the content of the zirconium oxide, and further, in the depth direction element analysis by XPS, Mn existing as the manganese oxide.
- the depth position A having the maximum element concentration is located closer to the surface side of the film layer 30 than the depth position B having the maximum element concentration of Zr existing as a zirconium oxide, and is defined as the depth position A.
- the distance in the depth direction from the depth position B is 2 nm or more.
- the manganese oxide reduces the tin oxide existing in the vicinity of the film layer 30 to reduce the tin oxide, while the manganese oxide becomes an oxide having a higher oxidation number, so that the film has a high barrier property. And suppress the permeation of oxygen and sulfur. Then, in combination with the barrier property of the zirconium oxide in the film layer 30, the formation of tin oxide and tin sulfide is reduced, the yellowing resistance and the coating film adhesion are improved, and the sulfide blackening resistance is also improved.
- the Sn-based plated steel sheet 1 according to the present embodiment there is no problem even if a known film is formed on the surface of the Sn-based plated steel sheet having the Sn-based plated layer 20 and the film layer 30 as described above.
- a known film examples include various chemical conversion-treated films made of P-based compounds, Al-based compounds, and the like.
- the Sn-based plated steel sheet 1 according to the present embodiment is not subjected to chromate treatment. Therefore, it is preferable that the Sn-based plated steel sheet 1 according to the present embodiment does not have a chromate layer.
- the Sn-based plated steel sheet 1 has been described as having the Sn-based plated layer 20 on only one side, the present invention is not limited to this.
- the Sn-based plated steel sheet 1 may have Sn-based plated layers 20 on both sides.
- the above-mentioned film layer 30 may be provided only on at least one Sn-based plating layer 20.
- the Sn-based plated steel sheet 1 may have a Sn-based plating layer 20 on one surface and various films other than the Sn-based plating layer 20 on the other surface.
- the Sn-based plated steel sheet according to the present embodiment may be manufactured by any method, and can be manufactured, for example, by the Sn-based plated steel sheet manufacturing method described below.
- the method for producing the Sn-based plated steel sheet 1 includes a step of forming a Sn-based plated layer 20 on at least one surface of the steel sheet 10 and a zinc oxide and a manganese oxide on the Sn-based plated layer 20. It has a step of forming a film layer 30 to be contained.
- a step of forming a Sn-based plated layer 20 on at least one surface of the steel sheet 10 and a zinc oxide and a manganese oxide on the Sn-based plated layer 20 It has a step of forming a film layer 30 to be contained.
- a steel sheet 10 as a base material of the Sn-based plated steel sheet 1 is prepared.
- the manufacturing method and material of the steel sheet to be used are not particularly specified, and for example, those manufactured through processes such as casting, hot rolling, pickling, cold rolling, annealing, and temper rolling may be used. it can.
- a Sn-based plating layer (Sn plating) is formed on at least one surface of the steel sheet.
- the method of applying Sn-based plating to the surface of the steel sheet is not particularly specified, but a known electroplating method is preferable, and the electroplating method includes, for example, electrolysis using a well-known ferrostan bath, halogen bath, alkaline bath, or the like. You can use the law.
- a melting method may be used in which the steel sheet is immersed in the molten Sn to perform Sn-based plating.
- a heat-melting treatment may be performed in which the steel sheet having the Sn-based plating layer is heated to 231.9 ° C. or higher, which is the melting point of Sn.
- the surface of the Sn-based plating layer becomes glossy, and an alloy layer of Sn and Fe is formed between the Sn-based plating layer and the steel sheet, further improving corrosion resistance and adhesion.
- the film layer containing zirconium oxide and manganese oxide is obtained by dipping the Sn-based plated steel plate in a dipping bath containing zirconium ions and manganese ions, or in a cathode electrolytic solution containing zirconium ions and manganese ions. By performing the electrolytic treatment, it can be formed on the surface of the Sn-based plating layer. However, in the dipping treatment, the surface of the Sn-based plating layer, which is the base, is etched to form a film layer containing a zirconium oxide and a manganese oxide.
- the cathode electrolysis treatment a uniform film can be obtained in combination with the forced charge transfer, the surface cleaning by hydrogen generation at the steel sheet interface, and the adhesion promoting effect by increasing the pH. Further, in this cathode electrolysis treatment, the nitrate ion and the ammonium ion coexist in the cathode electrolytic solution, so that the treatment can be performed in a short time of about several seconds to several tens of seconds. Therefore, the cathode electrolysis treatment is extremely advantageous industrially.
- the concentration of zirconium ions in the cathode electrolyte solution to be subjected to the cathode electrolysis treatment may be appropriately adjusted according to the production equipment, production speed (capacity), and the like.
- the zirconium ion concentration is preferably 100 ppm or more and 4000 ppm or less.
- the concentration of manganese ions is preferably 0.07 times or more and 2.50 times or less of the zirconium ion concentration.
- the solution containing zirconium ion and manganese ion contains other components such as fluorine ion, ammonium ion, nitrate ion, sulfate ion and chloride ion.
- the source of zirconium ions in the catholyte solution may be used, for example, zirconium complexes such as H 2 ZrF 6.
- Zr in the Zr complex as described above becomes Zr 4+ due to an increase in pH at the cathode electrode interface and exists in the cathode electrolyte.
- Such zirconium ions further react in the cathode electrolyte to form a zirconium oxide.
- Examples of the source of manganese ions include manganese sulfate, manganese nitrate, and manganese chloride.
- the solvent of the cathode electrolytic solution in the cathode electrolytic treatment for example, water such as distilled water can be used.
- the solvent is not defined in water such as distilled water, and can be appropriately selected depending on the substance to be dissolved, the forming method, and the like.
- nitric acid, aqueous ammonia, etc. may be added to the cathode electrolytic solution in order to adjust the pH of the cathode electrolytic solution and increase the electrolytic efficiency.
- the temperature of the cathode electrolytic solution during the cathode electrolytic treatment is not particularly specified, but is preferably in the range of, for example, 10 ° C. or higher and 50 ° C. or lower.
- the temperature of the cathode electrolytic solution during the cathode electrolytic treatment is not particularly specified, but is preferably in the range of, for example, 10 ° C. or higher and 50 ° C. or lower.
- the film formed is non-uniform depending on the composition of the cathode electrolytic solution, and defects, cracks, microcracks, etc. occur, making it difficult to form a dense film. It may be the starting point of corrosion.
- the pH of the cathode electrolytic solution is not particularly specified, but is preferably 3.0 or more and 5.0 or less. If the pH is less than 3.0, the efficiency of film formation may decrease depending on other conditions of the cathode electrolysis treatment, and if the pH is more than 5.0, the cathode electrolyte may decrease depending on the composition of the cathode electrolyte. A large amount of precipitation occurs inside, resulting in poor continuous productivity.
- the current density during the cathode electrolysis treatment is preferably, for example, 0.05 A / dm 2 or more and 50.00 A / dm 2 or less.
- the film formation efficiency may be lowered depending on other conditions of the cathode electrolysis treatment, resulting in a sparse film and the yellowing resistance and the sulfide blackening resistance may be lowered.
- the current density exceeds 50.00 A / dm 2
- hydrogen generation becomes excessive depending on other conditions of the cathode electrolysis treatment, coarse zirconium oxide and manganese oxide are formed, and yellowing resistance and coating adhesion are achieved.
- the property and sulfurization resistance blackening may be inferior.
- a more preferable range of current densities is 1.00 A / dm 2 or more and 10.00 A / dm 2 or less.
- the time of the cathode electrolysis treatment is not particularly limited.
- the time of the cathode electrolysis treatment may be appropriately adjusted according to the current density with respect to the content of the zirconium oxide (the amount of metal Zr) in the target film layer. Further, as the energization pattern at the time of the cathode electrolysis treatment, there is no problem whether it is continuous energization or intermittent energization.
- the peak position where the detection intensity for manganese oxide is maximum is higher than the peak position where the detection intensity for zirconium oxide is maximum.
- the peak position where the detection intensity for manganese oxide is maximum is more likely to exist on the surface side of the film layer than the peak position where the detection intensity for zirconium oxide is maximum.
- the Mn oxide precipitated on the surface of the coating layer is dissolved in the cathode electrolyte adhering to the coating layer by sufficiently washing and removing the low pH cathode electrolyte after the cathode electrolysis. It is presumed that it is suppressed.
- washing with water has the effect of removing the zirconium oxide adhering to the surface of the film layer. If the washing time with water is less than 2 seconds, it is insufficient to concentrate Mn on the surface of the film layer. On the other hand, if the washing time with water exceeds 10 seconds, the surface layer concentration of Mn is already sufficient, and only reduces the productivity in industrial production.
- the washing time with water is preferably 3 seconds or longer, and more preferably 4 seconds or longer.
- the depth position A where the element concentration of Mn existing as a manganese oxide is maximum and the depth position B where the element concentration of Zr existing as a zirconium oxide is maximum. Can be more reliably separated to 2 nm or more.
- the washing time with water is 4 seconds or more, the depth position A at which the element concentration of Mn existing as a manganese oxide is the maximum and the element concentration of Zr existing as a zirconium oxide are not lowered. It is possible to more reliably separate the depth position B from the maximum depth position B to 4 nm or more.
- the washing time with water is preferably 8 seconds or less, and particularly preferably 6 seconds or less.
- the depth position A where the element concentration of Mn existing as a manganese oxide is maximum and the depth position B where the element concentration of Zr existing as a zirconium oxide is maximum. Can be more reliably separated to 2 nm or more.
- the washing time with water is 6 seconds or less, the depth position A at which the element concentration of Mn existing as a manganese oxide is the maximum and the element concentration of Zr existing as a zirconium oxide are not lowered. It is possible to separate the depth position B, which has the maximum value, from the depth position B to 4 nm.
- the method of forming the film layer by the one-step cathode electrolysis treatment or the immersion treatment has been described above.
- the method for forming the film layer is not limited to the above method, and it is preferable to form the film layer by a plurality of stages of cathode electrolysis treatment.
- this step includes (a) a first treatment in which a Sn-based galvanized steel sheet is immersed in a first bath containing zirconium ions, or a Sn-based galvanized steel sheet is subjected to a cathode electrolysis treatment in a first bath. Then, (b) a second treatment of immersing the Sn-based galvanized steel sheet in a second bath containing manganese ions or performing a cathode electrolysis treatment on the Sn-based galvanized steel sheet in the second bath. Is preferable.
- the film layer is analyzed in the depth direction by X-ray photoelectron spectroscopy, it is possible to realize a film layer in which the abundance ratio of zirconium oxide to manganese oxide on the surface is 0 to 0.01 on a mass basis. .. That is, in the first treatment, a layer mainly composed of zirconium oxide is formed in the vicinity of the Sn-based plating layer, and further, in the second treatment, manganese oxide is mainly contained on the layer mainly composed of zirconium oxide. The layer can be formed.
- the film layer has a structure in which a film containing a zirconium oxide and a film containing a manganese oxide are laminated, the formation of zirconium oxide on the surface of the film layer is prevented, and the barrier property made of manganese oxide is high.
- the structure is covered with a film. That is, in the film layer, a concentration gradient of zirconium oxide and manganese oxide is generated in the thickness direction. Therefore, by combining the first treatment and the second treatment as described above, in the film layer containing the zirconium oxide and the manganese oxide, the manganese oxide and the zirconium oxide are ordered from the surface side of the film layer. It is also possible to form a large number of existing film layers.
- the film layer has a structure in which a film containing a zirconium oxide and a film containing a manganese oxide are laminated. Therefore, in the thickness direction of the film layer, the depth position A where the element concentration of Mn existing as a manganese oxide is the maximum and the depth position B where the element concentration of Zr existing as a zirconium oxide is the maximum are set. , It can be separated more reliably to 4 nm or more.
- the concentration of zirconium ions in the first bath (first cathode electrolyte) containing the zirconium ions to be used may be appropriately adjusted according to the production equipment, production speed (capacity), and the like.
- the zirconium ion concentration is preferably 100 ppm or more and 4000 ppm or less.
- the first bath preferably does not contain manganese ions or has a small content of manganese ions in order to increase the concentration of zirconium oxide in the formed film layer.
- the manganese ion concentration in the first bath is preferably 10 ppm or less.
- the other components of the first bath and various conditions of the first treatment can be the same as those of the cathode electrolysis treatment described above, and thus the description thereof will be omitted.
- the concentration of manganese ions in the second bath (second cathode electrolyte) containing manganese ions to be used may be appropriately adjusted according to the production equipment, production speed (capacity), and the like.
- the concentration of manganese ions is preferably 30 ppm or more and 10000 ppm or less.
- the second bath preferably does not contain manganese ions or has a small content of zirconium ions in order to increase the concentration of manganese oxide in the formed film layer.
- the zirconium ion concentration in the second bath is preferably 100 ppm or less.
- the other components of the second bath and various conditions of the second treatment can be the same as those of the cathode electrolysis treatment described above, and thus the description thereof will be omitted. Further, after the first treatment and the second treatment, water washing treatment may be performed respectively.
- the Sn-based plated steel sheet according to the present embodiment can be manufactured. After each of the above steps, a well-known treatment such as cleaning may be appropriately performed.
- the Sn-based plated steel sheet according to the present invention will be specifically described with reference to Examples.
- the examples shown below are merely examples of the Sn-based plated steel sheet according to the present invention, and the Sn-based plated steel sheet according to the present invention is not limited to the following examples.
- test material ⁇ 1. How to make test material> The standard manufacturing method of the test material will be described. The test materials of each example described later were produced according to the method for producing the test materials.
- a low-carbon cold-rolled steel sheet having a thickness of 0.2 mm is subjected to electrolytic alkali degreasing, water washing, dilute sulfuric acid immersion pickling, water washing, and then electro-Sn-based plating using a phenol sulfonic acid bath. After that, heat melting treatment was performed. Through these treatments, Sn-based plating layers were formed on both sides of the steel sheet.
- the standard adhesion amount of the Sn-based plating layer was about 2.8 g / m 2 per side. The amount of adhesion of the Sn-based plating layer was adjusted by changing the energization time.
- the steel sheet on which the Sn-based plating layer is formed is subjected to cathodic electrolysis treatment in an aqueous solution (cathode electrolytic solution) containing zirconium fluoride and manganese nitrate, and zirconium oxide and manganese oxide are applied to the surface of the Sn-based plating layer.
- a film layer containing the film was formed.
- the temperature of the cathode electrolytic solution is adjusted to 35 ° C.
- the pH of the cathode electrolytic solution is adjusted to 3.0 or more and 5.0 or less
- the current density of the cathode electrolytic treatment and the cathode electrolytic treatment time are aimed at. It was appropriately adjusted according to the content of zirconium oxide (amount of metal Zr) in the film layer.
- the amount of adhesion of the Sn-based plating layer per side was measured as follows. A plurality of test pieces of a steel sheet with a Sn-based plating layer having a known metal Sn content are prepared. Next, for each test piece, the intensity of fluorescent X-rays derived from metal Sn is measured in advance from the surface of the Sn-based plating layer of the test piece by a fluorescent X-ray analyzer (ZSX Primus manufactured by Rigaku Co., Ltd.).
- a calibration curve showing the relationship between the measured intensity of the fluorescent X-ray and the amount of metal Sn is prepared.
- the film layer is removed, and a test piece in which the film layer is not formed and the Sn-based plated layer is exposed is prepared.
- the intensity of fluorescent X-rays derived from metal Sn is measured on the exposed surface of the Sn-based plating layer by a fluorescent X-ray apparatus.
- the measurement conditions were X-ray source Rh, tube voltage 50 kV, tube current 60 mA, spectroscopic crystal LiF1, and measurement diameter 30 mm.
- manganese exists as an oxide. Defined to be.
- the content of the zirconium oxide (the amount of metal Zr) in the film layer was measured according to the method for measuring the amount of adhesion per side of the Sn-based plating layer (the amount of metal Sn in the Sn-based plating layer). That is, a test piece of a Sn-based plated steel sheet to be measured is prepared. The surface of the film layer of this test piece is measured for the intensity of fluorescent X-rays derived from metal Zr with a fluorescent X-ray analyzer (ZSX Primus manufactured by Rigaku Corporation). The content of zirconium oxide in the film layer (metal Zr amount) was calculated by using the obtained fluorescent X-ray intensity and the calibration curve for the metal Zr prepared in advance.
- the content of manganese oxide (metal Mn amount) in the film layer was measured according to the method for measuring the amount of adhesion per side of the Sn-based plating layer (metal Sn amount of the Sn-based plating layer). That is, a test piece of a Sn-based plated steel sheet to be measured is prepared. The surface of the film layer of this test piece is measured for the intensity of fluorescent X-rays derived from metal Mn by a fluorescent X-ray analyzer (ZSX Primus manufactured by Rigaku Co., Ltd.). The content of manganese oxide (metal Mn amount) in the film layer was calculated by using the obtained fluorescent X-ray intensity and the calibration curve for the metal Zr prepared in advance.
- the distribution of zirconium oxide and manganese oxide in the film layer was measured by XPS (PHI Quantera SXM manufactured by ULVAC-PHI). Specifically, a test piece of a Sn-based plated steel sheet to be measured is prepared. From the surface of the film layer of this test piece, analysis in the thickness direction (depth direction) by XPS (PHI Quantera SXM manufactured by ULVAC-PHI) was carried out, and Sn existing as a tin oxide, Sn existing as a metal Sn, and zirconium were analyzed.
- the gun was 1.0 V, 20 ⁇ A, the sputtering conditions were Ar +, the acceleration voltage was 1 kV, and the sputtering speed was 1.5 nm / min (SiO 2 conversion value).
- the case where the peak position where the detection intensity for manganese oxide is maximum exists on the surface side of the film layer by 4 nm or more from the peak position where the detection intensity for zirconium oxide is maximum is "A".
- the case where it exists on the surface side of the film layer of 2 nm or more and less than 4 nm is described as "B", and the case where it is not present is described as "C”.
- the coating film adhesion was evaluated as follows. After a wet test of a test material of a Sn-based galvanized steel sheet by the method described in [Yellow Degeneration], a commercially available epoxy resin paint for cans is applied to the surface at a dry mass of 7 g / m 2 for 10 minutes at 200 ° C. It was baked and left at room temperature for 24 hours. Then, the obtained Sn-based plated steel sheet was evaluated by making scratches reaching the surface of the steel sheet in a grid pattern (7 scratches in each of the vertical and horizontal directions at 3 mm intervals) and performing a tape peeling test at that portion.
- Sulfide-resistant black denaturation Sulfide blackening resistance was evaluated as follows. A commercially available epoxy resin paint for cans is applied to the surface of a test material of a Sn-based galvanized steel sheet prepared and wet-tested by the method described in the above [yellowing resistance] at a dry mass of 7 g / m 2 , and then 10 at 200 ° C. It was baked separately and left at room temperature for 24 hours. Then, the obtained Sn-based plated steel sheet is cut into a predetermined size, and the content is composed of 0.3% sodium dihydrogen phosphate, 0.7% sodium hydrogen phosphate, and 0.6% L-cysteine hydrochloride.
- Corrosion resistance after painting was evaluated as follows. A commercially available epoxy resin paint for cans is applied to the surface of a test material of a Sn-based galvanized steel sheet prepared and wet-tested by the method described in the above [yellowing resistance] at a dry mass of 7 g / m 2 , and then 10 at 200 ° C. It was baked separately and left at room temperature for 24 hours. Then, the obtained Sn-based plated steel sheet was cut into a predetermined size and immersed in commercially available tomato juice at 60 ° C. for 7 days, and then the presence or absence of rust was visually evaluated. If no rust is found, it is rated as "A”. If rust is found at an area ratio of 10% or less of the entire test surface, it is rated as "B”. NG ". Evaluations "A" and "B” were accepted.
- a Sn-based plated steel sheet was manufactured while changing the amount of adhesion between the zirconium oxide and the manganese oxide based on the method described in> Method for Producing Test Material>.
- Sn plating was prepared from a known ferrostan bath by an electrolytic method.
- the amount of energization during electrolysis was changed so that the amount of Sn adhered was in the range of 0.05 g / m 2 or more and 20 g / m 2.
- both a test piece subjected to the heat melting treatment after Sn plating and a test piece not subjected to the heat melting treatment were prepared.
- the Sn-based plated steel plate is used as a cathode in an aqueous solution having a zirconium ion concentration of 50 ppm or more and 5000 ppm or less and a manganese ion concentration of 3.5 ppm or more and 12500 ppm or less.
- a film layer containing various zirconium oxides and manganese oxides was formed on the Sn-based plated steel plate.
- the pH of the treatment liquid forming the film was 3.8, the liquid temperature was 35 ° C., and the amount of energization was appropriately changed.
- the immersion water washing time after the cathode electrolysis treatment was changed from 1 to 10 seconds.
- test pieces of Sn-based plated steel sheets according to A1 to A25 and a1 to a7 in which the adhesion amounts of zirconium oxide and manganese oxide were changed were obtained.
- XPS confirmed that the zirconium and manganese contained in the film were the zirconium oxide and the manganese oxide specified in the present invention, respectively.
- Table 1 shows the evaluation results of various performances performed on the above test pieces.
- the Sn-based plated steel sheets A1 to A25 according to the present invention have good performance.
- the performance is further excellent.
- a1 to a7, which are comparative examples, are inferior in any of yellowing resistance, coating film adhesion, sulfurization blackening resistance, and corrosion resistance after coating.
- Example 2> Next, the above ⁇ 1.
- a Sn-based plated steel sheet was produced while changing the distribution of zirconium oxide and manganese oxide in the film layer based on the method described in> Method for producing test material>.
- Sn plating was prepared from a known ferrostan bath by an electrolytic method so that the amount of Sn adhered was 2.8 g / m 2.
- the Sn-based plated steel sheet was cathodically electrolyzed (first treatment) in an aqueous solution containing zirconium ions without containing manganese ions, and then washed with water for the washing time shown in Table 2 below, and further, manganese containing no zirconium ions.
- Cathode electrolysis (second treatment) was performed in an aqueous solution containing ions to prepare test pieces B1 to B6.
- the test piece B7 was prepared by cathodic electrolysis in an aqueous solution containing zirconium ions and manganese ions and washing with water at the washing time shown in Table 2 below.
- test pieces of Sn-based plated steel sheets according to B1 to B7 in which the distributions of zirconium oxide and manganese oxide were changed in the film layer were obtained.
- the distribution of zirconium oxide and manganese oxide in the film layer of the prepared test piece was measured by XPS (PHI Quantera SXM manufactured by ULVAC-PHI). Specifically, a test piece of a Sn-based plated steel sheet to be measured is prepared. From the surface of the film layer of this test piece, analysis in the thickness direction (depth direction) by XPS (PHI Quantera SXM manufactured by ULVAC-PHI) was carried out, and Sn existing as a tin oxide, Sn existing as a metal Sn, and zirconium were analyzed.
- the case where the peak position where the detection intensity for manganese oxide is maximum exists on the surface side of the film layer by 4 nm or more from the peak position where the detection intensity for zirconium oxide is maximum is "A”.
- “B” was used when it was present on the surface side of the film layer of 2 nm or more and less than 4 nm, and "C” was used when it was not.
- the gun was 1.0 V, 20 ⁇ A, the sputtering conditions were Ar +, the acceleration voltage was 1 kV, and the sputtering speed was 1.5 nm / min (SiO 2 conversion value). Table 2 shows the evaluation results of various performances performed on the above test pieces.
- the Sn-based galvanized steel sheet according to the present invention is excellent in yellowing resistance, coating film adhesion, and sulfide blackening resistance without requiring conventional chromate treatment, and therefore, as an environment-friendly can material. It can be widely used for food cans, beverage cans, etc., and has extremely high industrial utility value.
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Abstract
Description
上記知見に基づき完成された本発明の要旨は、以下の通りである。
(2)前記皮膜層の表面において、前記X線光電子分光法による深さ方向元素分析における前記ジルコニウム酸化物の質量が、前記X線光電子分光法による深さ方向元素分析における前記マンガン酸化物の質量の0.01倍以下である、(1)に記載のSn系めっき鋼板。
(3)前記深さ位置Aと前記深さ位置Bとの間の深さ方向の距離が、4nm以上である、(1)又は(2)に記載のSn系めっき鋼板。
(4)前記皮膜層中における前記ジルコニウム酸化物の含有量は、金属Zr換算にて、片面当たり1.00mg/m2以上30.00mg/m2以下である、(1)~(3)の何れか1つに記載のSn系めっき鋼板。
(5)前記皮膜層中における前記ジルコニウム酸化物の含有量は、金属Zr換算にて、片面当たり2.00mg/m2以上10.00mg/m2以下である、(1)~(4)の何れか1つに記載のSn系めっき鋼板。
(6)前記皮膜層中における前記マンガン酸化物の金属Mn換算の含有量は、前記ジルコニウム酸化物の金属Zr換算の含有量に対し、質量基準で、0.05倍以上0.40倍以下である、(1)~(5)の何れか1つに記載のSn系めっき鋼板。
(7)前記皮膜層中における前記マンガン酸化物の金属Mn換算の含有量は、前記ジルコニウム酸化物の金属Zr換算の含有量に対し、質量基準で、0.10倍以上0.20倍以下である、(1)~(6)の何れか1つに記載のSn系めっき鋼板。
なお、本明細書において、「工程」という用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されるのであれば、本用語に含まれる。本明細書において、「鋼板」という用語は、Sn系めっき層及び皮膜層を形成する対象の母材鋼板(いわゆるめっき原板)を意味する。
まず、本実施形態に係るSn系めっき鋼板について、図1を参照しながら説明する。図1は、本実施形態に係るSn系めっき鋼板の構造の一例を模式的に示した説明図である。
本実施形態に係るSn系めっき鋼板1の母材として用いられる鋼板10は、特に規定されるものではなく、一般的な容器用のSn系めっき鋼板に用いられている鋼板であれば、任意のものを使用可能である。このような鋼板10として、例えば、低炭素鋼や極低炭素鋼などが挙げられる。
上記のような鋼板10の少なくとも片面には、Sn系めっきが施されて、Sn系めっき層20が生成される。かかるSn系めっき層20によって、鋼板10の耐食性は向上する。なお、本明細書における「Sn系めっき層」とは、金属Snによるめっきだけでなく、金属Snと金属Feの合金や、金属Ni、また、金属Sn以外の微量元素及び不純物の少なくとも一方とを含有したSn系めっき層も含む。
上述したようにSn系めっき層20上には、ジルコニウム酸化物とマンガン酸化物とを含有する皮膜層30が形成されている。本実施形態に係るSn系めっき鋼板1は、Sn系めっき層20の表面に、上記のようなジルコニウム酸化物とマンガン酸化物とが後述する量的関係で共存する皮膜層30を有することで、耐黄変性、塗膜密着性及び耐硫化黒変性をより一層向上させることができる。なお、ジルコニウム酸化物又はマンガン酸化物のみの皮膜層では、耐黄変性、塗膜密着性及び耐硫化黒変性を十分に改善出来ない。この理由は定かではないが、本発明者らの詳細な調査により以下のように考えている。
本実施形態に係るSn系めっき鋼板は、いかなる方法により製造されてもよいが、例えば、以下に説明するSn系めっき鋼板の製造方法により、製造することができる。
まず、Sn系めっき鋼板1の母材となる鋼板10を準備する。用いる鋼板の製造方法や材質は、特に規定されるものではなく、例えば、鋳造から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造されたものを用いることができる。
次いで、鋼板の少なくとも一方の表面上に、Sn系めっき層(Snめっき)を形成する。Sn系めっきを鋼板表面に施す方法は、特に規定するものではないが、公知の電気めっき法が好ましく、電気めっき法としては、例えば、周知のフェロスタン浴、ハロゲン浴、アルカリ浴などを用いた電解法を利用することができる。なお、溶融したSnに鋼板を浸漬することでSn系めっきする、溶融法を用いてもよい。
次に、Sn系めっき層の表面の少なくとも一部に、ジルコニウム酸化物とマンガン酸化物とを含有する皮膜層を形成する。これにより、本実施形態に係るSn系めっき鋼板が得られる。
試験材の標準的な作製方法について説明する。なお、後述する各例の試験材は、この試験材の作製方法に準じて作製した。
このように作製したSn系めっき鋼板について、以下に示す種々の評価をした。
Sn系めっき層の片面当たりの付着量(Sn系めっき層の金属Sn量)を、次の通り測定した。金属Snの含有量が既知である複数のSn系めっき層付き鋼板の試験片を準備する。次に、各試験片について、蛍光X線分析装置(リガク社製ZSX Primus)により、試験片のSn系めっき層の表面から、金属Snに由来する蛍光X線の強度を事前に測定する。そして、測定した蛍光X線の強度と金属Sn量との関係を示した検量線を準備しておく。その上で、測定対象となるSn系めっき鋼板について、皮膜層を除去し、皮膜層が形成されておらず、Sn系めっき層を露出させた試験片を準備する。このSn系めっき層を露出させた表面を蛍光X線装置により、金属Snに由来する蛍光X線の強度を測定する。得られた蛍光X線強度と予め準備した検量線とを利用することで、Sn系めっき層の片面当たりの付着量(つまり、金属Snの含有量)を算出した。
皮膜層中のZr及びMnがそれぞれ、ジルコニウム酸化物、マンガン酸化物として存在していることを確認するために、皮膜層の表面に対して、XPS(ULVAC-PHI製PHI Quantera SXM)による測定を実施し、皮膜層中におけるジルコニウム酸化物のZr 3d5/2、及び、Mn 2p3/2の結合エネルギーのピーク位置を調べた。測定条件は、X線源mono-AlKα線(hν=1466.6eV、100.8W)、X線径100μmφ、検出深さ数nm(取出し角45°)、分析範囲1400×100μmとした。そして、Zr 3d5/2の結合エネルギーのピーク位置が金属Zrの結合エネルギーのピーク位置(=484.9eV)よりも高エネルギー側に3.0eV以上4.0eV以下離れた位置であれば、ジルコニウムは酸化物として存在していると定義した。また、Mn 2p3/2の結合エネルギーのピーク位置が金属Mnの結合エネルギーのピーク位置よりも高エネルギー側に1.5eV以上3.5eV以下離れた位置であれば、マンガンは酸化物として存在していると定義した。
皮膜層中のジルコニウム酸化物の含有量(金属Zr量)は、Sn系めっき層の片面当たりの付着量(Sn系めっき層の金属Sn量)の測定方法に準じて測定した。つまり、測定対象となるSn系めっき鋼板の試験片を準備する。この試験片の皮膜層の表面を蛍光X線分析装置(リガク社製ZSX Primus)により、金属Zrに由来する蛍光X線の強度を測定する。得られた蛍光X線強度と予め準備した金属Zrに関する検量線とを利用することで、皮膜層中のジルコニウム酸化物の含有量(金属Zr量)を算出した。
皮膜層中のマンガン酸化物の含有量(金属Mn量)は、Sn系めっき層の片面当たりの付着量(Sn系めっき層の金属Sn量)の測定方法に準じて測定した。つまり、測定対象となるSn系めっき鋼板の試験片を準備する。この試験片の皮膜層の表面を蛍光X線分析装置(リガク社製ZSX Primus)により、金属Mnに由来する蛍光X線の強度を測定する。得られた蛍光X線強度と予め準備した金属Zrに関する検量線とを利用することで、皮膜層中のマンガン酸化物の含有量(金属Mn量)を算出した。
ジルコニウム酸化物とマンガン酸化物の皮膜層中での分布は、XPS(ULVAC-PHI製PHI Quantera SXM)により測定した。具体的には、測定対象となるSn系めっき鋼板の試験片を準備する。この試験片の皮膜層の表面から、XPS(ULVAC-PHI製PHI Quantera SXM)による厚み方向(深さ方向)の分析を実施し、錫酸化物として存在するSn、金属Snとして存在するSn、ジルコニウム酸化物として存在するZr、金属Zrとして存在するZr、マンガン酸化物として存在するMn、金属Mnとして存在するMn、の各元素濃度の合計が100%となるように、各酸化物及び金属の元素マンガン酸化物の元素濃度を求めた。
Sn系めっき鋼板の試験材を、40℃、相対湿度80%に保持した恒温恒湿槽中に4週間載置する湿潤試験を行い、湿潤試験前後における色差b*値の変化量△b*を求めて、評価した。△b*が1以下であれば「A」とし、1超過2以下であれば「B」とし、2超過3以下であれば「C」とし、3を超過していれば「NG」とした。評価「A」、「B」及び「C」を合格とした。b*は、市販の色差計であるスガ試験機製SC-GV5を用いて測定した。b*の測定条件は、光源C、全反射、測定径30mmである。
塗膜密着性は、以下のようにして評価した。
Sn系めっき鋼板の試験材を、[耐黄変性]に記載の方法で湿潤試験した後、表面に、市販の缶用エポキシ樹脂塗料を乾燥質量で7g/m2塗布し、200℃で10分焼き付け、24時間室温に置いた。その後、得られたSn系めっき鋼板に対し、鋼板表面に達する傷を碁盤目状に入れ(3mm間隔で縦横7本ずつの傷)、その部位のテープ剥離試験をすることで評価した。テープ貼り付け部位の塗膜が全て剥離していなければ「A」とし、碁盤目の傷部周囲で塗膜剥離が認められれば「B」とし、碁盤目の枡内に塗膜剥離が認められれば「NG」とした。評価「A」及び「B」を合格とした。
耐硫化黒変性は、以下のようにして評価した。
上記[耐黄変性]に記載の方法で作製及び湿潤試験したSn系めっき鋼板の試験材の表面に、市販の缶用エポキシ樹脂塗料を乾燥質量で7g/m2塗布した後、200℃で10分焼き付け、24時間室温に置いた。その後、得られたSn系めっき鋼板を所定のサイズに切断し、リン酸二水素ナトリウムを0.3%、リン酸水素ナトリウムを0.7%、L-システイン塩酸塩を0.6%からなる水溶液中に浸漬し、密封容器中で121℃・60分のレトルト処理を行い、試験後の外観から評価した。試験前後で外観の変化が全く認められなければ「A」とし、僅かに(10%以下)黒変が認められれば「B」とし、試験面の10%超過の領域に黒変が認められれば「NG」とした。評価「A」、「B」を合格とした。
塗装後耐食性は、以下のようにして評価した。
上記[耐黄変性]に記載の方法で作製及び湿潤試験したSn系めっき鋼板の試験材の表面に、市販の缶用エポキシ樹脂塗料を乾燥質量で7g/m2塗布した後、200℃で10分焼き付け、24時間室温に置いた。その後、得られたSn系めっき鋼板を所定のサイズに切断し、市販のトマトジュースに60℃で7日間浸漬した後の錆の発生有無を、目視にて評価した。錆が全く認められなければ「A」とし、試験面全体の10%以下の面積率で錆が認められれば「B」とし、試験面全体の10%超えの面積率で錆が認められれば「NG」とした。評価「A」及び「B」を合格とした。
上記<1.試験材の作製方法>に記載の方法に基づき、ジルコニウム酸化物とマンガン酸化物の付着量を変化させつつ、Sn系めっき鋼板を製造した。
表1に、上記試験片について行った各種性能の評価結果を示す。
次に、上記<1.試験材の作製方法>に記載の方法に基づき、ジルコニウム酸化物とマンガン酸化物の皮膜層中での分布を変化させつつ、Sn系めっき鋼板を製造した。
表2に、上記試験片について行った各種性能の評価結果を示す。
10 鋼板
20 Sn系めっき層
30 皮膜層
Claims (7)
- 鋼板と、
前記鋼板の少なくとも一方の面上に位置するSn系めっき層と、
前記Sn系めっき層の上に位置する皮膜層と、
を有し、
前記Sn系めっき層は、Snを、金属Sn換算にて、片面当たり0.10g/m2以上15.00g/m2以下含有し、
前記皮膜層は、ジルコニウム酸化物及びマンガン酸化物を含有し、
前記皮膜層中における前記ジルコニウム酸化物の含有量は、金属Zr換算にて、片面当たり0.20mg/m2以上50.00mg/m2以下であり、
前記皮膜層中における前記マンガン酸化物の金属Mn換算の含有量は、前記ジルコニウム酸化物の金属Zr換算の含有量に対し、質量基準で、0.01倍以上0.50倍以下であり、
X線光電子分光法による深さ方向元素分析において、前記マンガン酸化物として存在するMnの元素濃度が最大である深さ位置Aが、前記ジルコニウム酸化物として存在するZrの元素濃度が最大である深さ位置Bよりも、前記皮膜層の表面側に位置し、かつ、前記深さ位置Aと前記深さ位置Bとの間の深さ方向の距離が、2nm以上である、Sn系めっき鋼板。 - 前記皮膜層の表面において、前記X線光電子分光法による深さ方向元素分析における前記ジルコニウム酸化物の質量が、前記X線光電子分光法による深さ方向元素分析における前記マンガン酸化物の質量の0.01倍以下である、請求項1に記載のSn系めっき鋼板。
- 前記深さ位置Aと前記深さ位置Bとの間の深さ方向の距離が、4nm以上である、請求項1又は2に記載のSn系めっき鋼板。
- 前記皮膜層中における前記ジルコニウム酸化物の含有量は、金属Zr換算にて、片面当たり1.00mg/m2以上30.00mg/m2以下である、請求項1~3の何れか1項に記載のSn系めっき鋼板。
- 前記皮膜層中における前記ジルコニウム酸化物の含有量は、金属Zr換算にて、片面当たり2.00mg/m2以上10.00mg/m2以下である、請求項1~4の何れか1項に記載のSn系めっき鋼板。
- 前記皮膜層中における前記マンガン酸化物の金属Mn換算の含有量は、前記ジルコニウム酸化物の金属Zr換算の含有量に対し、質量基準で、0.05倍以上0.40倍以下である、請求項1~5の何れか1項に記載のSn系めっき鋼板。
- 前記皮膜層中における前記マンガン酸化物の金属Mn換算の含有量は、前記ジルコニウム酸化物の金属Zr換算の含有量に対し、質量基準で、0.10倍以上0.20倍以下である、請求項1~6の何れか1項に記載のSn系めっき鋼板。
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JPWO2021124510A1 (ja) | 2021-06-24 |
CN114829675B (zh) | 2024-03-08 |
KR20220103149A (ko) | 2022-07-21 |
US20220389590A1 (en) | 2022-12-08 |
EP4023789A4 (en) | 2022-10-05 |
EP4023789A1 (en) | 2022-07-06 |
JP7239020B2 (ja) | 2023-03-14 |
KR102599384B1 (ko) | 2023-11-08 |
US11859289B2 (en) | 2024-01-02 |
CN114829675A (zh) | 2022-07-29 |
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