WO2007046549A1 - 錫めっき鋼板およびその製造方法 - Google Patents
錫めっき鋼板およびその製造方法 Download PDFInfo
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- WO2007046549A1 WO2007046549A1 PCT/JP2006/321444 JP2006321444W WO2007046549A1 WO 2007046549 A1 WO2007046549 A1 WO 2007046549A1 JP 2006321444 W JP2006321444 W JP 2006321444W WO 2007046549 A1 WO2007046549 A1 WO 2007046549A1
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
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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
- 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
- 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
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
- Y10T428/12618—Plural oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12708—Sn-base component
- Y10T428/12722—Next to Group VIII metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
- Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
Definitions
- the present invention relates to a tin-plated steel sheet for cans used in DI cans, food cans, beverage cans, etc. It relates to the manufacturing method. Background art
- tin-plated steel plates called tinplate have been widely used as surface-treated steel plates for cans.
- a tinned steel sheet is usually plated by immersing the steel sheet in an aqueous solution containing a hexavalent chromium compound such as dichromic acid, or by electrolytic treatment or application to the steel sheet in this solution.
- a chromium film is formed on the surface.
- the formation of a matt metal film on the surface of the steel sheet prevents oxidation of the tinned surface during long-term storage and suppresses deterioration of the appearance (yellowing).
- the growth of tin oxide film is suppressed to prevent cohesion and destruction of tin oxide film and to ensure adhesion of paint.
- an aqueous solution containing hexavalent chromium oxide is used to form a chromate film on the tinned steel plate surface, ensuring safety in the working environment and wastewater treatment. It costs a lot of money.
- the chromate treatment liquid leaks due to an accident, there is a high risk of serious damage to the environment.
- Japanese Patent Publication No. 58-41352 discloses a chemical conversion treatment solution for a metal surface of pH 3-6 containing one or more of phosphate ion, chlorate and bromate, and tin ion. Is disclosed.
- tin-plated steel sheets with the current chromate treatment are usually manufactured at a high speed of 300 m / min or more, and are extremely productive. Therefore, in order to replace the new chemical conversion treatment with a tinned steel plate that is subjected to the chromium treatment, it is necessary to be able to process at least as fast as the current process.
- As a guideline for chemical conversion at a high speed of 300m / min or higher it is desirable to complete the chemical conversion in about 1 second. If the chemical conversion process is completed in less than 1 second, for example, if there is one relatively small vertical tank with an effective depth of about 2.5 m, it can be processed at 300 m / min.
- the processing time becomes longer, it is necessary to secure the passage time of the tank by increasing the size of the processing tank or increasing the number of processing tanks. As a result, both equipment costs and equipment maintenance costs are high, which is undesirable.
- the present invention has been made in view of such circumstances, and instead of a conventional chromate film, a tin-plated steel sheet having a phosphoric acid-based chemical conversion film that can suppress performance deterioration due to the growth of a tin oxide film on the surface layer. And its manufacturing method The Furthermore, the present invention provides a method for producing the steel sheet while maintaining high speed and high stability comparable to the conventional chromate treatment process. 1 Disclosure disclosure
- the present invention has a plating layer containing tin on at least one side of a steel plate, and on the plating layer?
- chemical conversion coating containing tin the adhesion amount of the chemical conversion coating is 1.0 to 50 ⁇ ⁇ / ⁇ ! 2 in terms of P per side, measured from the surface by X-ray photoelectron spectroscopy 0 Sn and P in the atomic ratios Sn / P obtained from the intensity of the [rho] 2 [rho peak and Sn3d peak of the chemical conversion coating is 1. a 0 to 1.5, and was determined from the intensity of the P2p peak and 01 s peak This is a tinned steel sheet characterized by an atomic ratio of 0 to P of 4.0 to 9.0. ⁇
- the tinned steel sheet has a ratio between the P0 bond reflection absorption intensity (I P ) in the infrared absorption spectrum of the chemical conversion coating film and the 0H bond reflection absorption intensity (I 0H ), 1 0 Ip. Is preferably from 0.18 to 0.30. '
- the present invention disclosed that after forming a plating layer containing tin on at least one surface of a steel sheet, the steel sheet was immersed in a chemical conversion treatment solution containing tin ions and phosphate ions, or cathodic electrolytic treatment. Then, it is also a method for producing a tinned steel sheet characterized by heating to 60 to 200 ° C.
- the tin ion is preferably a tetravalent tin ion.
- Fig. 1 shows the relationship between wave number and reflection absorptance in an infrared absorption spectrum.
- Figure 2 shows I in the heating temperature and infrared absorption spectrum. H / I P.
- FIG. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. '-The present inventors conducted extensive research in order to obtain a tin-plated steel sheet having a phosphoric acid-based chemical conversion film that can suppress the growth of the tin oxide film on the surface layer instead of the chromate film.
- the amount of chemical conversion coating is regulated, and the growth of the tin oxide film on the surface layer is suppressed, and elements that are considered to be greatly involved in performance improvement are: Sn, P It defines the 'atomic ratio, further, the ratio of the reflection absorption intensity P0 bond in the infrared absorption scan Bae-vector (I P.), the reflection absorption intensity 0H bond (I 0H), I. It was found that by adjusting the H I Ipo to 0.18 or more and 0.30 or less, growth of the tin oxide film on the surface layer was suppressed, and excellent appearance, paint adhesion and corrosion resistance were obtained.
- the tin-plated steel sheet of the present invention is a steel sheet having a plated layer containing tin on at least one side of the steel sheet, and having a chemical conversion treatment film containing P and tin on the plated layer.
- tin-plated steel plate refers to all steel plates that have been plated with tin.
- particularly preferred “tin-plated steel sheet” is an Fe—Sn—Ni alloy layer or an intermediate layer composed of a single layer of an Fe—Sn alloy layer, or an Fe—Ni alloy layer on the lowermost layer, and an Fe—Sn—
- This steel sheet has an intermediate layer composed of a composite layer of Ni alloy layers, and further has a plating layer containing tin, which is a metal Sn layer formed on the upper surface thereof.
- the adhesion amount of the plating layer is preferably 0.05 to 20 g / m 2 per side.
- the adhesion amount is 0.05 g / m 2 or more, sufficient corrosion resistance can be obtained. On the other hand, if it exceeds 20 g / ra 2 , the intimate layer becomes too thick, and the cost-effective merits may be lost.
- the amount of Sn deposited can be measured by coulometric method or surface analysis by fluorescent X-ray.
- the amount of the chemical conversion coating is required to be 1.0 to 50 mg / m 2 in terms of P. This is an important requirement in the present invention. If the adhesion amount is less than 1.0 mg / m 2 , the coating property of the chemical conversion film becomes insufficient, and the oxidation of tin cannot be suppressed, and the paint adhesion cannot be sufficiently obtained. On the other hand, if it exceeds 50 mg / m 2 , defects such as cracks are likely to occur in the film, and paint adhesion and corrosion resistance will deteriorate. 50 mg / ni 2 or less. The amount of adhesion is based on surface analysis using fluorescent X-rays. Can be measured. 1
- the atomic ratio Sn / P of Sn and P determined from the intensity of the P2p peak and Sn3d peak of the chemical conversion coating measured from the surface by X-ray photoelectron spectroscopy is 1.0 or more and 1.5 or less.
- the atomic ratio 0 / P of 0 and P obtained from the intensity of the P2p peak and the Oi s peak must be 4.0 or more and 9.0 or less. This is also an important requirement in the present invention, as is the amount of adhesion.
- Phosphoric acid and tin compounds include stannous phosphate (Sn (Pl 2 P0 4 ) 2 ), stannous phosphate (SnHP0 4 ), and stannous phosphate (Sn 3 (P0 4 ) 2 ). It exists and is in equilibrium in the aqueous solution shown in equations (1) and (2).
- the chemical conversion treatment film since the chemical conversion treatment film is also applied to the side of the can, the chemical conversion treatment film needs to exist stably against the contents containing moisture.
- Stannous oxalate is soluble in water and easily elutes in the contents, which may cause loss of film stability. Therefore, the chemical conversion coating must be stannic phosphate, stannic phosphate, or a mixture thereof.
- the atomic ratio Sn / P of Sn and P is 1.0 in the case of 100% stannic phosphate and 1.5 in the case of 100% stannic phosphate. Therefore, in the present invention, the atomic ratio of Sn and P, Sn / P, is 1.0 or more and 1.5 or less.
- 0 / P is stoichiometrically 4.0.
- the orthophosphate structure undergoes a dehydration polymerization reaction when heated at a high temperature, and 0 / P becomes less than 4.0.
- it takes the metaphosphate structure (P0 3 —), and 0 / P Becomes 3.0.
- P0 3 — metaphosphate structure
- 0 / P Becomes 3.0.
- 0 / P is often larger than 4.0. This indicates that water is incorporated into the film as an adsorbate or hydrate in addition to phosphoric acid and tin.
- the tin phosphate skin acts as a barrier that suppresses the permeation of water and oxygen from the surrounding environment to the tin plating layer.
- the chemical conversion coating itself becomes a source of oxygen and promotes oxidation of the tin plating layer.
- the film does not contain a lot of water that is a corrosion accelerating factor.
- it reaches 9.0 the growth of the tin oxide film cannot be sufficiently suppressed even if the chemical conversion film is present, and the surface is covered with the tin oxide film, and the color changes to yellow and the appearance is deteriorated. Practical adverse effects such as causing reduced adhesion due to cohesive failure.
- 0 / P is 4.0 or more and 9.0 or less.
- atomic ratios are based on the atomic concentration obtained by measuring the 01 s, P2p, and Sn3 d peaks from X-ray photoelectron spectroscopy from the surface, and using the X-ray photoelectron spectroscopy quantitative software. Can be obtained from the calculation.
- quantitative software is KRATOS VISI0N2. Since 01s is greatly affected by the adsorbed components and contamination on the outermost surface, it is preferable to analyze by reducing the influence of contamination by light sputtering etc. in order to correlate with the characteristics of the film.
- the relative sensitivity coefficient method is widely used for quantification, and the peak intensity or peak area intensity of the target element is used, and calculation is performed using a coefficient that is pre-installed in the apparatus or a coefficient that is obtained by measuring a standard substance. be able to.
- the ratio of the reflection absorption intensity (I P ) of P0 bond to the reflection absorption intensity (I H ) of 0H bond in the infrared absorption spectrum of the chemical conversion coating I. H / IP .
- Water in the chemical conversion coating film is absorbed by the infrared absorption spectrum of the chemical conversion coating film. It can also be quantified by the absorption intensity of P0 bond at 1444 (the ratio between i and 0H bond intensity (I 0H ), 1 01) / Ipo.
- FT-IR Fastier transform infrared spectrophotometer
- JIR- 100 the parallel polarization, incident angle incident light in the high-sensitivity reflection measurement was set to 70 °, resolution !!! - 1, integrated
- the number of measurements was 200, and the detector was measured with a broadband MCT detector.
- a reference sample a steel plate that was subjected only to tinning without a chemical conversion coating was used, and a difference spectrum from the reference sample was obtained. I. H and Ip. As shown in Fig.
- I 0H / Ipo force exceeds 0.30, too much water is present in the chemical conversion coating, so that it is not possible to sufficiently suppress the growth of tin oxide, and the surface is covered with oxide and turns yellow. In some cases, the appearance may be damaged, and the adhesion may be reduced due to cohesive failure of tin oxide. Therefore I 0H / I P. Is preferably 0.30 or less. Further, in order to maintain the performance stably, it is preferable to set it to 0.28 or less. Meanwhile, I. H / Ip. Is less than 0 ⁇ 18, the amount of water in the chemical conversion coating is small, but this is a result of excessive heating, and a large amount of tin oxide is formed on the surface. Adhesion may be impaired. Therefore I. H II P. Is preferably 0.18 or more. Next, the manufacturing method of the tinned steel plate of this invention is demonstrated.
- a chemical conversion treatment film containing P and tin is formed on a steel sheet having a plating layer containing tin on at least one side of the steel sheet.
- a forming method for example, 1) A steel plate is immersed in an aqueous solution containing a metal salt such as phosphoric acid, sodium phosphate or potassium phosphate. And 2) a method of dipping or cathodic electrolytic treatment of a steel sheet in a chemical conversion treatment solution containing tin ions, preferably tetravalent tin ions and phosphate ions.
- the method 1) above is general.
- the surface of the tin plating reacts with the phosphate source of metal salts such as phosphoric acid, sodium phosphate, potassium phosphate, etc.
- the phosphate source of metal salts such as phosphoric acid, sodium phosphate, potassium phosphate, etc.
- Stannous phosphate is formed.
- stannous phosphate is in equilibrium with stannous phosphate and stannous phosphate.
- Formula (3) when stannous phosphate is formed, hydrogen gas is generated at the same time.
- protons are consumed and pH increases, and stannic phosphate and stannic phosphate precipitate and a film is formed on the steel plate.
- the reaction time is as long as about 5 to 10 seconds. Therefore, it is disadvantageous for forming a film at high speed.
- the method of 2) above that is, the steel sheet is immersed in a chemical conversion treatment solution in which tin ions, preferably tetravalent tin ions are added in an aqueous solution containing phosphate ions, or cathodic electrolytic treatment.
- This method makes it possible to significantly increase the film deposition rate.
- the method 2) is preferable because the speed can be increased. The reason is considered as follows.
- Tetravalent tin ions dissolved in the bath Is reduced to divalent tin ions in the vicinity of the steel plate interface by the emitted electrons accompanying dissolution of the tin plating surface.
- the same effect as that obtained by adding a high concentration of valent tin ions in the vicinity of the interface is obtained, and the reaction rate is dramatically improved.
- electrolysis is performed using a steel sheet as a cathode, the reduction of tetravalent tin to divalent is promoted, and the reduction reaction of proton is promoted. Since the precipitation of acid 3 'tin is promoted, an even greater reaction promoting effect can be obtained.
- the coating film was formed in a short time of less than 1 second by dipping or cathodic electrolytically treating the steel sheet in a chemical conversion solution containing tetravalent tin ion in an aqueous solution containing phosphate ions. It is possible to form a film stably in the same processing time as the current chromate treatment.
- tin ions preferably tetravalent tin ions are used.
- a method of dipping or cathodic electrolysis of steel sheets in a chemical conversion solution containing phosphate ions is preferred, which enables stable treatment at a speed (high speed) comparable to the romate treatment process. It becomes.
- divalent tin ions stannous chloride and tin sulfate are used.
- tetravalent tin ions such as stannic chloride and stannic iodide are used.
- the addition method is not particularly limited, such as adding or dissolving stannic oxide in an acid. Further, in order to add phosphate ions, it is preferable to add orthophosphate, sodium phosphate, or the like, so that orthophosphate ions are contained in the chemical conversion solution. Furthermore, the treatment time may be appropriately determined according to the necessary amount of P deposition.
- the steel sheet on which the chemical conversion film has been formed as described above is heated to a temperature of 60 to 200 ° C.
- the chemical conversion coating obtained by the above-described electrolysis or immersion treatment contains a large amount of adsorbed water or hydration water in the chemical conversion coating as it is, and the atomic ratio 0 / P of the chemical conversion coating is 9.0 or less. Can not do it.
- the temperature needs to be 200 ° C or less.
- the heating temperature of the steel sheet needs to be 60-200 ° C in order to set the value to 0.18-30.30.
- the heating method is not particularly limited, and an industrial heating method of blowing hot air, infrared heating, induction heating, radiant heating, or the like is preferable.
- the chemical conversion solution, F e a metal salt of N i, for example, F e CI 2, N i C 1 2, F e S_ ⁇ 4, N i S_ ⁇ suitably added that a metal salt such as 4 Can do.
- an oxidizing agent such as sodium chlorate or nitrite, or an etching agent such as fluorine ion may be added as an accelerator.
- a surfactant such as sodium lauryl sulfate or acetylene glycol may be added as appropriate for the purpose of improving the uniform processability of the chemical conversion solution.
- an oxidizing agent may be appropriately added in order to increase the content of tin ions in the chemical conversion treatment liquid and form the chemical conversion treatment film in a short time.
- hydrogen peroxide, permanganic acid power sodium, sodium oxalate, nitric acid, peracetic acid, chlorate, perchlorate and the like are preferable.
- the tinned steel sheet of the present invention is obtained. Based on the above, an example of the manufacturing method will be described below as an embodiment of the present invention.
- a tin-based plating layer consisting of an alloy layer (intermediate layer) and a metal Sn layer (upper layer) is formed. Then, to remove the tin oxide film formed on the surface after the reflow process, 10 to 15 g Z and (hereinafter, L is short for litter) in carbonate aqueous sodium in l ⁇ 3 C // dm 2 Cathode treatment is performed. Subsequently, chemical conversion treatment is performed by dipping treatment or cathodic electrolysis treatment.
- a tin plating layer was formed with an adhesion amount of 10 g / m 2 per side, Heat melting (reflow) treatment was performed at a melting point (231 .. 9 ° C) or higher.
- a cathode treatment of 1 C / dm 2 was performed in a 10 g / L sodium carbonate aqueous solution at a bath temperature of 50 ° C.
- the bath temperature is 60 ° C and the current density is 10
- Cathodic electrolysis treatment was performed for 2 seconds. After that, it is squeezed with a ringer roll, and heated and dried under the condition that the steel plate temperature becomes 70 ° C with an infrared heating device, washed with water, and dried with cold air, so that the adhesion amount in terms of P is 8.3 mg / m 2 , A chemical conversion film containing P and tin was formed on the adhesion layer.
- the measurement of the P adhesion amount was performed by fluorescent X-ray analysis by comparison with a calibration plate obtained by wet analysis of the adhesion amount in advance.
- the atomic ratios Sn / P and ⁇ / P of the chemical conversion film were determined by X-ray photoelectron spectroscopy measurement from the surface, and Sn / P was 1.3 and O / P was 6.0. there were.
- a plating treatment was performed on both surfaces of a cold-rolled steel plate made of low carbon steel having a thickness of 0.2 mm by the same method as in Example 1 to form a plating layer.
- the conditions of current density and time shown in Table 1 in an aqueous solution containing the concentrations of phosphoric acid or sodium phosphate and stannic chloride pentahydrate or stannic iodide shown in Table 1 Then, negative electrode electrolysis was performed.
- the immersion treatment was performed for the time shown in Table 1.
- a chemical conversion treatment film containing P and tin is formed by squeezing with a ringer roll, heat drying with an infrared heating device under the conditions shown in Table 1, washing with water, and drying with cold air. did.
- Example 16 After forming a 0.2 mm thick low-carbon steel cold-rolled steel sheet on both sides with a commercially available plating bath and a tinned layer with a coating weight of 10 g / m 2 per side Then, heat melting (reflow) treatment was performed at a melting point of tin (2 3 1.9 ° C) or higher. Next, in order to remove the tin oxide formed on the surface after the reflow treatment, a cathode treatment of 1 C / dm 2 was performed in an aqueous sodium carbonate solution at a bath temperature of 50 ° C and lOgZL.
- a plating process was performed on both surfaces of a cold-rolled steel plate made of low-carbon steel having a thickness of 0.2 mm by the same method as in Example 1 to form a plating layer.
- cathodic electrolysis was performed in an aqueous solution to which the concentrations of phosphoric acid and stannous chloride or tin sulfate shown in Table 1 were added under the conditions of current density and time shown in Table 1.
- the immersion treatment was performed for the time shown in Table 1. After that, it is squeezed with a ring mouth and heated and dried under the conditions shown in Table 1 using an infrared heating device, washed with water, and then dried with cold air to convert P and tin. A film was formed. '
- a tinned steel sheet having a chemical conversion film forming method and a P deposition amount or composition outside the range of the present invention was manufactured.
- a plating process was performed on both surfaces of a cold-rolled steel plate made of low-carbon steel having a thickness of 0.2 mm by the same method as in Example 1 to form a plating layer.
- orthophosphoric acid at the concentrations shown in Table 1 and stannic chloride Cathodic electrolysis was performed in an aqueous solution containing pentahydrate or stannous chloride dihydrate in the conditions of current density and time shown in Table 1.
- the immersion treatment was performed for the time shown in Table 1.
- baking was performed at 210 ° C. for 10 minutes. Next, it was immersed in commercially available tomato juice at 60 ° C for 10 days, and the presence or absence of peeling of the coating film and generation of wrinkles was visually evaluated.
- the present invention it is possible to obtain a tin-plated steel sheet that suppresses the growth of a tin oxide film and has an excellent appearance, paint adhesion, and corrosion resistance.
- the tinned steel sheet of the present invention does not form a chromate film on the upper layer of the tinned layer, which has the effect of improving the film properties but is undesirable due to environmental problems.
- the tinned steel sheet of the present invention has a conventional High-speed processing that is comparable to that of Rome-treated tin-plated steel sheets is possible, and it has excellent productivity in industrial production.
- Example 1 ⁇ ⁇ Example 2 ⁇ ⁇ Example 3 ⁇ ⁇ ⁇ Example 4, ⁇ ⁇ ⁇ Example 5 ⁇ ⁇ Example 6 ⁇ ⁇ ⁇ Example 7 ⁇ ⁇ ⁇ Example 8 ⁇ ⁇ ⁇ Example 9 ⁇ ⁇ ⁇ Example 10 ⁇ ⁇ ⁇ Example 11 ⁇ ⁇ , ⁇ Example 12 ⁇ ⁇ ⁇ Example 13 ⁇ ⁇ ' ⁇ Example 14 ⁇ ⁇ ⁇ Example 15 ⁇ ⁇ ⁇ Example 16 ⁇ ⁇ ⁇ ⁇ Example 18 ⁇ ⁇ Example 19 ⁇ ⁇ ⁇ Comparative Example 1 ⁇ ⁇ ⁇ Comparative Example 2 XX ⁇ Comparative Example 3 ⁇ ⁇ ⁇ Comparative Example 4 ⁇ ⁇ ⁇ Comparative Example 5 XXX Comparative Example 6 XX Comparative Example 7 XXX Industrial applicability ''
- the tin-plated steel of the present invention has excellent appearance, paint adhesion and corrosion resistance, so it can be used in various applications, mainly for cans used in DI cans, food cans, beverage cans, etc. It can be used on the way. '
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2624852A CA2624852C (en) | 2005-10-20 | 2006-10-20 | Tin-plated steel sheet and method for manufacturing the same |
US12/083,590 US8147983B2 (en) | 2005-10-20 | 2006-10-20 | Tin-plated steel sheet |
CN2006800388720A CN101292061B (zh) | 2005-10-20 | 2006-10-20 | 镀锡钢板及其制造方法 |
EP06822413.8A EP1942208B1 (en) | 2005-10-20 | 2006-10-20 | Method for manufacturing tin-plated steel sheet |
ES06822413.8T ES2566771T3 (es) | 2005-10-20 | 2006-10-20 | Método para fabricar chapa de acero estañada |
Applications Claiming Priority (4)
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JP2005305765 | 2005-10-20 | ||
JP2005-305765 | 2005-10-20 | ||
JP2006-032171 | 2006-02-09 | ||
JP2006032171 | 2006-02-09 |
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WO2007046549A1 true WO2007046549A1 (ja) | 2007-04-26 |
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PCT/JP2006/321444 WO2007046549A1 (ja) | 2005-10-20 | 2006-10-20 | 錫めっき鋼板およびその製造方法 |
Country Status (9)
Country | Link |
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US (1) | US8147983B2 (ja) |
EP (1) | EP1942208B1 (ja) |
KR (1) | KR101021458B1 (ja) |
CN (1) | CN101292061B (ja) |
CA (1) | CA2624852C (ja) |
ES (1) | ES2566771T3 (ja) |
MY (1) | MY151771A (ja) |
TW (1) | TWI322194B (ja) |
WO (1) | WO2007046549A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008230117A (ja) * | 2007-03-22 | 2008-10-02 | Jfe Steel Kk | 樹脂被覆錫めっき鋼板、缶および缶蓋 |
Families Citing this family (10)
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JP5633117B2 (ja) * | 2008-05-12 | 2014-12-03 | Jfeスチール株式会社 | 錫めっき鋼板の製造方法および錫めっき鋼板ならびに化成処理液 |
JP5338163B2 (ja) * | 2008-07-10 | 2013-11-13 | Jfeスチール株式会社 | 錫めっき鋼板の製造方法 |
JP5861249B2 (ja) * | 2010-09-15 | 2016-02-16 | Jfeスチール株式会社 | 容器用鋼板の製造方法 |
CN102011124B (zh) * | 2010-10-14 | 2011-12-14 | 宁波翔博机械有限公司 | 一种镀锡钢板的表面处理方法 |
US20120095605A1 (en) | 2011-09-17 | 2012-04-19 | Tran Bao Q | Smart building systems and methods |
US8359750B2 (en) | 2011-12-28 | 2013-01-29 | Tran Bao Q | Smart building systems and methods |
DE102012000414B4 (de) | 2012-01-12 | 2014-03-20 | Thyssenkrupp Rasselstein Gmbh | Verfahren zur Passivierung von Weißblech, sowie verzinntes Stahlband oder -blech |
CN104099659A (zh) * | 2014-06-23 | 2014-10-15 | 武汉钢铁(集团)公司 | 电镀锡板表面锡氧化膜的在线去除方法 |
EP3786319B1 (en) | 2015-01-26 | 2023-08-09 | Toyo Kohan Co., Ltd. | Method for producing surface-treated steel plate |
TWI714284B (zh) * | 2018-09-27 | 2020-12-21 | 日商Toto股份有限公司 | 水龍頭金屬零件 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5841352B2 (ja) * | 1979-12-29 | 1983-09-12 | 日本パ−カライジング株式会社 | 金属表面の皮膜化成処理液 |
JPH06173024A (ja) * | 1992-12-09 | 1994-06-21 | Nippon Parkerizing Co Ltd | ぶりき材表面処理液及び表面処理方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5524516A (en) | 1978-08-10 | 1980-02-21 | Babcock Hitachi Kk | Drawing off unit for dust-containing particle |
JPS5947396A (ja) | 1982-09-08 | 1984-03-17 | Toyo Kohan Co Ltd | シ−ムレス缶用電気めつきぶりき |
US5498300A (en) * | 1992-12-09 | 1996-03-12 | Henkel Corporation | Composition and process for treating tinplate |
JP4114302B2 (ja) * | 2000-05-11 | 2008-07-09 | Jfeスチール株式会社 | 錫めっき鋼板 |
JP3876652B2 (ja) | 2001-06-21 | 2007-02-07 | Jfeスチール株式会社 | ポリエステル樹脂被覆錫めっき鋼板 |
JP4379005B2 (ja) * | 2002-06-05 | 2009-12-09 | Jfeスチール株式会社 | Si含有化成皮膜を有する錫系めっき鋼板の製造方法 |
-
2006
- 2006-10-20 ES ES06822413.8T patent/ES2566771T3/es active Active
- 2006-10-20 WO PCT/JP2006/321444 patent/WO2007046549A1/ja active Application Filing
- 2006-10-20 US US12/083,590 patent/US8147983B2/en not_active Expired - Fee Related
- 2006-10-20 TW TW095138715A patent/TWI322194B/zh not_active IP Right Cessation
- 2006-10-20 KR KR1020087009178A patent/KR101021458B1/ko not_active IP Right Cessation
- 2006-10-20 EP EP06822413.8A patent/EP1942208B1/en not_active Not-in-force
- 2006-10-20 CN CN2006800388720A patent/CN101292061B/zh not_active Expired - Fee Related
- 2006-10-20 CA CA2624852A patent/CA2624852C/en not_active Expired - Fee Related
- 2006-10-20 MY MYPI20081160 patent/MY151771A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5841352B2 (ja) * | 1979-12-29 | 1983-09-12 | 日本パ−カライジング株式会社 | 金属表面の皮膜化成処理液 |
JPH06173024A (ja) * | 1992-12-09 | 1994-06-21 | Nippon Parkerizing Co Ltd | ぶりき材表面処理液及び表面処理方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1942208A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008230117A (ja) * | 2007-03-22 | 2008-10-02 | Jfe Steel Kk | 樹脂被覆錫めっき鋼板、缶および缶蓋 |
Also Published As
Publication number | Publication date |
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CN101292061A (zh) | 2008-10-22 |
KR20080046742A (ko) | 2008-05-27 |
EP1942208A1 (en) | 2008-07-09 |
ES2566771T3 (es) | 2016-04-15 |
TWI322194B (en) | 2010-03-21 |
CN101292061B (zh) | 2011-02-02 |
US8147983B2 (en) | 2012-04-03 |
EP1942208A4 (en) | 2011-06-22 |
TW200722556A (en) | 2007-06-16 |
CA2624852C (en) | 2013-07-09 |
MY151771A (en) | 2014-07-14 |
US20090155621A1 (en) | 2009-06-18 |
CA2624852A1 (en) | 2007-04-26 |
EP1942208B1 (en) | 2016-01-06 |
KR101021458B1 (ko) | 2011-03-16 |
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