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WO2013027842A1 - Sn-PLATED STAINLESS STEEL SHEET WITH EXCELLENT ADHESION OF DEPOSIT AND MANUFACTURING PROCESS THEREFOR - Google Patents

Sn-PLATED STAINLESS STEEL SHEET WITH EXCELLENT ADHESION OF DEPOSIT AND MANUFACTURING PROCESS THEREFOR Download PDF

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Publication number
WO2013027842A1
WO2013027842A1 PCT/JP2012/071512 JP2012071512W WO2013027842A1 WO 2013027842 A1 WO2013027842 A1 WO 2013027842A1 JP 2012071512 W JP2012071512 W JP 2012071512W WO 2013027842 A1 WO2013027842 A1 WO 2013027842A1
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Prior art keywords
stainless steel
steel plate
plating
steel sheet
sulfuric acid
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PCT/JP2012/071512
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French (fr)
Japanese (ja)
Inventor
義勝 西田
正司 平岡
政義 多々納
藤井　孝浩
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日新製鋼株式会社
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Publication of WO2013027842A1 publication Critical patent/WO2013027842A1/en

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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
    • 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

Definitions

  • the present invention relates to a Sn-plated stainless steel plate having good plating adhesion, in which Sn plating is directly performed on the surface of a stainless steel plate without performing base plating (pre-plating) such as Ni plating, and a manufacturing method thereof.
  • Sn plating is generally performed by electroplating, but when stainless steel is used as a base material, in order to ensure the adhesion of Sn plating, base plating (pre-plating) such as Ni strike plating is performed, and then on top of that. It is common to apply Sn plating.
  • pre-plating such as Ni strike plating
  • Ni is a metal that easily causes allergies to the human body, it is desirable to make parts free of Ni, especially in devices used around us, such as mobile terminals.
  • Sn plating is performed using stainless steel as a base material, the underlying Ni plating plays an important role in securing plating adhesion, and Ni-free Sn-plated stainless steel parts will become widespread. Not reached.
  • An object of the present invention is to provide a Ni-free Sn-plated stainless steel sheet having good plating adhesion.
  • the purpose is stainless steel that has been subjected to cathodic electrolysis and is immersed in water having a dissolved oxygen content of 4 mg / L or less as required, and remains wet with the solution after cathodic electrolysis and has not been exposed to atmospheric contact in the dry state.
  • This is achieved by a Sn-plated stainless steel plate having good plating adhesion, in which a Sn-plated layer having a thickness of 0.1 to 1.5 ⁇ m is formed on the surface of the steel plate without interposing a base plating layer.
  • atmospheric contact in a dry state is a state in which the steel sheet surface is not wet with liquid and the steel sheet surface is in direct contact with the atmosphere.
  • the Sn-plated stainless steel sheet according to the present invention is an object obtained by applying Sn plating to “a stainless steel sheet not subjected to atmospheric contact in a dry state”.
  • the surface is kept wet with the electrolysis liquid and on the surface of the stainless steel plate in the state wetted with the liquid having the surface properties shown in (A) below, or the cathodic electrolysis and After washing with water, the surface remains wet with the liquid (washing water), and a thickness of 0.1 to 0.1 on the surface of the stainless steel plate having the surface properties shown in (A) below without interposing a base plating layer.
  • An Sn-plated stainless steel sheet having a good plating adhesion formed by forming a 1.5 ⁇ m Sn-plated layer is provided.
  • Stainless steel is an alloy steel having improved corrosion resistance with a Cr content of 10.5 mass% or more and a C content of 1.2 mass% or less, as shown in the number 3801 of JIS G0203: 2009. is there.
  • various stainless steel types are targeted depending on the application, and there is no need to pay particular attention to the component composition of the stainless steel.
  • Standard steel grades include austenitic, austenitic / ferritic, ferritic, martensitic and precipitation hardening steel grades as defined in JIS G4305: 2005, and austenitic and ferritic grades as defined in JIS G4312: 1991. Each steel grade is mentioned. Specific examples of component ranges include the following for each of austenite and ferrite.
  • Austenitic stainless steel grades By mass%, C: 0.0001 to 0.15%, Si: 0.001 to 4.0%, Mn: 0.001 to 2.5%, P: 0.001 to 0.045%, S: 0.0005 to 0.03%, Ni: 6.0 to 28.0%, Cr: 15.0 to 26.0%, Mo: 0 to 7.0%, Cu: 0 to 3.5%, Nb : 0 to 1.0%, Ti: 0 to 1.0%, Al: 0 to 0.1%, N: 0 to 0.3%, B: 0 to 0.01%, V: 0 to 0.0. 5%, W: 0 to 0.3%, Ca, Mg, Y, REM (rare earth elements) total: 0 to 0.1%, balance Fe and inevitable impurities.
  • Ferritic stainless steel type By mass%, C: 0.0001 to 0.15%, Si: 0.001 to 1.2%, Mn: 0.001 to 1.2%, P: 0.001 to 0.04%, S: 0.0005 to 0.03%, Ni: 0 to 0.6%, Cr: 10.5 to 32.0%, Mo: 0 to 2.5%, Cu: 0 to 1.0%, Nb: 0 -1.0%, Ti: 0-1.0%, Al: 0-5.0%, N: 0-0.025%, B: 0-0.01%, V: 0-0.5% W: 0 to 0.3%, Ca, Mg, Y, REM (rare earth element) total: 0 to 0.1%, balance Fe and inevitable impurities.
  • a step of subjecting a stainless steel plate to a cathodic electrolysis treatment with a current of 50 C / dm 2 in a sulfuric acid aqueous solution having a sulfuric acid concentration of 1 to 30% by mass (cathode electrolysis treatment step); After the cathode electrolytic treatment, the stainless steel plate is dipped in an electric Sn plating solution with the surface of the stainless steel plate wet with the sulfuric acid aqueous solution to form an Sn plating layer having an average film thickness of 0.1 to 1.5 ⁇ m per side.
  • the following water washing step may be inserted after the cathode electrolytic treatment step, and the Sn plating step may be performed as follows.
  • a step of immersing the stainless steel plate in water having a dissolved oxygen content of 4 mg / L or less in a state where the surface of the stainless steel plate is wet with the sulfuric acid aqueous solution after the cathode electrolytic treatment (water washing step);
  • the stainless steel plate is dipped in an electric Sn plating solution with the surface of the washed stainless steel plate wet with the washing water to form an Sn plating layer with an average film thickness of 0.1 to 1.5 ⁇ m per side.
  • a Sn-plated stainless steel plate having no Ni undercoat layer and having good plating adhesion was realized. Since there is no metallic Ni layer in the surface layer part of the parts using this, a factor causing Ni allergy to the human body is avoided.
  • Sn in the Sn plating layer reacts with the underlying Ni by aging, and intermetallic compounds (Ni 3 Sn, Ni 3 Sn). 2 ) Since it is consumed for the production
  • the Sn plating layer usually has to be secured to 1 ⁇ m or more.
  • the Sn-plated stainless steel sheet of the present invention does not react with Ni, so the amount of Sn plating deposited is the minimum necessary (for example, a thickness of 0.1 to less than 1.0 ⁇ m, or about 0.1 to 0.7 ⁇ m). ) And lead to saving of Sn.
  • the surface activated by the electrolytic pickling is introduced into the Sn plating bath while maintaining the wet state in the liquid.
  • An air atmosphere may be used between the processes, and a special line configuration such as providing a cover for forming a non-oxidizing gas atmosphere is not required.
  • Graph of Cartesian coordinate system in which the horizontal axis represents the surface temperature (° C) of the stainless steel plate when exiting from the liquid into the gas phase space, and the vertical axis represents the residence time in the gas phase space (sec) until dipping in the liquid of the next process .
  • the inventors have made various studies on a technique for forming an Sn plating layer having good adhesion on the surface of a stainless steel plate without performing Ni strike plating.
  • the surface of the stainless steel plate was preliminarily activated by electrolytic pickling, and then washed with water, and then it was considered that a process of applying electric Sn plating would be effective.
  • the presence of a passive film can be cited as a factor that degrades the plating adhesion of stainless steel. If the strong passive film that initially exists is removed by electrolytic treatment by cathodic reduction, the adhesion will be improved in subsequent plating processes. There is a high possibility that good plating can be realized. However, it has been difficult to stably form an Sn plating layer with good adhesion in the above process.
  • the inventors examined in detail the relationship between the environment in which the surface of the stainless steel plate was exposed to the Sn plating adhesion after the cathode electrolytic treatment and before the electroplating with Sn. As a result, it was thought that a thin oxide film was formed again on the surface activated by the cathode electrolytic treatment through the water washing step, which might inhibit the plating adhesion. Therefore, a device for maintaining the active surface formed by cathodic electrolysis until the time when it is introduced into the Sn plating solution is required. The inventors have found that the following method is extremely effective for improving the Sn plating property by detailed examination.
  • the stainless steel plate is immersed in washing water in a state where the surface of the stainless steel plate is wet with the cathode electrolytic treatment liquid. After washing with water, the stainless steel plate is immersed in a Sn plating bath while the surface of the stainless steel plate is wet with washing water.
  • Ordinary rinsing water has a dissolved oxygen content of 7 mg / L or more, and it is considered that a thin oxide film that inhibits Sn plating properties is formed when rinsing with such water.
  • the stainless steel plate In order to maintain the surface of the stainless steel plate wet with the liquid, in the case of the stainless steel plate after cathodic electrolysis, the stainless steel plate when it is pulled out of the bath and exits to the gas phase space (normal temperature atmosphere). It is effective to control the residence time in the gas phase space until the substrate is immersed in the washing water or the electric Sn plating solution in the next step according to the surface temperature. Specifically, the surface temperature (° C.) of the stainless steel plate when it enters the gas phase space after the cathode electrolytic treatment, the residence time in the gas phase space (sec) until it is immersed in the washing water or the electric Sn plating solution in the next step.
  • the surface temperature (° C.) of the stainless steel plate when it enters the gas phase space after the cathode electrolytic treatment, the residence time in the gas phase space (sec) until it is immersed in the washing water or the electric Sn plating solution in the next step.
  • the conditions belonging to the area (including the boundary except for the straight line FA) surrounded by the straight line connecting ABCDE are used. By doing so, it is possible to maintain the state of “not receiving atmospheric contact in the dry state” after the cathode electrolytic treatment and immerse in the liquid of the next step.
  • the residence time of the gas phase space until the electrode is immersed in the Sn plating solution after washing with water is also similar to the region surrounded by the straight line connecting ABCDE in FIG.
  • the coordinates of each point in the orthogonal coordinate system are A (10,0), B (10,60), C (20,60), D (30,35), E (60,5), F ( 60,0).
  • the cathode electrolyte is preferably a sulfuric acid aqueous solution.
  • an aqueous sulfuric acid solution By covering the surface of the stainless steel plate with an aqueous sulfuric acid solution, the effect of inhibiting the formation of a new oxide film is exerted, which is effective in keeping the Sn plating adhesion more stable and good.
  • the sulfuric acid concentration of the aqueous sulfuric acid solution used for the cathode electrolytic treatment may be controlled in the range of 1 to 30% by mass. You may manage in the range of 1-10 mass%.
  • the liquid temperature during cathode electrolysis is preferably in the range of 20 to 60 ° C. If the temperature is too low, it is difficult to obtain an activated surface, and if the temperature is too high, the amount of evaporation of the liquid increases, which is uneconomical. In order to obtain an activated surface by removing the passive film on the surface of the stainless steel plate, it is extremely effective to set the current amount of cathode electrolysis to 50 C / dm 2 or more.
  • the electrolysis conditions sulfuric acid concentration, liquid temperature, cathode current density
  • the energization amount is less than 50 C / dm 2 (for example, less than 5 to 50 C / dm 2 ).
  • good Sn plating adhesion can be easily realized in various stainless steel types by setting the energization amount to 50 C / dm 2 or more. Since excessive energization becomes uneconomical, it is desirable that the current be in the range of 500 C / dm 2 or less, and it may be controlled to 450 C / dm 2 or less.
  • the cathode current density can be adjusted in the range of 1 ⁇ 25A / dm 2, and more preferably in the range of 5 ⁇ 15A / dm 2.
  • the cathode electrolytic treatment After the cathode electrolytic treatment, as described above, it is necessary to immerse the stainless steel sheet in the Sn plating solution while maintaining the state where the surface of the stainless steel sheet is not subjected to atmospheric contact in the dry state.
  • a “steel strip” As a plating original plate (base steel plate).
  • the steel strip is passed through a continuous line in which the electrolytic pickling equipment and the electric Sn plating equipment are continuously arranged, thereby receiving atmospheric contact in the dry state from the cathode electrolytic treatment process to the Sn plating process. It becomes possible to maintain the surface state which is not.
  • a water washing equipment including a nitrogen sealing device for reducing dissolved oxygen in the water for washing may be inserted between the electrolytic pickling equipment and the electric Sn plating equipment.
  • the surface layer about 5 nm deep from the outermost surface of the stainless steel plate can be obtained. Based on the information, the state of the oxide film formed on the stainless steel plate surface can be known.
  • the surface properties of the stainless steel plate in a state wetted with the liquid immediately before being immersed in the Sn plating bath are actually about the stainless steel plate sample subjected to electrolytic treatment or further water washing under the same conditions as the production line by the laboratory. After the liquid on the surface of the sample is dried with air (for example, warm air from a dryer), immediately after analyzing the outermost surface with XPS, the surface properties that are wet with the liquid are identified. be able to. If the storage time in the room temperature atmosphere from the time the sample is air-dried to the XPS analysis is within 30 minutes, the change in surface properties during the storage time can be almost ignored.
  • the presence form of Fe and Cr in the outermost layer of the stainless steel sheet is mainly composed of a metal component, an oxide component, and a hydroxide component, but according to XPS analysis, the atomic% of Fe present as metal Fe and Fe and Cr, respectively, The atomic% of Cr existing as metal Cr can be grasped.
  • XPS X-ray photoelectron spectroscopy
  • the Sn plating can be performed by a conventional electric Sn plating method performed on a stainless steel plate subjected to Ni strike plating.
  • the plating solution include an aqueous solution containing metasulfone stannic tin and ascorbic acid (antioxidant) as main components and an additive such as 2-propanol. Even if the liquid that continues to wet the surface of the plating original plate is introduced into the plating solution together with the plating original plate, there is no particular problem because the amount is very small relative to the amount of the plating solution.
  • the amount of Sn plating layer consumed for the production of an intermetallic compound with Ni is estimated as described above, so that Sn per one side is obtained.
  • the thickness of the plating layer is 1 ⁇ m or more.
  • the thickness of the Sn plating layer can be made thinner than before.
  • the average thickness of the Sn plating layer per side is 0.1 ⁇ m or more, good solder wettability can be obtained. More preferably, the thickness is 0.3 ⁇ m or more.
  • the formation of an excessive Sn plating layer becomes uneconomical and causes a decrease in plating adhesion, so that the average thickness of the Sn plating layer per side is preferably 1.5 ⁇ m or less. You may manage to less than 1.0 micrometer or 0.7 micrometer.
  • the electrodeposition stress remains in the Sn plating layer formed by the electric Sn plating method, if it is allowed to stand at room temperature after plating, whiskers (crystals protruding in a needle shape) are formed from the surface of the plating layer due to the electrodeposition stress. It is often a problem. In order to suppress the formation of whiskers, it is effective to reduce the thickness of the Sn plating layer to 0.3 ⁇ m or less. However, in order to stably prevent the generation of whiskers without being affected by the thickness of the Sn plating layer, it is desirable to use so-called reflow treatment. Specifically, the Sn-plated steel sheet is heated to 250 to 350 ° C. to melt the Sn plating layer once, and then cooled and solidified.
  • Example 1 Using the stainless steel plate shown in Table 1 as a raw material, a Sn plated stainless steel plate was prepared in the order of cathode electrolytic treatment in sulfuric acid aqueous solution, electric Sn plating, and reflow treatment.
  • Steel A is an austenitic stainless steel
  • steel B and steel C are ferritic stainless steels.
  • a step of immersing the steel sheet in the Sn plating solution while maintaining the surface of the steel sheet wet with the sulfuric acid aqueous solution that is the cathode electrolytic treatment liquid, or the steel sheet after the cathode electrolytic treatment Washing was performed by a method of immersing the steel sheet in a washing bath while the surface was wet with the electrolytic solution, and the step of immersing the washed steel sheet in the Sn plating solution was performed while maintaining the surface wet with the rinsing water.
  • the atmosphere of the gas phase space pulled up from the cathode electrolytic treatment bath or the water washing bath is room temperature air.
  • the dissolved oxygen concentration in the washing water was adjusted in the range of 2 to 9 mg / L by blowing nitrogen into the water.
  • the amount of dissolved oxygen was measured with a dissolved oxygen meter.
  • air was blown onto the surface of the steel sheet to dry the steel sheet surface and left in the room temperature atmosphere for 24 hours, and then the next step was performed. In some examples, the reflow process is omitted.
  • an Sn-plated stainless steel plate was prepared by a conventional method of applying electric Sn plating to a steel plate that had been subjected to Ni strike plating with a thickness of 0.5 ⁇ m as a base plating. Tables 2 to 4 show cathode electrolysis conditions, presence / absence of washing, presence / absence of drying, the amount of dissolved oxygen in washing water, the average thickness of the Sn plating layer per side, and the presence / absence of reflow treatment.
  • Sn plating was performed under the following conventional general conditions. ⁇ Sn plating solution Main components: stannous metasulfonate, ascorbic acid (antioxidant) Additive: 2-propanol, etc., Sn plating conditions Anode: Sn plate Liquid temperature: 35 ° C Current density: 5 to 20 A / dm 2
  • the analysis was performed using AXIS-NOVA manufactured by KRATOS, the X-ray source was K ⁇ ray of monochromated Al, the analysis area was 0.3 mm ⁇ 0.7 mm, the photoelectron extraction angle was 90 °, and the pass energy was 20 eV. From the photoelectron spectra of the Fe2p orbital and Cr2p orbital, the peak separation of the metal component, oxide component, and hydroxide component is performed, respectively. From these areas, “exist as metal Fe in the total number of Fe atoms and Cr atoms” "The sum of the number of Fe atoms and the number of Cr atoms present as metallic Cr" (hereinafter referred to as "sum of the metal components of Fe and Cr”) was determined.
  • Sn plating adhesiveness and solder wettability were evaluated with the following method.
  • solder wettability As samples for evaluating solder wettability, Sn-plated stainless steel plates (initial samples) produced by the above-described method and samples obtained by subjecting these samples to accelerated aging treatment were prepared. ⁇ Accelerated aging treatment conditions Temperature: 105 °C Humidity: 100% RH Atmospheric pressure: 1216 hPa (1.2 atm) Holding time: 1h
  • a Sn-3% Ag-0.5% Cu Pb-less solder was prepared as the solder, and the zero cross time was measured by a solder bath equilibrium method defined in JIS C60068-2-54 using a solder wettability tester. .
  • the solder bath temperature was 255 ° C., and a chlorine-free flux for general electronic parts was used as the flux.
  • a sample having a zero cross time of 2.0 sec or less in the initial sample and 4.0 sec or less in the sample after the accelerated aging is evaluated as having good solder wettability practical for various electronic component applications. Further, a sample having a zero crossing time of 1.0 sec or less in the initial sample and 3.0 sec or less in the sample after the accelerated aging is evaluated as having particularly excellent solder wettability.
  • the cathode steel plate was not washed after the cathode electrolysis treatment, or washed with washing water having a dissolved oxygen amount of 4 mg / L or less.
  • the surface property in which the sum of the metal components of Fe and Cr obtained by the XPS analysis described above immediately before being introduced into the Sn plating bath is 28.0 atomic% or more. Both plating adhesion and solder wettability were evaluated as acceptable. Nos. 19, 49, and 79 are omitted from the reflow process, but it is separately possible that the generation of whiskers is remarkably suppressed by reducing the average thickness of the Sn plating layer to 0.3 ⁇ m or less. confirmed.
  • Comparative Examples No. 1, 31, and 61 did not perform cathode electrolysis, so that good adhesion could not be obtained.
  • Nos. 2, 3, 32, 33, 62, and 63 had a sum of the metal components of Fe and Cr of 28.0 atomic% or more because the steel plate surface was dried after the cathode electrolytic treatment and before the immersion of the Sn plating solution. Thus, the surface properties were not obtained, and the plating adhesion was poor.
  • Nos. 16-18, 46-48, 76-78 are surfaces whose sum of the metal components of Fe and Cr is 28.0 atomic% or more due to contact with washing water containing a large amount of dissolved oxygen after cathodic electrolysis. No properties were obtained and the plating adhesion was poor. No.
  • Example 2 Using a stainless steel plate of steels A, B, and C (plate thickness is described in Table 1) shown in Table 1, Sn-plated steel plates were produced in the following two process patterns.
  • Pattern 1 Cathodic electrolytic treatment ⁇ (vapor phase space) ⁇ Electric Sn plating
  • Pattern 2 Cathodic electrolytic treatment ⁇ (vapor phase space) ⁇ Washing ⁇ (Vapor phase space) ⁇ Electric Sn plating
  • the cathode electrolytic treatment was performed under the conditions of a stainless steel plate immersed in an electrolytic treatment solution made of a sulfuric acid aqueous solution having a concentration of 5% by mass, a current density of 10 A / dm 2 , and an energization time of 5 seconds (energization amount 50 C / dm 2 ).
  • the temperature of the electrolytic treatment solution was varied. In order to accurately set the surface temperature of the stainless steel plate when it entered the gas phase space after the cathode electrolytic treatment, the stainless steel plate was immersed in the electrolytic treatment solution for 10 minutes, and then cathode electrolysis was performed.
  • Washing with water in pattern 2 was performed by immersing the stainless steel plate in flushing water with a dissolved oxygen concentration of 2 to 3 mg / L by blowing nitrogen into the water.
  • the temperature of the washing water was varied.
  • the stainless steel plate was immersed in washing water for 10 minutes. It has been confirmed by a separate experiment that the surface temperature of the stainless steel plate when it enters the gas phase space by immersion for 10 minutes is equal to the temperature of the washing water.
  • the electrical Sn plating conditions were the same as in Example 1 except that the current density was kept constant at 10 A / dm 2 .
  • the Sn plating thickness per side is 0.5 ⁇ m.
  • No reflow treatment was applied after Sn plating.
  • a cathode electrolytic treatment tank, a rinsing tank, and an electric Sn plating tank were disposed in the glove box, and the atmosphere of the gas phase space was room temperature air or room temperature nitrogen.
  • the residence time of each gas phase space was changed, and it was observed whether the surface was kept wet with the liquid or whether there was a dry part.
  • the plating adhesiveness was evaluated by the method similar to Example 1.
  • FIG. The results are shown in Tables 5 and 6.
  • the hyphen display relating to washing in Tables 5 and 6 means that no washing was performed (Pattern 1).
  • Nos. 101 to 114 in Table 5 are those in which the gas phase space was made atmospheric in the process without water washing (pattern 1).
  • FIG. 1 the surface temperature (° C.) of the stainless steel plate when it exits from the liquid into the gas phase space is plotted on the horizontal axis, and the gas phase space residence time (sec) until dipping in the liquid of the next process is plotted on the vertical axis.
  • a graph of the coordinate system is shown.
  • the plots corresponding to the conditions of Nos. 101 to 114 are illustrated by circle marks or circle marks.
  • the horizontal axis corresponds to the surface temperature (° C.) of the stainless steel plate when the stainless steel plate comes out into the gas phase space after the cathode electrolytic treatment
  • the vertical axis represents the time until the stainless steel plate is immersed in the electric Sn plating solution after the cathode electrolytic treatment.
  • O marks indicate examples of the present invention (Nos. 101 to 108) in which the steel sheet surface was kept wet while staying in the gas phase space and the plating adhesion was good.
  • the ⁇ marks indicate comparative examples (Nos. 109 to 114) in which the steel sheet surface cannot be kept wet during the stay in the gas phase space, and there is a dry portion, and the plating adhesion is poor. Adopting the conditions belonging to the region (including the boundary) surrounded by the straight line connecting ABCDEFA in FIG. 1, the wet state is maintained and good plating adhesion was gotten.
  • Nos. 115 to 134 in Table 5 are those in which the gas phase space was made atmospheric in the process with water washing (pattern 2).
  • the examples of the present invention of Nos. 115 to 122 are both “in the gas phase space after the cathode electrolytic treatment and before the water washing, and in the gas phase space after the water washing and before the electric Sn plating”
  • the relationship between the residence time of the gas phase space is a condition that belongs to the region (including the boundary) surrounded by the straight line connecting ABCDE in FIG. Plating adhesion was obtained.
  • the comparative examples No. 123 to 128 show the conditions in the gas phase space after the cathode electrolytic treatment and before the water washing, and the comparative examples No.
  • Nos. 201 to 209 in Table 6 are those in which the gas phase space is nitrogen in the process without water washing (Pattern 1), and Nos. 210 to 222 are those in which the gas phase space is nitrogen in the process with water washing (Pattern 2). It is.
  • the gas phase space stays in a condition deviating from the area surrounded by the straight line connecting ABCDE in FIG. 1, the surface is kept wet. Due to the absence, good Sn plating adhesion could not be obtained even though the gas phase space was nitrogen.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

[Problem] To provide an Ni-free Sn-plated stainless steel sheet with excellent adhesion of a deposit. [Solution] An Sn-plated stainless steel sheet with excellent adhesion of a deposit, obtained by forming an Sn deposit having a thickness of 0.1 to 1.5μm, without a pre-plating layer, on the surface of a stainless steel sheet which has undergone cathodic electrolysis treatment and then, as necessary, immersion in water having a dissolved oxygen content of 4mg/L or less and which has been therefore kept in a liquid-wetted state after the cathodic electrolysis treatment and thus has not been brought into contact, in a dry state, with the atmosphere. The Sn-plated stainless steel sheet can be manufactured by a manufacturing process which includes: a step of subjecting a stainless steel sheet to cathodic electrolysis treatment in an aqueous sulfuric acid solution having a sulfuric acid concentration of 1 to 30mass% at a quantity of electricity of 50C/dm2 or more; and a step of subjecting the treated stainless steel sheet, the surface of which is still wet with the aqueous sulfuric acid solution, to immersion in an Sn electroplating solution to form an Sn deposit having an average film thickness of 0.1 to 1.5μm per side.

Description

めっき密着性の良好なＳｎめっきステンレス鋼板およびその製造法Sn-plated stainless steel sheet with good plating adhesion and method for producing the same
　本発明は、Ｎｉめっき等の下地めっき（プレめっき）を施すことなく、ステンレス鋼板の表面上に直接Ｓｎめっきを施しためっき密着性の良好なＳｎめっきステンレス鋼板、およびその製造法に関する。 The present invention relates to a Sn-plated stainless steel plate having good plating adhesion, in which Sn plating is directly performed on the surface of a stainless steel plate without performing base plating (pre-plating) such as Ni plating, and a manufacturing method thereof.
　電気・電子機器に使用するコネクタその他の通電部品には従来から銅合金が多用されているが、耐食性、強度、ばね性などが重視される場合にはステンレス鋼も使用される。これらの通電部品のなかでもはんだ付けに供される部品には、はんだ濡れ性を確保するためにＳｎめっきを施したものが採用されることが多い。 Conventionally, copper alloys have been widely used for connectors and other current-carrying parts used in electrical and electronic equipment, but stainless steel is also used when corrosion resistance, strength, springiness, etc. are important. Of these current-carrying parts, the parts subjected to soldering are often Sn-plated parts to ensure solder wettability.
　Ｓｎめっきは一般に電気めっき法により行われるが、ステンレス鋼を基材とする場合にはＳｎめっきの密着性を確保するためにＮｉストライクめっき等の下地めっき（プレめっき）を施して、その上にＳｎめっきを施すことが一般的である。 Sn plating is generally performed by electroplating, but when stainless steel is used as a base material, in order to ensure the adhesion of Sn plating, base plating (pre-plating) such as Ni strike plating is performed, and then on top of that. It is common to apply Sn plating.
特許第４２３８１１７号公報Japanese Patent No. 4238117
　Ｎｉは人体に対しアレルギーを引き起こす要因となりやすい金属であることから、特に携帯端末をはじめ身の回りで使用される機器においては、部品のＮｉフリー化を図ることが望ましい。しかし、ステンレス鋼を基材としてＳｎめっきを施す際にはめっき密着性を確保するうえで下地のＮｉめっきが重要な役割を有しており、Ｎｉフリー化したＳｎめっきステンレス鋼部品は普及するに至っていない。 Since Ni is a metal that easily causes allergies to the human body, it is desirable to make parts free of Ni, especially in devices used around us, such as mobile terminals. However, when Sn plating is performed using stainless steel as a base material, the underlying Ni plating plays an important role in securing plating adhesion, and Ni-free Sn-plated stainless steel parts will become widespread. Not reached.
　本発明は、めっき密着性のよいＮｉフリー化Ｓｎめっきステンレス鋼板を提供することを目的とする。 An object of the present invention is to provide a Ni-free Sn-plated stainless steel sheet having good plating adhesion.
　上記目的は、カソード電解処理され、必要に応じて溶存酸素量４ｍｇ／Ｌ以下の水へ浸漬され、カソード電解処理後に液で濡れた状態を維持して乾燥状態での大気接触を受けていないステンレス鋼板の表面上に、下地めっき層を介することなく厚さ０.１～１.５μｍのＳｎめっき層を形成してなる、めっき密着性の良好なＳｎめっきステンレス鋼板によって達成される。 The purpose is stainless steel that has been subjected to cathodic electrolysis and is immersed in water having a dissolved oxygen content of 4 mg / L or less as required, and remains wet with the solution after cathodic electrolysis and has not been exposed to atmospheric contact in the dry state. This is achieved by a Sn-plated stainless steel plate having good plating adhesion, in which a Sn-plated layer having a thickness of 0.1 to 1.5 μm is formed on the surface of the steel plate without interposing a base plating layer.
　ここで、「乾燥状態での大気接触」とは、鋼板表面が液で濡れておらず、鋼板表面が直接大気に触れる状態である。本発明に従うＳｎめっきステンレス鋼板は「乾燥状態での大気接触を受けていないステンレス鋼板」にＳｎめっきを施したものが対象となる。 Here, “atmospheric contact in a dry state” is a state in which the steel sheet surface is not wet with liquid and the steel sheet surface is in direct contact with the atmosphere. The Sn-plated stainless steel sheet according to the present invention is an object obtained by applying Sn plating to “a stainless steel sheet not subjected to atmospheric contact in a dry state”.
　また本発明では、
　カソード電解処理されたのち、表面がその電解処理の液で濡れた状態を維持して下記（Ａ）に示す表面性状を有する液で濡れている状態のステンレス鋼板の表面上、あるいはカソード電解処理および水洗を経て、表面が液（水洗の水）で濡れた状態を維持して下記（Ａ）に示す表面性状を有するステンレス鋼板の表面上に、下地めっき層を介することなく厚さ０.１～１.５μｍのＳｎめっき層を形成してなる、めっき密着性の良好なＳｎめっきステンレス鋼板が提供される。
　（Ａ）当該液で濡れた表面を空気乾燥させたのちＸ線光電子分光法（ＸＰＳ）により最表面の分析を行った場合、Ｆｅ原子数とＣｒ原子数の合計に占める金属Ｆｅとして存在するＦｅ原子数と金属Ｃｒとして存在するＣｒ原子数の和が２８.０％以上となる表面性状 In the present invention,
After the cathodic electrolysis treatment, the surface is kept wet with the electrolysis liquid and on the surface of the stainless steel plate in the state wetted with the liquid having the surface properties shown in (A) below, or the cathodic electrolysis and After washing with water, the surface remains wet with the liquid (washing water), and a thickness of 0.1 to 0.1 on the surface of the stainless steel plate having the surface properties shown in (A) below without interposing a base plating layer. An Sn-plated stainless steel sheet having a good plating adhesion formed by forming a 1.5 μm Sn-plated layer is provided.
(A) When the outermost surface is analyzed by X-ray photoelectron spectroscopy (XPS) after the surface wetted with the liquid is air-dried, Fe present as metal Fe in the total number of Fe atoms and Cr atoms Surface properties where the sum of the number of atoms and the number of Cr atoms present as metallic Cr is 28.0% or more
　「ステンレス鋼」とは、ＪＩＳ Ｇ０２０３：２００９の番号３８０１に示されているように、Ｃｒ含有量１０.５質量％以上、Ｃ含有量１.２質量％以下として耐食性を向上させた合金鋼である。本発明では用途に応じて種々のステンレス鋼種が対象となり、ステンレス鋼の成分組成には特にこだわる必要はない。規格鋼種としては、ＪＩＳ Ｇ４３０５：２００５に規定されるオーステナイト系、オーステナイト・フェライト系、フェライト系、マルテンサイト系、析出硬化系の各鋼種、およびＪＩＳ Ｇ４３１２：１９９１に規定されるオーステナイト系、フェライト系の各鋼種が挙げられる。具体的に成分範囲を例示すれば、オーステナイト系およびフェライト系それぞれ以下のようなものを挙げることができる。 “Stainless steel” is an alloy steel having improved corrosion resistance with a Cr content of 10.5 mass% or more and a C content of 1.2 mass% or less, as shown in the number 3801 of JIS G0203: 2009. is there. In the present invention, various stainless steel types are targeted depending on the application, and there is no need to pay particular attention to the component composition of the stainless steel. Standard steel grades include austenitic, austenitic / ferritic, ferritic, martensitic and precipitation hardening steel grades as defined in JIS G4305: 2005, and austenitic and ferritic grades as defined in JIS G4312: 1991. Each steel grade is mentioned. Specific examples of component ranges include the following for each of austenite and ferrite.
　オーステナイト系ステンレス鋼種；
　質量％で、Ｃ：０.０００１～０.１５％、Ｓｉ：０.００１～４.０％、Ｍｎ：０.００１～２.５％、Ｐ：０.００１～０.０４５％、Ｓ：０.０００５～０.０３％、Ｎｉ：６.０～２８.０％、Ｃｒ：１５.０～２６.０％、Ｍｏ：０～７.０％、Ｃｕ：０～３.５％、Ｎｂ：０～１.０％、Ｔｉ：０～１.０％、Ａｌ：０～０.１％、Ｎ：０～０.３％、Ｂ：０～０.０１％、Ｖ：０～０.５％、Ｗ：０～０.３％、Ｃａ、Ｍｇ、Ｙ、ＲＥＭ（希土類元素）の合計：０～０.１％、残部Ｆｅおよび不可避的不純物からなる組成を有するもの。 Austenitic stainless steel grades;
By mass%, C: 0.0001 to 0.15%, Si: 0.001 to 4.0%, Mn: 0.001 to 2.5%, P: 0.001 to 0.045%, S: 0.0005 to 0.03%, Ni: 6.0 to 28.0%, Cr: 15.0 to 26.0%, Mo: 0 to 7.0%, Cu: 0 to 3.5%, Nb : 0 to 1.0%, Ti: 0 to 1.0%, Al: 0 to 0.1%, N: 0 to 0.3%, B: 0 to 0.01%, V: 0 to 0.0. 5%, W: 0 to 0.3%, Ca, Mg, Y, REM (rare earth elements) total: 0 to 0.1%, balance Fe and inevitable impurities.
　フェライト系ステンレス鋼種；
　質量％で、Ｃ：０.０００１～０.１５％、Ｓｉ：０.００１～１.２％、Ｍｎ：０.００１～１.２％、Ｐ：０.００１～０.０４％、Ｓ：０.０００５～０.０３％、Ｎｉ：０～０.６％、Ｃｒ：１０.５～３２.０％、Ｍｏ：０～２.５％、Ｃｕ：０～１.０％、Ｎｂ：０～１.０％、Ｔｉ：０～１.０％、Ａｌ：０～５.０％、Ｎ：０～０.０２５％、Ｂ：０～０.０１％、Ｖ：０～０.５％、Ｗ：０～０.３％、Ｃａ、Ｍｇ、Ｙ、ＲＥＭ（希土類元素）の合計：０～０.１％、残部Ｆｅおよび不可避的不純物からなる組成を有するもの。 Ferritic stainless steel type;
By mass%, C: 0.0001 to 0.15%, Si: 0.001 to 1.2%, Mn: 0.001 to 1.2%, P: 0.001 to 0.04%, S: 0.0005 to 0.03%, Ni: 0 to 0.6%, Cr: 10.5 to 32.0%, Mo: 0 to 2.5%, Cu: 0 to 1.0%, Nb: 0 -1.0%, Ti: 0-1.0%, Al: 0-5.0%, N: 0-0.025%, B: 0-0.01%, V: 0-0.5% W: 0 to 0.3%, Ca, Mg, Y, REM (rare earth element) total: 0 to 0.1%, balance Fe and inevitable impurities.
　また、上記のめっき密着性の良好なＳｎめっきステンレス鋼板の製造法として、
　ステンレス鋼板に硫酸濃度１～３０質量％の硫酸水溶液中で通電量５０Ｃ／ｄｍ2のカソード電解処理を施す工程（カソード電解処理工程）、
　前記カソード電解処理後にステンレス鋼板表面が前記硫酸水溶液で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬し、片面当たりの平均膜厚が０.１～１.５μｍのＳｎめっき層を形成する工程（Ｓｎめっき工程）、
　さらに必要に応じて、めっき後のステンレス鋼板を２５０～３５０℃に加熱したのち冷却してＳｎめっき層を溶融・凝固させる処理（リフロー処理）を施す工程、
を有する製造法が提供される。 Moreover, as a manufacturing method of said Sn plating stainless steel plate with favorable plating adhesiveness,
A step of subjecting a stainless steel plate to a cathodic electrolysis treatment with a current of 50 C / dm 2 in a sulfuric acid aqueous solution having a sulfuric acid concentration of 1 to 30% by mass (cathode electrolysis treatment step);
After the cathode electrolytic treatment, the stainless steel plate is dipped in an electric Sn plating solution with the surface of the stainless steel plate wet with the sulfuric acid aqueous solution to form an Sn plating layer having an average film thickness of 0.1 to 1.5 μm per side. Process (Sn plating process),
Furthermore, if necessary, a process of applying a treatment (reflow treatment) to heat and cool the plated stainless steel plate to 250 to 350 ° C. and then to cool and solidify the Sn plating layer,
A manufacturing method is provided.
　前記カソード電解処理工程の後に下記の水洗工程を挿入し、Ｓｎめっき工程を下記のようにして行ってもよい。
　前記カソード電解処理後にステンレス鋼板表面が前記硫酸水溶液で濡れている状態で当該ステンレス鋼板を溶存酸素量４ｍｇ／Ｌ以下の水に浸漬して水洗する工程（水洗工程）、
　前記水洗後のステンレス鋼板表面が前記水洗の水で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬し、片面当たりの平均膜厚が０.１～１.５μｍのＳｎめっき層を形成する工程（Ｓｎめっき工程）。 The following water washing step may be inserted after the cathode electrolytic treatment step, and the Sn plating step may be performed as follows.
A step of immersing the stainless steel plate in water having a dissolved oxygen content of 4 mg / L or less in a state where the surface of the stainless steel plate is wet with the sulfuric acid aqueous solution after the cathode electrolytic treatment (water washing step);
The stainless steel plate is dipped in an electric Sn plating solution with the surface of the washed stainless steel plate wet with the washing water to form an Sn plating layer with an average film thickness of 0.1 to 1.5 μm per side. Step to perform (Sn plating step).
　本発明によれば、Ｎｉ下地めっき層を有しないＳｎめっきステンレス鋼板であって、めっき密着性の良好なものが実現された。これを使用した部品の表層部には金属Ｎｉ層がないので、人体に対してＮｉアレルギーを引き起こす要因が回避される。また、従来、Ｎｉストライクめっき層の上にＳｎめっき層を形成したＳｎめっきステンレス鋼板では、エージングによりＳｎめっき層中のＳｎが下地のＮｉと反応して金属間化合物（Ｎｉ3Ｓｎ、Ｎｉ3Ｓｎ2）の生成に消費されるため、Ｓｎめっき層が薄いと最表面まで金属間化合物の層に変化してしまうことがある。そうなると十分なはんだ濡れ性が確保できなくなるので、Ｓｎめっき層は通常１μｍ以上は確保する必要があった。これに対し本発明のＳｎめっきステンレス鋼板ではＮｉとの反応が生じないからＳｎめっきの付着量を必要最小限（例えば厚さ０.１～１.０μｍ未満、あるいは０.１～０.７μｍ程度）に抑えることができ、Ｓｎの節約にも繋がる。さらに本発明のＳｎめっきステンレス鋼板の製造に際しては、電解酸洗により活性化された表面は液に濡れた状態を維持したままＳｎめっき浴に導入されるので、連続ラインにおいて電解酸洗後の各工程間は大気雰囲気とすれば良く、非酸化性ガス雰囲気とするための覆いを設けるといった特殊なライン構成を必要としない。 According to the present invention, a Sn-plated stainless steel plate having no Ni undercoat layer and having good plating adhesion was realized. Since there is no metallic Ni layer in the surface layer part of the parts using this, a factor causing Ni allergy to the human body is avoided. Conventionally, in a Sn-plated stainless steel sheet in which a Sn plating layer is formed on a Ni strike plating layer, Sn in the Sn plating layer reacts with the underlying Ni by aging, and intermetallic compounds (Ni 3 Sn, Ni 3 Sn). 2 ) Since it is consumed for the production | generation of ( 2 ), when Sn plating layer is thin, it may change to the layer of an intermetallic compound to the outermost surface. In such a case, sufficient solder wettability cannot be ensured. Therefore, the Sn plating layer usually has to be secured to 1 μm or more. In contrast, the Sn-plated stainless steel sheet of the present invention does not react with Ni, so the amount of Sn plating deposited is the minimum necessary (for example, a thickness of 0.1 to less than 1.0 μm, or about 0.1 to 0.7 μm). ) And lead to saving of Sn. Furthermore, in the production of the Sn-plated stainless steel sheet of the present invention, the surface activated by the electrolytic pickling is introduced into the Sn plating bath while maintaining the wet state in the liquid. An air atmosphere may be used between the processes, and a special line configuration such as providing a cover for forming a non-oxidizing gas atmosphere is not required.
液中から気相空間に出たときのステンレス鋼板表面温度（℃）を横軸、次工程の液中に浸漬するまでの気相空間滞在時間（ｓｅｃ）を縦軸とする直交座標系のグラフ。Graph of Cartesian coordinate system in which the horizontal axis represents the surface temperature (° C) of the stainless steel plate when exiting from the liquid into the gas phase space, and the vertical axis represents the residence time in the gas phase space (sec) until dipping in the liquid of the next process .
　発明者らは、Ｎｉストライクめっきを施すことなく、ステンレス鋼板の表面に密着性の良いＳｎめっき層を形成させる手法について種々研究を重ねてきた。その１つの案として、ステンレス鋼板の表面を予め電解酸洗して十分に活性化したのち水洗し、その後、電気Ｓｎめっきを施す工程が有効ではないかと考えられた。ステンレス鋼のめっき密着性を劣化させる要因として不動態皮膜の存在が挙げられ、当初存在している強固な不動態皮膜をカソード還元による電解処理によって除去しておけば、その後のめっき工程で密着性の良いめっきが実現できる可能性が高い。しかしながら、上記工程では密着性の良いＳｎめっき層を安定して形成させることは困難であった。 The inventors have made various studies on a technique for forming an Sn plating layer having good adhesion on the surface of a stainless steel plate without performing Ni strike plating. As one of the proposals, the surface of the stainless steel plate was preliminarily activated by electrolytic pickling, and then washed with water, and then it was considered that a process of applying electric Sn plating would be effective. The presence of a passive film can be cited as a factor that degrades the plating adhesion of stainless steel. If the strong passive film that initially exists is removed by electrolytic treatment by cathodic reduction, the adhesion will be improved in subsequent plating processes. There is a high possibility that good plating can be realized. However, it has been difficult to stably form an Sn plating layer with good adhesion in the above process.
　検討の結果、カソード電解による活性化を行った後、Ｓｎめっきを施すまでの間にステンレス鋼表面には迅速に新たな酸化皮膜が形成され、それがめっき密着性を阻害する要因となるものと推察された。一般的に電気めっきに供する基材の表面は活性化処理後に十分に水洗し、異物の付着がないように管理することが重要であるとされている。すなわち、カソード電解処理後の鋼板は水洗工程を経たのちめっき工程に供されるのが通常である。 As a result of the investigation, a new oxide film is rapidly formed on the stainless steel surface after activation by cathode electrolysis and before Sn plating is applied, which becomes a factor that hinders plating adhesion. Inferred. In general, it is important that the surface of the base material used for electroplating is sufficiently washed after the activation treatment and managed so that no foreign matter adheres to it. That is, the steel sheet after the cathodic electrolysis is usually subjected to a washing process and then to a plating process.
　そこで発明者らは、カソード電解処理後、電気Ｓｎめっきに供するまでの間にステンレス鋼板表面が曝される環境と、Ｓｎめっき密着性の関係について詳細に検討した。その結果、水洗工程を経ることによってカソード電解処理により活性化された表面に再び薄い酸化皮膜が形成され、それがめっき密着性を阻害するのではないかと考えられた。したがって、カソード電解によって形成された活性な表面をＳｎめっき液に導入される時点まで維持するための工夫が必要となる。発明者らは詳細な検討により以下の手法がＳｎめっき性の向上に極めて有効であることを見出した。 Therefore, the inventors examined in detail the relationship between the environment in which the surface of the stainless steel plate was exposed to the Sn plating adhesion after the cathode electrolytic treatment and before the electroplating with Sn. As a result, it was thought that a thin oxide film was formed again on the surface activated by the cathode electrolytic treatment through the water washing step, which might inhibit the plating adhesion. Therefore, a device for maintaining the active surface formed by cathodic electrolysis until the time when it is introduced into the Sn plating solution is required. The inventors have found that the following method is extremely effective for improving the Sn plating property by detailed examination.
（１）カソード電解処理の後、水洗を省略して、前記カソード電解処理後にステンレス鋼板表面が前記電解液で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬してしまう。
　なお、水洗を省略しても表面が濡れている状態でＳｎめっき液に入れてしまえば、異物付着に起因するめっき欠陥の問題も回避できることが確認された。
（２）カソード電解処理の後に水洗を行う場合は、溶存酸素量が４ｍｇ／Ｌ以下に調整された水に浸漬する。その際、ステンレス鋼板表面がカソード電解処理液で濡れている状態でそのステンレス鋼板を水洗水に浸漬することが好ましい。水洗後はステンレス鋼板表面が水洗水で濡れている状態でそのステンレス鋼板をＳｎめっき浴に浸漬する。
　通常の水洗水は溶存酸素量が７ｍｇ／Ｌ以上であり、そのような水で水洗するとＳｎめっき性を阻害する薄い酸化皮膜が形成されるものと考えられる。
（３）ステンレス鋼板表面が液で濡れている状態を維持するためには、カソード電解処理後のステンレス鋼板の場合、その浴から引き上げられて気相空間（常温大気）に出たときのステンレス鋼板の表面温度に応じて次工程の水洗水または電気Ｓｎめっき液に浸漬されるまでの気相空間滞在時間をコントロールすることが有効である。具体的には、カソード電解処理後に気相空間に出たときのステンレス鋼板表面温度（℃）を横軸、次工程の水洗水または電気Ｓｎめっき液に浸漬するまでの気相空間滞在時間（ｓｅｃ）を縦軸とする図１の直交座標系において、Ａ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（直線ＦＡ上を除き境界を含む）に属する条件を採用することにより、カソード電解処理後に「乾燥状態での大気接触を受けていない」状態を維持して次工程の液に浸漬することができる。水洗後に電気Ｓｎめっき液に浸漬されるまでの気相空間滞在時間についても、同様に図１のＡ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（直線ＦＡ上を除き境界を含む）に属する条件を採用することにより、水洗後に「乾燥状態での大気接触を受けていない」状態を維持して次工程の電気Ｓｎめっき液に浸漬することができる。ここで、当該直交座標系における各点の座標はＡ（１０，０）、Ｂ（１０，６０）、Ｃ（２０，６０）、Ｄ（３０，３５）、Ｅ（６０，５）、Ｆ（６０，０）である。 (1) After the cathode electrolytic treatment, washing with water is omitted, and the stainless steel plate is immersed in the electric Sn plating solution in a state where the surface of the stainless steel plate is wet with the electrolytic solution after the cathode electrolytic treatment.
In addition, even if it omits water washing, if it put into Sn plating liquid in the state where the surface is wet, it was confirmed that the problem of the plating defect resulting from foreign material adhesion can also be avoided.
(2) When washing with water after the cathode electrolytic treatment, it is immersed in water whose dissolved oxygen amount is adjusted to 4 mg / L or less. At that time, it is preferable to immerse the stainless steel plate in washing water in a state where the surface of the stainless steel plate is wet with the cathode electrolytic treatment liquid. After washing with water, the stainless steel plate is immersed in a Sn plating bath while the surface of the stainless steel plate is wet with washing water.
Ordinary rinsing water has a dissolved oxygen content of 7 mg / L or more, and it is considered that a thin oxide film that inhibits Sn plating properties is formed when rinsing with such water.
(3) In order to maintain the surface of the stainless steel plate wet with the liquid, in the case of the stainless steel plate after cathodic electrolysis, the stainless steel plate when it is pulled out of the bath and exits to the gas phase space (normal temperature atmosphere). It is effective to control the residence time in the gas phase space until the substrate is immersed in the washing water or the electric Sn plating solution in the next step according to the surface temperature. Specifically, the surface temperature (° C.) of the stainless steel plate when it enters the gas phase space after the cathode electrolytic treatment, the residence time in the gas phase space (sec) until it is immersed in the washing water or the electric Sn plating solution in the next step. In the Cartesian coordinate system of FIG. 1 with the vertical axis () as the vertical axis, the conditions belonging to the area (including the boundary except for the straight line FA) surrounded by the straight line connecting ABCDE are used. By doing so, it is possible to maintain the state of “not receiving atmospheric contact in the dry state” after the cathode electrolytic treatment and immerse in the liquid of the next step. Similarly, the residence time of the gas phase space until the electrode is immersed in the Sn plating solution after washing with water is also similar to the region surrounded by the straight line connecting ABCDE in FIG. By adopting the conditions belonging to (including the boundary except for), it is possible to maintain the state of “not subject to atmospheric contact in a dry state” after washing with water and to immerse it in the electric Sn plating solution in the next step. Here, the coordinates of each point in the orthogonal coordinate system are A (10,0), B (10,60), C (20,60), D (30,35), E (60,5), F ( 60,0).
　特にカソード電解液を硫酸水溶液とすることが好ましい。ステンレス鋼板表面を硫酸水溶液で覆うことによって酸化皮膜の新たな形成を抑止する効果が発揮され、Ｓｎめっき密着性をより安定して良好に保つうえで効果的である。 In particular, the cathode electrolyte is preferably a sulfuric acid aqueous solution. By covering the surface of the stainless steel plate with an aqueous sulfuric acid solution, the effect of inhibiting the formation of a new oxide film is exerted, which is effective in keeping the Sn plating adhesion more stable and good.
　カソード電解処理に使用する硫酸水溶液の硫酸濃度は１～３０質量％の範囲でコントロールすればよい。１～１０質量％の範囲に管理してもよい。カソード電解時の液温は２０～６０℃の範囲とすることが好ましい。温度が低過ぎると活性化された表面が得られにくく、温度が高過ぎると液の蒸発量が多くなり不経済となる。ステンレス鋼板表面の不動態皮膜を除去して活性化された表面を得るためには、カソード電解の通電量を５０Ｃ／ｄｍ2以上とすることが極めて有効である。通電量が５０Ｃ／ｄｍ2未満（例えば５～５０Ｃ／ｄｍ2未満）でも、良好なＳｎめっき密着性を得るための電解条件（硫酸濃度、液温、カソード電流密度）を見つけることは多くの場合可能であるが、通電量を５０Ｃ／ｄｍ2以上とすることで種々のステンレス鋼種において良好なＳｎめっき密着性を容易に実現することができる。過剰な通電は不経済となるので、５００Ｃ／ｄｍ2以下の範囲とすることが望ましく、４５０Ｃ／ｄｍ2以下に管理してもよい。カソード電流密度は１～２５Ａ／ｄｍ2の範囲で調整することができ、５～１５Ａ／ｄｍ2の範囲とすることがより好ましい。 The sulfuric acid concentration of the aqueous sulfuric acid solution used for the cathode electrolytic treatment may be controlled in the range of 1 to 30% by mass. You may manage in the range of 1-10 mass%. The liquid temperature during cathode electrolysis is preferably in the range of 20 to 60 ° C. If the temperature is too low, it is difficult to obtain an activated surface, and if the temperature is too high, the amount of evaporation of the liquid increases, which is uneconomical. In order to obtain an activated surface by removing the passive film on the surface of the stainless steel plate, it is extremely effective to set the current amount of cathode electrolysis to 50 C / dm 2 or more. It is often the case that the electrolysis conditions (sulfuric acid concentration, liquid temperature, cathode current density) for obtaining good Sn plating adhesion are found even when the energization amount is less than 50 C / dm 2 (for example, less than 5 to 50 C / dm 2 ). Although it is possible, good Sn plating adhesion can be easily realized in various stainless steel types by setting the energization amount to 50 C / dm 2 or more. Since excessive energization becomes uneconomical, it is desirable that the current be in the range of 500 C / dm 2 or less, and it may be controlled to 450 C / dm 2 or less. The cathode current density can be adjusted in the range of 1 ~ 25A / dm 2, and more preferably in the range of 5 ~ 15A / dm 2.
　カソード電解処理後には、前述のように、ステンレス鋼板の表面が乾燥状態での大気接触を受けていない状態を維持したまま当該ステンレス鋼板をＳｎめっき液中に浸漬してしまう必要がある。大量生産現場ではめっき原板（基材鋼板）として「鋼帯」を使用することが一般的である。その場合、電解酸洗設備と電気Ｓｎめっき設備を連続して配置した連続ラインに鋼帯を通板させることで、カソード電解処理工程からＳｎめっき工程までの間、乾燥状態での大気接触を受けていない表面状態を維持することが可能となる。水洗を行う場合は、電解酸洗設備と電気Ｓｎめっき設備の間に例えば水洗水中の溶存酸素を減少させるための窒素封入装置を備える水洗設備を挿入すればよい。 After the cathode electrolytic treatment, as described above, it is necessary to immerse the stainless steel sheet in the Sn plating solution while maintaining the state where the surface of the stainless steel sheet is not subjected to atmospheric contact in the dry state. In a mass production site, it is common to use a “steel strip” as a plating original plate (base steel plate). In that case, the steel strip is passed through a continuous line in which the electrolytic pickling equipment and the electric Sn plating equipment are continuously arranged, thereby receiving atmospheric contact in the dry state from the cathode electrolytic treatment process to the Sn plating process. It becomes possible to maintain the surface state which is not. In the case of performing water washing, for example, a water washing equipment including a nitrogen sealing device for reducing dissolved oxygen in the water for washing may be inserted between the electrolytic pickling equipment and the electric Sn plating equipment.
　発明者らの研究によれば、液で濡れている状態を維持して良好なＳｎめっき密着性が得られるステンレス鋼板の表面性状は下記（Ａ）で示すように特定することができる。
　（Ａ）当該液で濡れた表面を空気乾燥させたのちＸ線光電子分光法（ＸＰＳ）により最表面の分析を行った場合、Ｆｅ原子数とＣｒ原子数の合計に占める金属Ｆｅとして存在するＦｅ原子数と金属Ｃｒとして存在するＣｒ原子数の和が２８.０％以上となる表面性状 According to the studies by the inventors, the surface properties of a stainless steel plate that maintains good wettability with the liquid and can obtain good Sn plating adhesion can be specified as shown in (A) below.
(A) When the outermost surface is analyzed by X-ray photoelectron spectroscopy (XPS) after the surface wetted with the liquid is air-dried, Fe present as metal Fe in the total number of Fe atoms and Cr atoms Surface properties where the sum of the number of atoms and the number of Cr atoms present as metallic Cr is 28.0% or more
　ＸＰＳによる分析ではステンレス鋼板の最表面から深さ５ｎｍ程度の表層部における情報が得られる。その情報に基づけばステンレス鋼板表面に形成されている酸化皮膜の状態を知ることができる。Ｓｎめっき浴に浸漬される直前の液で濡れている状態にあるステンレス鋼板の表面性状は、実際にはラボによりその製造ラインと同一の条件で電解処理あるいはさらに水洗を施したステンレス鋼板サンプルについて、そのサンプルの表面の液を空気（例えばドライヤーの温風）で乾燥させたのち、すぐにＸＰＳにて最表面を分析することによって、当該液で濡れている状態にあった表面の性状を特定することができる。サンプルを空気乾燥させてからＸＰＳ分析に供するまでの常温大気中での保管時間が３０ｍｉｎ以内であれば、その保管時間中における表面性状の変化はほぼ無視することができる。 In the analysis by XPS, information on the surface layer about 5 nm deep from the outermost surface of the stainless steel plate can be obtained. Based on the information, the state of the oxide film formed on the stainless steel plate surface can be known. The surface properties of the stainless steel plate in a state wetted with the liquid immediately before being immersed in the Sn plating bath are actually about the stainless steel plate sample subjected to electrolytic treatment or further water washing under the same conditions as the production line by the laboratory. After the liquid on the surface of the sample is dried with air (for example, warm air from a dryer), immediately after analyzing the outermost surface with XPS, the surface properties that are wet with the liquid are identified. be able to. If the storage time in the room temperature atmosphere from the time the sample is air-dried to the XPS analysis is within 30 minutes, the change in surface properties during the storage time can be almost ignored.
　ステンレス鋼板最表層のＦｅおよびＣｒの存在形態は金属成分、酸化物成分および水酸化物成分が主体であるが、ＸＰＳ分析によれば、ＦｅおよびＣｒについてそれぞれ金属Ｆｅとして存在するＦｅの原子％および金属Ｃｒとして存在するＣｒの原子％を把握することができる。詳細な検討の結果、液で濡れている状態のステンレス鋼板を空気乾燥させたサンプルのＸ線光電子分光法（ＸＰＳ）による最表面の分析において、Ｆｅ原子数とＣｒ原子数の合計に占める金属Ｆｅとして存在するＦｅ原子数と金属Ｃｒとして存在するＣｒ原子数の和が２８.０％以上であれば、その液で濡れている状態のステンレス鋼板を電気Ｓｎめっき浴に導入してＳｎめっきを施したとき、良好なめっき密着性を実現することができる。その理由については現時点で未解明であるが、金属Ｆｅとして存在するＦｅと金属Ｃｒとして存在するＣｒの割合が多い表面酸化皮膜は、Ｆｅ、Ｃｒの酸化物や水酸化物の割合が少なく、かつ薄い皮膜であると考えられ、液で濡れている状態では活性な表面状態が維持されているものと推察される。 The presence form of Fe and Cr in the outermost layer of the stainless steel sheet is mainly composed of a metal component, an oxide component, and a hydroxide component, but according to XPS analysis, the atomic% of Fe present as metal Fe and Fe and Cr, respectively, The atomic% of Cr existing as metal Cr can be grasped. As a result of detailed examination, in the analysis of the outermost surface by X-ray photoelectron spectroscopy (XPS) of a sample obtained by air-drying a stainless steel plate wet with a liquid, metal Fe accounts for the total number of Fe atoms and Cr atoms. If the sum of the number of Fe atoms present as Cr and the number of Cr atoms present as Cr is 28.0% or more, a stainless steel plate wet with the solution is introduced into an electric Sn plating bath and Sn plating is performed. When this is done, good plating adhesion can be achieved. The reason for this is unclear at present, but the surface oxide film having a large proportion of Fe present as metal Fe and Cr present as metal Cr has a small proportion of oxides and hydroxides of Fe, Cr, and It is thought that it is a thin film, and it is inferred that the active surface state is maintained when wet with the liquid.
　Ｓｎめっきは、Ｎｉストライクめっきを施したステンレス鋼板に対して行われている従来の電気Ｓｎめっき法によって実施できる。例えば、めっき液としては、メタスルホンサン第一錫、アスコルビン酸（酸化防止剤）を主成分とし、２－プロパノール等の添加剤を加えた水溶液が挙げられる。めっき原板の表面を濡らし続けた液がめっき原板とともにめっき液中に導入されても、めっき液の量に対して非常に少量であるため特に問題はない。 The Sn plating can be performed by a conventional electric Sn plating method performed on a stainless steel plate subjected to Ni strike plating. For example, examples of the plating solution include an aqueous solution containing metasulfone stannic tin and ascorbic acid (antioxidant) as main components and an additive such as 2-propanol. Even if the liquid that continues to wet the surface of the plating original plate is introduced into the plating solution together with the plating original plate, there is no particular problem because the amount is very small relative to the amount of the plating solution.
　従来、Ｎｉストライクめっきを施したステンレス鋼板表面にＳｎめっきを施す場合は、前述のようにエージングによってＳｎめっき層がＮｉとの金属間化合物の生成に消費される量を見込んで、片面当たりのＳｎめっき層の厚さを１μｍ以上とすることが多い。これに対し本発明に従えばＮｉフリーであるためにＮｉとの金属間化合物の生成を考慮する必要がないため、従来よりＳｎめっき層の厚さを薄くすることができる。種々検討の結果、片面当たりのＳｎめっき層の平均厚さを０.１μｍ以上とすれば、良好なはんだ濡れ性を得ることができる。０.３μｍ以上とすることがより好ましい。ただし、過剰なＳｎめっき層の形成は不経済となり、また、めっき密着性を低下させる要因ともなるので、片面当たりのＳｎめっき層の平均厚さは１.５μｍ以下とすることが望ましい。１.０μｍ未満、あるいは０.７μｍに管理してもよい。 Conventionally, when Sn plating is applied to the surface of a stainless steel plate subjected to Ni strike plating, the amount of Sn plating layer consumed for the production of an intermetallic compound with Ni is estimated as described above, so that Sn per one side is obtained. In many cases, the thickness of the plating layer is 1 μm or more. On the other hand, according to the present invention, since it is Ni-free, it is not necessary to consider the formation of an intermetallic compound with Ni, so that the thickness of the Sn plating layer can be made thinner than before. As a result of various studies, if the average thickness of the Sn plating layer per side is 0.1 μm or more, good solder wettability can be obtained. More preferably, the thickness is 0.3 μm or more. However, the formation of an excessive Sn plating layer becomes uneconomical and causes a decrease in plating adhesion, so that the average thickness of the Sn plating layer per side is preferably 1.5 μm or less. You may manage to less than 1.0 micrometer or 0.7 micrometer.
　電気Ｓｎめっき法によって形成したＳｎめっき層には電着応力が残存しているため、めっき後に常温で放置するとその電着応力に起因してめっき層表面からウイスカ（針状に突起した結晶）が生成することがあり、しばしば問題となる。ウイスカの生成を抑制するためにはＳｎめっき層の厚さを０.３μｍ以下に薄くすることが有効である。ただし、Ｓｎめっき層の厚さに影響されずにウイスカの生成を安定的に防止するためには、いわゆるリフロー処理に供することが望ましい。具体的にはＳｎめっき後の鋼板を２５０～３５０℃に加熱してＳｎめっき層を一旦溶融させたのち冷却して凝固させる。 Since the electrodeposition stress remains in the Sn plating layer formed by the electric Sn plating method, if it is allowed to stand at room temperature after plating, whiskers (crystals protruding in a needle shape) are formed from the surface of the plating layer due to the electrodeposition stress. It is often a problem. In order to suppress the formation of whiskers, it is effective to reduce the thickness of the Sn plating layer to 0.3 μm or less. However, in order to stably prevent the generation of whiskers without being affected by the thickness of the Sn plating layer, it is desirable to use so-called reflow treatment. Specifically, the Sn-plated steel sheet is heated to 250 to 350 ° C. to melt the Sn plating layer once, and then cooled and solidified.
《実施例１》
　表１に示すステンレス鋼板を素材に用いて、硫酸水溶液中でのカソード電解処理、電気Ｓｎめっき、リフロー処理を順次行う工程にてＳｎめっきステンレス鋼板を作製した。Ａ鋼はオーステナイト系ステンレス鋼、Ｂ鋼およびＣ鋼はフェライト系ステンレス鋼である。カソード電解処理の後、一部の例を除き、カソード電解処理液である硫酸水溶液で鋼板表面が濡れた状態を維持したまま、その鋼板をＳｎめっき液に浸漬する工程、あるいはカソード電解処理後に鋼板表面が電解液で濡れたまま鋼板を水洗浴に浸漬する方法で水洗を行い、表面が水洗水で濡れた状態を維持したまま水洗後の鋼板をＳｎめっき液に浸漬する工程を実施した。カソード電解処理浴あるいは水洗浴から引き上げられる気相空間の雰囲気は常温大気である。水洗水中の溶存酸素濃度は水中に窒素を吹き込むことにより２～９ｍｇ／Ｌの範囲で調整した。溶存酸素量は溶存酸素計で測定した。一部の例ではカソード電解処理後あるいは水洗後に鋼板表面に空気を吹き付けて鋼板表面を乾燥させ、常温大気中に２４時間放置したのち、次工程を実施した。また、一部の例ではリフロー処理を省略した。さらに、比較のために下地めっきとして膜厚０.５μｍのＮｉストライクめっきを施した鋼板に電気Ｓｎめっきを施す従来の手法にてＳｎめっきステンレス鋼板を作製した。カソード電解条件、水洗の有無、乾燥の有無、水洗水中の溶存酸素量、片面当たりのＳｎめっき層の平均厚さ、リフロー処理の有無については、表２～表４中に示してある。 Example 1
Using the stainless steel plate shown in Table 1 as a raw material, a Sn plated stainless steel plate was prepared in the order of cathode electrolytic treatment in sulfuric acid aqueous solution, electric Sn plating, and reflow treatment. Steel A is an austenitic stainless steel, and steel B and steel C are ferritic stainless steels. After the cathode electrolytic treatment, except for some examples, a step of immersing the steel sheet in the Sn plating solution while maintaining the surface of the steel sheet wet with the sulfuric acid aqueous solution that is the cathode electrolytic treatment liquid, or the steel sheet after the cathode electrolytic treatment Washing was performed by a method of immersing the steel sheet in a washing bath while the surface was wet with the electrolytic solution, and the step of immersing the washed steel sheet in the Sn plating solution was performed while maintaining the surface wet with the rinsing water. The atmosphere of the gas phase space pulled up from the cathode electrolytic treatment bath or the water washing bath is room temperature air. The dissolved oxygen concentration in the washing water was adjusted in the range of 2 to 9 mg / L by blowing nitrogen into the water. The amount of dissolved oxygen was measured with a dissolved oxygen meter. In some cases, after the cathode electrolytic treatment or after washing with water, air was blown onto the surface of the steel sheet to dry the steel sheet surface and left in the room temperature atmosphere for 24 hours, and then the next step was performed. In some examples, the reflow process is omitted. Furthermore, for comparison, an Sn-plated stainless steel plate was prepared by a conventional method of applying electric Sn plating to a steel plate that had been subjected to Ni strike plating with a thickness of 0.5 μm as a base plating. Tables 2 to 4 show cathode electrolysis conditions, presence / absence of washing, presence / absence of drying, the amount of dissolved oxygen in washing water, the average thickness of the Sn plating layer per side, and the presence / absence of reflow treatment.
　Ｓｎめっきは以下に示す従来一般的な条件で行った。
・Ｓｎめっき液
　主成分：メタスルホン酸第一錫、アスコルビン酸（酸化防止剤）
　添加剤：２－プロパノール、他
・Ｓｎめっき条件
　陽極：Ｓｎ板
　液温：３５℃
　電流密度：５～２０Ａ／ｄｍ2 Sn plating was performed under the following conventional general conditions.
・ Sn plating solution Main components: stannous metasulfonate, ascorbic acid (antioxidant)
Additive: 2-propanol, etc., Sn plating conditions Anode: Sn plate Liquid temperature: 35 ° C
Current density: 5 to 20 A / dm 2
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
〔ＸＰＳ分析〕
　一方、上記の各Ｓｎめっきステンレス鋼板の製造工程において、Ｓｎめっき浴に浸漬する前までの工程をラボ的に再現し、Ｓｎめっき浴に浸漬する直前の状態に相当する試料（後述のめっき密着性を調べた試料と同一条件で作製したもの）について、表面が液で濡れている状態にあるもの（表２～表４において「乾燥なし」と表示されるもの）は表面をドライヤーの温風（８０℃以下）で乾燥させたのち、ただちにＸＰＳにて最表面の分析を行った。分析はＫＲＡＴＯＳ製ＡＸＩＳ－ＮＯＶＡを用い、Ｘ線源は単色化ＡｌのＫα線、分析面積は０.３ｍｍ×０.７ｍｍ、光電子の取り出し角９０°、パスエネルギーは２０ｅＶで行った。Ｆｅ２ｐ軌道とＣｒ２ｐ軌道の光電子スペクトルから、それぞれ金属成分、酸化物成分、水酸化物成分のピーク分離を行い、それらの面積から、「Ｆｅ原子数とＣｒ原子数の合計に占める金属Ｆｅとして存在するＦｅ原子数と金属Ｃｒとして存在するＣｒ原子数の和」（以下「ＦｅとＣｒの金属成分の和」という）を求めた。 [XPS analysis]
On the other hand, in the manufacturing process of each of the above Sn-plated stainless steel sheets, the process before dipping in the Sn plating bath is reproduced in a laboratory, and a sample corresponding to the state immediately before dipping in the Sn plating bath (plating adhesion described later) The sample whose surface was wet with the liquid (those that are displayed as “no drying” in Tables 2 to 4) were subjected to hot air from the dryer ( After drying at 80 ° C. or less, the outermost surface was immediately analyzed by XPS. The analysis was performed using AXIS-NOVA manufactured by KRATOS, the X-ray source was Kα ray of monochromated Al, the analysis area was 0.3 mm × 0.7 mm, the photoelectron extraction angle was 90 °, and the pass energy was 20 eV. From the photoelectron spectra of the Fe2p orbital and Cr2p orbital, the peak separation of the metal component, oxide component, and hydroxide component is performed, respectively. From these areas, “exist as metal Fe in the total number of Fe atoms and Cr atoms” "The sum of the number of Fe atoms and the number of Cr atoms present as metallic Cr" (hereinafter referred to as "sum of the metal components of Fe and Cr") was determined.
　上記の各Ｓｎめっきステンレス鋼板について、以下の方法でＳｎめっき密着性およびはんだ濡れ性を評価した。
〔めっき密着性〕
　Ｓｎめっきステンレス鋼板に１８０°密着曲げを施し、曲げ部の外側表面にＪＩＳ Ｚ１５２２に規定されるセロハン粘着テープを貼付したのち、そのセロハン粘着テープを剥がす方法により、Ｓｎめっき密着性を調べた。試験数ｎ＝１０で試験を行い、目視によりめっき金属がセロハン粘着テープに付着したサンプルが１つもないものを◎（めっき密着性；優秀）、それ以外を×（めっき密着性；不良）と判定した。 About each said Sn plating stainless steel plate, Sn plating adhesiveness and solder wettability were evaluated with the following method.
[Plating adhesion]
The Sn-plated stainless steel sheet was subjected to 180 ° bend bending, and after the cellophane adhesive tape specified in JIS Z1522 was applied to the outer surface of the bent portion, Sn plating adhesion was examined by a method of peeling the cellophane adhesive tape. The number of tests is n = 10, and when there is no sample in which the plated metal adheres to the cellophane adhesive tape by visual observation, ◎ (plating adhesion: excellent) and the others are judged as x (plating adhesion: poor). did.
〔はんだ濡れ性〕
　はんだ濡れ性を評価する試料として、上記の手法で作製したＳｎめっきステンレス鋼板（初期試料）、およびそれらの試料に下記の条件で加速エージング処理を施した試料を用意した。
・加速エージング処理条件
　温度：１０５℃
　湿度：１００％Ｒ.Ｈ.
　気圧：１２１６ｈＰａ（１.２ａｔｍ）
　保持時間：１ｈ (Solder wettability)
As samples for evaluating solder wettability, Sn-plated stainless steel plates (initial samples) produced by the above-described method and samples obtained by subjecting these samples to accelerated aging treatment were prepared.
・ Accelerated aging treatment conditions Temperature: 105 ℃
Humidity: 100% RH
Atmospheric pressure: 1216 hPa (1.2 atm)
Holding time: 1h
　はんだとして、Ｓｎ－３％Ａｇ－０.５％ＣｕのＰｂレスはんだを用意し、はんだ濡れ性試験機を用いてＪＩＳ Ｃ６００６８－２－５４に規定されるはんだ槽平衡法によりゼロクロスタイムを測定した。はんだ浴温は２５５℃とし、フラックスとして一般電子部品用の塩素なしフラックスを使用した。ゼロクロスタイムが初期試料において２.０ｓｅｃ以下であり、上記加速エージング後の試料において４.０ｓｅｃ以下であるものは、種々の電子部品用途において実用的な良好なはんだ濡れ性を有すると評価される。また、ゼロクロスタイムが初期試料において１.０ｓｅｃ以下であり、上記加速エージング後の試料において３.０ｓｅｃ以下であるものは、特に優秀なはんだ濡れ性を有すると評価される。そこで試験数ｎ＝５で試験を行い、５個の試料のうち最も大きい値となったゼロクロスタイム値をその試料の成績値として採用し、以下の基準ではんだ濡れ性を判定し、○評価以上を合格とした。
・初期試料
　◎：ゼロクロスタイム成績値が１.０ｓｅｃ以下
　○：ゼロクロスタイム成績値が１.０ｓｅｃを超え～２.０ｓｅｃ以下
　×：ゼロクロスタイム成績値が２.０ｓｅｃを超える
・加速エージング後の試料
　◎：ゼロクロスタイム成績値が３.０ｓｅｃ以下
　○：ゼロクロスタイム成績値が３.０ｓｅｃを超え～４.０ｓｅｃ以下
　×：ゼロクロスタイム成績値が４.０ｓｅｃを超える
　これらの結果を表２（Ａ鋼）、表３（Ｂ鋼）、表４（Ｃ鋼）に示す。 A Sn-3% Ag-0.5% Cu Pb-less solder was prepared as the solder, and the zero cross time was measured by a solder bath equilibrium method defined in JIS C60068-2-54 using a solder wettability tester. . The solder bath temperature was 255 ° C., and a chlorine-free flux for general electronic parts was used as the flux. A sample having a zero cross time of 2.0 sec or less in the initial sample and 4.0 sec or less in the sample after the accelerated aging is evaluated as having good solder wettability practical for various electronic component applications. Further, a sample having a zero crossing time of 1.0 sec or less in the initial sample and 3.0 sec or less in the sample after the accelerated aging is evaluated as having particularly excellent solder wettability. Therefore, the test was performed with the number of tests n = 5, and the zero cross time value, which was the largest value among the five samples, was adopted as the result value of the sample, and the solder wettability was judged according to the following criteria. Was passed.
・ Initial sample ◎: Zero cross time performance value is 1.0 sec or less ○: Zero cross time performance value exceeds 1.0 sec to 2.0 sec or less ×: Zero cross time performance value exceeds 2.0 sec ・ Sample after accelerated aging ◎ : Zero cross time performance value is 3.0 sec or less. ○: Zero cross time performance value exceeds 3.0 sec to 4.0 sec or less. X: Zero cross time performance value exceeds 4.0 sec. Table 2 (Steel A) It shows in Table 3 (B steel) and Table 4 (C steel).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表２～表４に示されるように、カソード電解処理後に水洗を行わないか溶存酸素量が４ｍｇ／Ｌ以下である水洗水で水洗し、その後、鋼板表面が液で濡れたままその鋼板をＳｎめっき液に浸漬しＳｎめっきを施した本発明例のものは、Ｓｎめっき浴に導入する直前において上述のＸＰＳ分析によって求まるＦｅとＣｒの金属成分の和が２８.０原子％以上となる表面性状を有しており、めっき密着性およびはんだ濡れ性がともに合格評価であった。なお、Ｎｏ.１９、４９、７９はリフロー処理を省略したものであるが、Ｓｎめっき層の平均厚さを０.３μｍ以下に薄くしたことにより、ウイスカの生成が顕著に抑制されることが別途確認された。 As shown in Tables 2 to 4, the cathode steel plate was not washed after the cathode electrolysis treatment, or washed with washing water having a dissolved oxygen amount of 4 mg / L or less. In the example of the present invention, which was immersed in a plating solution and subjected to Sn plating, the surface property in which the sum of the metal components of Fe and Cr obtained by the XPS analysis described above immediately before being introduced into the Sn plating bath is 28.0 atomic% or more. Both plating adhesion and solder wettability were evaluated as acceptable. Nos. 19, 49, and 79 are omitted from the reflow process, but it is separately possible that the generation of whiskers is remarkably suppressed by reducing the average thickness of the Sn plating layer to 0.3 μm or less. confirmed.
　これに対し、比較例Ｎｏ.１、３１、６１はカソード電解を行わなかったことにより良好な密着性が得られなかった。Ｎｏ.２、３、３２、３３、６２、６３はカソード電解処理後、Ｓｎめっき液浸漬前の段階で鋼板表面が乾燥したことによりＦｅとＣｒの金属成分の和が２８.０原子％以上となる表面性状が得られず、めっき密着性に劣った。Ｎｏ.１６～１８、４６～４８、７６～７８はカソード電解処理後に溶存酸素の多い水洗水との接触を受けたことによりＦｅとＣｒの金属成分の和が２８.０原子％以上となる表面性状が得られず、めっき密着性に劣った。Ｎｉストライクめっきを施したＮｏ.２８、５８、８８はＳｎめっき層厚さが０.１μｍと薄かったことから加速エージングによってＳｎめっき層のほとんど全部がＮｉとの金属間化合物に変化してしまい、はんだが濡れなかった。なお、Ｎｏ.２９、５９、８９はめっき密着性およびはんだ濡れ性に優れる従来一般的なＳｎめっきステンレス鋼板であるが、Ｎｉアレルギーを引き起こす要因を有している。 In contrast, Comparative Examples No. 1, 31, and 61 did not perform cathode electrolysis, so that good adhesion could not be obtained. Nos. 2, 3, 32, 33, 62, and 63 had a sum of the metal components of Fe and Cr of 28.0 atomic% or more because the steel plate surface was dried after the cathode electrolytic treatment and before the immersion of the Sn plating solution. Thus, the surface properties were not obtained, and the plating adhesion was poor. Nos. 16-18, 46-48, 76-78 are surfaces whose sum of the metal components of Fe and Cr is 28.0 atomic% or more due to contact with washing water containing a large amount of dissolved oxygen after cathodic electrolysis. No properties were obtained and the plating adhesion was poor. No. 28, 58 and 88 subjected to Ni strike plating had a Sn plating layer thickness as thin as 0.1 μm, so almost all of the Sn plating layer was changed to an intermetallic compound with Ni by accelerated aging. The solder did not get wet. Nos. 29, 59, and 89 are conventional and general Sn-plated stainless steel plates that are excellent in plating adhesion and solder wettability, but have factors that cause Ni allergy.
《実施例２》
　表１に示した鋼Ａ、Ｂ、Ｃ（板厚は表１中に記載）のステンレス鋼板を用いて、下記の２通りの工程パターンにてＳｎめっき鋼板を作製した。
　パターン１：カソード電解処理→（気相空間）→電気Ｓｎめっき
　パターン２：カソード電解処理→（気相空間）→水洗→（気相空間）→電気Ｓｎめっき Example 2
Using a stainless steel plate of steels A, B, and C (plate thickness is described in Table 1) shown in Table 1, Sn-plated steel plates were produced in the following two process patterns.
Pattern 1: Cathodic electrolytic treatment → (vapor phase space) → Electric Sn plating Pattern 2: Cathodic electrolytic treatment → (vapor phase space) → Washing → (Vapor phase space) → Electric Sn plating
　カソード電解処理は、５質量％濃度の硫酸水溶液からなる電解処理液にステンレス鋼板を浸漬し、電流密度１０Ａ／ｄｍ2、通電時間５秒（通電量５０Ｃ／ｄｍ2）の条件で行った。電解処理液の温度は種々変動させた。カソード電解処理後に気相空間に出たときのステンレス鋼板表面温度を正確に設定するために、電解処理液にステンレス鋼板を１０分間浸漬し、その後カソード電解を施した。１０分間の浸漬により気相空間に出たときのステンレス鋼板表面温度は電解処理液の温度と等しくなることを別途実験により確認してある。なお、通電時間が５秒と短いため、通電による板温の上昇は無視できる。 The cathode electrolytic treatment was performed under the conditions of a stainless steel plate immersed in an electrolytic treatment solution made of a sulfuric acid aqueous solution having a concentration of 5% by mass, a current density of 10 A / dm 2 , and an energization time of 5 seconds (energization amount 50 C / dm 2 ). The temperature of the electrolytic treatment solution was varied. In order to accurately set the surface temperature of the stainless steel plate when it entered the gas phase space after the cathode electrolytic treatment, the stainless steel plate was immersed in the electrolytic treatment solution for 10 minutes, and then cathode electrolysis was performed. It has been confirmed by a separate experiment that the surface temperature of the stainless steel plate when it enters the gas phase space by immersion for 10 minutes is equal to the temperature of the electrolytic treatment solution. In addition, since energization time is as short as 5 seconds, the rise in plate temperature due to energization can be ignored.
　パターン２における水洗は、水中に窒素を吹き込むことにより溶存酸素濃度を２～３ｍｇ／Ｌとした水洗水にステンレス鋼板を浸漬する方法にて行った。水洗水の温度は種々変動させた。ここでは水洗後に気相空間に出たときのステンレス鋼板表面温度を正確に設定するために、水洗水にステンレス鋼板を１０分間浸漬した。１０分間の浸漬により気相空間に出たときのステンレス鋼板表面温度は水洗水の温度と等しくなることを別途実験により確認してある。 Washing with water in pattern 2 was performed by immersing the stainless steel plate in flushing water with a dissolved oxygen concentration of 2 to 3 mg / L by blowing nitrogen into the water. The temperature of the washing water was varied. Here, in order to accurately set the surface temperature of the stainless steel plate when it comes into the gas phase space after washing with water, the stainless steel plate was immersed in washing water for 10 minutes. It has been confirmed by a separate experiment that the surface temperature of the stainless steel plate when it enters the gas phase space by immersion for 10 minutes is equal to the temperature of the washing water.
　電気Ｓｎめっき条件は、電流密度を１０Ａ／ｄｍ2と一定にしたことを除き、実施例１と同様とした。片面当たりのＳｎめっき厚さは０.５μｍである。Ｓｎめっき後にはリフロー処理を施していない。
　グローブボックス内にカソード電解処理槽、水洗槽、電気Ｓｎめっき槽を配置し、気相空間の雰囲気は常温大気または常温窒素とした。上記パターン１、２において各気相空間滞在時間を変化させ、表面が液で濡れたままの状態を維持しているか乾燥している部分があるかを観察した。そして、得られたＳｎめっき鋼板について、実施例１と同様の手法でめっき密着性を評価した。結果を表５、表６に示す。表５、表６中の水洗に関するハイフン表示は水洗を行わなかったこと（パターン１）を意味する。 The electrical Sn plating conditions were the same as in Example 1 except that the current density was kept constant at 10 A / dm 2 . The Sn plating thickness per side is 0.5 μm. No reflow treatment was applied after Sn plating.
A cathode electrolytic treatment tank, a rinsing tank, and an electric Sn plating tank were disposed in the glove box, and the atmosphere of the gas phase space was room temperature air or room temperature nitrogen. In each of the patterns 1 and 2, the residence time of each gas phase space was changed, and it was observed whether the surface was kept wet with the liquid or whether there was a dry part. And about the obtained Sn plating steel plate, the plating adhesiveness was evaluated by the method similar to Example 1. FIG. The results are shown in Tables 5 and 6. The hyphen display relating to washing in Tables 5 and 6 means that no washing was performed (Pattern 1).
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表５のＮｏ.１０１～１１４は水洗なしの工程（パターン１）において気相空間を大気としたものである。図１に、液中から気相空間に出たときのステンレス鋼板表面温度（℃）を横軸、次工程の液中に浸漬するまでの気相空間滞在時間（ｓｅｃ）を縦軸とする直交座標系のグラフを示す。図１中にはＮｏ.１０１～１１４の条件に相当するプロットを○印または●印で例示してある。この場合、横軸はカソード電解処理後にステンレス鋼板が気相空間に出たときの当該ステンレス鋼板表面温度（℃）に相当し、縦軸はカソード電解処理後電気Ｓｎめっき液に浸漬するまでの気相空間滞在時間（ｓｅｃ）に相当する。○印は、当該気相空間滞在中に鋼板表面が濡れた状態を維持し、めっき密着性が良好であった本発明例（Ｎｏ.１０１～１０８）である。●印は、当該気相空間滞在中に鋼板表面が濡れた状態を維持できず乾燥した部分があり、めっき密着性が不良であった比較例（Ｎｏ.１０９～１１４）である。図１のＡ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（境界を含む）に属する条件を採用することにより、濡れた状態が維持され、良好なめっき密着性が得られた。 Nos. 101 to 114 in Table 5 are those in which the gas phase space was made atmospheric in the process without water washing (pattern 1). In FIG. 1, the surface temperature (° C.) of the stainless steel plate when it exits from the liquid into the gas phase space is plotted on the horizontal axis, and the gas phase space residence time (sec) until dipping in the liquid of the next process is plotted on the vertical axis. A graph of the coordinate system is shown. In FIG. 1, the plots corresponding to the conditions of Nos. 101 to 114 are illustrated by circle marks or circle marks. In this case, the horizontal axis corresponds to the surface temperature (° C.) of the stainless steel plate when the stainless steel plate comes out into the gas phase space after the cathode electrolytic treatment, and the vertical axis represents the time until the stainless steel plate is immersed in the electric Sn plating solution after the cathode electrolytic treatment. This corresponds to the phase space residence time (sec). O marks indicate examples of the present invention (Nos. 101 to 108) in which the steel sheet surface was kept wet while staying in the gas phase space and the plating adhesion was good. The ● marks indicate comparative examples (Nos. 109 to 114) in which the steel sheet surface cannot be kept wet during the stay in the gas phase space, and there is a dry portion, and the plating adhesion is poor. Adopting the conditions belonging to the region (including the boundary) surrounded by the straight line connecting ABCDEFA in FIG. 1, the wet state is maintained and good plating adhesion was gotten.
　表５のＮｏ.１１５～１３４は水洗ありの工程（パターン２）において気相空間を大気としたものである。このうちＮｏ.１１５～１２２の本発明例は、カソード電解処理後水洗前の気相空間、および水洗後電気Ｓｎめっき前の気相空間において、いずれも「液中から出たときの表面温度と気相空間滞在時間の関係」が図１のＡ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（境界を含む）に属する条件を採用したものであり、良好なめっき密着性が得られた。一方、Ｎｏ.１２３～１２８の比較例はカソード電解処理後水洗前の気相空間における条件が、またＮｏ.１２９～１３４の比較例は水洗後電気Ｓｎめっき前の気相空間における条件がそれぞれ図１のＡ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域から外れため、工程の途中で表面が濡れた状態を維持できない事態が生じた。その結果、めっき密着性に劣った。 Nos. 115 to 134 in Table 5 are those in which the gas phase space was made atmospheric in the process with water washing (pattern 2). Of these, the examples of the present invention of Nos. 115 to 122 are both “in the gas phase space after the cathode electrolytic treatment and before the water washing, and in the gas phase space after the water washing and before the electric Sn plating” The relationship between the residence time of the gas phase space is a condition that belongs to the region (including the boundary) surrounded by the straight line connecting ABCDE in FIG. Plating adhesion was obtained. On the other hand, the comparative examples No. 123 to 128 show the conditions in the gas phase space after the cathode electrolytic treatment and before the water washing, and the comparative examples No. 129 to 134 show the conditions in the gas phase space after the water washing and before the electric Sn plating. Since the region deviated from the area surrounded by the straight line connecting ABCDE 1 to FA, the surface could not be kept wet during the process. As a result, the plating adhesion was poor.
　表６のＮｏ.２０１～２０９は水洗なしの工程（パターン１）において気相空間を窒素としたもの、Ｎｏ.２１０～２２２は水洗ありの工程（パターン２）において気相空間を窒素としたものである。図１のＡ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域から外れる条件で気相空間に滞在させた比較例のものは、表面が濡れた状態を維持しきれなかったことにより、気相空間を窒素としたにもかかわらず、良好なＳｎめっき密着性が得られなかった。 Nos. 201 to 209 in Table 6 are those in which the gas phase space is nitrogen in the process without water washing (Pattern 1), and Nos. 210 to 222 are those in which the gas phase space is nitrogen in the process with water washing (Pattern 2). It is. In the comparative example in which the gas phase space stays in a condition deviating from the area surrounded by the straight line connecting ABCDE in FIG. 1, the surface is kept wet. Due to the absence, good Sn plating adhesion could not be obtained even though the gas phase space was nitrogen.

Claims (9)

  1. 　カソード電解処理され、その後に前記電解処理の液で濡れた状態を維持して乾燥状態での大気接触を受けていないステンレス鋼板の表面上に、下地めっき層を介することなく厚さ０.１～１.５μｍのＳｎめっき層を形成してなる、めっき密着性の良好なＳｎめっきステンレス鋼板。 On the surface of a stainless steel plate that has been subjected to cathodic electrolysis and then kept wet with the electrolysis solution and has not been subjected to atmospheric contact in a dry state, a thickness of 0.1 to A Sn-plated stainless steel sheet having a good plating adhesion, formed by forming a 1.5 μm Sn-plated layer.
  2. 　カソード電解処理および溶存酸素量４ｍｇ／Ｌ以下の水への浸漬を経ることにより、カソード電解処理後に液で濡れた状態を維持して乾燥状態での大気接触を受けていないステンレス鋼板の表面上に、下地めっき層を介することなく厚さ０.１～１.５μｍのＳｎめっき層を形成してなる、めっき密着性の良好なＳｎめっきステンレス鋼板。 On the surface of the stainless steel plate that has been subjected to cathodic electrolysis and immersion in water having an amount of dissolved oxygen of 4 mg / L or less so that it remains wet with the liquid after cathodic electrolysis and has not been exposed to atmospheric contact in the dry state. A Sn-plated stainless steel plate having good plating adhesion, formed by forming a Sn plating layer having a thickness of 0.1 to 1.5 μm without interposing a base plating layer.
  3. 　カソード電解処理されたのち、表面がその電解処理の液で濡れた状態を維持して下記（Ａ）に示す表面性状を有するステンレス鋼板の表面上に、下地めっき層を介することなく厚さ０.１～１.５μｍのＳｎめっき層を形成してなる、めっき密着性の良好なＳｎめっきステンレス鋼板。
    　（Ａ）当該液で濡れた表面を空気乾燥させたのちＸ線光電子分光法（ＸＰＳ）により最表面の分析を行った場合、Ｆｅ原子数とＣｒ原子数の合計に占める金属Ｆｅとして存在するＦｅ原子数と金属Ｃｒとして存在するＣｒ原子数の和が２８.０％以上となる表面性状     After the cathodic electrolysis treatment, the surface remains wet with the electrolysis solution, and the thickness of the surface of the stainless steel plate having the surface properties shown in the following (A) is 0. A Sn-plated stainless steel sheet having a good plating adhesion formed by forming a Sn plating layer of 1 to 1.5 μm.
    (A) When the outermost surface is analyzed by X-ray photoelectron spectroscopy (XPS) after the surface wetted with the liquid is air-dried, Fe present as metal Fe in the total number of Fe atoms and Cr atoms Surface properties where the sum of the number of atoms and the number of Cr atoms present as metallic Cr is 28.0% or more
  4. 　カソード電解処理および水洗を経て、表面が水洗の液で濡れた状態を維持して下記（Ａ）に示す表面性状を有するステンレス鋼板の表面上に、下地めっき層を介することなく厚さ０.１～１.５μｍのＳｎめっき層を形成してなる、めっき密着性の良好なＳｎめっきステンレス鋼板。
    　（Ａ）当該液で濡れた表面を空気乾燥させたのちＸ線光電子分光法（ＸＰＳ）により最表面の分析を行った場合、Ｆｅ原子数とＣｒ原子数の合計に占める金属Ｆｅとして存在するＦｅ原子数と金属Ｃｒとして存在するＣｒ原子数の和が２８.０％以上となる表面性状     After the cathode electrolytic treatment and water washing, the surface is kept wet with the water washing liquid, and the thickness is 0.1 on the surface of the stainless steel plate having the surface properties shown in (A) below without interposing the undercoat layer. A Sn-plated stainless steel sheet having a good plating adhesion formed by forming a 1.5-μm Sn plating layer.
    (A) When the outermost surface is analyzed by X-ray photoelectron spectroscopy (XPS) after the surface wetted with the liquid is air-dried, Fe present as metal Fe in the total number of Fe atoms and Cr atoms Surface properties where the sum of the number of atoms and the number of Cr atoms present as metallic Cr is 28.0% or more
  5. 　ステンレス鋼板に硫酸濃度１～３０質量％の硫酸水溶液中で通電量５０Ｃ／ｄｍ2以上のカソード電解処理を施す工程、
    　前記カソード電解処理後にステンレス鋼板表面が前記硫酸水溶液で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬し、片面当たりの平均膜厚が０.１～１.５μｍのＳｎめっき層を形成する工程、
    を有するめっき密着性の良好なＳｎめっきステンレス鋼板の製造法。     A step of subjecting a stainless steel plate to a cathodic electrolysis treatment with a current of 50 C / dm 2 or more in a sulfuric acid aqueous solution having a sulfuric acid concentration of 1 to 30 mass%
    After the cathode electrolytic treatment, the stainless steel plate is dipped in an electric Sn plating solution with the surface of the stainless steel plate wet with the sulfuric acid aqueous solution to form an Sn plating layer having an average film thickness of 0.1 to 1.5 μm per side. The process of
    A method for producing a Sn-plated stainless steel sheet having good plating adhesion.
  6. 　ステンレス鋼板に硫酸濃度１～３０質量％の硫酸水溶液中で通電量５０Ｃ／ｄｍ2以上のカソード電解処理を施す工程、
    　前記カソード電解処理後に、下記（ａ）の条件を満たすように気相空間滞在時間をコントロールすることにより、ステンレス鋼板表面が前記硫酸水溶液で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬し、片面当たりの平均膜厚が０.１～１.５μｍのＳｎめっき層を形成する工程、
    を有するめっき密着性の良好なＳｎめっきステンレス鋼板の製造法。
    　（ａ）カソード電解処理後に気相空間に出たときのステンレス鋼板表面温度（℃）を横軸、カソード電解処理後電気Ｓｎめっき液に浸漬するまでの気相空間滞在時間（ｓｅｃ）を縦軸とする図１の直交座標系において、Ａ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（直線ＦＡ上を除き境界を含む）に属する条件。     A step of subjecting a stainless steel plate to a cathodic electrolysis treatment with a current of 50 C / dm 2 or more in a sulfuric acid aqueous solution having a sulfuric acid concentration of 1 to 30 mass%
    After the cathode electrolytic treatment, the stainless steel plate is immersed in the electric Sn plating solution while the surface of the stainless steel plate is wet with the sulfuric acid aqueous solution by controlling the gas phase space residence time so as to satisfy the following condition (a). A step of forming a Sn plating layer having an average film thickness of 0.1 to 1.5 μm per side;
    A method for producing a Sn-plated stainless steel sheet having good plating adhesion.
    (A) The stainless steel plate surface temperature (° C.) when entering the gas phase space after the cathode electrolysis treatment is plotted on the horizontal axis, and the gas phase space residence time (sec) until being immersed in the electric Sn plating solution after the cathode electrolysis treatment is plotted on the vertical axis. In the Cartesian coordinate system of FIG. 1, a condition belonging to a region (including a boundary except on the straight line FA) surrounded by a straight line connecting ABCDFEFA.
  7. 　ステンレス鋼板に硫酸濃度１～３０質量％の硫酸水溶液中で通電量５０Ｃ／ｄｍ2以上のカソード電解処理を施す工程、
    　前記カソード電解処理後にステンレス鋼板表面が前記硫酸水溶液で濡れている状態で当該ステンレス鋼板を溶存酸素量４ｍｇ／Ｌ以下の水に浸漬して水洗する工程、
    　前記水洗後のステンレス鋼板表面が前記水洗の水で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬し、片面当たりの平均膜厚が０.１～１.５μｍのＳｎめっき層を形成する工程、
    を有するめっき密着性の良好なＳｎめっきステンレス鋼板の製造法。     A step of subjecting a stainless steel plate to a cathodic electrolysis treatment with a current of 50 C / dm 2 or more in a sulfuric acid aqueous solution having a sulfuric acid concentration of 1 to 30 mass%
    A step of immersing the stainless steel plate in water having a dissolved oxygen content of 4 mg / L or less and washing with water in a state where the surface of the stainless steel plate is wet with the sulfuric acid aqueous solution after the cathode electrolytic treatment;
    The stainless steel plate is dipped in an electric Sn plating solution with the surface of the washed stainless steel plate wet with the washing water to form an Sn plating layer with an average film thickness of 0.1 to 1.5 μm per side. The process of
    A method for producing a Sn-plated stainless steel sheet having good plating adhesion.
  8. 　ステンレス鋼板に硫酸濃度１～３０質量％の硫酸水溶液中で通電量５０Ｃ／ｄｍ2以上のカソード電解処理を施す工程、
    　前記カソード電解処理後に、下記（ｂ）の条件を満たすように気相空間滞在時間をコントロールすることにより、ステンレス鋼板表面が前記硫酸水溶液で濡れている状態で当該ステンレス鋼板を溶存酸素量４ｍｇ／Ｌ以下の水に浸漬して水洗する工程、
    　前記水洗後に、下記（ｃ）の条件を満たすように気相空間滞在時間をコントロールすることにより、ステンレス鋼板表面が前記水洗の水で濡れている状態で当該ステンレス鋼板を電気Ｓｎめっき液に浸漬し、片面当たりの平均膜厚が０.１～１.５μｍのＳｎめっき層を形成する工程、
    を有するめっき密着性の良好なＳｎめっきステンレス鋼板の製造法。
    　（ｂ）カソード電解処理後に気相空間に出たときのステンレス鋼板表面温度（℃）を横軸、カソード電解処理後水洗水に浸漬するまでの気相空間滞在時間（ｓｅｃ）を縦軸とする図１の直交座標系において、Ａ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（直線ＦＡ上を除き境界を含む）に属する条件。
    　（ｃ）水洗後に気相空間に出たときのステンレス鋼板表面温度（℃）を横軸、水洗後電気Ｓｎめっき液に浸漬するまでの気相空間滞在時間（ｓｅｃ）を縦軸とする図１の直交座標系において、Ａ－Ｂ－Ｃ－Ｄ－Ｅ－Ｆ－Ａを結ぶ直線に囲まれた領域（直線ＦＡ上を除き境界を含む）に属する条件。     A step of subjecting a stainless steel plate to a cathodic electrolysis treatment with a current of 50 C / dm 2 or more in a sulfuric acid aqueous solution having a sulfuric acid concentration of 1 to 30 mass%
    After the cathode electrolytic treatment, by controlling the residence time in the gas phase so as to satisfy the following condition (b), the stainless steel plate is dissolved in the sulfuric acid aqueous solution so that the stainless steel plate has a dissolved oxygen amount of 4 mg / L. A step of immersing in the following water and washing with water,
    After the rinsing, by controlling the residence time in the gas phase so as to satisfy the following condition (c), the stainless steel plate is immersed in the electric Sn plating solution while the surface of the stainless steel plate is wet with the water of the rinsing. Forming a Sn plating layer having an average film thickness of 0.1 to 1.5 μm per side;
    A method for producing a Sn-plated stainless steel sheet having good plating adhesion.
    (B) The stainless steel plate surface temperature (° C.) when entering the gas phase space after the cathode electrolysis treatment is taken as the horizontal axis, and the gas phase space residence time (sec) until being immersed in washing water after the cathode electrolysis treatment is taken as the vertical axis. In the Cartesian coordinate system of FIG. 1, conditions that belong to a region (including a boundary except on the straight line FA) surrounded by a straight line connecting ABCDEFFA.
    (C) Stainless steel plate surface temperature (° C.) when exiting into the gas phase space after washing with water, and the vertical axis representing the residence time (sec) in the gas phase space until immersing in the electric Sn plating solution after washing with water. In the Cartesian coordinate system, a condition belonging to an area (including a boundary except for the straight line FA) surrounded by a straight line connecting ABCDEFFA.
  9. 　さらに、前記Ｓｎめっき層を形成する工程の後に、
    　めっき後のステンレス鋼板を２５０～３５０℃に加熱したのち冷却してＳｎめっき層を溶融・凝固させる処理（リフロー処理）を施す工程、
    を有する請求項５～８のいずれかに記載のめっき密着性の良好なＳｎめっきステンレス鋼板の製造法。     Furthermore, after the step of forming the Sn plating layer,
    A process of heating the plated stainless steel sheet to 250 to 350 ° C. and then cooling to melt and solidify the Sn plating layer (reflow process);
    The method for producing a Sn-plated stainless steel sheet having good plating adhesion according to any one of claims 5 to 8.
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JP6016988B1 (en) * 2015-05-29 2016-10-26 日新製鋼株式会社 Stainless steel foil for battery exterior and manufacturing method thereof
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