Technical field
[0001]
　The present disclosure relates to a Sn-based alloy plated steel sheet.
BACKGROUND
[0002]
　Sn (tin) alloy plated steel sheet, as a container for steel, such as beverage cans and food cans, are widely used. This is because Sn is safe to the human body, and a beautiful metallic. The Sn-based alloy plated steel sheet, in order to suppress and ensure adhesion and corrosion resistance of the steel sheet and the coating film, appearance change due to the tin oxide growth during storage prior to painting (yellowing), hexavalent chromate of solution by chromate treatment, such as electrolytic treatment or the immersion treatment using, chromate film on the Sn-based alloy plated layer is often subjected.
[0003]
　On the other hand, in recent years, from growing awareness of the environment and safety, not only does not contain hexavalent chromium in the final product, it is required not to perform chromate treatment itself. However, Sn-based alloy plated steel sheet has no chromate film, as described above, the appearance by the growth of tin oxide yellowing or paint adhesion is lowered.
[0004]
　Therefore, Sn-plated steel sheet or an Sn-based alloy plated steel sheet was a film processing to replace the chromate film have been proposed.
[0005]
　For example, Patent Document 1 below, by treatment with a solution containing a phosphoric acid ion and a silane coupling agent, Sn-plated steel sheet has been proposed to form a film containing P and Si.
　Patent Document 2 below, by treatment with a solution containing aluminum phosphate, Al and P, Ni, and at least one Co and Cu, to form a coating comprising the reaction product of a silane coupling agent Sn-based alloy plated steel sheet has been proposed.
　Patent Document 3 below, subjected to heat treatment to Zn alone plated layer disappears after the Zn plated on Sn plating layer, the production method of the Sn-plated steel sheet having no chromate film have been proposed.
　Patent Document 4 and Patent Document 5 below, zirconium, phosphate, Sn-based alloy plated steel sheet having a chemical conversion film containing phenol resin (container steel plate) has been proposed.
　In the following Patent Document 6, a Sn plating layer, after Sn plating layer formed, in a phosphate aqueous solution, cathodic electrolysis treatment and then formed by performing an anodic electrolysis treatment, chemical conversion comprising tin oxide and tin phosphate Sn-plated steel sheet or an Sn-based alloy plated steel sheet having a treatment layer (container steel plate) has been proposed.
　In the following Patent Document 7, tin oxide, and, Zr, Sn-plated steel sheet or an Sn-based alloy plated steel sheet with a coating containing Ti and P (container steel plate) has been proposed. Patent Document 6, when forming a film, it is proposed to be carried out alternating electrolysis performed alternately a cathode electrolytic treatment and anodic electrolysis.
　In the following Patent Document 8, Sn-plated steel sheet or an Sn-based alloy plated steel sheet having Zr and Si (container steel plate) has been proposed. Patent Document 8, when forming a film, it is proposed to be carried out alternating electrolysis performed alternately a cathode electrolytic treatment and anodic electrolysis.
[0006]
Patent Document 1: JP 2004-60052 JP
Patent Document 2: JP 2011-174172 Patent Publication
Patent Document 3: JP 63-290292 Patent Publication
Patent Document 4: JP 2007-284789 Patent Publication
Patent Document 5: JP open 2010-13728 JP
Patent Document 6: JP 2009-249691 Patent Publication
Patent Document 7: WO 2015/001598 Patent
Patent Document 8: JP 2014-88587 JP
[0007]
Non-Patent Document 1: Surface Science Society of Japan, ed., "Surface analytical chemistry book selection X-ray photoelectron spectroscopy", Maruzen Co., Ltd., P. 83
Summary of the Invention
Problems that the Invention is to Solve
[0008]
　However, the Sn-based alloy plated steel sheet and a manufacturing method proposed in the above Patent Documents 1 to 8, can not be sufficiently suppressed the growth of tin oxide over time, yellowing resistance, coating adhesion and, there is a problem of poor sulfidation blackening.
[0009]
　The present disclosure has been made in view of the above problems, without the conventional chromate treatment, yellowing resistance, paint adhesion, and, the more excellent Sn-based alloy plated steel sheet by sulfidation blackening It is to provide.
Means for Solving the Problems
[0010]
　The means for solving the above problems includes the following aspects.
[0011]
(1) and the steel plate,
　is formed on at least one surface of said steel sheet, a Fe-Ni-Sn alloy layer, and a composite plating layer having a island Sn layer located on the Fe-Ni-Sn alloy layer,
　the formed on the surface of the composite plating layer, and the film layer containing the zirconium oxide and tin oxide,
　have,
　the composite plating layer, by mass%, the metal Ni equivalent amount 2 mg / m 2 or more 200 mg / m 2 and following Ni, 0.1 g / m as the metal Sn terms of the amount of 2 or more 10 g / m 2 containing the following Sn,
　the content of the zirconium oxide in the coating layer is 0 in the metal Zr content .2Mg / m 2 or more 50 mg / m 2 or less, Sn3d
　by X-ray photoelectron spectroscopy of the tin oxide in the coating layer 5/2 peak position of the binding energy of the peak position of the binding energy of metals Sn Remote 1.6eV or more large, Sn-based alloy plated steel sheet.
(2) thickness of the coating layer is at 2nm or 100nm or less, Sn-based alloy plated steel sheet according to (1).
(3) the coating layer, the mass ratio per unit area, P amount / metal Zr content further contains phosphorus of 0.2 to 1., Sn-based alloy according to (1) or (2) plated steel sheet.
Effect of the invention
[0012]
　According to the present disclosure described above, without performing conventional chromate treatment, yellowing resistance, paint adhesion, and, it is possible to provide a further excellent Sn-based alloy plated steel sheet by sulfidation blackening Become.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
FIG. 1 is a diagram of an example of an element concentration profile in the thickness direction of the composite plating layer and film layer of the Sn-based composite-plated steel sheet of the present disclosure (the depth direction).
DESCRIPTION OF THE INVENTION
[0014]
　It is described in detail below the present disclosure.
　In the present specification, the numerical range expressed using "to" means a range including numerical values described before and after "to" as the lower and upper limits.
　As used herein, the term "process" not only separate steps, if even that can not be clearly distinguished from other processes intended purpose of the process is achieved, the term include.
　As used herein, the term "steel sheet" refers to a base steel of the object to form a composite plating layer and coating layer (so-called plated original plate).
[0015]
　The present disclosure described below, food cans, and widely container steel sheet used for cans applications other such beverage cans, a manufacturing method of a container for steel. More specifically, without performing the conventional chromate treatment, yellowing resistance, coating adhesion, a process for producing a more excellent Sn-based alloy plated steel sheet and Sn-based alloy plated steel sheet by sulfidation blackening.
[0016]
　Specifically, Sn-based alloy plated steel sheet of the present disclosure, the steel sheet and, formed on at least one surface of the steel sheet, Fe-Ni-Sn alloy layer and the island is located in the Fe-Ni-Sn alloy layer a composite plated layer having a Sn layer is formed on the surface of the Sn-based alloy plated layer has a coating layer containing the zirconium oxide and tin oxide, a.
[0017]
　More specifically, in Sn-based alloy plated steel sheet of the present disclosure, the composite plating layer, by mass%, 2 mg / m as a metal Ni equivalent amount 2 or more 200 mg / m 2 0 and less Ni, metal Sn in terms of quantity. 1 g / m 2 or more 10 g / m 2 and less Sn, containing.
　The content of zirconium oxide in the coating layer is, 0.2 mg / m of a metal Zr content 2 or 50 mg / m 2 or less.
　Sn3d by X-ray photoelectron spectroscopy of the tin oxide in the coating layer 5/2 peak position of the binding energy is greater than 1.6eV than the peak position of the binding energy of metals Sn.
[0018]

　steel sheet, it is not particularly defined, as long as the steel sheet used in the general Sn-based alloy plated steel sheet, it is possible to use an arbitrary one. Steel sheet, for example, low carbon steel, and the like ultra low carbon steel. Further, using the manufacturing method and material of the steel sheet not particularly defined, for example, hot rolling the casting, pickling, cold rolling, annealing, be mentioned steel sheet manufactured through the process of temper rolling or the like can.
[0019]

　at least one surface of the steel sheet, a composite plated layer (hereinafter, simply referred to as "composite plating layer") is formed. The composite plating layer per surface 2 mg / m as a metal Ni equivalent amount 2 200 mg / m or more 2 and less Ni, per side 0.1 g / m as the metal Sn terms of the amount of 2 or more 10 g / m 2 and less Sn, and Fe-Ni-Sn alloy layer containing, and island-like Sn located Fe-Ni-Sn alloy layer, and a.
　Incidentally, Fe-Ni-Sn alloy layer, and a portion of some or all Ni Sn is formed by alloying with molten heat treatment.
[0020]
[Fe-Ni-Sn alloy
　layer] Fe-Ni-Sn alloy layer has the effect of improving the corrosion resistance. This is because the Ni and Sn is electrochemically metal nobler than iron to form an alloy layer with Fe, due to possible to improve corrosion resistance of Fe itself.
[0021]
　Here, the effect of improving corrosion resistance by Ni is determined by the amount of Ni in the composite plating layer. Then, the amount of Ni in the composite plating layer can be adjusted by the amount of Ni in the Ni plating layer or Fe-Ni plating layer to form the composite plating layer.
　The amount of Ni is, per side 2 mg / m as a metal Ni equivalent amount 2 equal to or more than the effect of corrosion resistance is exhibited. The effect of improving corrosion resistance as the amount of Ni is large to increase. On the other hand, the amount of Ni is, per side 200 mg / m as a metal Ni equivalent amount 2 the effect of improvement of the corrosion resistance when the excess is saturated and also economically undesirable to increase more than that. Also, poor sulfidation blackening. Therefore, the amount of Ni is per side 2 mg / m as a metal Ni equivalent amount 2 or more 200 mg / m 2 or less. The amount of Ni is more preferably, 2 mg / m per one side as a metallic Ni equivalent amount 2 or more 180 mg / m 2 or less.
[0022]
[Island Sn layer]
　Fe-Ni-Sn island Sn layer formed on the alloy layer has the effect of improving the corrosion resistance and paint adherence. Sn is under atmospheric corrosion environment is a metal nobler than iron, preventing corrosion of Fe as a barrier-type film. On the other hand, Sn is an acidic corrosive environment, such as acidic beverage cans, and sacrificial protection of iron, it improves the corrosion resistance. Further, since the Sn layer is present in an island shape, the anchor effect, and, by the growth inhibiting effect of the tin oxide due to the presence of Fe-Ni-Sn alloy layer which corresponds to the sea, to improve the coating adhesion. Further, since the growth of tin oxide is suppressed, there is yellowing suppressing effect.
　Incidentally, the island Sn layer, when observing the composite plated layer in the thickness direction, the surface of the sea portion of the Fe-Ni-Sn alloy layer as a (i.e. the continuous phase), and the island portion and Sn layer (dispersed phase), a plurality islands of Sn layer is a layer which is present in a state of being scattered in the sea portion.
[0023]
　Here, the corrosion resistance improving effect and the coating film adhesion improvement effect by Sn is determined by the amount of Sn in the composite plated layer. Then, the amount of Sn in the composite plating layer can be adjusted by the amount of Sn in the Sn plating layer for forming a composite plating layer.
　The amount of Sn is, per side 0.1 g / m as the metal Sn terms of the amount of 2 should be as or more. As the amount of Sn is increased, the effect of corrosion resistance and paint adherence improvement increases, while the amount of Sn is, per side 10 g / m as the metal Sn equivalent amount 2 when the excess, the effect of improving corrosion resistance saturated and, further increase is not preferable from the viewpoint of economy. Further, there is a tendency to decrease even coating adhesion. Therefore, the amount of Sn is per side 0.1 g / m as the metal Sn terms of the amount of 2 or more 10 g / m 2 or less. The amount of Sn is more preferably, per side 0.2 g / m as the metal Sn equivalent amount 2 8 g / m or more 2 or less.
[0024]
　Ni amount and Sn content of the composite plating layer, ICP emission spectrometry, or GDS (glow discharge optical emission spectroscopy) is measured by a calibration curve method using. In particular, a Sn-based alloy plated steel sheet has coating layer is formed on the composite plating layer, when measuring the metal content of Ni and Sn metal of the composite plating layer, a calibration curve using a GDS (glow discharge optical emission spectroscopy) the law is suitable.
[0025]
　Specifically, the measurement method by ICP emission spectrometry is as follows.
　First, no coating layer is formed on the composite plating layer, to prepare a test piece of steel sheet composite plating layer is exposed (test specimen of a steel sheet in which only the composite plated layer is formed). By dipping the test piece in 10% nitric acid were dissolved composite plating layer containing Ni and Sn, ICP emission spectrometry Ni and Sn in the lysate obtained (e.g., manufactured by Agilent Technologies 799Ce, carrier use with Ar gas.) obtained by. Then, the intensity signal obtained by the analysis, a calibration curve concentration was prepared from the known solution, based on the formation area of the composite plating layer of the test piece, the adhesion amount of the composite plating layer (Ni amount, and the amount of Sn) the seek.
[0026]
　The measurement method according to a calibration curve method using a GDS (glow discharge optical emission spectroscopy) is as follows.
　First, using the reference sample Ni amount and Sn content of the composite plating layer is known, previously obtained relation between the intensity signals and sputtering rate of Ni and Sn in the composite plating layer in the reference sample by GDS while performing sputtering , make a calibration curve.
　On the other hand, to prepare a test piece of steel sheet which film layer is formed on the composite plating layer (test piece of the steel sheet to the composite plated layer and film layer are sequentially formed). From the surface of the coating layer of the test piece, while the sputtering was performed an analysis by GDS, measures the intensity signal of Ni and Sn in the composite plating layer. Intensity signal obtained Ni and Sn, the sputtering rate, and a calibration curve prepared, obtaining the Ni amount and the Sn amount of the composite plating layer.
　Here, the composite plating layer, the intensity signal of Zr is from the maximum value 1/2 consisting of the depth of the intensity signal of Zr, the intensity signal of Fe, becomes 1/2 of the maximum value of the intensity signals of Fe It is defined as a region of depth. Then, the average value of the amount of Ni and Sn content of the area, the Ni content and the Sn content of the composite plating layer.
[0027]
[Formation method of the composite plating layer]
　This Fe-Ni-Sn alloy layer, island-shaped Sn layer was formed composite plating layer is formed, for example, as follows. First, to form at least one surface serving as a base to Ni plating layer or Fe-Ni-plated layer of the steel sheet. Next, a Sn plating layer on the Ni plating layer or Fe-Ni-plated layer. Then, by heating and melting treatment and a Ni plating layer or Fe-Ni plating layer and the Sn plating layer, the composite plating layer is formed. That is, by melt heat treatment, the Fe of the steel sheet, and Ni of the Ni plating layer or Fe-Ni plated layer, a portion of Sn of the Sn-plated layer, but alloyed, Fe-Ni-Sn alloy layer is formed Rutotomoni, Sn plating layer of the balance of the island Sn layer.
[0028]
　The method of Ni plating and Fe-Ni plating, but there are no particular provisions, it is possible to use a known electroplating process. For example, a plating method using a sulfuric acid bath or chloride bath.
[0029]
　The Sn plating, as a method of applying to the surface of the Ni plating layer or Fe-Ni plating layer is not particularly intended to define, for example, a known electroplating method is preferred. The electroplating method, for example, can be utilized electrolytic method using a known Ferrostan bath, and halogen baths and alkaline baths.
[0030]
　After Sn plating, which is the melting point of Sn to 231.9 ° C. or higher, subjected to a heating and melting process of heating the coated steel plate. This heating and melting treatment, and Sn plating layer is melted, and an alloy with Ni plating layer or Fe-Ni plating layer underlying, Fe-Ni-Sn alloy layer is formed, further, island-shaped Sn layer is formed that.
[0031]

　Sn-based alloy plated steel sheet of the present disclosure, the surface of the composite plating layer formed on the surface of the steel sheet, containing both zirconium oxide and tin oxide having a coating layer.
　The content of zirconium oxide in the coating layer, the amount of metal Zr (i.e. metal Zr in terms of weight) on one surface per 0.2 mg / m 2 or more 50 mg / m 2 or less. The content of zirconium oxide in the coating layer is a zirconium content oxide per surface.
　Tin oxide in the coating layer is, Sn3d by XPS 5/2 peak position of the binding energy of a large tin oxide or 1.6eV than the peak position of the binding energy of metals Sn.
[0032]
　The above Sn3d 5/2 and, P. Non-Patent Document 1 As described in 83, showing the electron energy level in the Sn.
[0033]
Sn3d 　by XPS of the tin oxide 5/2 peak position of the binding energy of a peak position obtained by the surface of the coating layer was measured by XPS. However, the surface of the coating layer, further chemical conversion layer, if the layer of such coating layer is formed, after removing these layers, SiO by sputtering 2 film was depth 0.5 ~ 2 nm etching in terms of targeting surface of the layer, Sn3d by XPS 5/2 measures the peak position of the binding energy.
[0034]
　Here, Sn-based composite-plated steel sheet of the present disclosure, the surface of the composite plating layer, by having a coating layer of zirconium oxide as described above and a tin oxide coexist, yellowing resistance, coating adhesion, and, it is possible to further improve the sulfidation blackening. Incidentally, the coating layer of only tin oxide, or, in the coating layer of zirconium oxide alone, yellowing resistance, paint adhesion, and can not sufficiently improve the sulfidation blackening. The reason for this is not clear, is believed to be as follows by a detailed investigation of the inventors of the present invention.
[0035]
　Conventionally, tin oxide to produce and grow on the surface of the composite plating layer is different from the tin oxide of the present disclosure, Sn3d by XPS 5/2 1 than the peak position of the binding energy peak position Sn metal binding energy of. was found to be tin oxide is less than 6 eV. This is oxygen deficient, i.e. tin oxide (hereinafter, defined as "oxygen deficient tin oxide".) Having an oxygen vacancy and the estimated oxidation of the tin surface of the composite plating layer proceeds with time, the oxygen deficient tin oxide is grown. On the other hand, Sn3d by XPS 5/2 tin oxide peak position of the binding energy is 1.6eV higher than the peak position of the binding energy of metals Sn, the oxygen vacancies than oxygen deficient tin oxide as described above more stable than less (hereinafter, defined as "stable tin oxide."). Therefore, if stable tin oxide is present on the surface of the composite plating layer, the growth rate of the oxygen deficient tin oxide is slow. However, in the long term increase in oxygen deficient tin oxide, appearance or inferior strange or coating adhesion yellow. However, a stabilized tin oxide and zirconium oxide may coexist, growth of oxygen deficient tin oxide is suppressed.
[0036]
　To achieve growth inhibiting effect of oxygen deficient tin oxide, per side 0.2 mg / m of a metal Zr amount 2 or more 50 mg / m 2 or less of zirconium oxide is needed in the coating layer. The content of zirconium oxide is, 0.2 mg / m of a metal Zr content 2 if less than not only the growth inhibiting effect of oxygen deficient tin oxide is insufficient, even sulfidation blackening Otoriru. The content of zirconium oxide is, 50 mg / m of a metal Zr amount 2 when it exceeds, because the zirconium oxide is excessive, degrading the paint adherence. The content of zirconium oxide, a metal Zr content per surface, preferably 1.0 mg / m 2 or more 30 mg / m 2 is less, more preferably in the range of 2.0 mg / m 2 or more 10 mg / m 2 or less it is in the range of.
[0037]
　Tin oxide, Sn3d by XPS 5/2 peak position of the binding energy of is 1.6eV is larger than necessary than the peak position of the binding energy of metals Sn. By the peak position of the binding energy is greater than or equal to 1.6 eV, tin oxide is a stable tin oxide, the growth of oxygen deficient tin oxide is suppressed. On the other hand, Sn3d by XPS 5/2 if the difference is less than 1.6eV and the peak position of the binding energy peak position and Sn metal binding energy of tin oxide is oxygen deficient tin oxide, oxygen-deficient growth of tin oxide to proceed.
[0038]
　Since the higher the tin oxide high bond energy is stabilized, Sn3d tin oxide 5/2 upper limit value of the peak position of the binding energy is not intended to define, in reality, the binding energy of metals Sn is 2.0eV large value of about from peak position.
　That, Sn3d by XPS of the tin oxide 5/2 peak position of binding energy, it is greater at 2.0eV below the range of 1.6eV than the peak position of the binding energy of metals Sn.
　Here, the measurement method described later "Sn3d by XPS of the tin oxide 5/2 peak position of the binding energy is greater peak position 1.6eV higher than the peak position of the binding energy of metals Sn" If is measured, the coating layer, other than the stabilized tin oxide, tin oxide and other structures (e.g., Sn3d by XPS 5/2 less than 1.6eV than the peak position of the binding energy peak position Sn metal binding energy of such as oxygen deficient tin oxide) no problem be included.
[0039]
　The coating layer, a mass ratio per unit area, P amount / metal Zr content is preferably phosphorus to be 0.2 or more and 1 or less is contained further. By containing the P above mass ratio, it becomes zirconium oxide and further has coating layer containing tin oxide dense, easily improving the growth inhibiting effect of the tin oxide. If the amount of P / metal Zr content is less than 0.2, it may become poor growth inhibiting effect of the tin oxide. If the amount of P / metal Zr amount is greater than 1 is, P becomes excessive, the growth inhibitory effects of the tin oxide at the time of the zirconium oxide and tin oxide coexist may become poor. Mass ratio of the amount of P and the metal Zr per unit area, more preferably 0.3 to 0.8.
[0040]
　Coating layer containing the zirconium oxide and tin oxide may be both mixed state of may be a solid solution of oxides, regardless of its presence state. Further, such as Fe, Ni, Cr, Ca, Na, Mg, Al, Si or the like in the coating layer, there is no problem even contain any elements.
[0041]
　Here, an example of element concentration profile in the thickness direction of the composite plating layer and film layer of the Sn-based composite-plated steel sheet of the present disclosure (the depth direction) in FIG. Element concentration profile shown in FIG. 1, by analysis in the depth direction of the XPS, a diagram of measuring the distribution of element concentration from the surface of the coating layer to the surface of the steel sheet through the composite plated layer.
　As shown in FIG. 1, Sn-based composite-plated steel sheet of the present disclosure, it can be seen that the surface of the composite plating layer, coating layer and the zirconium oxide and tin oxide coexist exists.
[0042]
　The thickness of the coating layer, SiO by XPS 2 in terms of thickness is preferably 2nm or 100nm or less. When the thickness of the coating layer is less than 2nm, the poor oxygen permeation inhibiting effect for the thickness of the coating layer is too thin, it may oxygen deficient tin oxide tends to grow. On the other hand, when the thickness of the coating layer is 100nm greater is tin oxide itself is likely to cohesive failure for the thickness of the coating layer is too thick, it may be inferior in coating adhesion and corrosion resistance after coating. Not only that, yellowing resistance may sometimes become appearance assume a yellowish from immediately after production of a good thing. The thickness of the coating layer is more preferably 30nm or less the range of 4 nm.
　The thickness of the coating layer, in the XPS depth profiling, Sn which is present as tin oxide, Sn which is present as metallic tin, Zr present as zirconium oxide, the sum of the element concentration is taken as 100%, the surface from a thickness of up area element concentration than 10% of the metal tin (Sn which is present as metallic tin), SiO 2 is a value obtained by conversion thickness.
[0043]
　In coating layer, the content of zirconium oxide (metal Zr amount) and the amount of P, the dissolution of the present disclosure Sn-based alloy plated steel sheet, for example, which was dissolved by immersion in an acidic solution such as hydrofluoric acid and sulfuric acid, the resulting liquid high-frequency inductively coupled plasma (inductively coupled plasma: ICP) and a value measured by chemical analysis such as emission spectroscopy. Alternatively, the content of zirconium oxide (metal Zr amount) and P amount may be determined by fluorescent X-ray measurement.
[0044]
　In the following, a method for forming a coating layer containing zirconium oxide and tin oxide, is described.
　To form the coating layer, first, to the surface of the composite plated layer of the steel sheet to the composite plated layer is formed, to form a zirconium oxide layer containing zirconium oxide.
[0045]
　Zirconium oxide layer containing zirconium oxide, immersing the composite plating layer during immersion bath containing zirconium ion, or by performing a cathodic electrolysis treatment in the cathode electrolyte solution containing zirconium ion, the composite plating layer it can be formed on the surface of the. However, in the immersion process, the zirconium oxide layer surface of the composite plated layer is underlying containing zirconium oxide by being etched is formed. Therefore, the amount of deposition of the composite plating layer tends to become uneven, Also, since the processing time becomes longer, the industrial production is disadvantageous. On the other hand, at the cathode electrolytic treatment, adhesion-promoting effect by forced charge transfer and surface cleaning and pH increase due to hydrogen generation on the steel sheet surface is also coupled, it is possible to obtain a uniform film. In addition, the cathode electrolytic treatment, by in the cathode electrolyte and nitrate ions and ammonium ions coexist, it is possible short treatment for about several seconds to several tens of seconds. For this reason, the industrial is very advantageous.
　Therefore, the formation of zirconium oxide layer containing zirconium oxide, it is preferable to use a method by cathodic electrolysis treatment.
[0046]
　The concentration of zirconium ions in the catholyte in carrying out the cathodic electrolytic treatment, production facilities may be appropriately adjusted depending on the production rate (capacity). For example, a zirconium ion concentration is preferably 100ppm or 4000ppm or less. Further, the solution containing zirconium ions, fluorine ions, ammonium ions, nitrate ions, no problem also include other components such as sulfate ion.
[0047]
　Incidentally, the coating layer containing the zirconium oxide and tin oxide, the mass ratio per unit area, in order to contain 0.2 to 1.0 P as P amount / metal Zr amount, the of the immersion bath and cathodic electrolysis bath, it may be contained a 1/10 or more than three times the phosphate ions zirconium ion concentration.
[0048]
　The source of zirconium ions in the catholyte is, for example, H 2 ZrF 6 can be used zirconium complexes such as. Zr in Zr complexes as described above, Zr by increase in pH at the cathode electrode interface 4+ present in catholyte becomes. Such Zr ions further react with the cathode electrolytic solution, a zirconium oxide. If it contains phosphoric acid in the catholyte, zirconium phosphate is also formed.
[0049]
　As the solvent for the catholyte when the cathode electrolytic treatment, for example, water can be used such as distillation water. However, the solvent is not intended to be defined in the water, such as distilled water, dissolved substances, depending on the forming method and the like, it can be appropriately selected.
[0050]
　Here, the liquid temperature of the catholyte when the cathode electrolytic treatment is not particularly intended to define, for example, preferably in the range of 10 ° C. or higher 50 ° C. or less. By performing cathodic electrolysis at 50 ° C. or less, formed by very fine particles, it is possible to form a tissue of dense and uniform film layer. On the other hand, if the liquid temperature is lower than 10 ° C., the formation efficiency of the film is poor, requires cooling of the solution when the outside air temperature is high such as in summer, not only economical but also decreases corrosion resistance after coating . The liquid when the temperature exceeds 50 ° C., the zirconium oxide film tissue formed is not uniform, defects, cracks, dense film formed micro cracks generated becomes difficult, starting point of corrosion undesirable because it becomes.
[0051]
　Further, pH of the catholyte is not particularly intended to define, it is preferably 3 to 5. If the pH is less than 3, poor production efficiency of zirconium oxide, if the pH is greater than 5, a large amount occurs precipitated in catholyte, poor continuous productivity.
[0052]
　In order to raising the efficiency of electrolysis to adjust the pH of the catholyte, in the catholyte, such as nitric acid, ammonia water or the like may be added.
[0053]
　Also, the current density at the time of cathodic electrolysis treatment, for example, 0.05 A / dm 2 or more 50A / dm 2 is preferably not more than. Current density is 0.05 A / dm 2 when it is less than can lead to reduction in formation efficiency of zirconium oxide, yellowing resistance and resistance to become formation of the coating layer containing a stable zirconium oxide is difficult well sulfide blackening decreases, also decreases corrosion resistance after coating. Current density is 50A / dm 2 for the case where more than the formation efficiency is too large zirconium oxide, zirconium oxide less coarse and adhesion is formed, which is not preferable. More preferred current density range of, 1A / dm 2 or more 10A / dm 2 or less.
[0054]
　Incidentally, in forming the zirconium oxide layer, the time of the cathode electrolytic treatment, not to question. The content of zirconium oxide film layer which aimed to (metallic Zr amount) may be adjusted time appropriate cathodic electrolytic treatment in accordance with the current density.
[0055]
　As the energization pattern when the cathode electrolytic treatment, there is no problem even it is intermittently energized a continuous energization.
[0056]
　Coating layer containing zirconium oxide and tin oxide, a zirconium oxide layer containing zirconium oxide, obtained by anodic electrolysis at an anode electrolyte. Not particularly defined for specific components of the anolyte when anodic electrolysis treatment. However, the liquid property of anolyte, it is preferred that the alkaline weakly acidic. The alkaline weakly acidic here, pH is meant 3 to 14. If pH is within this range, the solubility of the composite plating layer at the anode electrolytic solution becomes gentle, it is possible to stably form a coating layer containing a stable tin oxide.
[0057]
　As examples of the anode electrolyte when anodic electrolysis treatment, hydroxides of alkali metals and alkaline earth metals, alkali metals and alkaline earth metal salts (carbonates, phosphates, organic acid salts, borates , and an aqueous solution containing an electrolyte such as sulfuric acid salts, etc.). Specifically, for example, as the anolyte, sodium carbonate, sodium bicarbonate, sodium diphosphate, trisodium citrate, ammonium one tartrate, aqueous solutions containing an electrolyte such as sodium sulfate.
　The lower limit of the concentration of the electrolyte is not particularly defined, it is preferable that the concentration satisfying the above-0.1 S / m as the electrical conductivity. But not limit the concentration of these electrolytes also specifically defined, when the concentration of the electrolyte is too large precipitates during storage, because it can cause problems such as pipe clogging, and less solubility in 0 ℃ each electrolyte it is preferable. The concentration of the electrolyte is preferably in electric conductivity as the concentration satisfying the following 0.5S / m or more 4S / m, more preferably, at a concentration satisfying the following 1S / m than 2.5S / m electrical conductivity is there.
　The electric conductivity may be measured using a commercially available electric conductivity meter, for example, it is possible to use a conductivity cell CT-27112B, such as manufactured by DKK-TOA Corporation.
[0058]
　As a solvent for the anolyte when anodic electrolysis treatment, for example, water can be used such as distillation water. However, the solvent is not intended to be restricted to water such as distilled water.
[0059]
　Here, the liquid temperature of the anolyte when anodic electrolysis treatment is not particularly intended to define, preferably in the range of less than 60 ° C. 5 ° C. or higher, more preferably in the range of 15 ℃ above 50 ° C. or less is there. If the liquid temperature is too low, poor efficiency of electrolysis, stable tin oxide is less likely to generate. On the other hand, if the liquid temperature is too high, the evaporation of the solvent the anolyte is inferior in prominent workability and operation stability, is difficult to obtain a uniform stable tin oxide.
[0060]
　The current density at the time of anodic electrolysis treatment is not particularly intended to define, for example, 0.5A / dm 2 or more 10A / dm 2 preferably has the following range. Current density 0.5A / dm 2 or more 10A / dm 2 when it is below, the stable tin oxide can be formed uniformly and stably. Current density 0.5A / dm 2 when it is less than, it is necessary to increase the electrolytic treatment time, cheaper occur a decrease in corrosion resistance after painting associated with the dissolution of the composite plating layer. On the other hand, the current density is 10A / dm 2 when exceeding significantly the hydrogen generated on the composite plating layer is not preferred on productivity for dissolution of the composite plating layer due to pH increase occurs, uneven tin oxide formation yellowing and sulfidation blackening tends to decrease by. Preferred current density range, 1.0A / dm 2 or more 3A / dm 2 or less.
[0061]
　The time of anodic electrolysis treatment is not particularly defined. Current density, electrode length, depending on the production rate (sheet passing speed), etc., can be arbitrarily determined.
[0062]
　The above-described cathode electrolytic treatment and the thickness of the coating layer formed through an anodic electrolytic treatment, mainly energization amount when anodic electrolysis can be controlled by (quantity of electricity), the thickness of the as the amount of current is large coating layer It becomes thicker. Recommended, in order to obtain a coating layer of 100nm or less in thickness than 2nm is the amount of current during anodic electrolysis 0.5 C / dm 2 or more 30C / dm 2 is preferably not more than. To obtain a 30nm or less of the coating layer or 4nm is the amount of current during anodic electrolysis 1C / dm 2 or more 15C / dm 2 is preferably not more than.
[0063]
　As the energization pattern when anodic electrolysis, there is no problem even it is intermittently energized a continuous energization.
Example
[0064]
　Subsequently, while showing Examples and Comparative Examples, the Sn-based alloy plated steel sheet and a manufacturing method thereof of the present disclosure will be specifically described. Incidentally, embodiments described below, merely only one example of a Sn-based alloy plated steel sheet and a manufacturing method thereof of the present disclosure, those Sn-based alloy plated steel sheet and a manufacturing method thereof of the present disclosure be limited to the following examples is Absent.
[0065]

　a method for manufacturing a test material. The test materials of the examples below were produced according to the manufacturing method of the test material.
　First, with respect to low-carbon cold-rolled steel sheet having a thickness of 0.2 mm, as a pretreatment, electrolytic alkali degreasing, washing with water, dilute sulfuric acid immersion pickling, washed with water, and the Ni plating with sulfuric acid bath. Coating weight of the Ni plating layer per surface 1 mg / m of a metal Ni equivalent amount 2 or more 300 mg / m 2 was less. Furthermore, on the Ni plating layer, by using a phenolsulfonic acid bath, it was subjected to electrical Sn plating. Adhesion amount of Sn plated layer per surface 0.08 g / m of a metal Sn terms of the amount of 2 or more 15 g / m 2 was less. The Ni plating layer and Sn plating layer produced through these processes are formed on both sides steel heat melting treatment to the island-like Sn layer located Fe-Ni-Sn alloy layer and the Fe-Ni-Sn alloy layer composite plated layer to prepare a steel sheet formed on both surfaces with and.
[0066]
　Then, the composite plating layer of the steel sheet formed on both surfaces, and cathodic electrolysis in an aqueous solution containing zirconium fluoride, to form a zirconium oxide layer on the surface of the composite plating layer. The liquid temperature of the catholyte was set to 35 ° C., and, pH of the catholyte was adjusted to be 3 to 5, the current density and the cathodic electrolysis treatment time of the cathode electrolytic treatment, the coating layer of the aimed and adjusted appropriately according to the content of zirconium oxide (metal Zr content).
[0067]
　Further, the steel sheet to form a composite plating layer and a zirconium oxide layer, and an anode electrolysis in electric conductivity 2.0S / m of sodium hydrogen carbonate solution (anolyte), zirconium oxide layer, zirconium oxide was coating layer containing tin oxide and. The liquid temperature of the anolyte is a 25 ° C., and the current density of the anodic electrolysis 2A / dm 2 was set to. Note that in some level, changing the type and anodic electrolysis treatment conditions of anolyte. Anodic electrolysis treatment time were suitably adjusted. PH of anolyte was determined with a glass electrode.
[0068]
　Thus the Sn-based alloy plated steel sheet produced was of various evaluations described below.
[0069]
[Amount of adhesion of the composite plating layer (Ni amount, and the amount of Sn)
　amount of adhesion of the composite plating layer (Ni amount, and the amount of Sn) was measured by the "measurement method by ICP emission spectrometry," described above.
[0070]
[The content of zirconium oxide coating layer (metal Zr amount) and the P content]
　The content of zirconium oxide coating layer (metal Zr amount) and the P content was determined as follows.
　The content of metal Zr content and P content were prepared test pieces of a plurality of coating layers with steel is known. Then, each test piece, by a fluorescent X-ray analyzer (manufactured by Rigaku Corporation ZSX Primus), from the surface of the coating layer of the specimen to measure the intensity of the fluorescent X-ray derived from the metal Zr and P in advance. Then, a calibration curve showing the relationship between the intensity and the metal Zr and P of the measured X-ray fluorescence, were prepared, respectively.
　On top of that, to prepare a test piece of Sn-based composite plated steel sheet to be measured. The surface of the coating layer of the specimen X-ray fluorescence analyzer (Rigaku ZSX Primus), was measured intensity of the fluorescent X-ray derived from metallic Sn, metallic Zr and P. Obtained by utilizing the calibration curve for the previously prepared metal Zr and P and X-ray fluorescence intensity was calculated the content of zirconium oxide coating layer (metal Zr amount) and the P content.
　Incidentally, measurement conditions, X-rays source Rh, tube voltage 50 kV, tube current 60 mA, the analyzing crystal LiF1, was measured diameter 30 mm.
[0071]
[Sn3d tin oxide in the coating layer in the XPS 5/2 peak position of the binding energy]
　to the surface of the coating layer, to perform measurements by XPS (ULVAC-PHI manufactured PHI Quantera SXM), the coating layer Sn3d tin oxide 5/2 was examined peak position of the binding energy (in the table referred to as "XPS energy peak position").
　Incidentally, measurement conditions, X-rays source mono-AlK ray (hν = 1466.6eV, 100.8W), X diameter 100Myuemufai, detection depth of several nm (takeoff angle 45 °), was analyzed range 1400 × 100 [mu] m.
　Then, Sn3d tin oxide 5/2 if 1.6eV higher than the large peak position of binding energy peak position Sn metal binding energy of (= 484.9eV), as stable tin oxide is mainly formed It was evaluated as "OK". If it is less than 1.6 eV, oxygen deficient tin oxide was evaluated as "NG" as being predominantly formed. Evaluate the "OK" was passed.
[0072]
[Coating layer thickness]
　The thickness of the coating layer was measured by XPS (ULVAC-PHI manufactured PHI Quantera SXM). Specifically, to prepare a test piece of Sn-based alloy plated steel sheet to be measured. From the surface of the coating layer of the test piece, and performing analyzes XPS (ULVAC-PHI manufactured PHI Quantera SXM) due to the thickness direction (depth direction), Sn which is present as tin oxide, Sn which is present as metallic tin, zirconium oxide there Zr, the sum of the element concentration is 100 percent things, from the surface, the thickness of up element concentration following 10% region of the metal tin (Sn which is present as metallic tin) SiO 2 in terms of thickness calculated.
　Incidentally, measurement conditions, X-rays source mono-AlK ray (hν = 1466.6eV, 100.8W), X diameter 100Myuemufai, detection depth of several nm (takeoff angle 45 °), analytical range 1400 × 100 [mu] m, neutralized gun 1.0 V, 20 .mu.A, sputtering conditions Ar + , the acceleration voltage 1 kV, sputter rate 1.5 nm / min (SiO 2 was converted value).
[0073]
[Yellowing resistance]
　The test material of Sn-based alloy plated steel sheet, 40 ° C., subjected to humidity test for placing 4 weeks 80% relative humidity constant temperature and humidity bath maintained at, the color difference b * value before and after the humidity test the amount of change △ b * the asking, was evaluated. If △ b * is 1 or less is "A", if 1 exceed 2 hereinafter as "B", if 2 exceed 3 below as "C", and "NG" if exceeded 3 . Evaluation "A", was passed the "B" and "C". b * was measured using a Suga Tester manufactured by SC-GV5 a commercial colorimeter. b * measurement conditions, the light source C, total reflection, a measurement diameter 30 mm.
[0074]
[Coating adhesion]
　coating adhesion was evaluated as follows.
　The test material of Sn-based alloy plated steel sheet, after humidity test by the method described in [yellowing, the surface, a commercially available cans epoxy resin paint dry mass at 7 g / m 2 was applied, at 200 ° C. 10 min baking, placed in room temperature for 24 hours. Thereafter, the obtained Sn based composite-plated steel sheets, put flaws reaching the steel sheet surface in a grid pattern (scratches at 3mm apart by vertically and horizontally seven), it was evaluated by the tape peeling test at that site. If not, release coating of tape applying sites are all set to "A", as long recognized coating peeling wound portion around the crosscut and "B", the coating film peeling is observed in the cross-cut of the square if the "NG". Evaluation "A", and the "B" was passed.
[0075]
[Sulfidation blackening]
　sulfidation blackening was evaluated as follows.
　Above the surface of the coating adhesion in Test material Sn-based alloy plated steel sheet was produced and humidity test by the method described in, 7 g / m on a dry weight of an epoxy resin paint commercial cans 2 after coating, 200 ° C. in baked 10 minutes, placed in room temperature for 24 hours. Thereafter, the resulting Sn-based composite-plated steel sheet is cut into a predetermined size, sodium dihydrogen phosphate 0.3%, sodium hydrogen phosphate 0.7%, the L- cysteine hydrochloride from 0.6% become immersed in an aqueous solution, subjected to retort processing 121 ° C. · 60 minutes in a sealed container was evaluated from the appearance after the test. If the change in appearance was observed at all before and after the test was "A", slightly (10% less) as long recognized blackened as "B", as long recognized blackening 10% excess area of the test surface and "NG". Evaluation "A" and "B" was passed.
[0076]
[Corrosion resistance after painting]
　after painting corrosion resistance was evaluated in the following manner.
　Above the surface of the coating adhesion in Test material Sn-based alloy plated steel sheet was produced and humidity test by the method described in, 7 g / m on a dry weight of an epoxy resin paint commercial cans 2 after coating, 200 ° C. in baked 10 minutes, placed in room temperature for 24 hours. Thereafter, the resulting Sn-based composite-plated steel sheet was cut into a predetermined size, the occurrence or non-occurrence of rust after immersion for 7 days at 60 ° C. in a commercially available tomato juice, was visually evaluated. If rust is observed at all the "A", as long recognized rust 10% or less of the area of the entire test surface and "B", as long recognized rust area ratio of more than 10% of the total test surface " It was NG ". Evaluation "A" and "B" was passed.
[0077]

　Table 1 shows the result in the case of changing the content of the Ni content and the Sn content and the zirconium oxide film layer in the composite plated layer. Zirconium concentration in the solution containing zirconium fluoride was set to 1400 ppm. After forming the zirconium oxide layer, relative to the zirconium oxide layer, the electrical conductivity of 2.0S / m of sodium hydrogen carbonate solution (liquid: weakly acidic to alkaline, pH = 8) and anodic electrolytic treatment in to form a coating layer. The liquid temperature of the anolyte is a 25 ° C., energization amount of the anodic electrolytic treatment 2C / dm 2 was set to.
[0078]
　As a comparison, it was prepared together with the following test materials.
　Are Comparative Examples a1 ~ a2: after forming the composite plating layer on both surfaces of the steel sheet to form a zirconium oxide layer, the test material is not an anodic electrolysis in a zirconium oxide layer
　as a comparative example a9: composite on both sides of the steel sheet after forming the plating layer, prior to forming the zirconium oxide layer, in the electric conductivity of 2.0S / m, the liquid temperature 25 ° C. in sodium bicarbonate solution (anolyte), density of 2A current / dm 2 under the conditions of the anodic electrolysis treatment was performed, then, to form a zirconium oxide layer, the test material is not an anodic electrolysis in a zirconium oxide layer
　as a comparative example a10: after the formation of the composite plating layer on both surfaces of the steel sheet, liquid temperature 35 ° C. , in an aqueous solution containing pH4 of zirconium fluoride, a current density of 3A / dm 2 under the conditions of, to form a zirconium oxide layer in an alternating electrolysis treatment performed alternately a cathode electrolytic treatment and anodic electrolysis treatment, Rukoniumu oxide layer on the test material is not an anodic electrolysis treatment
　is a comparative example a11: after the formation of the duplex to the composite plated layer of the steel sheet, a composite plated layer of the steel sheet, the electric conductivity of 2.0S / m, the liquid temperature 25 ℃ among sodium bicarbonate solution (anolyte), a current density of 2A / dm 2 was carried anodic electrolysis treatment, then the test material does not form a zirconium oxide layer
　in Table 1 is a comparative example a1 ~ a2 , properties of the zirconium oxide layer in a9, a10 (eg not subjected to anodic electrolysis in a zirconium oxide layer) is described in the column of "film layer".
　Further, properties of the tin oxide layer in a11 is a comparative example will be listed in the "coating layer".
[0079]
[Table 1]

[0080]
　As is apparent from Table 1, the range of the present disclosure A1 ~ A17 are all performance is good. On the other hand, a1 ~ a8 are comparative examples, the yellowing resistance, coating adhesion, sulfidation blackening, it is understood that any of the corrosion resistance after coating is deteriorated.
　In particular, as a comparative example a9, after the formation of duplex on the composite plated layer of the steel sheet, before the formation of the zirconium oxide layer, be performed an anodic electrolysis treatment, the zirconium oxide layer is then formed , it can be seen that stable tin oxide is not primarily formed.
　As comparative examples a10, be formed zirconium oxide layer in an alternating electrolysis treatment performed alternately a cathode electrolytic treatment and anodic electrolysis treatment, the zirconium oxide layer stabilized tin oxide is formed primarily it can be seen that does not.
　Like the a11 is a comparative example, without forming a zirconium oxide layer, when carrying out the anodic electrolytic treatment to the composite plated layer of the steel sheet, the tin oxide layer is formed as a film layer. However, the tin oxide layer, it can be seen that not a stable tin oxide layer.
[0081]

　Table 2 shows the result in the case of changing the thickness of the coating layer. The thickness of the coating layer was changed by changing the energization amount of the anodic electrolysis.
[0082]
[Table 2]

[0083]
　As is apparent from Table 2, the thicker the thickness of the coating layer, is a measure of yellowing △ b * is tends to decrease, if the thickness of the coating layer is 4nm or more, △ b * is particularly small it can be seen.
[0084]

　Table 3 shows the results of a case that contains phosphorus in the film layer. These test material is a cathodic electrolytic treatment solution containing zirconium ions 1400ppm obtained by addition of phosphate ion 60 ppm ~ 5000 ppm, and the steel sheet composite plating layer was formed was produced by cathodic electrolysis treatment.
[0085]
[table 3]

[0086]
　As is apparent from Table 3, that the phosphorus contained in the coating layer, is a measure of yellowing △ b * is tends to decrease, P amount / metal Zr amount is 0.2 or more 1 less is test material is found to be particularly △ b * is small.
[0087]

　Table 4 to Table 7 shows the result when the conditions for forming the zirconium oxide layer (cathode electrolytic treatment conditions) with the formation of the coating layer conditions and (anodic electrolysis treatment condition) were variously changed.
　As a comparison, it was prepared together with the following test materials.
　Are Comparative Examples d1 ~ d2: after forming the composite plating layer on both surfaces of the steel sheet to form a zirconium oxide layer, the test material is not an anodic electrolysis in a zirconium oxide layer
　In Table 4 to Table 7, Comparative Example characteristics of the zirconium oxide layer in d1 ~ d2 (example not subjected to anodic electrolysis in a zirconium oxide layer) is are described in the column of "film layer".
[0088]
[Table 4]

[0089]
[table 5]

[0090]
[Table 6]

[0091]
[Table 7]

[0092]
　As is apparent from Table 4 to Table 7, the performance of the test material produced with reference to the conditions specified in this disclosure, it can be seen that both are good.
[0093]
　Having described in detail the present disclosure, the present disclosure is not limited to such an example. It would be appreciated by those ordinarily skilled in the art that belongs present disclosure, within the scope of the technical idea described in the claims, it is intended to cover various changes and modifications , also such modifications are intended to fall within the technical scope of the present disclosure.
Industrial Applicability
[0094]
　Thus, Sn-based alloy plated steel sheet of the present disclosure, without the need for conventional chromate treatment, yellowing resistance, coating adhesion, since it is excellent in sulfidation resistance blackening, as a can material is environmentally friendly , food cans, can be widely used, such as in beverage cans, use value of the industry is extremely high.
[0095]
　Japanese disclosure of patent application 2016-103381 its entirety is incorporated herein by reference.
　All documents described herein, patent applications, and technical standards, each individual publication, patent application, and that the technical specification is incorporated by reference to the same extent as if marked specifically and individually, It incorporated by reference herein.

claims
[Requested item 1]
　And the steel sheet,
　is formed on at least one surface of said steel sheet, a Fe-Ni-Sn alloy layer, and the island-shaped Sn layer located on the Fe-Ni-Sn alloy layer, and a composite plating layer having,
　the composite plating layer the formed on the surface, and the film layer containing the zirconium oxide and tin oxide,
　have,
　the composite plating layer, by mass%, the metal Ni equivalent amount 2 mg / m 2 or more 200 mg / m 2 or less of Ni and, 0.1 g / m as the metal Sn equivalent amount 2 10 g / m or more 2 and less Sn, contain,
　content of the zirconium oxide in the coating layer is a metal Zr amount 0.2 mg / m 2 or more 50 mg / m 2 or less, Sn3d
　by X-ray photoelectron spectroscopy of the tin oxide in the coating layer 5/2 peak position of the binding energy of, than the peak position of the binding energy of metals Sn 1 More .6eV large, Sn-based alloy plated steel sheet.
[Requested item 2]
　The thickness of the coating layer is at 2nm or 100nm or less, Sn-based alloy plated steel sheet according to claim 1.
[Requested item 3]
　The coating layer has a weight ratio per unit area, further contains phosphorus P amount / metal Zr amount is 0.2 or more and 1 or less, Sn-based alloy plated steel sheet according to claim 1 or 2.