[0001]The present invention relates to a method of manufacturing a container for a steel sheet and a container for steel.
Background technique
[0002]
　As a container for beverage and food, Ni-plated steel sheet, a metal container obtained by canning steel sheets (container steel plate) such as a Sn-plated steel sheet or an Sn-based alloy plated steel sheets are widely used. Such when the metal container is used as a beverage container or food container, it is necessary to apply a coating to the metal container surface after canning before or canning.
　However, in recent years, in view of global environmental protection, in order to reduce waste and exhaust gas such as carbon dioxide gas resulting from the coating of the waste solvent and the like, are performed often pasted on the metal surface of the film, instead of applying paint it has become way.
[0003]
　To ensure corrosion resistance and coating adhesion or film adhesion, the steel sheet subjected to anti-rust treatment (chromate treatment) by chromate using hexavalent chromate or the like have been used as a base for paint or film ( for example, see Patent Document 1 below). Steel subjected to these chromate treatment, organic solvent resistance, fingerprint resistance, scratch resistance, to improve the lubricity or the like, an organic resin on the coating layer formed by chromate treatment (chromate film layer) coating layer is formed consisting of.
[0004]
　However, recently, hexavalent chromium used for the chromate treatment because it is harmful environmental, the use of hexavalent chromium is avoided. On the other hand, the chromate film layer is excellent because of its corrosion resistance and coating adhesion or film adhesion are, if not carried out such chromate treatment, corrosion resistance and coating adhesion or film adhesion decreases significantly.
　Therefore, it subjected to rustproofing alternative to chromate treatment to the surface of the container steel sheet, and to form a rust preventing layer having good corrosion resistance and coating adhesion or film adhesion come to be required. The rust preventive treatment alternative to chromate treatment, a method such as has been proposed below.
[0005]
　For example, Patent Document 2 and Patent Document 3 below, the Sn plated steel sheet containing Sn-plated steel sheet or an alloy Sn, and a method of cathodic electrolytic treatment is disclosed by chemical conversion treatment solution containing Zr-containing compound and F-containing compounds there.
[0006]
　Patent Document 4 below, the chemical conversion treatment liquid using comprising at least one of phosphate ion or Ti ions or Zr ions, relative to the Sn-plated steel sheet, a method of performing the electrolytic treatment or other chemical treatment It has been disclosed.
[0007]
　Patent Document 5 below, and the inorganic treating layer containing no phosphate ions include Zr ions and F ions, and a metal material having an organic-treated layer, the processing method is disclosed.
[0008]
　Patent Document 6 below, using a chemical conversion treatment solution containing Zr ions and organic, a method for electrolytic treatment or the immersion process the Ni-plated steel sheet is disclosed.
[0009]
　Patent Documents 7 to 10 below, Zr ion, with a solution that contains phosphate ion and nitrate ion, a method for electrolytic treatment is disclosed a steel sheet. In particular, Patent Document 9 below, a method to promote the formation of Zr film by increasing the nitrate ions is disclosed.
CITATION
Patent Literature
[0010]
Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-239855
Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-325402
Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-23422
Patent Document 4: Japanese Patent Laid-Open SHO 54- Publication No. 68734
Patent Document 5: Japanese Laid-open Patent Publication No. 2006-9047
Patent Document 6: Japanese Laid-open Patent Publication No. 2008-50641
Patent Document 7: Japanese Laid-open Patent Publication No. 2009-84623
Patent Document 8: international Publication 2011 / No. 118588
Patent Document 9: Japanese Patent Publication No. 4920800
Patent Document 10: Japanese Patent Application Publication No. 4886811
Summary of the Invention
Problems that the Invention is to Solve
[0011]
　As described above, in Patent Documents 2 to Patent Document 10, by performing the electrolysis in a solution containing Zr ions and F ions, a technique of forming a film containing a Zr compound on the steel sheet is disclosed. However, in these technologies, there may not be sufficient film adhesion such as polyester.
　Adhesive between the film formed on the film and steel plate, by using a primer or the like, it is possible to improve the film adhesion. However, the adhesive, by using a primer or the like, an adhesive, the manufacturing process of such baking process for the coating process and the adhesion securing primer such increases. In addition, such a method is not necessarily economic.
[0012]
　If the continuous electrolytic treatment performing film formation, the chemical conversion treatment liquid contains organic matter such as phenol resin, organic matter is decomposed on the anode, or phenol resin is inevitably insolubilized interaction with metal ions etc., it may be difficult to properly maintain the concentration of the phenolic resin contained in the chemical conversion treatment solution.
　For the reasons stated above, since the film containing the phenol resin may not be stably formed, the chemical conversion treatment liquid is desirable without phenol resin.
[0013]
　Container steel sheet for use in food containers, it is necessary to have a sulfidation blackening. In Patent Documents 2 to 10, has not been disclosed for this sulfidation blackening.
　The vessel steel plate, for example, fish meat, when used for food containers for the high protein food contents of the beans or the like, the retort processing after food packing (high-temperature heat sterilization treatment in the presence of water vapor), the container at least one of the inner and contents are sometimes discolored rarely black. Such a blackening phenomenon is referred to as sulfide blackening.
　Sulfur contained in the food, and thermally decomposed by retort treatment, hydrogen sulfide (H 2 S) and thiols (HS - ) and the like are generated. The hydrogen sulfide and thiols, undergo a structure and metal reaction vessel inner surface, the metal sulfide black is produced, sulfide blackening occurs.
　Because of this sulfide blackening is, the appearance of the container is deteriorated. Further, consumers, the metal sulfides generated black, misinterpreting the corrosion of metal corrosion or contents of the container inner surface. Therefore, it is necessary to avoid as much as possible to generate a sulfide blackening.
[0014]
　Container steel sheet, in addition to the sulfurization blackening and film adhesiveness, weldability, it is required to have a corrosion resistance and paint adhesion.
[0015]
　The present invention has been made in view of the above circumstances, to provide excellent film adhesion, sulfidation blackening, weldability, a method of manufacturing a container for a steel sheet and a container for steel sheet having corrosion resistance and paint adhesion and an object thereof.
Means for Solving the Problems
[0016]
　The present invention is to solve the above problems, in order to achieve the above object, adopts the following means.
(1) for containers steel sheet according to one embodiment of the present invention, comprises a steel plate, a Ni plating layer formed on at least one surface of the steel sheet, and a chemical conversion coating layer formed on the Ni plating layer there. The Ni plating layer, a metal Ni content 10 ~ 1000 mg / m 2 by weight of Ni, the chemical conversion coating layer is 5 ~ 30 mg / m of a metal Zr amount 2 contains a Zr compound of. Was determined by a scanning probe microscope, the chemical conversion average roughness Ra of the outermost surface of the treatment film layer is 10 nm ~ 100 nm, the amount of change in the measured yellowness per measuring point in the outermost surface of the chemical conversion coating layer the following (2) when defining represented ΔYI as in formula, the average value of the absolute value of the ΔYI obtained for a plurality of the measurement points included in the unit area of the outermost surface is 5.0 or less.
[0017]
[Number 1]

[0018]
(2) A container for steel sheet according to the above (1), the Ni plating layer may contain an alloy Ni.
[0019]
(3) A container for steel sheet according to (1) or (2), wherein the chemical conversion coating layer, 2 ~ 20 mg / m in the amount of P 2 may further contain a phosphoric acid compound.
[0020]
(4) A container for steel sheet according to (1) or (2), wherein the chemical conversion coating layer may be formed by performing a cathodic electrolysis treatment in the chemical conversion treatment solution containing Zr ions and F ions good.
[0021]
(5) A container for steel sheet according to the above (3), the chemical conversion coating layer, Zr ion, may be formed by performing a cathodic electrolysis treatment in a solution containing F ions and phosphate ions.
[0022]
(6) A method of manufacturing a container for a steel sheet according to one embodiment of the present invention, on at least one surface of the steel sheet, the metal Ni amount 10 ~ 1000 mg / m 2 and Ni plating step of forming a Ni plating layer containing Ni in; performed using a chemical conversion treatment solution containing at least Zr ions and F ions, a first cathode electrolytic treatment temperature of the chemical conversion treatment liquid is 10 ~ 40 ° C., at a temperature of 45 ~ 60 ° C. of the chemical conversion treatment solution there second cathode electrolytic treatment by performing, the Ni plating layer and the cathode electrolytic treatment to form a chemical conversion coating layer on the surface of the, at least use to the cleaning process of at least 0.5 seconds 40 ° C. or more washing water a cleaning process performs; having.
[0023]
(7) In the method for manufacturing a container for a steel sheet according to (6), after the Ni plating process, at least a portion of the Ni plating layer may have alloying heat treatment for alloying.
[0024]
(8) In the method for manufacturing a container for a steel sheet according to the above (6) or (7), wherein the chemical conversion treatment liquid, phosphate ions, may additionally contain at least one of nitrate ions and ammonium ions.
Effect of the invention
[0025]
　According to the above aspect, it is possible to provide excellent film adhesion, sulfidation blackening, weldability, a method of manufacturing a container for a steel sheet and a container for steel sheet having corrosion resistance and paint adhesion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026]
FIG. 1 is a configuration diagram of a container for the steel sheet of the present invention.
It is a flowchart showing an example of a method for manufacturing a container for a steel sheet of the present invention; FIG.
DESCRIPTION OF THE INVENTION
[0027]
　The present inventors have, as a new coating layer in place of chromate film layer, intensive studies the use of the chemical conversion coating layer containing Zr compound.
　Retort at the result, the provision of surface properties with respect to the chemical conversion coating layer further comprises a phosphate compound is added to the chemical conversion coating layer or a Zr compound containing Zr compound, the chemical conversion coating layer formed on the steel sheet, and the specific conditions by defining the difference between the change in yellowness of the processed (YI value) (△ YI value), superior over conventional chromate film layer film adhesion, sulfidation blackening, weldability, corrosion resistance, and paint adhesion and it found that sex can be obtained, leading to the present invention.
[0028]
　Hereinafter, preferred embodiments of the present invention will be described in detail.
[0029]
　Using a solution (chemical conversion treatment solution) containing Zr ions and F ions, by performing cathodic electrolysis treatment at a high temperature followed cold, chemical conversion coating layer containing Zr compound on steel plate Ni plating layer is formed a method for forming a will be described in detail. Further, the container steel sheet defining the variation (△ YI value) of yellowness after retort treatment (YI value) of the surface roughness and specific conditions of the chemical conversion coating layer, will be described in detail.
[0030]
　Figure 1 shows a block diagram of a container for the steel plate 1 according to a first embodiment of the present invention.
　Vessel steel plate 1 has a steel plate 2, the Ni plating layer 3 formed on the steel plate 2, and a chemical conversion coating layer 4 formed on the Ni plating layer 3.
[0031]
　Steel plate 2 used in this embodiment is not particularly limited, but usually, it is possible to use a steel sheet used as a container material. Preparation of the steel sheet, and there is no particular limitation, such as the material, hot rolling from a conventional billet manufacturing processes, pickling, cold rolling, annealing, and only needs to be manufactured through the temper rolling or the like process .
[0032]
　Vessel steel plate 1 has a Ni plating layer 3 on the steel plate 2.
　The content of Ni in the Ni plating layer 3, 10 ~ 1000mg / m of a metal Ni content 2 is.
[0033]
　Ni has good paint adhesion, film adhesion, has a corrosion resistance and weldability, In order to exert these effects, 10 mg / m of a metal Ni amount 2 or more is necessary and Ni.
　The effect increases metallic Ni content increases are improved, the amount of metal Ni is 1000 mg / m 2 if it exceeds, the above effect is saturated. Therefore, the content of Ni from an economic point of view, 1000 mg / m of a metal Ni amount 2 or less.
　A preferable content of Ni in the Ni plating layer 3, 10 mg / m of a metal Ni amount 2 or more 800 mg / m 2 or less.
[0034]
　Metal Ni content in the Ni plating layer 3, for example, can be measured by fluorescent X-ray method. In this case, a metal Ni amount known Ni deposition amount sample advance identifies a calibration curve for the metal Ni amount, to identify the relative metal Ni content using the calibration curve.
[0035]
　Ni plating layer 3 may be formed on both surfaces of the steel plate 2 may be formed from the viewpoint of reducing manufacturing costs on only one side of the steel plate 2. The steel plate 2 which is Ni-plated layer 3 on only one side of the steel plate 2 is formed when the can manufacturing process, for example, the surface Ni-plated layer 3 is formed is processed to become the inner surface of the container it is preferable.
　After forming the Ni plating layer 3 may be performed alloying heat treatment with respect to the Ni plating layer 3. The alloying heat treatment, at least a portion of the Ni plating layer 3 is alloyed, on the steel plate 2 alloy Ni plating layer containing Fe-Ni alloy is formed. Incidentally, alloy Ni plating layer may contain Ni that is not part alloyed.
[0036]
　When used as a container for a steel sheet, the surface remains the Ni plating layer 3, be attached to the film on the metal surface, or even paint is applied, coupling is sulfur and Ni contained in the beverage or food and, NiS like black is formed.
　Further, in the Ni plating defect site, for example in the case of using the steel sheet as the original plate, Fe is exposed. In this case, it bound sulfur and Fe, black FeS, Fe 2 S 3 , and Fe 2 S is formed.
[0037]
　To reduce these blackening phenomenon, containers for steel plate 1, the upper layer of Ni plating layer 3 has a chemical conversion coating layer 4.
[0038]
　Of the surface of the chemical conversion coating layer 4, it is described the surface roughness of the surface (outermost surface) in close contact with the film.
　The adhesion of the film, the mechanical adhesion (anchoring effect, etc.), chemical adhesion (primary bonding and interatomic attraction, etc.), and physical contact is (secondary binding-intermolecular attraction, etc.). In the present embodiment, among these, in particular a result of focusing on mechanical contact, defines a surface roughness of the chemical conversion coating layer 4 surface (specific surface area). By increasing the surface roughness (specific surface area), the mechanical adhesion (anchoring effect or the like) resistance is increased, by adherable area with the film increases, a chemical adhesion (between the primary bonding and atomic attraction, etc.) believe that also in physical contact (secondary binding-intermolecular attraction, etc.), the effect of increasing these adherable area.
[0039]
　In the present embodiment, Zr coating weight of the chemical conversion coating layer 4, 5 ~ 30mg / m of a metal Zr content 2 is essential that it is.
　Zr coating weight of 5 mg / m 2 for the mass, can not be obtained stably surface roughness which will be described later, it is not preferable. On the other hand, Zr coating weight of 30 mg / m 2 when exceeding, the surface roughness (to be described later) is obtained stably, unfavorably weldability during three-piece can forming is insufficient.
　Zr coating weight of the chemical conversion coating layer 4 is more preferably, 6 ~ 15 mg / m of a metal Zr content 2 is, more preferably, 8 ~ 13 mg / m 2 is.
[0040]
　Here, Zr coating weight of the chemical conversion coating layer 4, for example, can be measured by fluorescent X-ray method. In this case, by using a coating weight sample of the Zr amount known Ni plating layer 3 in advance identify a calibration curve relating amount of Zr, it identifies a relatively Zr coating weight using the calibration curve.
[0041]
　In the outermost surface of the chemical conversion coating layer 4, 1 m 2 is essential and that the average roughness of 5μm angle planar portion of any 20 points per (Ra) is 10nm or more 100nm or less.
　When the When the average roughness is less than 10nm, although the primary adhesion of the film can be secured, can manufacturing process, the end processing such as the post-processing of the film adhesion (secondary adhesion) can not be stably secured There are, it is not preferable. Further, When the above average roughness is 100nm exceeded, the Zr coating weight of the chemical conversion coating layer 4 5 ~ 30 mg / m 2 it is difficult to, to cause poor appearance, and film adhesion effect from saturating as not preferred.
[0042]
　When the thickness of the film itself is less than 5μm, there is an impact on the surface properties of the film applied to the surface of the container, which is not preferable. The thickness of the film used is preferably within the range of 5 [mu] m ~ 80 [mu] m, more preferably, 10 [mu] m ~ 60 [mu] m, even more preferably in the range of 15 [mu] m ~ 45 [mu] m.
[0043]
　Method of measuring the average roughness (Ra) is average roughness (Ra) may be used measurable device nm order. For example, scanning tunneling microscope (Scanning Tunneling Microscope: STM), atomic force microscopy: a scanning probe microscope represented by (Atomic Force Microscope AFM) (Scanning Probe Microscope: SPM) is to use a shape measuring device, such as it can.
[0044]
　1m of the outermost surface of the chemical conversion coating layer 4 by using a scanning probe microscope 2 method for measuring the average roughness of 5μm angle planar portion of any 20 points per (Ra) is described.
　1 m 2 and any 20 points per a meaning of "20 points of the outermost surface portion of any chemical conversion coating layer 4 on one side", the double-sided means that to measure 40 points. Measurement point is preferably the point away at least more than 10cm.
　More specifically, if the large sheet of 1 m × 1 m, sampling the measurement points, sampling points or more away 10cm from that point, it is preferable to measure.
　The scanning area of the measurement conditions for each point, 5 [mu] m × 5 [mu] m is preferred. In addition, the main measurement conditions such as the number of data points, it does not matter if in accordance with the measurement conditions shown in Table 1.
　Defining the average roughness (Ra) is described in the international standard ISO4287, a arithmetic average height of the roughness curve, the average value of the absolute value deviation from the mean line and is defined, in the definition conformity may be calculated.
[0045]
[Table 1]

[0046]
　When measured with a scanning probe microscope, roughness of such underlying Ni plating layer 3 of the chemical conversion coating layer 4 may affect the roughness of the chemical conversion coating layer 4. The average roughness of the present embodiment, the roughness of the outermost surface of the chemical conversion coating layer 4 including the effect of roughness such as Ni plating layer 3. Also, when the measuring surface is curved, it is preferably subjected to appropriate plane correction. Further, the curved portion of the outside the correction range, it is preferable to measure the other part.
[0047]
　In the present embodiment, 1m having undergone 5 hours retorting at 130 ° C. 2 is the average of the absolute value of the difference between the change in the yellowness index at any 20 points per (YI value) (△ YI value) 5.0 is required and that within it.
[0048]
　First, a retort process of the present embodiment, sterilization by saturated steam at high temperature and high pressure (autoclave sterilization, autoclaving) using an apparatus for processing (high-pressure steam sterilizer), and the Ni plating layer 3 according to this embodiment It means to process the container steel sheet 1 having a chemical conversion film layer 4.
　Incidentally, DOS is oiled in the surface of commonly vessel steel plate for the purpose of rust (sebacic acid bis (2-ethylhexyl)), ATBC (2- (acetyloxy) -1,2,3-tri-carboxylic acid tributyl), etc., may be oiled in the surface of the container steel sheet for 1.
　In retort processing, the temperature inside the apparatus described above is maintained for 5 hours the state of 130 ° C.. Incidentally, this 5 hours, heating time and cooling time is not included in the processing time. Since the heating time and the cooling time is considered to be different by the device, it is preferable to adjust the conditions within the range of ± 20 minutes.
[0049]
　Yellowness difference in change of (YI value) (△ YI value) and has a YI value of the container for the steel plate 1, the container for the steel plate 1 after the surface treatment was subjected 5 hours retorting at 130 ° C. It means the difference between the YI value.
[0050]
　The yellow index (YI value), the hue from a colorless or white is the degree of color change to yellow direction, color from colorless or white is displayed as the amount of plus when turn yellow direction. When the yellow index is displayed in a negative value indicates that the hue may change color to blue direction. Yellowness, with a measuring white difference meter, determine the tristimulus values ​​X, Y, Z, is calculated by substituting them into equation (1) below.
[0051]
　　YI value = 100 (1.28X-1.06Z) ÷ Y ··· (1)
[0052]
　Yellow index (YI value), tristimulus values ​​of the color of the (perceived sensitivity of the red, blue and yellow felt by the human eye) in a numerical value, yellowish higher the YI value indicates a high value on the plus side , tinged with blue-white taste enough to show a high value on the minus side.
[0053]
　Yellowness difference in change of (YI value) (△ YI value), as described above, the YI value of the container for the steel plate 1, retorting the container for the steel plate 1 after the surface treatment 130 ° C. / 5 hours It means the difference between the YI value after having been subjected to. In other words, the difference between the change in yellowness index (YI value) (△ YI value) is calculated by the following equation (2).
[0054]
[Number 2]

[0055]
　Thus indicating that the yellowness of the variation △ YI is the case of the positive amount, the yellowness index of the container for the steel sheet 1 by retorting increased. On the other hand, in the case of the amount of variation △ YI negative yellowness, reduced yellowness containers steel plate 1 by retorting, indicating that assume a vessel steel plate 1 is blue-white tint.
[0056]
　Ni plating layer 3, in the visual and yellowish, YI value indicates a positive value. By forming the upper layer on the chemical conversion film layer 4 of Ni plating layer 3, often, YI values indicate a higher positive value. This chemical conversion coating layer 4 itself is for exhibiting a white to pale yellow.
　Further, in accordance with the amount of Zr of the chemical conversion coating layer 4 is increased, YI value tends to further show a high value in the positive. This is because the chemical conversion coating layer 4 itself as described above can exhibit a white to light yellow, the pale about yellow shades according Zr amount contained is emphasized.
[0057]
　On the other hand, to form a chemical conversion coating layer 4 on the Ni plating layer 3, by performing 5 hours retorted at a temperature of 130 ° C., in many cases, △ YI value is often shows a positive value but in some cases it may indicate a negative value. As will be described later, △ even YI value is a positive, even ΔYI value is a negative, the magnitude of the ΔYI value (i.e., the degree of change in yellowness index) and, a correlation between the sulfidation blackening there is. Therefore, in this embodiment, as an indicator of sulfidation blackening, using the absolute value of the ΔYI value.
[0058]
　The measurement of yellowness of the present embodiment (YI value) may be used spectrophotometer in conformity with JIS Z-8722 condition c. (Including specular reflection light) yellow index (YI value) of the measurement method as less affected by the surface properties are SCI performs measurement. The measurement conditions yellowness (YI value), the light source, humidity, and temperature, etc., it is necessary to perform measurements under certain conditions.
[0059]
　In the present embodiment, the variation in which △ YI value of yellowness index (YI value) is used as an indicator of coating degree of the Ni plating layer 3 and the chemical conversion film layer 4. If there is a defect in the Ni plating layer 3 or the chemical conversion coating layer 4, the amount of change in the yellowness index (YI value) △ YI value indicates a high value. On the other hand, when there is no defect in the Ni plating layer 3 and the chemical conversion coating layer 4 is the amount of change in yellowness index (YI value) △ YI value indicates a low value.
　As if there is a defect in the Ni plating layer 3 or the chemical conversion coating layer 4, for example, or if Ni plating layer 3 by microporous defect chemical conversion film layer 4 is formed nonuniformly oxidized by retorting If you want, and the like.
[0060]
　At each measurement point, to identify the absolute value of the ΔYI value by the above method, averaging by the number of measurement points to "absolute value of the ΔYI value" all obtained. This value, in the present embodiment, 1m after subjected to retort treatment for 5 hours at a temperature of 130 ° C. 2 absolute difference between the change in yellowness index at any 20 points per (YI value) (△ YI value) the average of the values.
[0061]
　If it is within the average of 5.0 of the absolute value of the above △ YI value, dense and uniform Ni plating layer 3 and the chemical conversion coating layer 4 is formed.
　△ average of the absolute value of YI value may exceed 5.0, which means that not so dense and uniform Ni plating layer 3 and / or chemical conversion coating layer 4 is formed.
　Thus, the average of the absolute values of △ YI value is 5.0 or less. △ average of the absolute value of the YI value is preferably 3.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less.
[0062]
　The present inventors have found that the absolute value of ΔYI values ​​before and after retort processing, along with showing the coating degree of the chemical conversion coating layer 4 was found that there is a correlation between the sulfidation blackening and ΔYI value. That, △ when the average of the absolute value YI value is high value, no sulfidation blackening the container steel plate 1 is excellent, when the average of the absolute values ​​of △ YI value is low has a sulfidation blackening the container steel plate 1 is excellent.
[0063]
　In retort processing, conversion because the coating degree of the treated film layer 4 water molecules or oxygen molecules enter the lower portion, Ni of the chemical conversion coating layer 4 Ni plating layer 3 on the layer lower than, more iron in the steel sheet 2 such as the metal is oxidized. That is, the oxidation state of the metal such as Ni and iron caused by the retort process is affected by the coating degree of the Ni plating layer 3 and the chemical conversion film layer 4.
　On the other hand, .DELTA.YI value represents the amount of change yellowness containers steel plate 1. Here, yellowness containers steel sheet for 1 oxidation state of the metal such as Ni or iron, are affected by the Zr content of the chemical conversion coating layer 4.
　Therefore, the average of the absolute values of ΔYI value is considered to indicate a coating degree of the chemical conversion coating layer 4 (degree of uniformity and compactness).
[0064]
　On the other hand, conversion coating degree of treated film layer 4 (uniform and the degree of compactness) hydrogen sulfide from the lower portion molecules or thiol ions, since enters sulfur molecules, the Ni plating layer 3 on the lower layer than the chemical conversion coating layer 4 Ni, even metals such as iron in the steel sheet 2 is sulfurized. As a result, by the metal sulfide is formed, sulfide blackening occurs. In other words, sulfidation blackening is affected by the coating degree of the Ni plating layer 3 and the chemical conversion coating layer 4 (degree of uniformity and compactness).
[0065]
　For the above reasons, the ΔYI value indicating the amount of change in yellowness of the container for the steel plate 1, and the sulfurization blackening considered to have a correlation.
[0066]
　The present inventors have found that in order to have a good sulfidation blackening and excellent film adhesion vessel steel plate 1, there needs to be two layers having different functions formed on the chemical conversion coating layer 4 It was considered.
　Based on this finding, the chemical conversion coating layer 4, water molecules from the surface, in order to suppress transmitted through the foreign molecules such as hydrogen sulfide molecules, having a uniform and dense layer on the Ni plating layer 3, the uniformly and on the dense layer in order to ensure the film adhesion, it has a high roughness layer.
　In the present specification, referred to as the former uniform and dense layer Daiichi Kasei treated film layer, called the latter roughness higher layer and the second chemical conversion coating layer.
[0067]
　In this embodiment, the chemical conversion coating layer 4, sulfidation blackening is formed in order to ensure the corrosion resistance and film adhesion. Zr compound contained in the chemical conversion coating layer 4 is believed to be Zr hydrous oxide which is composed of Zr oxide and hydroxide Zr. When the chemical conversion treatment solution further contains a phosphate ion is Zr hydrous oxide - believed to be phosphoric acid compound. These Zr compounds excellent sulfidation blackening has corrosion resistance, and film adhesion.
　Therefore, sulfidation blackening the Zr compound amount of the chemical conversion coating layer 4 is increased, corrosion resistance, and film adhesion is improved. Zr compound amount of the chemical conversion coating layer 4, a metal Zr weight, 4 mg / m 2 if more, the above effect is exhibited.
[0068]
　Zr amount of compound Daiichi Kasei treatment film layer is, 4 mg / m of a metal Zr amount 2 or more, more preferably 6 mg / m 2 or more, more preferably 8 mg / m 2 is at least.
　Zr compound amount of the second chemical conversion coating layer is, 1 mg / m of a metal Zr amount 2 or more, more preferably 3 mg / m 2 or more, more preferably 6 mg / m 2 is at least.
[0069]
　In accordance with an increase in the Zr compound amount, sulfidation blackening, corrosion resistance and film adhesion is improved. However, the total Zr amount of compound contained in Daiichi Kasei treatment film layer and a second chemical conversion coating layer is 30 mg / m of a metal Zr content 2 exceeds, too thick chemical conversion coating layer 4 chemical conversion coating layer 4 itself adhesion to the deterioration of the. Furthermore, since the electric resistance of the chemical conversion coating layer 4 is increased, the weldability is deteriorated.
　Furthermore, the total Zr amount of compound contained in Daiichi Kasei treatment film layer and a second chemical conversion coating layer is 30 mg / m of a metal Zr amount 2 by weight, there is a case where Zr compound powdery precipitates on the surface.
[0070]
　Accordingly, Zr compound amount of Daiichi Kasei treatment film layer is, 20 mg / m of a metal Zr content 2 preferably less, more preferably 15 mg / m 2 or less, more preferably 10 mg / m 2 or less.
　Further, Zr compound amount of the second chemical conversion coating layer is, 10 mg / m of a metal Zr content 2 preferably less, more preferably 8 mg / m 2 or less, more preferably 5 mg / m 2 or less.
[0071]
　In view of the above, the total Zr amount of compound contained in the chemical conversion film layer 4, 5 ~ 30 mg / m of a metal Zr amount 2 to.
[0072]
　When phosphoric acid compounds such as Zr- phosphate compound of the chemical conversion coating layer 4 is increased, it exhibits better sulfidation blackening, corrosion resistance, and film adhesion. However, can recognize this effect, phosphoric acid compound content is 0.5 mg / m in the amount of P 2 or more, can be clearly recognized 2 mg / m at the P content 2 is not less than.
[0073]
　Therefore, phosphoric acid compound amount such Zr- phosphate compound of Daiichi Kasei treated film layer, 2 mg / m by P amount 2 or more, more preferably 3 mg / m 2 or more, more preferably 4 mg / m 2 is greater than or equal to.
　Further, Zr- phosphoric acid compound amount such as phosphoric acid compound in the second chemical conversion coating layer, 0.5 mg / m at P amount 2 or more, more preferably 1.5 mg / m 2 or more, more preferably the 3 mg / m 2 is at least.
[0074]
　On the other hand, Zr- sulfidation blackening the phosphoric acid compound content, such as phosphoric acid compounds is increased, corrosion resistance, film adhesion is improved. However, phosphoric acid compound amount such Zr- phosphate compound of the chemical conversion coating layer 4 is 20 mg / m in the amount of P 2 exceeds, Zr- phosphate compound such as phosphoric acid compound is too thick. Therefore, the adhesion itself phosphate compound is deteriorated, the electrical resistance of the chemical conversion coating layer 4 is deteriorated weldability increases. Furthermore there is a case where Zr-P compound powdery precipitates on the surface.
[0075]
　Thus, Daiichi Kasei Zr- phosphoric acid compound amount such as phosphoric acid compound treatment film layer is, 15 mg / m in the amount of P 2 preferably less, more preferably 10 mg / m 2 or less, more preferably 8 mg / M 2 is less than or equal to.
　Further, phosphoric acid compound amount of such secondary chemical Zr- phosphoric acid compound treatment film layer is, 8 mg / m in the amount of P 2 preferably less, more preferably 5 mg / m 2 or less, more preferably 3 mg / M 2 is less than or equal to.
[0076]
　Thus, the total phosphate amount of compound such as Zr- phosphoric acid compound contained in the Daiichi Kasei treatment film layer and a second chemical conversion coating layer, 2 ~ 20 mg / m in the amount of P 2 is preferably set to. More preferably, Zr- phosphoric acid compound amount such as phosphoric acid compound 4 ~ 15 mg / m 2 is, more preferably, Zr- phosphoric acid compound amount such as phosphoric acid compound 2.5 ~ 10 mg / m 2 in is there.
　Although the details will be described later, in order to stably form a chemical conversion film layer 4, the chemical conversion treatment liquid preferably contains no phenolic resin. Therefore, the chemical conversion coating layer 4 preferably does not contain a phenolic resin.
[0077]
　The metal Zr amount chemical conversion coating layer 4 contains in this embodiment, P amount, and metal Ni amount Ni plating layer 3 contains, for example, be measured by quantitative analysis methods such as X-ray fluorescence analysis possible it is. In this case, a metal Ni amount known Ni deposition amount sample advance identifies a calibration curve for the metal Ni amount, identify the metal Ni content in relatively Ni plating layer 3 by using this calibration curve can do.
[0078]
　The metal Zr amount known Ni deposition amount sample, and, using the P amount known Ni deposition amount samples, a calibration curve of the calibration curve and the amount of P relates to a metal Zr amount in advance to identify in advance, these calibration curves the relatively metals Zr amount and the amount of P can be identified using.
[0079]
　Hereinafter, a method for manufacturing a container for a steel sheet 1 according to this embodiment.
　Figure 2 is a flow chart showing an example of a method for manufacturing a container for a steel sheet 1 according to this embodiment.
[0080]
　In this embodiment, Ni plating layer 3 is formed on at least one surface of the steel plate 2 (step S1). A method of forming a Ni plating layer 3 is not particularly limited. For example, electroplating, may be a known technique such as vacuum deposition or sputtering.
　Further, as described above, after forming the Ni plating layer 3 may be performed alloying heat treatment with respect to the Ni plating layer 3. The alloying heat treatment on the steel plate 2, the alloy Ni plating layer containing Fe-Ni alloy is formed. Incidentally, alloy Ni plating layer may contain Ni that is not part alloyed.
　As the conditions for the alloying heat treatment, hydrogen 3 vol%, in non-oxidizing atmosphere of nitrogen 97vol%, 650 ℃ ~ 850 ℃ , those exemplified in the heat treatment at 20sec ~ 50 sec.
[0081]
　Examples of a method of forming a chemical conversion film layer 4, there is a dip treatment and a cathode electrolytic treatment.
　Immersion treatment (optionally, phosphate ions) Zr ions, F ions in the acidic to dissolve the solution, a method of immersing the steel plate 2 forming the Ni plating layer 3. However, in the immersion process, since the chemical conversion coating layer 4 underlying etched is formed, adhesion of the chemical conversion coating layer 4 becomes uneven. Moreover, since the longer time required for the formation of the chemical conversion coating layer 4, the industrial production is disadvantageous.
[0082]
　On the other hand, at the cathode electrolytic treatment, the hydrogen evolution at the interface between the forced charge transfer and the steel plate 2 as the chemical conversion treatment liquid, the chemical conversion treated surface of the coating layer 4 formed is cleaned. Further, the cathode electrolytic treatment, by the pH of the chemical conversion treatment solution is increased, the adhesion of the chemical conversion coating layer 4 is accelerated.
　For the above reasons, by performing cathode electrolytic treatment with respect to the steel plate 2 that Ni plating layer 3 is formed, it is possible to form a uniform chemical conversion film layer 4.
[0083]
　In the present embodiment, with respect to the steel plate 2 that Ni plating layer 3 is formed by performing cathodic electrolysis treatment in the chemical conversion treatment solution containing Zr ions and F ions, the chemical conversion coating layer 4 containing Zr oxide It is formed. By performing cathodic electrolysis treatment with phosphoric acid was added chemical conversion treatment liquid, the chemical conversion coating layer 4 containing a Zr oxide and Zr phosphate compound is formed.
[0084]
　In the method of manufacturing a container for a steel plate 1 according to the present embodiment, using at least two or more cathodic electrolytic cell, a chemical conversion coating layer 4 is formed by cathodic electrolysis treatment. In the cathode electrolytic treatment, after performing the first cathode electrolytic treatment (step S3) that the temperature of the chemical conversion solution and 10 ° C. ~ 40 ° C., followed by the the temperature of the chemical conversion solution and 45 ° C. ~ 60 ° C. second cathode electrolysis process (step S5) performed.
[0085]
　The first cathode electrolytic treatment described above, Daiichi Kasei treated film layer on the Ni plating layer 3 is formed. The second cathode electrolytic treatment described above, the second chemical conversion coating layer formed on the Daiichi Kasei treated film layer.
　By the temperature of the chemical conversion treatment liquid makes a first cathode electrolytic treatment is 10 ° C. ~ 40 ° C., a dense Daiichi Kasei treated film layer formed, while securing the sulfidation blackening, to ensure corrosion resistance.
　By performing the second cathode electrolytic treatment temperature of the chemical conversion liquid is 45 ° C. ~ 60 ° C., to form a second chemical conversion coating layer, mainly to ensure film adhesion and coating adhesion.
[0086]
　Incidentally, the chemical conversion is only the second cathodic electrolysis treatment, the chemical conversion treatment formation promoting coating layer 4 containing Zr compound is effective at, denseness of the chemical conversion coating layer 4 is insufficient, i.e. having a microporous defect It is considered to be a treatment film layer 4. Therefore, there are cases where it is difficult to ensure the sulfidation blackening and the corrosion resistance.
[0087]
　Temperature of the chemical conversion treatment liquid of the first cathodic electrolysis treatment is 10 ℃ ~ 40 ℃.
　The chemical conversion treatment solution below temperature 10 ° C., the capacity increase of the cooling device is required. A decrease in temperature of the chemical conversion solution to below 10 ° C., compactness of the chemical conversion coating layer 4 since the saturated, can not be more dense chemical conversion coating layer 4 is formed. The temperature is below 10 ° C. the chemical conversion treatment liquid is slow formation rate of the chemical conversion coating layer 4. The temperature is below 10 ° C. of the chemical conversion treatment solution, the solubility of the components of the chemical conversion treatment solution is reduced, insoluble matter is produced. For these reasons, undesirable to the temperature of the chemical conversion treatment liquid is less than 10 ° C..
　On the other hand, when the temperature of the chemical conversion solution exceeds 40 ° C., can not form a dense chemical conversion coating layer 4, it is difficult to ensure the sulfidation blackening and the corrosion resistance. Therefore, it is difficult to exert the function of Daiichi Kasei treated film layer described above.
　Temperature of the chemical conversion treatment liquid of the first cathodic electrolysis treatment is preferably, 20 ℃ ~ 35 ℃.
[0088]
　The temperature of the chemical conversion solution of the second cathodic electrolysis treatment is 45 ℃ ~ 60 ℃.
　The temperature is lower than 45 ° C. the chemical conversion treatment solution, it is difficult to ensure the surface roughness defined in the present embodiment.
　On the other hand, when the temperature of the chemical conversion solution exceeds 60 ° C., although it is possible to secure a surface roughness defined in the present embodiment, it can not be ensured the stability of the chemical conversion solution. In particular, when performing cathodic electrolysis treatment continuously decomposes F complex components such as the Zr gradually, for floating in the chemical conversion solution becomes insoluble material adheres to the surface of the chemical conversion coating layer 4 etc., adversely affected.
　The temperature of the chemical conversion solution of the second cathodic electrolysis treatment is preferably, 45 ℃ ~ 55 ℃.
[0089]
　When the strip passing speed exceeds 150 meters / minute, the temperature of the chemical conversion solution of the second cathode electrolytic treatment is required at a high temperature 10 ° C. or higher than the temperature of the chemical conversion solution of the first cathode electrolytic treatment. This follow strip passing speed increases, for example, chemical conversion treatment solution of the first cathode electrolytic cell is adhered to the steel plate, by mixing the second cathode electrolytic cell, a chemical conversion treatment of the second cathode electrolytic cell may lead to a decrease in liquid temperature, there may be a case that as a result prevent the efficient formation of the chemical conversion second chemical conversion coating layer of the coating layer 4 of the present invention.
[0090]
　Current density, the structure of the cathode electrolytic treatment apparatus, also depends on the sheet passing speed if elongated steel plates, for example, 0.1 ~ 20A / dm 2 is.
[0091]
　In the method of manufacturing the container for the steel sheet 1 of the present embodiment, it is preferred to use at least two or more cathodic electrolytic cell. This is at least 1 tank and the cathode electrolytic cell for the first cathode electrolytic treatment, the at least tank is to a cathode electrolytic cell for the second cathode electrolytic treatment.
　Cathodic electrolytic cell may be a horizontal type in vertical, as long as the structure of the front and back surfaces of the steel plate 2 can cathodic electrolysis treatment is not particularly limited.
[0092]
　In the present embodiment, as the chemical conversion treatment solution may be a known chemical conversion treatment solution. For example, as described in Patent Documents 9 and 10, it is possible to use a chemical conversion treatment solution containing F ions Zr ions and 120 ppm ~ 4000 ppm of 100 ppm ~ 7500 ppm.
　Further, as the chemical conversion treatment solution used in the cathode electrolytic treatment, the addition to the Zr ions and F ions, phosphate ions and of 50 ppm ~ 5000 ppm, may be used a chemical conversion treatment solution containing the following nitrate ions and ammonium ions 20000ppm .
[0093]
　Incidentally, pH of the chemical conversion treatment solution is preferably from 3.0 to 4.5 when it is desired to lower the pH after adding nitric acid, appropriately adjusted by adding ammonia if it is desired to raise the pH Bayoi.
[0094]
　Better film adhesion, sulfidation blackening, and to ensure corrosion resistance, Zr ions, as well as F ions, it is preferable to add a phosphate ion.
[0095]
　More preferably coexist and nitrate ions and ammonium ions in the chemical conversion treatment solution. By chemical conversion treatment solution containing the ions, it is possible to shorten the processing time of the cathode electrolytic treatment. In addition, by chemical conversion treatment liquid containing the above ions, contributes to the improvement of corrosion resistance and film adhesion Zr oxides, it is possible to promote the deposition of the chemical conversion coating layer 4 including the Zr- phosphate compound. Accordingly, chemical conversion treatment liquid may contain the ions in the industrially very advantageous.
　Therefore, the formation of the chemical conversion coating layer 4 of the present embodiment is used cathodic electrolysis treatment, it is further desirable to perform the cathodic electrolysis treatment in a chemical conversion treatment solution containing a nitrate ion and ammonium ion.
[0096]
　Using a chemical conversion treatment liquid containing organic substances such as phenol resin, when performing film formation by continuous electrolytic treatment, organic substances, such as when or phenolic resins organic matter is decomposed on the anode by interaction with metal ions there is a case in which inevitably insoluble. Therefore, it becomes difficult to maintain the concentration of organic substances such as phenol resin contained in the chemical conversion treatment liquid appropriately.
　For the reasons stated above, since the film containing the phenol resin may not be stably formed, the chemical conversion treatment liquid is desirable without phenol resin.
[0097]
　F ions from being contained in the chemical conversion treatment solution is incorporated into the chemical conversion film layer 4 with Zr compound. F ions in the chemical conversion coating layer 4 has no effect on the primary coating adhesion, which causes to deteriorate the secondary paint adhesion and corrosion resistance. This is because the F ions steam or corrosive solution in the chemical conversion film layer 4 is eluted, F ions the chemical conversion coating layer 4 and the film, to decompose the bond between the organic film layer of paint or the like, or, It is thought to be due to corrosion of the steel plate 2.
[0098]
　To reduce the F ion amount of the chemical conversion coating layer 4, after the second cathode electrolytic treatment, for cleaning treatment to the container for the steel plate 1 (step S7). Examples of the cleaning treatment, dipping treatment and spraying treatment.
　The temperature of the washing water used in the washing process is increased, by increasing the processing time of the cleaning process, it is possible to further reduce the F ion amount of the chemical conversion coating layer 4.
　To reduce the F ion amount of the chemical conversion coating layer 4, the immersion treatment or spray treatment using a 40 ° C. or more of washing water may be performed more than 0.5 seconds. Temperature of the washing water is below 40 ° C., or the treatment time is less than 0.5 seconds, it is impossible to reduce the F ion amount of the chemical conversion coating layer 4, various characteristics described above can not be exhibited.
[0099]
　Well above F ions, nitrate ions present in the chemical conversion solution, ammonium ions, which may be incorporated in the chemical conversion film layer 4 with Zr compound. May reduce these ions may be performed a cleaning process by immersion or spraying with the washing water.
　When reducing the nitrate ions and ammonium ions in the chemical conversion coating layer 4 also, higher temperatures of the wash water, or by increasing the processing time can be reduced more nitrate ions, ammonium ion content.
[0100]
　F ions, nitrate ions and ammonium ions, by dipping or spraying the above, it is preferred to remove from unless the chemical conversion coating layer 4 as possible. However, it may not be necessarily removed completely, but may be inevitably remain.
Example
[0101]
　It described Examples and Comparative Examples of the present invention below, and the results are shown in Table 5. Examples shown below is only one example of a method for manufacturing a container for a steel sheet and a container for steel sheet according to the embodiment of the present invention, a method of manufacturing a container for a steel sheet and a container for steel sheet according to the embodiment of the present invention, the following not limited to the embodiment shown in.
[0102]

　(A1) after the cold rolling, after the annealing and temper rolling steel sheet was degreased and pickled, on both sides, nickel sulfate hexahydrate 75 g / L, nickel chloride · 6 hydrate 140 g / L, bath temperature 50 ° C. using a watt bath having a composition of boric acid 40 g / L, pH 4, the current density of 5A / dm 2 plated with Ni at conditions to prepare a Ni-plated steel sheet. Coating weight was adjusted with the electrolysis time.
　(A2) on both sides of the rolled steel sheet cold nickel sulfate 240 g / L, nickel chloride 45 g / L, bath temperature 50 ° C. using a Watt bath having a composition of boric acid 30 g / L, current density 5A / dm 2 after performing Ni plating conditions, by performing an alloying heat treatment to form a Ni diffusion layer, further, subjected to degreasing and pickling to prepare a Ni-plated steel sheet. Coating weight was adjusted with the electrolysis time.
[0103]
　Deposition of Ni plating of the resulting Ni-plated steel sheet was measured by a fluorescent X-ray method. For the above (A1) and (A2), the lowest value of the coating weight of Ni plating, the optimum value and maximum value are shown in Table 2 below, respectively.
[0104]
[Table 2]

[0105]

　Ni plating steel sheet produced by the method of the above (A1) or (A2), was immersed in the chemical conversion treatment solution containing various ionic species shown in Table 3, energization times that shown in Table 4, It was subjected to cathodic electrolysis treatment at a temperature conditions. Incidentally, the chemical conversion treatment liquid, hexafluoro zirconium in distilled water (IV) ammonium, hydrogen fluoride, dissolved ammonium nitrate and phosphoric acid, and the pH was adjusted to 3.5.
[0106]

　after forming the chemical conversion coating layer by the above treatment, the steel sheet was immersed 0.5 to 5 seconds in distilled water at 20 ° C. - 40 ° C.. Thereafter, the steel sheet was immersed 0.5 to 3 seconds in distilled water at 80 ° C. - 90 ° C. The.
[0107]
　Current density (0.5 ~ 30A / dm 2 by adjusting) and electrolysis time (between 0.5 to 5 seconds), was adjusted Zr coating weight and P coating weight.
[0108]
[table 3]

[0109]
[Table 4]

[0110]

　for the test material subjected to the above processing, the performance evaluation was performed for each item in the following (A) ~ (H). The evaluation results are shown in Table 5.
[0111]
(A) the surface roughness
　test material of the chemical conversion coating layer side 1 m 2 per any 20 sites cut (at least more than 10cm distant sites), in Table 1 in Pointprobe (TM) NCH-10T (nanoworld manufactured AG Corporation) It was measured at the indicated conditions. The resulting data, determine the respective surface roughness (Ra) using (image processing software in the public domain at the open source developed by the National Institutes of Health (NIH)) is an image processing software ImageJ, average roughness to determine the degree.
[0112]
(B) yellowness
　chemical conversion coating layer side 1m of test material 2 yellow index (YI cut per any 20 sites (at least more than 10cm distant sites) to a size of 50 mm × 100 mm 0 were measured value). The chemical conversion coating layer side evaluated in the table, using Z clave S-020A (Miura Co., Ltd.), was carried out for 5 hours retorted 130 ° C.. Removed at the point when the temperature in the apparatus becomes 60 ° C. or less, in terms of dried, it was measured yellowness index (YI value).
　Measurement of YI value, using a spectrocolorimeter CM-2600d (manufactured by Konica Minolta Co.), SCI in (specular including light) mode, retorted before yellowness (YI 0 ) and yellowness after retorting was measured each of (YI). From this value, YI and YI 0 the absolute value of a certain △ YI value difference between, by dividing these sum by the number of measurement points to determine the average of the absolute values of ΔYI value.
[0113]
(C) sulfidation blackening
　cut out test material to a size of 55 mm × 55 mm, end the length of 5mm (a portion steel end face is exposed by the shearing) was masked with tape. 1 wt Na% 2 was immersed in S solution (adjusted to pH = 7 with lactic acid), it was carried out for 60 minutes retorted at a temperature of 125 ° C.. The appearance of each steel sheet after retort treatment was visually evaluated.
　Evaluation, Excellent (no discoloration) Good (There slight discoloration), Average, which (there discoloration equivalent chromate treated material), Fair (large little discoloration degree than chromate treatment material), discoloration degree than Poor (chromate treatment material It was evaluated in five stages of large).
　A case where the Average or more of the evaluation results were obtained was passed.
[0114]
(D) Film adhesion
　to both surfaces of the test material, a biaxially oriented PET film having a thickness of 20μm was laminated at 170 ° C., it was can-working by drawing and ironing step by step. Flaw of the film, float, to observe the peeling was evaluated film adhesion from their area ratio.
　Evaluation, Excellent (flaw of the film, lifting, peeling no), Good (scratches film, floating, the area ratio of peeling is less 0% and 0.5%), Average (flaw of the film, lifting, of the release less than 0.5% to 3% area fraction), Fair (flaw of the film, lifting, or less than 3% to 15% area ratio of peeling), Poor (flaw of the film, lifting, the area ratio of the release of 15 percent or broken evaluated in five stages of the process infeasibility).
　A case where the Average or more of the evaluation results were obtained was passed.
[0115]
(E) Weldability
　using a wire seam welder, under the conditions of the welding wire speed 80 m / min, was welded to the test material by changing the current. Comprehensively judging from the width of the proper current range welding defects such as sufficient minimum current value and the dust and welding spatter welding strength is obtained consists of a maximum current value starts conspicuous was evaluated weldability.
　Evaluation, Excellent (proper current range than 1500A), Good (less than proper current range over 800A 1500A), (less than the current proper current range 100A or 800A) Fair, 4 stages of Poor (less than proper current range 100A) in were evaluated.
　A case where the Good results of the evaluation were obtained was passed.
[0116]
(F) the primary coating adhesion
　epoxy test material - phenolic resin was applied was subjected to baking treatment at 200 ° C. 30 min. Put a grid cut of a depth reaching the base iron at 1mm intervals, and peeling with tape. Observing the peeling conditions, from the release area ratio was evaluated primary coating adhesion.
　Evaluation, Excellent (peeling area ratio is 0%), Good (peeling area ratio is 0% or less than 5%), Fair (peeling area ratio is less than 5% 30%), Poor (peeling area ratio is over 30% ) was evaluated in four stages.
　A case where the Good results of the evaluation were obtained was passed.
[0117]
(G) a secondary coating adherence
　epoxy test material - phenolic resin was applied was subjected to baking treatment at 200 ° C. 30 min. Put a grid cut of a depth reaching the base iron at 1mm intervals, then subjected to retort treatment at 125 ° C. 30 min. Dried, and peeled off the coating tape. Observing the peeling conditions were evaluated secondary paint adhesion from the release area ratio.
　Evaluation, Excellent (peeling area ratio is 0%), Good (peeling area ratio is 0% or less than 5%), Fair (peeling area ratio is less than 5% 30%), Poor (peeling area ratio is over 30% ) was evaluated in four stages.
　A case where the Good results of the evaluation were obtained was passed.
[0118]
(H) corrosion
　epoxy test material - phenolic resin was applied was subjected to baking treatment at 200 ° C. 30 min. Then, put the grid cut having a depth reaching the base steel, the test solution consisting of -1.5% saline mixture of 1.5% citric acid, was immersed at 45 ° C. 72 hours. Washed, dried and subjected to tape peeling. Observing the corroded condition of the coating film corrosion under conditions and the flat plate portion of the cross-cut portions, from both the evaluation of the corrosion area ratio of the width and the flat plate portion of the coating film under corrosion was evaluated corrosion resistance.
　Evaluation, Excellent (less than under coating corrosion width 0.2mm and corroded area ratio of 0% of the flat portion), Good (less coating corrosion under width 0.2 ~ 0.3 mm and the corrosion area ratio of 0% of the flat portion 1% or less), Fair (coating corrosion under width 0.3 ~ 0.45mm less than and less than 1% 5% corrosion area ratio of the flat portion), Poor (under coating corrosion width 0.45mm or greater than the flat plate portion It was evaluated in four stages of the corrosion area ratio of 5 percent).
　A case where the Good results of the evaluation were obtained was passed.

[Claim 1]Steel plate and;
　; at least one surface which is formed on the Ni plating layer and the steel sheet
　and the Ni-plated chemically formed on layer treated film layer;
comprises a,
　the Ni plating layer, 10 ~ 1000 mg / m of a metal Ni amount 2 by weight of Ni;
　the chemical conversion coating layer, 5 ~ 30 mg / m of a metal Zr content 2 contain Zr compounds of
　was determined by a scanning probe microscope, the average roughness of the outermost surface of the chemical conversion coating layer degree Ra of 10 nm ~ 100 nm,
　when defining the ΔYI represented the amount of change in the measured yellowness per measuring point in the outermost surface of the chemical conversion coating layer by the following equation (2),
　said outermost surface a plurality of said average values of the absolute values of the obtained the ΔYI measurement points is 5.0 or less, included in the unit area
, characterized in that the container for the steel sheet.
[Number 1]

[Claim 2]
　The Ni plating layer contains an alloy Ni
, characterized in that the container for steel sheet according to claim 1.
[Claim 3]
　The chemical conversion coating layer, 2 ~ 20 mg / m in the amount of P 2 further contains a phosphoric acid compound
, wherein the container for steel sheet according to claim 1 or claim 2.
[Claim 4]
　The chemical conversion coating layer is formed by performing a cathodic electrolysis treatment in the chemical conversion treatment solution containing Zr ions, and F ions
, characterized in that the container for steel sheet according to claim 1 or claim 2.
[Claim 5]
　The chemical conversion coating layer, Zr ions, is formed by performing a cathodic electrolysis treatment in the chemical conversion treatment solution containing F ions and phosphate ions
, characterized in that the container for steel sheet according to claim 3.
[Claim 6]
　On at least one surface of the steel sheet, the metal Ni amount 10 ~ 1000 mg / m 2
　; Ni plating process and to form a Ni plating layer containing Ni in performed using a chemical conversion treatment solution containing at least Zr ions and F ions, the conversion and the first cathodic electrolysis treatment temperature of the processing solution is 10 ~ 40 ° C., by performing a second cathode electrolytic treatment temperature of the chemical conversion treatment liquid is 45 ~ 60 ° C., the surface of the Ni plating layer a cathode electrolytic treatment to form a chemical conversion coating layer;
　and cleaning process utilizing at least 40 ° C. or more washing water for washing processes at least 0.5 seconds;
having
, characterized in that, for containers method of manufacturing a steel plate.
[Claim 7]
　After said Ni plating process, at least a portion of the Ni plating layer having an alloying heat treatment step of alloying
, wherein the method for producing a container for steel sheet according to claim 6.
[8.]
　The chemical conversion treatment solution, phosphate ions, which further contains at least one of nitrate ions and ammonium ions
and wherein the method of manufacturing a container for a steel sheet according to claim 6 or claim 7.