[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 containers for beverage or 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 paint waste solvents, a film instead of applying paint often pasted on the surface of the metal container it has come to be carried out.
[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, if necessary, organic solvent resistance, fingerprint resistance, scratch resistance, to improve the lubricity, etc., coating layer formed by chromate treatment (chromate film layer) coating layer made of an organic resin is formed on the.
[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, since it has excellent corrosion resistance and coating adhesion or film adhesion to steel, such a case without chromate treatment, corrosion resistance and coating adhesion or film adhesion is significantly reduced and will.
　Therefore, subjected to rustproofing alternative to chromate on the surface of the container steel sheet has come to be required to form a rust-preventive layer having excellent corrosion resistance and coating adhesion or film adhesion. 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, includes a Zr ion and F, an inorganic treating layer containing no phosphate ions, the processing method and a metal material having an organic process layers 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 8, a method to promote the formation of Zr film by adding a large amount of nitrate ions is disclosed.
CITATION
Patent Literature
[0010]
Patent Document 1: Japanese Patent 2000-239855 JP
Patent Document 2: Japanese Patent 2005-325402 JP
Patent Document 3: Japanese Patent 2005-23422 JP
Patent Document 4: Japanese Sho 54- 68734 JP
Patent Document 5: Japanese Patent 2006-9047 JP
Patent Document 6: Japanese Patent 2008-50641 JP
Patent Document 7: Japanese Patent 2009-84623 JP
Patent Document 8: WO 2011 / 118588 Patent
Patent Document 9: Japanese Patent No. 4920800 discloses
Patent Document 10: Japanese Patent No. 4886811 Publication
Summary of the Invention
Problems that the Invention is to Solve
[0011]
　As described above, in Patent Documents 2 to 10, a technique for forming a film containing a Zr compound is disclosed on a steel plate by performing the electrolysis in a solution containing Zr ions and F ions. However, in these technologies, there may not be sufficient adhesion to the surface of the metal container of the film such as polyester.
　Adhesive between the film and the steel plate film formed on the (metal container), 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, who without phenol resin is preferable.
[0013]
　Container steel sheet for use in food containers, it is necessary to have a sulfidation blackening. In the above Patent Documents 2-8, it has not been disclosed for this sulfidation blackening.
　The vessel steel plate, for example, fish meat, when used in a food container to high protein food contents of the beans and the like, the retort processing after food packing (high-temperature heat sterilization treatment in the presence of water vapor), and the container inner surface at least one of the contents is sometimes rarely discolored to black. Sulfide blackening, such a black strange phenomenon is referred to as sulfide blackening.
[0014]
　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 sulfide darkening is not as much as possible occur.
[0015]
　Container steel sheet, in addition to the sulfurization blackening and film adhesiveness, weldability, paint adhesion, and is required to have corrosion resistance.
[0016]
　The present invention has been made in view of the above circumstances, provide excellent film adhesion, sulfidation blackening, weldability, paint adhesion, and a method of manufacturing a container for a steel sheet and a container for steel sheet having a corrosion resistance an object of the present invention is to.
Means for Solving the Problems
[0017]
　The present invention is to solve the above problems, adopts the following means in order to achieve the object.
(1) for containers steel sheet according to one embodiment of the present invention comprises steel plates and a Sn plating layer formed on at least one surface of the steel sheet, and the chemical conversion coating layer formed on the Sn plating layer . The Sn plating layer, 300 ~ 5600 mg / m of a metal Sn amount 2 by weight of Sn, the chemical conversion coating layer, 5 ~ 30 mg / m of a metal Zr content 2 contain Zr compound of scanning probe microscopy was determined by the average roughness Ra of the outermost surface of the chemical conversion coating layer is 10 ~ 100 nm. When defined as 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 (1), a plurality of the included in the unit area of the outermost surface the average value of the absolute values of the obtained the ΔYI measurement points is 5.0 or less.
[0018]
[Number 1]

[0019]
(2) A container for steel sheet according to the above (1), the lower layer of the Sn plating layer may be Ni plating layer containing Ni is formed.
[0020]
　(3) A container for steel sheet according to the above (2), the Sn plating layer, 300 ~ 3000 mg / m of a metal Sn amount 2 may contain Sn of.
[0021]
(4) A container for steel sheet according to the above (3), the Ni plating layer, 5 ~ 150 mg / m of a metal Ni content 2 may contain Ni in.
[0022]
(5) A container for steel sheet according to the above (1), the Sn plating layer may contain a Sn alloy.
[0023]
(6) A container for steel sheet according to any one aspect of the above (2) to (4), wherein the Sn plated layer contains Sn alloy, the Ni plating layer may contain a Ni alloy.
[0024]
A container for steel sheet according to any one aspect of (7) above (1) to (6), wherein the chemical conversion coating layer, 2 ~ 20 mg / m in the amount of P 2 further contain a phosphoric acid compound good.
[0025]
(8) A container for steel sheet according to any one aspect of the above (1) to (6), wherein the chemical conversion coating layer by performing a cathodic electrolysis treatment in the chemical conversion treatment solution containing Zr ions and F ions it may be formed.
[0026]
(9) A container for steel sheet according to (7), wherein the chemical conversion coating layer, Zr ions, in the chemical conversion treatment solution containing F ions and P ions may be formed by performing a cathodic electrolysis treatment .
[0027]
(10) A method of manufacturing a container for a steel sheet according to one embodiment of the present invention, the surface of the steel sheet, the plating step of forming a Sn-plated layer containing Sn, the chemical conversion treatment solution containing at least Zr ions and F ions performed using, by performing a first cathode electrolytic treatment temperature of the chemical conversion treatment liquid is 10 ~ 40 ° C., and a second cathode electrolytic treatment temperature of the chemical conversion treatment liquid is 45 ~ 60 ° C., the having a cathode electrolytic treatment to form a chemical conversion coating layer on the surface of the Sn plating layer, and a cleaning process for cleaning the above processing 0.5 seconds using at least 40 ° C. or more washing water, the.
[0028]
The method of manufacturing a container for a steel sheet according to (11) above (10), in the plating step, the surface of the steel sheet, after forming a Ni plating layer containing Ni, on the surface of the Ni plating layer, wherein the Sn plating layer may be formed.
[0029]
(12) Yes In the method for manufacturing a container for a steel sheet according to (10) or (11), wherein after the plating step, the molten 溶錫 treatment step of alloying at least a portion of the Sn contained in the Sn plating layer it may be.
[0030]
(13) In the method for manufacturing a container for a steel sheet according to any one aspect of the above (10) to (12), wherein the chemical conversion treatment solution further, phosphate ions, also contain at least one nitrate ion and ammonium ion good.
Effect of the invention
[0031]
　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
[0032]
It is a structural view of a container for steel sheet according to the first embodiment of FIG. 1 the present invention.
It is a structural view of a container for steel sheet according to the second embodiment of the present invention; FIG.
3 is a flowchart showing an example of a method of manufacturing containers for steel sheet according to the first embodiment of the present invention.
It is a flowchart illustrating an example of FIG. 4] The method for producing a container for a steel sheet according to the second embodiment of the present invention.
DESCRIPTION OF THE INVENTION
[0033]
　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.
　As a result, with respect to the chemical conversion coating layer further comprises a phosphate compound in the chemical conversion coating layer comprising a chemical conversion coating layer or a Zr compound containing Zr compounds, surface properties and specific conditions of the chemical conversion coating layer formed on the steel plate the amount of change in yellowness index (YI value) after the retort treatment with (△ YI value) by defining a conventional chromate film layer more excellent film adhesion and sulfidation blackening, weldability, paint adhesion and then found that the resulting corrosion resistance, leading to the present invention.
[0034]
　The following describes in detail preferred embodiments of the present invention.
[0035]
　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 sheet Sn 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.
[0036]
[First Embodiment]
　FIG. 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 Sn-plated layer 3 formed on the steel plate 2, and a chemical conversion coating layer 4 formed on the Sn-plated layer 3.
[0037]
　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. The production method of the steel plate 2 and the material, etc. is not particularly limited, 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 .
[0038]
　The content of Sn in the Sn-plated layer 3, 300 mg / m of a metal Sn amount 2 ~ 5600 mg / m 2 is.
　Note that the "Sn plating layer" in this specification includes not only the plating layer containing a metal Sn, comprising a plating layer of a metal Sn of plating and trace elements were added by the metal Sn of unavoidable impurities are mixed. Note that the unavoidable impurities, the production means inevitably mixed elemental.
[0039]
　Sn has excellent workability has the weldability and corrosion resistance, In order to exert these effects, 300 mg / m as a metal Sn amount 2 or more is necessary for Sn.
　The effect increases metallic Sn amount is increased improved, the amount of metal Sn is 5600 mg / m 2 if it exceeds, the above effect is saturated. Therefore, the content of Sn from an economic point of view, 5600 mg / m of a metal Sn content 2 is preferably not more than.
　More preferred range of the content of Sn in the Sn-plated layer 3 in the present embodiment, 560 ~ 5600 mg / m 2 is.
[0040]
　Metal Sn content in the Sn-plated layer 3, for example, can be measured by fluorescent X-ray method. In this case, a metal Sn amount known sample, in advance identify calibration curve for the metal Sn amount, to identify the relative metal Sn amount using the calibration curve.
[0041]
　Sn 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 Sn-plated layer 3 on only one side of the steel plate 2 is formed when the can manufacturing process, for example, the surface Sn plating layer 3 is formed is processed to become the inner surface of the container it is preferable.
[0042]
　In the present embodiment, after the formation of the Sn-plated layer 3 may be subjected to a melt 溶錫 process. By melting 溶錫 process is performed, a part of Sn contained in the Sn-plated layer 3 is Fe alloyed contained in the steel plate 2. In this specification, the Sn-plated layer 3 melted 溶錫 processing has been performed, is referred to as alloy Sn plating layer. Alloy Sn plating layer may also contain Sn (free Sn) which are not alloyed. In the present specification, alloy Sn plating layer does not refer to only form Sn or Sn alloy covers the entire surface of the steel plate 2, the surface of the steel plate 2 is partially coated, exposed steel plate 2 is a part and (referred to as islands Sn) form is also defined to refer.
[0043]
　In the melt溶錫process, the steel plate 2 that Sn plating layer 3 is formed, and heated to the melting point (232 ° C.) or more Sn, melting the Sn-plated layer 3, and then water-cooled.
　The reason for the melting溶錫processing is as follows.
　Sn contained in the Sn-plated layer 3 prior to the melt溶錫process is a particulate, adhesion is relatively weak, it is dull. By subjecting the molten溶錫process, the appearance quality of the corrosion resistance and surface (mirror finish quality, etc.) can be further improved.
[0044]
　By melting溶錫treatment after the formation of the case (Sn plated layer 3 only Sn plating layer 3 on the surface of the steel plate 2 is formed is carried out, the case where the alloy Sn plating layer is formed on the surface of the steel plate 2 including), be attached to the surface of the film Sn-plated layer 3, or even by applying paint to the surface of the Sn-plated layer 3, the sulfur contained in the beverage or in food, and passes through the film or paint film, combined with sn, SnS or SnS black 2 may form a.
　Also, if the Sn-plated layer 3 is not melted溶錫process, Sn contained in the Sn-plated layer 3 as described above is in particulate form, adhesion is relatively weak. Therefore, in the Sn plating layer 3, composed of a plurality of fine pores (microporous) plating defect site is present. In this case, it bound and Fe contained in the sulfur and the steel plate 2, black FeS, Fe 2 S 3 , and Fe 2 S is formed.
[0045]
　To reduce these blackening phenomenon, container steel sheet 1 according to this embodiment, the upper layer of the Sn-plated layer 3, having a chemical conversion film layer 4.
[0046]
　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), increased mechanical adhesion, by adherable area with the film is increased, even in the chemical adhesion and physical adhesion, increase these adherable area there is an effect of.
[0047]
　In the present embodiment, Zr content of the chemical conversion coating layer 4, 5 ~ 30mg / m of a metal Zr content 2 is.
　Zr content 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 content is 30 mg / m 2 if it exceeds, the surface roughness can be obtained stably, but because weldability during three-piece can forming is insufficient, undesirably.
　Zr content 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 of a metal Zr content 2 is.
[0048]
　Here, Zr content of the chemical conversion coating layer 4, for example, can be measured by fluorescent X-ray method. In this case, a Zr amount known sample, in advance identify a calibration curve relating amount of Zr, it identifies a relatively Zr content using the calibration curve. Using Zr amount known sample on the Sn-plated layer 3, it is more preferable to preliminarily identify a calibration curve relating amount of Zr.
[0049]
　In the outermost surface of the chemical conversion coating layer 4, 1 m 2 average roughness of 5μm angle planar portion of any 20 points per (Ra) is 10nm or more 100nm or less.
　When the average roughness is less than 10nm, although the primary adhesion of the film can be secured, can-processing and end processing such as the post-processing of the film adhesion (secondary adhesion) is may not be ensured in a stable manner Yes, it is not preferable. Further, When the above average roughness is 100nm greater is the Zr content 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.
[0050]
　When the thickness of the film is 5μm or less, may affect the surface properties of the film applied to the surface of the container for the steel plate 1, it is not preferred. The thickness of the film is preferably in 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.
[0051]
　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.
[0052]
　Using a scanning probe microscope, 1m of the outermost surface of the chemical conversion coating layer 4 2 describes a method of measuring the average roughness of 5μm angle planar portion of any 20 points per (Ra).
　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 is sufficient 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 it may be calculated in accordance.
[0053]
[Table 1]

[0054]
　When measuring the roughness of the chemical conversion coating layer 4 with a scanning probe microscope, roughness such as a lower-layer of the Sn-plated layer 3 of the chemical conversion coating layer 4, it may affect the roughness of the chemical conversion coating layer 4 is there. 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 Sn 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.
[0055]
　In the present embodiment, the amount of change in the measured yellowness per measuring point at the outermost surface of the chemical conversion coating layer 4 is defined as .DELTA.YI. Here, the amount of change in yellowness index (YI value) A (.DELTA.YI value), yellowness of the container for the steel sheet 1 and (YI value), 5 hours retorted at a temperature of 130 ° C. relative to the vessel for steel 1 It means the difference between the YI value after applying.
　In addition, in the present embodiment, the unit area of the outermost surface of the chemical conversion coating layer 4 (1 m 2 average of the absolute values of ΔYI obtained for the measurement point of the plurality (e.g., 20) included therein)
[0056]
　Note that the retort processing, sterilization by saturated steam at high temperature and high pressure (autoclave sterilization, autoclaving) using an apparatus for processing (high-pressure steam sterilizer), Sn-plated layer 3 and the chemical conversion coating layer according to the embodiment It means to process the container steel sheet 1 and a 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.. The 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.
[0057]
　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 calorimetric color difference meter, determine the tristimulus values ​​X, Y, Z, is calculated by substituting them into equation (2) below.
[0058]
　　YI value = 100 × (1.28X-1.06Z) ÷ Y ··· (2)
[0059]
　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.
[0060]
　The amount of change in yellowness index (YI value) (△ YI value), as described above, the YI value of the container for the steel sheet 1 was subjected 5 hours retorted at a temperature of 130 ° C. relative to the vessel for steel 1 It means the difference between the YI value after. That is, the amount of change of yellowness index (YI value) (△ YI value) is calculated by the following equation (1).
[0061]
[Number 2]

[0062]
　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.
　By forming the upper layer on the chemical conversion film layer 4 of the Sn-plated 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.
[0063]
　On the other hand, to form a chemical conversion coating layer 4 on the Sn-plated layer 3, by performing 5 hours retorted at a temperature of 130 ° C., although △ YI value often indicates a negative value, a positive value there is also the case shown. As will be described later, also △ YI value is a positive, △ even YI value is a negative, △ YI value of the size (that is, the degree of change in yellowness), the between the sulfidation blackening correlation. Therefore, in this embodiment, as an indicator of sulfidation blackening, using the absolute value of △ YI value.
[0064]
　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.
[0065]
　In the present embodiment, the absolute value of the yellowness index variation in which △ YI value (YI value) is used as an index showing the coating degree of the Sn-plated layer 3, and the chemical conversion film layer 4. When the Sn plating layer 3 or the chemical conversion coating layer 4 is defective, 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 Sn 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.
　The case where there is a defect in the Sn plating layer 3 or the chemical conversion coating layer 4, for example, may by microporous defect chemical conversion film layer 4 be a heterogeneous or Sn plating layer 3 is oxidized by retorting and the like.
[0066]
　At each measurement point, by the above method calculates the absolute value of the ΔYI value, averaged 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 yellowness at any 20 points per amount of change (YI value) (△ YI value) and the average value.
[0067]
　If the average of the absolute value of the above △ YI value of 5.0 or less, dense and uniform Sn plated 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 it is not at least one of formation and dense and uniform Sn plated layer 3 the chemical conversion film layer 4.
　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.
[0068]
　The present inventors have found that the absolute value of the ΔYI value, 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 container steel sheet 1 does not have an excellent sulfidation blackening, if the average of the absolute values ​​of △ YI value is low the container for the steel sheet 1 has an excellent sulfidation blackening.
[0069]
　In retort processing, conversion because the coating degree of the treated film layer 4 water molecules or oxygen molecules enter the lower portion, Sn of the chemical conversion coating layer 4 Sn 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 Sn and iron caused by the retort process is affected by the coating degree of the Sn-plated 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 is affected by the oxidation state of the metal such as Sn or iron.
　Therefore, the average of the absolute values of ΔYI value is considered to indicate a coating degree of the chemical conversion coating layer 4.
[0070]
　On the other hand, the chemical conversion coating layer 4 of the coating degree of hydrogen molecules sulfide from the lower part, since thiol ions or sulfur molecules from entering, the Sn-plated layer 3 on the lower layer than the chemical conversion coating layer 4 Sn, even in the steel sheet 2 of metal such as iron is sulfide. 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 Sn-plated layer 3, and the chemical conversion film layer 4.
[0071]
　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.
[0072]
　The present inventors have found that in order to exert a sulfidation blackening the container steel plate 1 is excellent and good film adhesion, that the chemical conversion film layer 4 are two layers having different functions forms knowledge was obtained of the preferred.
　Based on this finding, in the present embodiment, the chemical conversion coating layer 4, in order to suppress transmitted through the foreign molecule, such as water molecules and hydrogen sulfide molecules from the surface, a uniform and dense layer on the Sn plated layer 3 a, the uniform and on the dense layer in order to ensure the film adhesion, 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.
[0073]
　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.
[0074]
　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.
[0075]
　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, the chemical conversion coating layer 4 adhesion itself is deteriorated. Furthermore, since the electric resistance of the chemical conversion coating layer 4 is increased, the weldability of containers steel plate 1 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 content 2 exceeds the surface of the chemical conversion coating layer 4 (i.e., the second chemical conversion coating sometimes Zr compound powdery on the surface) of the layer is deposited.
[0076]
　Accordingly, Zr compound amount of Daiichi Kasei treated film layer, 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, 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.
[0077]
　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.
[0078]
　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, that this effect can be recognized, 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.
[0079]
　Therefore, phosphoric acid compound amount such Zr- phosphoric acid compound in Daiichi Kasei treatment 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, phosphoric acid compound amount such Zr- 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.
[0080]
　On the other hand, Zr- sulfidation blackening the phosphoric acid compound amount is increased, such as phosphoric acid compounds, corrosion resistance, and 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, adhesion between itself phosphate compound is deteriorated. Further, since the electric resistance of the chemical conversion coating layer 4 is increased, the weldability of containers steel plate 1 is deteriorated. Furthermore, 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-P compounds of the powdery on the surface of the chemical conversion coating layer 4 is deposited If there is a.
[0081]
　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.
[0082]
　Thus, the total phosphate amount of compound such as Zr- phosphate compound contained in the chemical conversion film layer 4, 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 organic substances such as phenol resin. Therefore, the chemical conversion coating layer 4 preferably does not contain an organic substance such as phenolic resin.
[0083]
　The metal Zr amount chemical conversion coating layer 4 contains in this embodiment, the metal Sn of P amount and the Sn plating layer 3 is, for example, can be determined by quantitative analysis methods such as X-ray fluorescence analysis is there. In this case, a metal Sn amount known Sn-plated steel sheet samples, previously identified a calibration curve for the metal Sn amount, it is possible to identify the relative metal Sn amount by using this calibration curve.
[0084]
　Further, using a metal Zr amount known samples and the amount of P known sample, in advance identify a calibration curve of the calibration curve and the amount of P relates to a metal Zr weight, relatively metals Zr amount using these calibration curves and it is possible to identify the P amount.
[0085]
　Hereinafter, a method for manufacturing a container for a steel sheet 1 according to this embodiment.
　Figure 3 is a flow chart showing an example of a method for manufacturing a container for a steel sheet according to the first embodiment of the present invention.
[0086]
　In the present embodiment, Sn plating layer 3 is formed on at least one surface of the steel plate 2 (Step S3). A method of forming a Sn-plated layer 3 is not particularly limited. For example, in the Ferrostan bath, electroplating, it may be a known technique such as vacuum deposition or sputtering.
[0087]
　As described above, it may be subjected to melt 溶錫 treatment after Sn plating layer 3 formed. The conditions for melt 溶錫 treatment, 232 ° C. (Sn melting point) ~ 280 ° C., and heat treatment at 0.5 sec ~ 30 sec, and melting the Sn plated layer, examples may be cited immediately water-cooled.
[0088]
　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 Sn-plated layer 3. However, in the immersion process, since the base (Sn plating layer 3) was etched chemical conversion coating layer 4 is formed, the 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.
[0089]
　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 Sn plating layer 3 is formed, it is possible to form a uniform chemical conversion film layer 4.
[0090]
　In the present embodiment, with respect to the steel plate 2 that Sn 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 both Zr oxide and Zr phosphate compound is formed.
[0091]
　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 S7) for 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 S9) carried out.
[0092]
　The first cathode electrolytic treatment described above, Daiichi Kasei treated film layer on the Sn-plated 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.
[0093]
　For the technique of forming a chemical conversion coating layer 4 containing Zr compound by performing cathodic electrolysis treatment in the chemical conversion treatment liquid at least containing a Zr ion and F ions, techniques disclosed in the above patent document and the like have been made. However, in the above patent documents and the like, by changing the cathodic electrolysis treatment condition stepwise, does not disclose a technique for multi-layered chemical conversion film layer 4.
[0094]
　Meanwhile, 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.
[0095]
　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 the temperature is below 10 ° C. of the chemical conversion treatment liquid, 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, if the temperature of the chemical conversion treatment 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 function as Daiichi Kasei treatment film layer described above.
　Temperature of the chemical conversion treatment liquid of the first cathodic electrolysis treatment is preferably, 20 ℃ ~ 35 ℃.
[0096]
　The temperature of the chemical conversion solution of the second cathodic electrolysis treatment is 45 ℃ ~ 60 ℃.
　When the temperature of the chemical conversion solution but less than 45 ° C., it becomes difficult to ensure the surface roughness defined in the present embodiment.
　On the other hand, when the temperature of the chemical conversion treatment liquid is 60 ° C. greater, 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, the cathode when the electrolytic process continuously performed decomposes F complex components such as the Zr gradually, for floating in the treatment liquid became insoluble matter, etc. adhering to the chemical conversion film layer 4 surface ,Adversely affect.
　The temperature of the chemical conversion solution of the second cathodic electrolysis treatment is preferably, 45 ℃ ~ 55 ℃.
[0097]
　If the line 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 follows the line speed becomes faster, 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, the chemical conversion treatment liquid of the second cathode electrolytic cell may lead to a decrease in temperature, there may be a case that prevents the efficient formation of the second chemical conversion coating layer having a two-layer structure of the chemical conversion coating layer 4 of the present invention as a result.
[0098]
　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.
[0099]
　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 sheet can cathodic electrolysis treatment is not particularly limited.
[0100]
　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, in addition to the Zr ions and F ions, of 50 ppm ~ 5000 ppm phosphate ion, or, even using the chemical conversion treatment liquid containing less nitrate ions and ammonium ions 20000ppm good.
[0101]
　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.
[0102]
　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.
[0103]
　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, corrosion resistance and film adhesion contributes Zr oxide to improved, it is possible to promote the deposition of the chemical conversion coating layer 4 including the Zr- phosphate compound. Therefore, the chemical conversion treatment liquid containing the ions is industrially very advantageous.
　Therefore, the formation of the chemical conversion coating layer 4 of the present embodiment, it is desirable to use a cathode electrolytic treatment, in particular, it is more desirable to perform the cathodic electrolysis treatment in a chemical conversion treatment solution containing a nitrate ion and ammonium ion.
[0104]
　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 substances such as phenol resin on the anode is decomposed and metal ions there is a case in which inevitably insoluble in the interaction. 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 organic substances such as phenol resin may not be stably formed, the chemical conversion treatment liquid it is desirable not to contain organic substances such as phenol resin.
[0105]
　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, by F ions steam or corrosive solution in the chemical conversion film layer 4 is eluted, the F ions are decomposed chemical conversion coating layer 4 and the film, the bond between the organic film layer of paint or the like, or it is believed to be due to corrosion of the steel plate 2.
[0106]
　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 S11). 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 may be performed more than 0.5 seconds using a 40 ° C. or more cleaning water. 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.
[0107]
　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 and ammonium ion content.
[0108]
　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.
[0109]
[Second Embodiment]
　FIG. 2 shows a block diagram of a container for the steel sheet 11 according to a second embodiment of the present invention.
　The vessel steel plate 11 includes a steel plate 12, the Ni plating layer 15 formed on the steel plate 12, the Sn-plated layer 13 formed on the Ni plating layer 15, a chemical conversion treatment, which is formed on the Sn-plated layer 13 and a coating layer 14.
[0110]
　Ni plating layer 15 is formed on at least one surface of the steel plate 12. Ni plating layer 15 may be composed of metal Ni, or may be composed of Fe-Ni alloy plating.
　Since Ni is a metal having excellent corrosion resistance, by vessel steel plate 11 has a Ni plating layer 15, it is possible to ensure corrosion resistance.
[0111]
　Corrosion resistance higher Ni content of the Ni plating layer 15 is large is improved. Ni content, 5 mg / m of a metal Ni 2 if more, has excellent corrosion resistance. On the other hand, Ni content, 150 mg / m of a metal Ni 2 exceeds, the above effect saturates. Further, Ni since is an expensive metal, Ni content, 150 mg / m of a metal Ni 2 also becomes economically disadvantageous exceeding.
　Therefore, Ni content of the Ni plating layer 15, 5 mg / m of a metal Ni 2 ~ 150 mg / m 2 is preferably set to.
[0112]
　Sn-plated layer 13 is formed in order to ensure the corrosion resistance and weldability.
[0113]
　The content of Sn in the Sn-plated layer 13, 300 mg / m of a metal Sn amount 2 equal to or more than the corrosion resistance by Sn is exhibited. Therefore, the metal Sn amount in the Sn-plated layer 13 in the present embodiment, 300 mg / m 2 and more.
　Although the above effect, the amount of metal Sn is 5600 mg / m 2 saturates exceeds. Therefore, from an economic point of view, Sn content, 5600 mg / m 2 or less.
　More preferred range of the content of Sn in the Sn-plated layer 13 in the present embodiment, 300 ~ 3000 mg / m 2 is. The content of Sn in the Sn-plated layer 13 is 300 ~ 3000 mg / m 2 in the case of, in the case of performing melt溶錫treatment after the formation of the Sn-plated layer 13 (forming the alloy Sn plating layer), an alloy Sn plating layer is formed in an island shape. By alloy Sn plating layer is formed in an island shape, it is possible to alloy Sn plating layer as compared with the case of uniformly coat the steel plate 2, exhibits better corrosion resistance and weldability.
[0114]
　In this embodiment, like the first embodiment, it may be performed molten溶錫treatment after Sn plating layer 13 formed.
　By melt溶錫treatment on the steel plate 2, the alloy Ni plating layer is formed containing a Fe-Ni or Sn-Fe-Ni alloy, it is on the alloy Ni plating layer alloy Sn plating layer is formed.
　In this specification, the Ni plating layer 15 melt溶錫processing has been performed, is referred to as alloy Ni plating layer. Alloy Ni plating layer, as described above, contains a Fe-Ni or Sn-Fe-Ni alloy may contain Ni (free Ni) that are not alloyed.
　Alloy Sn plating layer contains Sn-Fe alloy or Sn-Fe-Ni alloy may contain Sn (free Sn) which are not alloyed. The content of Sn in the Sn-plated layer 13 is 300 ~ 3000 mg / m 2 in the case of, as described above, alloy Sn plating layer is formed in an island shape. When the alloy Sn plating layer is formed in an island shape, the lower layer of the alloy Ni plating layer is exposed.
[0115]
　From the viewpoint of reducing manufacturing costs, Ni plating layer 15 and Sn plating layer 13 is, for the points which may be is not necessarily formed on both surfaces of the steel plate 12 is the same as the first embodiment.
[0116]
　Chemical conversion coating layer 14 in the present embodiment has the same structure and components and the chemical conversion coating layer 4 in the first embodiment, the description thereof is omitted. Note that point it is preferable that the chemical conversion coating layer 14 does not contain organic substances such as phenol resin is the same as the first embodiment.
[0117]
　Hereinafter, a method for manufacturing a container for a steel sheet 11 according to the second embodiment.
　Figure 4 is a flow chart showing an example of a method for manufacturing a container for a steel sheet 11 according to a second embodiment of the present invention.
[0118]
　In this embodiment, Ni plating layer 15 is formed on at least one surface of the steel sheet 12 (step S101). As a method of Ni plating and Fe-Ni alloy plating, for example, generally known methods which are performed in the electroplating (e.g., cathode electrolysis) it can be utilized.
　When forming the Ni plating layer 15 by diffusion plating method, after forming the Ni plating layer 15 on the surface of the steel sheet 12, but the diffusion treatment for forming a diffusion layer in the annealing furnace is carried out, the diffusion process simultaneously with longitudinal or diffusion process may be performed nitriding treatment. Even when subjected to nitriding treatment, the effect of effect and nitrided layer of Ni as Ni plating layer 15 in this embodiment is never interfere, can exert these effects together.
[0119]
　After the above Ni plating or Fe-Ni plating, Sn plating layer 13 is formed (step S103).
　Method of forming the Sn-plated layer 13, but is not particularly limited, for example, may be used a method in which plating by immersing the steel plate 12 in a known electroplating method or molten Sn.
[0120]
　After formation of the Sn-plated layer 13 may be subjected to a melt 溶錫 process. Effect of melt 溶錫 process is as described above. As the conditions for melt 溶錫 treatment, 232 ° C. (Sn melting point) ~ 280 ° C., and heat treatment at 0.5 sec ~ 30 sec, and melting the Sn plated layer, examples may be cited immediately water-cooled.
[0121]
　After the formation of the Sn-plated layer 13, to form a chemical conversion film layer 14.
　Method of forming a conversion coating layer 14 in this embodiment, similarly to the method of forming the chemical conversion coating layer 4 in the first embodiment, the first cathodic electrolysis treatment (step S107) and the second cathode electrolytic treatment (Step S109) consisting of. Since these first cathode electrolytic treatment and the second cathode electrolytic treatment is the same as the first embodiment, the description thereof is omitted.
[0122]
　After the second cathode electrolytic treatment, for cleaning process (step S111). Cleaning process of this embodiment is the same as the cleaning process of the first embodiment, the description thereof is omitted.
　Note that point it is preferable that the chemical conversion treatment solution does not contain organic substances such as phenol resin is the same as the first embodiment.
Example
[0123]
　Described Examples and Comparative Examples of the present invention are described below. Note that the embodiments described 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 It is not limited to the following examples.
[0124]
(First Embodiment)
: (A1 and A2 production method of a plated steel plate)
　using the method of the following procedure (A1) or (A2), thickness 0.17 ~ 0.23 mm on the steel sheet to form a Sn plating layer.
(A1) after the cold rolling, after the original sheet whose pressure annealing and tone were degreased and pickled, PSA (phenol sulfonic acid) 60 g / L, tin sulfate: 54g / L (Sn as 30 g / L), additives (ethoxylated -α- naphthol) 3 g / L, additive bath temperature 50 ° C. using a Ferrostan bath having a composition of (ethoxy-naphthol sulfonic acid) 3 g / L, current density 7 ~ 10A / dm 2 Sn plating condition to form a layer. Coating weight was adjusted with the electrolysis time.
(A2) after the cold rolling, after the original sheet whose pressure annealing and tone were degreased and pickled, PSA (phenol sulfonic acid) 60 g / L, tin sulfate: 54g / L (Sn as 30 g / L), additives (ethoxylated -α- naphthol) 3 g / L, additive bath temperature 50 ° C. using a Ferrostan bath having a composition of (ethoxy-naphthol sulfonic acid) 3 g / L, current density 7 ~ 10A / dm 2 Sn plating condition to form a layer. Coating weight was adjusted with the electrolysis time. Then, the Sn-plated steel sheet was heated at 260 ° C., to melt the Sn plating layer was performed immediately water-cooled (melt溶錫process).
[0125]
　Sn content of the resulting plated steel sheet was measured by a fluorescent X-ray method. The Sn content of each level is shown in Table 2.
[0126]
[Table 2]

[0127]

　The plated steel sheet produced by the method of the above (A1) or (A2), was subjected to cathodic electrolysis treatment in current times and temperature conditions shown in Table 2. The composition of the chemical conversion treatment liquid shown in Table 3. Incidentally, the chemical conversion treatment liquid, hexafluoro zirconium in distilled water (IV) ammonium, hydrogen fluoride, dissolved ammonium nitrate and phosphoric acid, the pH was adjusted to 3.5.
[0128]
[table 3]

[0129]

　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.
[0130]
　Current density (0.1 ~ 30A / dm 2 ), by adjusting the electrolysis time (0.5 to 5 seconds), to adjust the Zr content and the P content of each level.
[0131]

　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 4.
[0132]
(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) in an image processing software ImageJ (image processing software in the public domain at the open source developed by the National Institutes of Health (NIH)), the average roughness I was asked.
[0133]
(B) yellowness
　chemical conversion coating layer side 1m of test material 2 a per arbitrary 20 sites (at least more than 10cm distant sites) was cut to a size of 50 mm × 100 mm. The chemical conversion coating layer side evaluated in the table, using Z clave S-020A (Miura Co., Ltd.), was carried out for 5 hours retort at a temperature of 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.
[0134]
(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, Exellent (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.
[0135]
(D) Film adhesion
　to both surfaces of the test material, pasting a biaxially oriented PET film having a thickness of 20μm at 170 ° C., was can-working by drawing and ironing step by step. Flaw of the film, float, and to observe the peeling was evaluated film adhesion from their area ratio.
　Evaluation Excellent (flaw of the film, float, and there is no peeling), Good (scratches film, float, and the area ratio of peeling is less 0% and 0.5%), Average (flaw of the film, float, and less than 0.5% 3% area ratio of peeling), Fair (flaw of the film, floating, and separation of the area ratio is less than 3% 15%), Poor (flaw of the film, float, and the area ratio of the release There was evaluated in five stages of the process infeasibility) was greater or breaking 15%.
　A case where the Average or more of the evaluation results were obtained was passed.
[0136]
(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 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 (or proper current range of the secondary side 1500A), Good (less than secondary side of the current proper current range over 800A 1500A), Fair (less than the current proper current range of the secondary side 100A or 800A) , it was evaluated in four stages of Poor (less than the current proper current range of the secondary side 100A).
　A case where the Good results of the evaluation were obtained was passed.
[0137]
(F) the primary coating adhesion
　epoxy test material - phenolic resin was applied, was carried out for 30 minutes to baking treatment at a temperature of 200 ° C.. Put a grid cut of a depth reaching the base iron at 1mm intervals, and peeling with tape. Observing the peeling conditions were evaluated primary coating 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.
[0138]
(G) a secondary coating adherence
　epoxy test material - phenol resin was coated, was carried out for 30 minutes to baking treatment at a temperature of 200 ° C.. Put a grid cut of a depth reaching the base iron at 1mm intervals, was followed for 30 minutes retorted at a temperature of 125 ° C.. After drying, peeling the coating film tape, to observe 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.
[0139]
(H) corrosion
　epoxy test material - phenolic resin was applied, was carried out for 30 minutes to baking treatment at a temperature of 200 ° C.. 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 a temperature of 45 ° C. 72 hours. After washing and drying, it was subjected to a tape peeling. Observing the corrosion condition of the coating film corrosion under conditions and the flat plate portion of the cross-cut portion, from 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 0% corrosion area ratio of the flat portion), Good (under coating corrosion width is less than 0.2 ~ 0.3 mm and the corrosion area ratio of the flat plate portion There follows 0 percent 1 percent), Fair (under coating corrosion width 0.3 ~ 0.45 mm below and flat portions of the corrosion area ratio is less than 1% 5%), Poor (under coating corrosion width 0 .45mm greater or a flat portion of the corroded area ratio was evaluated at four levels greater than 5%).
　A case where the Good results of the evaluation were obtained was passed.
[0140]
[Table 4]

[0141]
　Level C1 ~ C13 within the scope of the present invention are all, the average roughness (Ra) is 10 ~ 100 nm, the average of the absolute values of △ YI value was 5.0 or less. These levels C1 ~ C13 has excellent sulfidation blackening, weldability, and had a primary coating adhesion, secondary paint adhesion, and a coating film under corrosion.
　On the other hand, the level C15 ~ C22 that do not satisfy any of the requirements of the average roughness (Ra) or △ YI value of the present invention, (including processability) film adhesion, sulfidation blackening, weldability, primary paint adhesion sex, secondary paint adhesion, or at least some of the properties of the corrosion resistance was found to be inferior.
[0142]
　Levels C14 is a case of increasing than a specified amount of Ni amount and Sn content, the performance of the chemical conversion coating layer was found to be saturated.
[0143]
(Second Embodiment)
: (A3 ~ A5 method of manufacturing a plated steel sheet)
　using the method of the following procedure (A3) ~ (A5), thickness 0.17 ~ 0.23 mm on the steel sheet to form a Ni plating layer and Sn plating layer.
[0144]
(A3) after the cold rolling, the original sheet whose pressure annealing and tone, after degreasing and pickling, nickel sulfate hexahydrate 75 g / L, nickel chloride hexahydrate 140 g / L, ferrous sulfate heptahydrate 110g / L, boric acid 30 g / L, sulfuric acid with a composition of citric acid 3 g / L - bath temperature 50 ° C. with hydrochloric acid bath, current density of 5A / dm 2 Fe-Ni alloy plating condition to form a layer. Next, PSA (phenol sulfonic acid) 60 g / L, tin sulfate: 54 g / L (Sn as 30 g / L), the additive (ethoxylated -α- naphthol) 3 g / L, additive (ethoxy naphthol sulfonic acid) 3 g / bath temperature 50 ° C. using a Ferrostan bath having a composition of L, the current density 7A / dm 2 to form a Sn plating layer under the conditions of. Coating weight was adjusted with the electrolysis time. Then, the Sn-plated steel sheet was heated at 260 ° C., to melt the Sn plating layer was performed immediately water-cooled (melt溶錫process).
(A4) after the cold rolling, the original sheet whose pressure annealing and tone has nickel sulfate hexahydrate 75 g / L, nickel hexahydrate 140 g / L chloride, the composition of boric acid 40 g / L, pH 4 bath temperature 50 ° C. using a watts bath, current density of 5A / dm 2 to form an Ni plating layer in conditions. To form a Ni diffusion layer during annealing, after degreasing and pickling, PSA (phenol sulfonic acid) 60 g / L, tin sulfate: 54 g / L (Sn as 30 g / L), the additive (ethoxylated -α- naphthol) 3 g / L, additive bath temperature 50 ° C. using a Ferrostan bath having a composition of (ethoxy-naphthol sulfonic acid) 3 g / L, current density 7A / dm 2 to form a Sn plating layer under the conditions of. Then, the Sn-plated steel sheet was heated at 260 ° C., to melt the Sn plating layer was performed immediately water-cooled (melt溶錫process).
(A5) after the cold rolling, after the original sheet whose pressure annealing and tone were degreased and pickled, nickel sulfate hexahydrate 75 g / L, nickel chloride hexahydrate 140 g / L, ferrous sulfate heptahydrate 110g / L, boric acid 30 g / L, sulfuric acid with a composition of citric acid 3 g / L - bath temperature 50 ° C. with hydrochloric acid bath, current density of 5A / dm 2 Fe-Ni alloy plating condition to form a layer. Next, PSA (phenol sulfonic acid) 60 g / L, tin sulfate: 54 g / L (Sn as 30 g / L), the additive (ethoxylated -α- naphthol) 3 g / L, additive (ethoxy naphthol sulfonic acid) 3 g / bath temperature 50 ° C. using a Ferrostan bath having a composition of L], a current density of 7A / dm 2 to form a Sn plating layer under the conditions of.
[0145]
　Ni content and the Sn content of the formed Ni plating layer and the Sn plating layer was measured by a fluorescent X-ray method. The Ni content and the Sn content of each level is shown in Table 5.
[0146]
[table 5]

[0147]

　The plated steel sheet produced by the method of the above (A3) ~ (A5), was immersed in the chemical conversion treatment liquid shown in Table 3, the cathodic electrolysis treatment in current times and temperature conditions shown in Table 5 went.
[0148]

　After the formation of the chemical conversion coating layer, washing treatment was performed in the same manner as the first embodiment.
[0149]

　for the test material subjected to the above process, in the first embodiment and the same method, the measurement of surface roughness and yellowness, sulfidation blackening, film adhesiveness, weldability, primary paint adhesion, secondary paint adhesion and corrosion resistance were performance evaluations. The evaluation results are shown in Table 6.
[0150]
[Table 6]

[0151]
　Both levels D1 ~ D17 within the scope of the present invention, the average of the absolute value of the average roughness (Ra) is 10 ~ 100 nm and ΔYI value was 5.0 or less. These levels D1 ~ D17 had excellent sulfidation blackening, film adhesiveness, weldability, primary paint adhesion, a secondary paint adhesion and corrosion resistance.
　Further, 2 mg / m as P amount during chemical conversion coating 2 by containing the above phosphoric acid, had better sulfidation blackening, film adhesion, corrosion resistance.
[0152]
　On the other hand, the level D18 ~ D25 is not satisfied at least one of the requirements of the average roughness (Ra) and ΔYI value of the present invention, sulfidation blackening, film adhesiveness, weldability, primary paint adhesion, secondary paint adhesion , and was found to be poor at least some of the properties of the corrosion resistance.
[0153]
　Having described in detail preferred embodiments of the present invention, the present invention is not limited to such an example. It would be appreciated by those skilled in the relevant field of technology of the present invention, within the scope of the technical idea described in the claims, it is intended to cover various modifications, combinations, for even these are understood as naturally belong to the technical scope of the present invention.
Industrial Applicability
[0154]
　According to the present invention, 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. Accordingly, the present invention has sufficient industrial applicability.
DESCRIPTION OF SYMBOLS
[0155]
　1,11 container steel
　2,12 steel
　3, 13 Sn plating layer
　4, 14 chemical conversion coating layer
　15 Ni plating layer

claims

[Claim 1]Steel plate and; at least one surface which is formed on the Sn plating layer and the steel sheet
　and the Sn in the formed plated layer was chemical conversion coating layer;
comprises a,
　the Sn plating layer, a metal Sn weight 300 ~ 5600 mg / m 2 by weight of Sn,
　the chemical conversion coating layer, a metal Zr amount 5 ~ 30 mg / m 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 ~ 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 (1),
　wherein the outermost surface more averages of the absolute values of the ΔYI obtained for the measurement point is 5.0 or less contained in the unit area
, characterized in that the container for the steel sheet.
[Number 1]

[Claim 2]
　Wherein the lower layer of the Sn plating layer, Ni plating layer containing Ni is formed
, characterized in that the container for steel sheet according to claim 1.
[Claim 3]
　The Sn plating layer, 300 ~ 3000 mg / m of a metal Sn amount 2 contains Sn of
, characterized in that the container for steel sheet according to claim 2.
[Claim 4]
　The Ni plating layer, 5 ~ 150 mg / m of a metal Ni amount 2 containing Ni in
, characterized in that the container for steel sheet according to claim 3.
[Claim 5]
　The Sn plating layer contains Sn alloy
, wherein the container for steel sheet according to claim 1.
[Claim 6]
　The Sn plating layer contains Sn alloy,
　the Ni plating layer contains Ni alloy
, characterized in that the container for steel sheet according to any one of the preceding claims 2.
[Claim 7]
　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 any one of claims 1 to 6.
[8.]
　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, according to any one of claims 1 to 6 container for steel plate.
[Claim 9]
　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 P ions
, characterized in that the container for steel sheet according to claim 7.
[Claim 10]
　On the surface of the steel sheet, plating process and to form a Sn plating layer containing Sn;
　performed using a chemical conversion treatment solution containing at least Zr ions and F ions, the temperature of the chemical conversion treatment liquid is 10 ~ 40 ° C. a first cathode electrolytic treatment, the chemical conversion treatment liquid temperature by performing a second cathode electrolytic treatment is 45 ~ 60 ° C., and a cathode electrolytic treatment to form a chemical conversion coating layer on the surface of the Sn plated layer ;
　; a cleaning process utilizing at least 40 ° C. or more washing water for washing processes at least 0.5 seconds
with a
method of manufacturing a container for a steel sheet, characterized in that.
[Claim 11]
　In the plating process, the surface of the steel sheet, after forming a Ni plating layer containing Ni, on the surface of the Ni plating layer, to form the Sn plating layer
, characterized in that, according to claim 10 method of manufacturing a container for steel plate.
[Claim 12]
　After the plating process, a melt溶錫treatment step of alloying at least a portion of the Sn contained in the Sn plating layer
, wherein the method for producing a container for steel sheet according to claim 10 or claim 11 .
[Claim 13]
　The chemical conversion treatment solution further comprises phosphate ions, contain at least one nitrate ion and ammonium ions
and wherein the method of manufacturing a container for a steel sheet according to any one of claims 12 to claim 10.