Technical field
[0001]
The present invention relates to a method for producing a chemical conversion treatment steel sheet and the chemical conversion treated steel sheet.
BACKGROUND
[0002]
By continued use of metal, there are cases where corrosion occurs. In order to prevent corrosion occurring in the metal, various techniques have been proposed. The proposed techniques, technologies and to plate the metal plate, a technique for performing various surface treatments can be given to a metal plate or plated surfaces.
[0003]
　For example, in Patent Document 1, the surface of the Al-Zn alloy coated steel sheet for use in building materials and appliances, vanadium compound, at least one of phosphoric acid and phosphate compounds, at least one of an epoxy group and an amino group silane compound having, and a technique of forming an organic resin film composed mainly of an organic resin comprising at least one water-soluble organic resin and a water dispersible organic resin is disclosed.
[0004]
　On the other hand, the production of a metal container for the purpose of preservation of beverages and foods, Ni-plated steel sheet, Sn-plated steel sheet or an Sn-based alloy plated steel sheet or the like is used. Al-Zn alloy coated steel sheet disclosed in Patent Document 1 is that the a plated steel sheet of a so-called sacrificial protection type, Ni-plated steel sheet, Sn-plated steel sheet or an Sn-based alloy plated steel sheet, a so-called barrier type is a plated steel sheet.
　Ni plated steel sheet, a Sn-plated steel sheet or an Sn-based alloy plated steel sheets, steel sheets for metal containers intended for storage of beverages and foods (hereinafter, referred to as containers for steel) is used as the adhesion to the paint or film and steel sheet and in order to ensure corrosion resistance, it is often subjected to chemical conversion treatment with hexavalent chromium on the surface of the plated steel sheet. The chemical conversion treatment using a solution containing hexavalent chromium, that chromate treatment.
[0005]
　However, hexavalent chromium used for the chromate treatment because it is harmful on the environment, as an alternative to chromate process performed on a conventional vessel for steel, Zr- chemical conversion coating such as a phosphate film has been developed. For example the following Patent Document 2, Zr, container steel sheet having a chemical conversion coating containing phosphoric acid and phenol resin is disclosed.
[0006]
　Examples of the food to be stored in a metal container using a container steel sheet, include meat and vegetables. Although meat and vegetables containing various proteins, amino acids these proteins including S which may contain (L- cysteine, L- methionine, L - (- -) sulfur-containing amino acids typified by cystine) .
　The addition of heat during sterilization processing for foods containing sulfur-containing amino acids, occurs a phenomenon that S in sulfur-containing amino acids are blackened combines with Sn or Fe or the like contained in the container steel sheet. This phenomenon, called sulfide blackening. Since the design of the metal inner surface of the container when the sulfide blackening occurs is reduced, and measures are calculated as sulfide blackening does not occur.
[0007]
　Also includes Patent Document 3, and Al ions, borate ions, Cu ions, Ca ions, metal Al, and at least one reaction promoter component selected from the group consisting of metal Cu, and Zr ions, and F ions in solution, carried out dipping or electrolysis treatment of the steel sheet, a manufacturing method of a container steel sheet for forming the Zr-containing coating is disclosed on the surface of the steel sheet.
CITATION
Patent Document
[0008]
Patent Document 1: Japanese Patent 2005-290535 JP
Patent Document 2: Japanese Patent 2007-284789 JP
Patent Document 3: Japanese Patent 2012-62521 JP
Summary of the Invention
Problems that the Invention is to Solve
[0009]
　Film formed by chromate treatment (hereinafter, referred to as chromate film), since even a small amount of adhesion of the coating is dense, container steel sheet a chromate film formed on the surface excellent corrosion resistance and sulfidation blackening a. However, as described above, since hexavalent chromium is harmful environmental, container steel sheet preferably contains no hexavalent chromium as possible.
　On the other hand, the chemical conversion film as described in the organic resin film and Patent Document 2 described in Patent Document 1, because it does not contain hexavalent chromium, it is preferable environmentally. However, the chemical conversion film as described in the organic resin film and Patent Document 2 described in Patent Document 1, to obtain a suitable sulfurization blackening, i.e. in order to form a dense coating, adhesion of the coating it is necessary to increase the amount. If you increase the coating weight of the film, along with adhesion to the underlying plated layer of the film and the film is decreased, weldability undesirably lowered. Also, to increase the coating weight of coating is undesirable economically.
[0010]
　In the method of manufacturing a container for a steel sheet described in Patent Document 3, since a small Al content in the chemical conversion coating, it may be difficult to obtain a suitable sulfidation blackening.
[0011]
　The present invention has been made in view of the above circumstances, even if a small adhesion amount of the chemical conversion coating layer, excellent resistant to corrosion and sulfidation blackening, the chemical conversion treatment steel sheet and the chemical conversion treated steel sheet and to provide a manufacturing method.
Means for Solving the Problems
[0012]
　The present invention is to solve the above problems, adopts the following means in order to achieve the object.
[0013]
(1) Chemical-treated steel sheet according to an embodiment of the present invention includes a steel sheet, a Fe-Sn alloy layer formed on at least one surface of the steel sheet, it is formed on the Fe-Sn alloy layer, the Fe- Sn total content of Sn alloy layer 0.10 ~ 30.0 g / m of a metal Sn content 2 and the Sn layer is formed on the Sn layer, 1.0 ~ 150 mg / m of a metal Zr content 2 and Zr compound, 1.0 ~ 100 mg / m in the amount of P 2 and phosphoric acid compound, 0.10 ~ 30.0 mg / m of a metal Al content 2 and the chemical conversion coating layer containing, and Al compound of , comprising a.
[0014]
(2) In the chemical conversion treated steel sheet according to (1), wherein the chemical conversion coating layer, 0.10 ~ 30.0 mg / m of a metal Al amount 2 Al of 2 O 3 may be contained.
[0015]
(3) In the chemical conversion treated steel sheet according to (1) or (2), wherein the chemical conversion coating layer, 1.0 ~ 120 mg / m in weight metal Zr 2 and the Zr compound of 2.0 with P amount ~ 70.0 mg / m 2 and the phosphoric acid compound, 0.20 ~ 20.0 mg / m of a metal Al content 2 and the Al compounds of may contain.
[0016]
(4) In the chemical conversion treated steel sheet according to any one aspect of the above (1) to (3), the Sn content of the sum of the Sn layer and the Fe-Sn alloy layer, a metal Sn amount, 0 ～ 20.0 g of .30 / M 2 may be.
[0017]
(5) In the chemical conversion treated steel sheet according to any one aspect of the above (1) to (4), the surface of the chemical conversion coating layer, may not be coated with a film or paint.
[0018]
(6) The method of producing chemical conversion treated steel sheet according to one embodiment of the present invention, the surface of the steel sheet, a metal Sn amount, 0.10 ~ 30.0 g / m 2 to form a Sn plating layer containing Sn plating a step, by performing melting溶錫processing on the Sn plating layer, and molten溶錫treatment step of forming the Fe-Sn alloy layer and Sn layer, and Zr ions 10 ~ 20000 ppm, and F ion 10 ~ 20000 ppm , and phosphate ions of 10 ~ 3000 ppm, including and 100 ~ 30000 ppm nitrate ions and sulfate ions in total, and Al ions 500 ~ 5000 ppm, and wherein the source of Al ions (NH 4 ) 3 AlF 6 be , using the chemical conversion treatment liquid temperature is less than 5 ° C. or higher ° C. 90, 1.0 ~ 100A / dm 2 of current density and 0.20 to 150 seconds electrolysis time conditions In by performing the electrolytic process, having an electrolyte treatment step of forming a chemical conversion coating layer on the Sn layer.
[0019]
(7) In the manufacturing method of the chemical conversion treated steel sheet according to (6), wherein the chemical conversion treatment liquid, and Zr ions 200 ~ 17000ppm, and F ions 200 ~ 17000ppm, and 100 ~ 2000 ppm phosphate ion, total in 1000 and nitrate ion and sulfate ion ~ 23000Ppm, it may contain, and Al ions 500 ~ 3000 ppm.
Effect of the invention
[0020]
　According to the above aspect, even if a small amount of adhesion of the chemical conversion coating layer, it is possible to provide excellent resistant to corrosion and sulfidation blackening method for producing a chemical conversion treatment steel sheet and the chemical conversion treated steel sheet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
[Figure 1A] Fe-Sn alloy layer on one side of the steel sheet is a schematic diagram showing the chemical conversion treated steel sheet Sn layer and the chemical conversion coating layer formed thereon.
[Figure 1B] Fe-Sn alloy layer on both surfaces of the steel sheet is a schematic diagram showing the chemical conversion treated steel sheet Sn layer and the chemical conversion coating layer formed thereon.
It is a flow diagram illustrating an example of the flow of the manufacturing method of FIG. 2 chemically treated steel plate.
It is a graph showing the FIG. 3 embodiment 1 results.
DESCRIPTION OF THE INVENTION
[0022]
　Reference will now be described in detail preferred embodiments of the present invention. In the present embodiment, components having the same configuration, and repeated explanation is omitted referring to the figures.
[0023]

　First, with reference to FIGS. 1A and 1B, a detailed description of the construction of the chemical conversion treated steel sheet according to the present embodiment. 1A and 1B are explanatory diagrams of the layer structure of the chemical conversion treated steel sheet according to the present embodiment shown schematically.
[0024]
　Chemical treated steel sheet 10 according to this embodiment, as shown in FIGS. 1A and 1B, it comprises a steel plate 103, a Fe-Sn alloy layer 105a, and the Sn layer 105b, and the chemical conversion coating layer 107.
[0025]
About steel 103]
　steel 103 is used as the base material of the chemical conversion treated steel sheet 10 according to this embodiment. There is no particular limitation on the steel sheet 103 used in the present embodiment, it is possible to use a known steel sheet 103 used as a container for steel. There is no particular limitation on the manufacturing method and material of the steel sheet 103, from the normal billet manufacturing process, hot rolling, pickling, cold rolling, annealing, temper rolling the steel sheet manufactured through a known process, such as 103 it is possible to use.
　Thickness of the steel sheet 103 in view of the practicality and economy when used as a container for steel, preferably 0.05 ~ 1 mm.
[0026]
[Fe-Sn alloy layer 105a and the Sn layer 105b]
　On the surface of the steel sheet 103, Fe-Sn alloy layer 105a and the Sn layer 105b containing Sn is formed. Fe-Sn alloy layer 105a and the Sn layer 105b is a plating layer of barrier type. Here, the barrier-type plating layer, using a Sn is electrochemically nobler metals than Fe constituting the steel sheet 103 as the base material, by forming a metal film of Sn on the surface of the steel sheet 103 corrosion factors so as not to act on the base material, which suppresses the plating layer corrosion of the steel plate 103.
[0027]
　On the other hand, sacrificial protection type of the plating layer has the opposite function to the barrier-type plating layer. The plating layer of sacrificial protection type, electrochemically less noble metals than Fe constituting the steel sheet 103 as the base material (for example, Zn as disclosed in Patent Document 1) a metal film on the surface of the steel sheet 103 by using a formed, by a metal such as Zn constituting the plating layer than Fe constituting the steel sheet 103 is corroded first, inhibiting corrosion of the steel plate 103.
　In the plating layer and the sacrificial protection type of the plating layer of barrier type, interaction with the chemical conversion coating layer 107 is different.
[0028]
　In the following, with reference to FIGS. 1A and 1B, an example of a Fe-Sn alloy layer 105a and the Sn layer 105b according to the present embodiment will be specifically described.
　Incidentally, as shown in FIG. 1A, Fe-Sn alloy layer 105a on one surface of the steel sheet 103, to Sn layer 105b and the chemical conversion coating layer 107 may be formed, as shown in FIG. 1B, both surfaces of the steel sheet 103 Fe-Sn alloy layer 105a, Sn layer 105b and the chemical conversion coating layer 107 may be formed on.
[0029]
　As shown in FIGS. 1A and 1B, Fe-Sn alloy layer 105a is formed on the surface of the steel sheet 103, Sn layer 105b is formed on the Fe-Sn alloy layer 105a. Although details will be described later, Fe-Sn alloy layer 105a and the Sn layer 105b is formed by forming the Sn plating layer (not shown) on the surface of the steel sheet 103 is formed by performing a melting溶錫treatment (reflow treatment) .
　Sn plating layer (not shown) is formed in order to ensure the corrosion resistance and weldability of the chemical treated steel sheet 10. Sn is not only Sn itself has high corrosion resistance, Fe-Sn alloy contained in the Fe-Sn alloy layer 105a also has excellent corrosion resistance and weldability.
[0030]
　While containing both Fe-Sn alloy layer 105a and the Sn layer 105b according to this embodiment is Sn, Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is, 0 per side with a metal Sn amount. ～ 30.0 g of 10 / M 2 is.
　Sn has excellent workability, having a weldability and corrosion resistance, by performing the melt溶錫treatment after Sn plating, together with further improve the corrosion resistance of the chemical conversion treated steel sheet 10, surface appearance (specular appearance of the chemical conversion treated steel sheet 10 ) can more preferably be able to. To achieve the above-mentioned effect, Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is, per side 0.10 g / m of a metal Sn content 2 is required to be at least.
　Further, workability of the more chemically treated steel plate 10 the content of Sn is increased, but weldability and corrosion resistance is improved, the Sn content of the sum of Fe-Sn alloy layer 105a and the Sn layer 105b, one side of a metal Sn amount per 30.0 g / m 2 if it exceeds, the above effect by Sn is saturated. Further, Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is, per side 30 g / m of a metal Sn amount 2 if it exceeds, economically undesirable. For the foregoing reasons, Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is per side 30.0 g / m of a metal Sn quantity 2 or less.
[0031]
　Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is, per side 0.30 g / m of a metal Sn amount 2 ~ 20.0 g / m 2 is more preferable. Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is a metal Sn amount per surface 0.30 g / m 2 by at least, can more reliably exhibit the above-described effects due to Sn it is. Further, Sn total content of Fe-Sn alloy layer 105a and the Sn layer 105b is, per side 20.0 g / m of a metal Sn content 2 that it is less, it is possible to further reduce the manufacturing cost.
[0032]
　Fe-Sn alloy layer 105a is a metal Fe content, 0.0010 ~ 100 g / m 2 containing Fe of. Further, Fe-Sn alloy layer 105a, in addition to Sn and Fe, may contain unavoidable impurities resulting mixed such trace elements and manufacturing process.
　In Fe-Sn alloy layer 105a, the total metal amount of Sn metal Fe content and Sn of Fe containing is not less than 50 wt%. Preferably, the Fe-Sn alloy layer 105a, the total metal amount of Sn metal Fe content and Sn of Fe containing is 70 mass% or more.
[0033]
　Sn layer 105b may be composed of Sn only, in addition to Sn, a metal Fe content 0.0010 ~ 6.0 g / m 2 may contain a Fe. Further, Sn layer 105b may contain inevitable impurities which result in contamination such as trace elements and manufacturing process.
　Moreover, the proportion of Sn in the Sn layer 105b is more than 50 wt% of metal Sn amount. Preferably, the proportion of Sn in the Sn layer 105b is 70 wt% or more metals Sn amount.
[0034]
　The ratio of the thickness of the Fe-Sn alloy layer 105a and the Sn layer 105b is not limited in particular, metallic Sn quantity described above only needs to be ensured.
[0035]
　However, when using a Fe-Sn alloy layer 105a and the Sn layer steel sheet 103 105b is formed on the surface as a container for steel, be laminated to the film on the surface of the Sn layer 105b, or even paint was applied, sulfide it is difficult to prevent blackening. As the reason, S contained in beverages and foods are contents are bonded to Sn, black SnS, SnS 2 is considered that such is formed.
　Note, S is, L- cysteine, L - (-) - cystine, are included in the beverages and food as a component of a sulfur-containing amino acids L- methionine, etc.).
　Further, when the Fe-Sn alloy layer 105a and the Sn layer 105b is not densely formed, part of the steel sheet 103 as the base material is exposed. In such a case, and the S contained in Fe and beverages and food in the steel sheet 103 or the like attached, black FeS, Fe 2 S 3 , Fe 2 sometimes S is formed.
　Above SnS, SnS 2 , FeS, Fe 2 S 3 , Fe 2 in order to reduce the blackening caused by S, etc., until now mainly surface chromate film of Fe-Sn alloy layer 105a and the Sn layer 105b It was formed.
[0036]
　Chemical treated steel sheet 10 according to this embodiment, in order to improve the sulfidation blackening, the upper layer of Fe-Sn alloy layer 105a and the Sn layer 105b, as an alternative to conventional chromate film, Zr compounds, phosphoric acid compounds and Al chemical conversion coating layer 107 containing a compound is formed.
[0037]
[Chemical processing film layer 107 '
　as shown in FIGS. 1A and 1B, on the Sn layer 105b, the chemical conversion coating layer 107 is formed. Chemical conversion coating layer 107 is a composite coating layer mainly composed of Zr compound, per side 1.0 ~ 150 mg / m of a metal Zr content 2 and Zr compounds of ~ 1.0 per one side in the P amount 100 mg / m 2 and phosphoric acid compound, per side 0.10 ~ 30.0 mg / m of a metal Al amount 2 containing, and Al compound of.
　In the present embodiment, the composite coating layer, Zr compounds, without mixing completely phosphoric acid compounds and Al compounds, represents a film layer is present in a partially mixed state.
[0038]
　Zr film containing the Zr compound, when formed on Sn layer 105b stacked three coating Al film containing phosphate film and Al compounds containing phosphate compound, the degree of effect on the corrosion resistance and adhesion obtained, not sufficient for practical use. However, as in this embodiment, a chemical conversion Zr compound in treated film layer 107 and the phosphoric acid compound and an Al compound by being mixed partially, is formed by overlapping three coating as described above than if there can be obtained an excellent corrosion resistance and adhesion.
[0039]
　Zr compound contained in the chemical conversion film layer 107 according to this embodiment has a function of improving corrosion resistance, adhesion and processability adhesion. The Zr compound according to the present embodiment, for example, oxidation Zr, phosphate Zr, include hydroxide and the like Zr and fluoride Zr is the chemical conversion coating layer 107, containing multiple aforementioned Zr compound. Preferred combinations of Zr compound is oxidized Zr, phosphate Zr and fluoride Zr.
[0040]
　Chemical content of the treated film layer Zr compound contained in 107, 1.0 mg / m per side of a metal Zr content 2 in the case described above, practically suitable corrosion resistance, adhesion and processability adhesiveness is ensured.
　On the other hand, with the increase of the content of Zr compound, corrosion resistance, adhesion and processability so as to improve the adhesive property. However, the content of Zr compound, per side 150 mg / m of a metal Zr content 2 exceeds, too thick chemical conversion coating layer 107 mainly cohesive failure causes, Sn layer of chemical conversion coating layer 107 with the adhesion is lowered relative to 105b, welding electrical resistance rises and falls. The content of Zr compound 150 mg / m of a metal Zr content 2 exceeds, due to adhesion of the chemical conversion coating layer 107 is not uniform, there is a case where the appearance is uneven.
　Accordingly, the content of Zr compound of the chemical conversion coating layer 107 according to the present embodiment (i.e., the content of Zr) is per side 1.0 mg / m of a metal Zr weight 2 ~ 150 mg / m 2 and. The content of Zr compound, more preferably, per side 1.0 ~ 120 mg / m of a metal Zr content 2 is. A metal Zr amount 120 g / m 2 by mass or less, it is possible to further reduce the manufacturing cost of the chemical conversion film layer 107.
[0041]
　Chemical conversion coating layer 107, in addition to the Zr compounds described above, further comprising one or more phosphorus acid compound.
[0042]
　Phosphoric acid compound according to the present embodiment has corrosion resistance, adhesion, and a function of improving the processability adhesion. Examples of the phosphoric acid compound according to the present embodiment, phosphoric acid phosphate ion and the steel sheet 103, Fe-Sn alloy layer 105a, and a compound contained in the Sn layer 105b and the chemical conversion coating layer 107 is formed by reacting Fe, phosphate Ni, phosphoric acid Sn, phosphate Zr, and phosphoric acid Al. Chemical conversion coating layer 107 may include one phosphoric acid compounds described above, may comprise two or more.
[0043]
　The more the content of the phosphoric acid compound contained in the chemical conversion film layer 107, the corrosion resistance of the chemical conversion treated steel sheet 10, adhesion and processability so as to improve the adhesive property. Specifically, the content of phosphoric acid compound in the chemical conversion coating layer 107 is converted to 1.0 mg / m in the amount of P 2 in the case of above, practically suitable corrosion resistance, adhesion and processability adhesion secured It is.
　On the other hand, as the content of the phosphoric acid compound is increased, the corrosion resistance, but also improved adhesion and processability adhesiveness, the content of phosphoric acid compound, per side 100 mg / m in the amount of P 2 exceeds, chemical too thick treated film layer 107 mainly cohesive failure cause, along with the adhesiveness is lowered to the Sn layer 105b of the chemical conversion coating layer 107, electrical resistance welding property is deteriorated increases. The content of phosphoric acid compound, per side 100 mg / m in the amount of P 2 by weight, due to the adhesion of the chemical conversion coating layer 107 is not uniform, there is a case where the appearance is uneven .
　Therefore, the content of phosphoric acid compound of the chemical conversion coating layer 107 according to this embodiment, one surface per 1.0 ~ 100 mg / m in the amount of P 2 and.
　The content of phosphoric acid compound of the chemical conversion coating layer 107, more preferably, per side 2.0 ~ 70.0 mg / m at the P content 2 is. The content of the phosphoric acid compound of the chemical conversion coating layer 107, per side 2.0 mg / m at the P content 2 By the above, it is possible to obtain a more favorable sulfidation blackening. Further, the content of phosphoric acid compound of the chemical conversion coating layer 107, per side 70.0 mg / m in the amount of P 2 is set to be lower than or equal, it is possible to further reduce the manufacturing cost of the chemical conversion coating layer 107 .
[0044]
　Chemical conversion coating layer 107, in addition to the Zr compound and phosphoric acid compounds described above, further containing Al compound. Al compound of the chemical conversion coating layer 107 is mainly present as Al oxides in the chemical conversion coating layer 107. A coating defect of the chemical conversion coating layer 107 mainly composed of Zr by Al oxide is reinforced, chemically treated steel sheet 10 can be obtained an excellent sulfidation blackening.
　Chemical conversion coating layer 107 mainly composed of Zr, since originally an extremely uniform film, the amount of Al compound added during chemical conversion coating layer 107 in order to reinforce the coating defects per side of a metal Al amount 0.10 mg / m 2 may be at least. The content of the Al compound is a metal Al amount per surface 0.10 mg / m 2 by at least, it is possible to suitably improve the sulfidation blackening chemical conversion treated steel sheet 10.
　On the other hand, as the content of the Al compound in the chemical conversion coating layer 107 is increased, but also improved sulfidation blackening, the content of the Al compound is, per side 30.0 mg / m of a metal Al content 2 exceeded Then, economically undesirable with sulfidation blackening is saturated. Therefore, the content of the Al compound contained in the chemical conversion film layer 107, per side 30.0 mg / m of a metal Al content 2 or less.
　The content of the Al compound in the chemical conversion coating layer 107, more preferably, one surface per 0.20 ~ 20.0 mg / m of a metal Al content 2 is. The content of the Al compound per surface 0.20 mg / m in weight metal Al 2 With more, it becomes possible to favorably improve the sulfidation blackening. Further, the content of the Al compound, per side 20.0 mg / m of a metal content of Al 2 With less, it is possible to further reduce the manufacturing cost of the chemical conversion film layer 107.
[0045]
　Al oxides in the chemical conversion coating layer 107 (Al 2 O 3 content of) is a metal Al content 0.10 ~ 30.0 mg / m 2 is preferably. When the content of Al oxides in the chemical conversion coating layer 107 is in the above range, a film defect of the chemical conversion coating layer 107 suitably reinforced, it is possible to obtain an excellent sulfidation blackening.
[0046]
　Further, it is possible by the inclusion of Al compound in the chemical conversion film layer 107, to reduce the content of phosphoric acid compound to improve the sulfidation blackening similarly to Al.
　Among the phosphate compound contained in the chemical conversion film layer 107, phosphate Zr that phosphate ions are generated by reacting with Zr ions, a large amount during the chemical conversion treatment liquid for forming a chemical conversion coating layer 107 It precipitates when present, chemical conversion treatment solution becomes cloudy.
　Here, Al compound, contributes to the improvement of sulfurization blackening than phosphoric acid compound. Therefore, by chemical conversion treatment film layer 107 contains Al compound, while suitably improved sulfidation blackening, it is possible to reduce the content of phosphoric acid compound which causes cloudiness of the chemical conversion treatment solution.
　Moreover, by reducing the content of phosphoric acid compound, it is possible to reduce the amount of F ions which inhibit the binding of binding and Al phosphate of Zr and phosphoric acid. As a result, it is possible to more easily precipitate Zr, it is possible to improve the electrolytic efficiency for forming a chemical conversion film layer 107.
[0047]
　Incidentally, the chemical conversion coating layer 107, Zr compounds described above, in addition to the phosphoric acid compound and Al compound may contain inevitable impurities which would mixed in such manufacturing process. Further, when the chemical conversion coating layer 107 containing Cr, the upper limit of the content of Cr is 2 mg / m 2 is.
[0048]
　Chemical treated steel sheet 10 according to this embodiment, even if with a reduced coating weight of the chemical conversion coating layer 107 shows excellent sulfidation blackening.
　For example, the surface is deposited a coating of the chemical conversion treated steel sheet 10, to form a coating film by baking. The mouth of the heat-resistant bottle to hold the 1 hour 0.6 mass% L-cysteine solution was boiled, the chemical conversion treated steel sheet 10 forming the coating film on the surface mounted and fixed as a lid, using a soaking furnace, etc. subjected to heat treatment for 30 minutes at 110 ° C. Te. In the chemical conversion treated steel sheet 10 after the heat treatment described above, when observing the appearance of the contact portion between the heat resistant bottle, in the case of using the chemical conversion treated steel sheet 10 according to this embodiment, blackening at least 50% of the area of the contact portion It does not occur.
[0049]
　As mentioned above, the chemical conversion treated steel sheet 10 according to this embodiment has excellent corrosion resistance and sulfidation blackening. Therefore, even if you do not cover the surface of the chemical conversion coating layer 107 with a film or coating, it is possible to use a chemical conversion treated steel sheet 10 as a container for steel.
[0050]

　chemically treated steel sheet 10, as described above, having a Fe-Sn alloy layer 105a, Sn layer 105b and the chemical conversion coating layer 107 on the steel plate 103. That is, in the chemical conversion treated steel sheet 10, and in contact with the steel plate 103 and the Fe-Sn alloy layer 105a, no further layers between the steel sheet 103 and the Fe-Sn alloy layer 105a. Similarly, and in contact with the Fe-Sn alloy layer 105a and the Sn layer 105b, no further layers between the Fe-Sn alloy layer 105a and the Sn layer 105b. Furthermore, a contact with the Sn layer 105b and the chemical conversion coating layer 107 does not have another layer between the Sn layer 105b and the chemical conversion coating layer 107.
[0051]

　where metal Sn content and metal Fe content in the Fe-Sn alloy layer 105a and the Sn layer 105b, for example, can be measured by fluorescent X-ray method. In this case, by using the metal Sn amount or metallic Fe amount known samples, in advance a calibration curve relating amount of Sn metal weight and metal Fe, the relatively metal Sn amount or metallic Fe amount using a calibration curve prepared Identify.
[0052]
　Metal Zr content in the chemical conversion coating layer 107, P amount and metal Al amount is, for example, can be measured by a quantitative analysis method such as X-ray fluorescence analysis. As for what compounds during the chemical conversion film layer 107 is present, X-rays photoelectron spectroscopy: By performing the analysis (X-ray Photoelectron Spectroscopy XPS) , it is possible to identify .
　Also, Al in the chemical conversion coating layer 107 2 O 3 content of the first X-ray photoelectric spectroscopy (X-ray Photoelectron Spectroscopy, XPS ) by Al 2 O 3 , the peak intensity ratio of the metal Al and other Al compounds the seek. On top of that, the peak intensity ratio determined by the total metal amount of Al and XPS determined by quantitative analysis of X-ray fluorescence analysis, etc. As described above, Al in the chemical conversion coating layer 107 2 O 3 content of calculate.
[0053]
　The measurement method of each component is not limited to the above method, it is possible to apply a known measurement method.
[0054]

　Next, with reference to FIG. 2, a manufacturing method of the chemical conversion treated steel sheet 10 according to the present embodiment will be described in detail. Figure 2 is a flow chart for explaining an example of a flow of a manufacturing method of the chemical conversion treated steel sheet 10 according to this embodiment.
[0055]
　[Pretreatment step]
　In the production method of the chemical conversion treated steel sheet 10 according to this embodiment, first, as necessary, a known pre-processing is performed on the steel plate 103 (step S101).
[0056]
　[Plating Step]
　After that, a Sn-plated layer (not shown) on the surface of the steel sheet 103 (Step S103). Method of forming the Sn-plated layer (not shown) is not particularly limited, and known or electroplating method, it is possible to use a method such as immersing the steel sheet 103 to the molten Sn.
[0057]
　Melt溶錫process (reflow process)
　step] After the formation of the Sn-plated layer (not shown), performs melt溶錫process (reflow process) (step S104). This forms a Fe-Sn alloy layer 105a and the Sn layer 105b on the surface of the steel sheet 103.
　Melt溶錫process, after formation of the Sn plating layer (not shown) on the steel plate 103 is heated to 200 ° C. or higher, once melted Sn-plated layer (not shown) is performed by subsequent quenching. The melt溶錫process, Sn plating layer located on the steel sheet 103 side Sn in (not shown) to Fe alloyed in the steel sheet 103, Fe-Sn alloy layer 105a is formed, the remainder of Sn, Sn layer 105b to the formation.
[0058]
　Electrolytic treatment step]
　Subsequently, the cathodic electrolysis treatment to form a chemical conversion film layer 107 (step S105).
　Chemical conversion coating layer 107 is formed by electrolytic treatment (e.g., a cathode electrolytic treatment). Chemical conversion solution used for forming a chemical conversion film layer 107 by an electrolytic process, 20000 ppm and less Zr ions than 10ppm, 20000 ppm and less F ions than 10ppm, and the following phosphate ions 10ppm or 3000 ppm, 100 ppm in total or comprising 30000ppm and less of nitrate and sulfate ions, 5000 ppm and less Al ions than 500 ppm, the. Further, the chemical conversion treatment liquid, as a source of Al ions (NH 4 ) 3 AlF 6 is used.
　Incidentally, nitrate ion and sulfate ion, the chemical conversion treatment liquid may be contained 10ppm or 3000ppm or less in total of both ions, to both ions and nitrate ions and sulfate ions may be included in the chemical conversion treatment solution , only one of the nitrate ions and sulfate ions may be included in the chemical conversion treatment solution.
[0059]
　Chemical conversion treatment liquid, preferably, 17000Ppm the following Zr ions above 200 ppm, 17000Ppm the following F ions above 200 ppm, and 2000ppm or less of phosphate ion above 100 ppm, 23000Ppm the following nitrate and sulphate ions than 1000ppm in total, preferably includes 3000 and following Al ions than 500 ppm, the.
　By the concentration of Zr ions above 200 ppm, it is possible to more reliably prevent decrease adhesion of Zr. Further, by making the concentration of F ions or 200 ppm, it is possible to more reliably prevent the cloudiness of the chemical conversion coating layer 107 due to the precipitation of phosphate.
[0060]
　Similarly, by the concentration of phosphate ions and more than 100 ppm, it is possible to more reliably prevent the cloudiness of the chemical conversion coating layer 107 due to the precipitation of phosphate. In addition, by setting at least one of the concentration of nitrate ions and sulfate ions 1000ppm or higher, it is possible to more reliably prevent a reduction in the deposition efficiency of the chemical conversion coating layer 107. In addition, by the concentration of Al ions than 500 ppm, more reliably it can be achieved the effect of improving the sulfidation blackening.
　Incidentally, the upper limit of each component of the chemical conversion treatment liquid by a value as described above, it is possible to reduce the manufacturing cost of the chemical conversion coating layer 107 more reliably.
[0061]
　The temperature of the chemical conversion treatment liquid is preferably less than 5 ° C. or higher 90 ° C.. When the temperature of the chemical conversion treatment solution is less than 5 ° C., since formation efficiency of the chemical conversion coating layer 107 is poor, not economical, which is not preferable. Further, if the temperature of the chemical conversion treatment liquid is 90 ° C. or more, the tissue of the chemical conversion coating layer 107 formed is uneven, cracked, defects such as micro cracks are generated in these defects such as corrosion to become a starting point, which is not preferable.
　It should be noted that the chemical conversion temperature of the processing solution, by higher than the surface temperature of the Fe-Sn alloy layer 105a and the Sn layer 105b is formed steel plate 103, since the reactivity of the chemical conversion treatment solution at the interface is increased, the chemical conversion coating deposition efficiency of the layer 107 is improved. Therefore, the temperature of the chemical conversion treatment liquid, higher than the surface temperature of the Fe-Sn alloy layer 105a and the Sn layer steel sheet 103 105b is formed is preferable.
[0062]
　Current density for performing electrolysis treatment, 1.0A / dm 2 or more 100A / dm 2 is preferably less. Current density 1.0A / dm 2 for the case is less than, as well as the amount of deposition of the chemical conversion coating layer 107 is reduced, there is a case where electrolytic treatment time is prolonged, which is not preferable. The current density is 100A / dm 2 when it is exceeded, chemical deposition amount of treated film layer 107 becomes excessive, among the formed chemical conversion coating layer 107, adhesion is insufficient chemical conversion coating layer 107 but since there is washed away (peeled) potential in the washing step with washing or the like after the electrolytic process, which is not preferable.
　Time performing electrolysis (electrolysis treatment time) is preferably less 150 seconds 0.20 seconds. When electrolytic treatment time is less than 0.20 seconds, chemical deposition amount of treated film layer 107 is lowered, unfavorably the desired performance can not be obtained. On the other hand, when the electrolysis treatment time is 150 seconds exceeded, the amount of deposition of the chemical conversion coating layer 107 becomes excessive, among the formed chemical conversion coating layer 107, adhesion is insufficient chemical conversion coating layer 107 , since there is washed away (peeled) potential in the washing step with washing or the like after the electrolytic process, which is not preferable.
[0063]
　Chemical pH of the treatment liquid is preferably in the range from 3.1 to 3.7 and more preferably 3.5 is around. The adjustment of the pH of the chemical conversion treatment liquid, if necessary, may be added nitric acid or ammonia.
　By performing the electrolysis treatment under the above conditions, the surface of the Sn layer 105b, it is possible to form a chemical conversion coating layer 107 according to this embodiment.
[0064]
　In forming the chemical conversion coating layer 107 according to this embodiment, the chemical conversion treatment solution used in the electrolytic treatment, may be further added tannic acid. By adding tannic acid to the chemical conversion treatment solution, tannic acid reacts with Fe in the steel sheet 103 to form a film of tannic acid Fe on the surface of the steel sheet 103. Film of tannic acid Fe, in order to improve the rust resistance and adhesion, the preferred.
[0065]
　The solvent for the chemical conversion treatment liquid, for example, deionized water, distilled water or the like can be used. Preferred electrical conductivity of the solvent in the chemical conversion treatment solution in the following 10 [mu] S / cm, more preferably 5 [mu] S / cm, more preferably not more than 3 [mu] S / cm. However, the solvent having the above chemical conversion treatment solution is not limited to this, depending on the formation conditions of the material or the formation method and the chemical conversion coating layer 107 dissolves, it can be appropriately selected. However, industrial productivity based on adhesion amount stability stable components, cost, environmental, it is preferable to use deionized water or distilled water.
[0066]
　The Zr source, for example, H 2 ZrF 6 can be used for Zr complexes such as. Zr in Zr complexes as described above, by hydrolysis with increasing pH in the cathode electrode interface, Zr 4+ present in the chemical conversion solution as. Such Zr ions, ZrO by a dehydration condensation reaction with the hydroxyl group (-OH) present on the metal surface by chemical conversion treatment solution 2 and Zr 3 (PO 4 ) 4 to form a compound such.
[0067]
　In the chemical conversion treatment solution, (NH 4 ) 3 AlF 6 is used as the source of Al. (NH 4 ) 3 AlF 6 to the use as a source of Al, Al state (hereinafter, AlF complex and referred) forming the F complexes present in the chemical conversion treatment liquid. Al of AlF in complex by forming the chemical conversion coating layer 107 was deposited with Zr in the electrolytic process, which contributes to the sulfurization blackening as described above.
　Further, Al, like Zr, is present as a cation in the chemical conversion treatment solution. Therefore, as a source of Al (NH 4 ) 3 AlF 6 By using, without increasing the concentration of phosphate ions in the chemical conversion treatment liquid, it is possible to supply the Al in the chemical conversion solution.
　On the other hand, as in Patent Document 3, Al as a source of Al 2 (SO 4 ) 3 in the case of using such, since AlF complex is not formed, Al does not suitably precipitated during the electrolytic treatment process, chemical conversion treatment the content of Al in the coating layer 107 is very small. In this case, since the chemical conversion coating layer 107 does not have a suitable sulfurization blackening, which is not preferable.
[0068]
　Post Processing Step]
　Subsequently, if necessary, with respect to Fe-Sn alloy layer 105a, Sn layer 105b and the chemical conversion treatment steel sheet 103 formed of the coating layer 107, a known post-processing is performed (step S107) .
　By treatment with the above-mentioned flow is carried out, the chemical conversion treated steel sheet 10 according to this embodiment is manufactured.
[0069]
　In the above description, when the has been described the case of forming a chemical conversion film layer 107 by an electrolytic process, which is allowed to apply a sufficient time to form a chemical conversion film, immersion rather than electrolytic treatment the process may form a chemical conversion film layer 107.
Example
[0070]
　Hereinafter, while showing an embodiment, a method of manufacturing a chemically treated steel sheet and the chemical conversion treated steel sheet according to an embodiment of the present invention will be specifically described. Note that the embodiments described below is an example of a manufacturing method of chemical conversion treatment steel sheet and the chemical conversion treated steel sheet according to an embodiment of the present invention, a manufacturing method of chemical conversion treatment steel sheet and the chemical conversion treated steel sheet according to an embodiment of the present invention is , it is not limited to the following examples.
[0071]
(Example 1)
　In Example 1, without changing the content of Zr compound and phosphoric acid compound in the chemical conversion coating layer, by changing the content of the Al compound, whether sulfidation blackening how changes , it was verified.
[0072]
　In Example 1, a generally steel plate used as a steel sheet for a container was used as the base material. By performing the melt溶錫process while forming the Sn plating layer on the steel sheet to form Fe-Sn alloy layer and the Sn layer on the steel plate. The total content of Sn in Fe-Sn alloy layer and Sn layer, in all samples, per side 2.8 g / m of a metal Sn amount 2 was.
　On top of that, the concentration of the Al compound in the chemical conversion coating layer instead of each sample to form a chemical conversion coating layer, to produce a plurality of samples. Here, in each sample, the content of Zr compound, per side 8 mg / m of a metal Zr content 2 is, the content of phosphoric acid compound, per side 3 mg / m at P amount 2 was.
[0073]
　Evaluation of sulfidation blackening was performed as follows. First, place the 0.6 wt% L-cysteine ​​solution was boiled for 1 hour in a heat-resistant bottle, above the sample ([phi] 40 mm) placed and fixed as a closure to the mouth of the heat-resistant bottle. Next, the heat-resistant bottle and capped, as described above, were carried out for 15 minutes heat treatment (retorting) at soaking furnace at 110 ° C.. Then, in each sample, make external observation of the contact portion between the heat bottles, on the basis of the following criteria were evaluated for 10 stages. Note that in the following evaluation criteria, if rating of 5 points or more, can withstand the practical use.
[0074]
　
　of the contact area between the sample and 0.6 wt% L-cysteine solution, at a ratio of the area has not changed to black, was scored from 1 to 10 points.
　　10: 100% - 90%
　　　9 points: less than 90% to 80%
　　　8 points: less than 80% to 70%
　　　7 points: less than 70% to 60%
　　　6 points: less than 60% to 50% or more
　　　5 point: less than 50% to 40% or more
　　　4 points: less than 40% to 30% or more
　　　3 points: 30% to less than 20% or more
　　　2 points: less than 20% to more than 10%
　　　1 point: less than 10% to 0% or more
[0075]
　The evaluation results obtained are shown in FIG. 3, the horizontal axis represents the content of the Al compound in the chemical conversion coating layer in each sample (metal Al content), and the vertical axis shows the evaluation results of the sulfidation blackening.
　As shown in FIG. 3, the content of Al compound, per side 0.10 mg / m of a metal Al content 2 is less than the evaluation results of the sulfidation blackening was scored 1. On the other hand, the content of Al compound, per side 0.10 mg / m of a metal Al content 2 in the above, the evaluation results of the sulfidation blackening is a score 7 or more, found to have excellent sulfidation blackening It became.
　This result, by containing a predetermined amount of Al compound in the chemical conversion coating layer, sulfidation blackening chemical conversion treated steel sheet having a chemical conversion film has been shown to dramatically improve.
[0076]
(Example 2)
　Next, while changing the component amounts of respective components contained in the chemical conversion film layer 107, whether sulfidation blackening how changes, was verified.
　More specifically, by using the steel sheet Fe-Sn alloy layer and the Sn layer was formed, to form a chemical conversion coating layer on the Sn layer.
　In the invention Example A1 ~ A18 and Comparative Examples a1 ~ a4, as a source of Al ions (NH 4 ) 3 AlF 6 while using, in Comparative Examples a5 and a6, Al as the source of Al ions 2 (SO 4 ) 3 and to form a chemical conversion coating layer using.
[0077]
　A1 for chemical conversion treated steel sheet of ~ A18 and a1 ~ a6, metal Zr content in the chemical conversion coating layer, as well as measured by the amount of P and metal Al amount fluorescent X-ray coating weight meter, corrosion resistance and sulfidation blackening evaluation was carried out.
　Further, Al of the chemical conversion coating layer 2 O 3 content of the first X-ray photoelectric spectroscopy (X-ray Photoelectron Spectroscopy, XPS ) Al by 2 O 3 , the peak intensity ratio of the metal Al and other Al compounds I was determined. On top of that, the fluorescent total metal content of Al was determined by quantitative analysis of X-ray analysis or the like and from the peak intensity ratio determined by XPS, Al of the chemical conversion coating layer as described above 2 O 3 calculated content of did.
[0078]
　
　corrosion resistance test solution was used 3% acetic acid. Cut out a chemical conversion treated steel sheet of the sample 35mm, and fixed put to the mouth of the heat-resistant bottle containing a corrosion test solution. After heat treatment of 60 minutes at 121 ° C., to evaluate corrosion degree of the sample by observing the contact portion between the sample and the corrosion test liquid. Specifically, the contact area between the sample and the corrosion test liquid, the proportion of the area that did not corrode, were subjected to the following 10 point scale. Incidentally, if the rating is 5 or more, it can be used as a container for steel.
[0079]
　　10: 100% - 90%
　　　9 points: less than 90% to 80%
　　　8 points: less than 80% to 70%
　　　7 points: less than 70% to 60%
　　　6 points: less than 60% to 50% or more
　　　5 point: less than 50% to 40% or more
　　　4 points: less than 40% to 30% or more
　　　3 points: 30% to less than 20% or more
　　　2 points: less than 20% to more than 10%
　　　1 point: less than 10% to 0% or more
[0080]
　In the field of corrosion resistance evaluation, the 10 points to 9 points "Very Good", "Good" 8 points to 5 points, was labeled "Not Good" is less than 4 points.
[0081]
　
　Evaluation of sulfidation blackening was performed as follows. Put 0.6 wt% L-cysteine solution was boiled for 1 hour in a heat-resistant bottle, above the sample ([phi] 40 mm) placed and fixed as a closure to the mouth of the heat-resistant bottle. Against heat bottles capped with sample at the soaking furnace, the 15 minutes heat treatment (retorting) was carried out at 110 ° C.. Then, in each sample, and observing the appearance of the contact portion between the heat bottles, on the basis of the same criteria as described above were evaluated for 10 stages. In Table 1 below, "Very Good" 10 points to 8 points, 7 points to 5 points below four points "Good" was labeled "Not Good".
[0082]
　The results obtained are shown in Table 1 below.
[0083]
[Table 1]

[0084]
　As apparent from Table 1, Examples A1 ~ A18 are all had excellent corrosion resistance and excellent sulfidation blackening. On the other hand, Comparative Examples a1 ~ a6 are either the corrosion resistance and sulfidation blackening was inferior. Incidentally, Al as the source of Al ions 2 (SO 4 ) 3 In Comparative Example a5 and a6 was used, Al quantity and Al 2 O 3 amount is significantly less, sulfidation blackening was also "Not Good".
[0085]
(Example 3)
　Next, and the content of Sn, the content of each component contained in the chemical conversion coating layer, whether sulfidation blackening how changes was verified.
　Table 2 Sn content of each sample, chemical treatment conditions (chemical conversion treatment solution conditions and electrolytic treatment conditions) are shown in Table 3. Metal Zr amount with the chemical conversion coating layer formed on each sample, P amount, metallic Al content Al and 2 O 3 amount shown in Table 4.
　Also, for each sample, it was evaluated corrosion and sulfidation blackening in the same manner as in Example 2. The results are shown in Table 4.
　Incidentally, invention examples in B1 ~ B31 and Comparative Examples b1 ~ b8, as a source of Al ions (NH 4 ) 3 AlF 6 while using, in Comparative Examples b9 and b10, Al as the source of Al ions 2 (SO 4 ) 3 and to form a chemical conversion coating layer using.
[0086]
[Table 2]

[0087]
[table 3]

[0088]
[Table 4]

[0089]
　As shown in Table 4, the present invention Examples B1 ~ B31 produced by the production method of the chemical conversion treated steel sheet according to the present embodiment, both had excellent corrosion resistance and sulfidation blackening. On the other hand, Comparative Examples b1 ~ b10, although both had excellent corrosion resistance, had poor sulfidation blackening. Incidentally, Al as the source of Al ions 2 (SO 4 ) 3 In Comparative Example b9 and b10 with, Al quantity and Al 2 O 3 amount is significantly less, sulfidation blackening was also "Not Good".
[0090]
　Having described in detail preferred embodiments of the present invention with reference to the accompanying drawings, 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 such modifications are intended to fall within the technical scope of the present invention.
Industrial Applicability
[0091]
　According to the embodiment, even when a small amount of adhesion of the chemical conversion coating layer, it is possible to provide excellent resistant to corrosion and sulfidation blackening method for producing a chemical conversion treatment steel sheet and the chemical conversion treated steel sheet .
DESCRIPTION OF SYMBOLS
[0092]
　　10 chemical conversion treated steel sheet
　103 sheet
　105a Fe-Sn alloy layer
　105b Sn layer
　107 chemical conversion treatment coating layer

The scope of the claims
[Requested item 1]
　And the steel sheet;
　and Fe-Sn alloy layer formed on at least one surface of said steel sheet;
　formed on the Fe-Sn alloy layer, Sn total content of the Fe-Sn alloy layer is in the amount of metal Sn 0.10 ~ 30.0 g / m 2 and Sn layer is;
　formed on the Sn layer, 1.0 ~ 150mg / m of a metal Zr content 2 and Zr compounds of, P amount 1.0 ~ 100 mg / m 2 and phosphoric acid compound, 0.10 ~ 30.0 mg / m of a metal Al content 2 and Al compound of a chemical conversion coating layer containing;
comprises
, wherein the chemical conversion treatment steel sheet.
[Requested item 2]
　The chemical conversion coating layer, 0.10 ~ 30.0 mg / m of a metal Al amount 2 Al of 2 O 3 containing
, characterized in that, the chemical conversion treated steel sheet according to claim 1.
[Requested item 3]
　The chemical conversion coating layer,
　1.0 ~ 120 mg / m of a metal Zr amount 2 the Zr compound and;
　P amount 2.0 ~ 70.0 mg / m 2 ; the phosphoric acid compound and
　0 in the metal Al amount .20 ~ 20.0 mg / m 2 and the Al compound in;
containing
, characterized in that, the chemical conversion treated steel sheet according to claim 1 or 2.
[Requested item 4]
　The Sn content of the sum of the Sn layer and the Fe-Sn alloy layer, a metal Sn amount, 0.30 ~ 20.0 g / m 2 is
characterized in that any of claims 1 to 3, conversion treated steel sheet according to any one of claims.
[Requested item 5]
　The chemical surface treatment film layer is not coated with a film or coating
, wherein the chemical conversion treated steel sheet according to any one of claims 1-4.
[Requested item 6]
　On the surface of the steel sheet, a metal Sn amount, 0.10 ~ 30.0 g / m 2 plating process and to form a Sn plating layer containing Sn of;
　by performing the melt溶錫processing on the Sn plating layer, Fe melting溶錫process and of forming a -Sn alloy layer and Sn
　layer; and Zr ions 10 ~ 20000 ppm, 10 and F ions ~ 20000 ppm, and phosphate ions 10 ~ 3000 ppm, nitrate ion 100 ~ 30000 ppm in total and a sulfuric acid ion, anda Al ions 500 ~ 5000 ppm, the source of Al ions (NH 4 ) 3 AlF 6 is, by using the temperature is less than 5 ° C. or higher 90 ° C. chemical conversion treatment liquid, 1.0 ~ 100A / dm 2 by performing the current density and electrolysis treatment under the conditions of electrolysis time from 0.20 to 150 seconds, a chemical conversion treatment on the Sn layer An electrolytic process for forming a film layer;
having
, characterized in that, the production method of the chemical conversion treated steel sheet.
[Requested item 7]
　The chemical conversion treatment
　solution, 200 ~ 17000ppm Zr
　ions; 200 ~ 17000Ppm of F ions
　and; of 100 ~ 2000 ppm phosphate ions and,
　nitrate and sulfate ions of 1000 ~ 23000ppm in
　total; 500 ~ Al ions 3000ppm When;
containing
, characterized in that, the production method of the chemical conversion treated steel sheet according to claim 6.