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, and the plating layer containing Ni is formed on at least one surface of the steel sheet, it is formed on the plating layer, 1 a metal Zr content. 0 ~ 150 mg / m 2 and Zr compounds of 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 amount 2 containing the Al compound of the comprising a chemical conversion coating layer. The plating layer, 5.0 ~ 3000 mg / m of a metal Ni amount 2 Ni plating layer containing Ni, or, 2.0 ~ 200 mg / m of a metal Ni content 2 and Ni of a metallic Sn quantity 0.10 ~ 10.0 g / m 2 and a Sn of a composite plating layer island Sn plating layer is formed on the Fe-Ni-Sn alloy layer.
[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 of a metal Zr content 2 and Zr compounds of 2.0 to a P amount 70.0 mg / m 2 and phosphoric acid compound, 0.20 ~ 20.0 mg / m of a metal Al content 2 and 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 Ni plating layer, a metal Ni content 10.0 ~ 2000 mg / m 2 may contain Ni in .
[0017]
(5) In the chemical conversion treated steel sheet according to any one aspect of the above (1) to (3), the composite plating layer, a metal Ni content 5.0 ~ 100 mg / m 2 and Ni of a metal Sn amount 0.30 ~ 7.0 g / m 2 and Sn of, and may contain.
[0018]
(6) In the chemical conversion treated steel sheet according to any one aspect of the above (1) to (5), the surface of the chemical conversion coating layer, may not be coated with a film or paint.
[0019]
(7) The method of producing chemical conversion treated steel sheet according to one embodiment of the present invention, the surface of the steel sheet, 5.0 ~ 3000 mg / m of a metal Ni amount 2 2 Ni plating layer containing Ni, or, a metal Ni amount .0 ~ 200 mg / m 2 of Ni and Sn metal amount 0.10 ~ 10.0 g / m 2 and a of Sn, the composite plating island Sn plating layer on the Fe-Ni-Sn alloy layer is formed a plating step of forming a layer, 10 a Zr ion ~ 20000 ppm, 10 and F ions ~ 20000 ppm, 10 phosphate ions ~ 3000 ppm, and 100 ~ 30000 ppm nitrate ions and sulfate ions in total, of 500 ~ 5000 ppm wherein and Al ions, wherein 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 solution, 1.0 ~ 100A dm 2 by performing electrolytic treatment under the conditions of electrolysis treatment time of the current density and 0.20 to 150 seconds, an electrolytic treatment step of forming a chemical conversion coating layer on the Ni plating layer or the composite plating layer, having.
[0020]
(8) In the manufacturing method of the chemical conversion treated steel sheet according to (7), 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
[0021]
　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
[0022]
Is an explanatory view of the layer structure shown schematically in FIG. 1A] chemically treated steel sheet Ni plating layer is formed on one surface of the steel sheet.
Is an explanatory view of the layer structure shown schematically in FIG. 1B] chemically treated steel sheet Ni plating layer is formed on both surfaces of the steel sheet.
Is an explanatory view schematically showing an example of FIG. 2A] chemically treated steel sheet composite plating layer formed on one side of the steel sheet.
Is an explanatory view schematically showing an example of FIG. 2B] chemically treated steel sheet composite plating layer is formed on both surfaces of the steel sheet.
3 is a flowchart illustrating an example of the flow method for producing a chemical conversion treated steel sheet according to the embodiment of the present invention.
It is a graph showing the FIG. 4 embodiment 1 results.
DESCRIPTION OF THE INVENTION
[0023]
　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.
[0024]

　First, with reference to FIGS. 1A ~ FIG 2B, 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.
[0025]
　Chemical treated steel sheet 10 according to this embodiment, as shown in FIGS. 1A ~ FIG 2B, it comprises a steel plate 103, one of the any of the Ni plating layer 105 and the composite plating layer 106, and the chemical conversion coating layer 107. Note that the one with the chemical conversion coating layer 107 or the Ni plating layer 105 and the composite plating layer 106, as shown in FIGS. 1A and 2A, may be formed only on one surface of the steel sheet 103 as shown in FIGS. 1B and 2B, it may be formed on the two surfaces facing each other of the steel plate 103.
[0026]
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 the known steel sheet for use 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.
[0027]
[Plating layer for]
　On the surface of the steel sheet 103, either one of the Ni-plated layer 105 and the composite plating layer 106 is formed. Ni plating layer 105 and the composite plating layer 106 are both plated layers of barrier type containing Ni. Here, the barrier-type plating layer, using Ni or Sn is electrochemically nobler metals than Fe constituting the steel sheet 103 as the base material, a metal film of Ni and Sn on the surface of the steel sheet 103 corrosion factor so as not to act on the base material by forming a suppressing plating layer corrosion of the steel plate 103.
[0028]
　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.
[0029]
　In the following, with reference to FIGS. 1A ~ FIG 2B, an example of a Ni plating layer 105 and the composite plating layer 106 according to the present embodiment will be specifically described.
[0030]
[When Ni-plated layer 105 on the surface of the steel sheet 103 is formed]
　with reference to FIG. 1A, in the case where Ni plating layer 105 is formed on the surface of the steel sheet 103 will be described in detail.
　Ni plating layer 105 comprises Ni, as shown in FIG. 1A, may be formed on one surface of the steel sheet 103, as shown in FIG. 1B, it may be formed on both surfaces of the steel plate 103. In Ni plating layer 105, Ni is per side 5.0 ~ 3000 mg / m of a metal Ni amount 2 is preferably contained in the range of.
　Ni has good paint adhesion, film adhesion, corrosion resistance and weldability. In order to exhibit an excellent effect described above, per side 5.0 mg / m as a metal Ni 2 it is necessary to contain more and Ni.
[0031]
　With increasing content of Ni, is improved excellent effect possessed by Ni, per side 3000 mg / m of a metal Ni content 2 is not economically preferable because its effect is saturated at greater. Therefore, the Ni content, per side 3000 mg / m of a metal Ni amount 2 or less.
　The content of Ni in the Ni plating layer is more preferably, per side 10.0 mg / m of a metal Ni content 2 2000 mg / m or more 2 or less. Per side 10.0 mg / m of a metal Ni amount 2 By containing the above Ni, the above-described effect becomes more pronounced. Further, the content of Ni, per side 2000 mg / m of a metal Ni amount 2 is set to be lower than or equal, it is possible to further reduce the manufacturing cost of the Ni-plated layer 105.
[0032]
　Proportion of Ni in the Ni plating layer 105 is more than 50 wt% of a metal Ni content in the layer center portion of the Ni plating layer 105. Preferably, the proportion of Ni in the Ni plating layer 105 is 70 mass% or more metals Ni content in the layer center portion of the Ni plating layer 105.
[0033]
　Ni plating layer 105, in addition to the above-described Ni, a metal Fe amount per surface 1.0 ~ 2000 mg / m 2 may contain Fe in. Further, Ni plating layer 105 may contain inevitable impurities which would mixed in such manufacturing process.
[0034]
[If composite plated layer 106 on the surface of the steel sheet 103 is formed]
　with reference to FIGS. 2A and 2B, the case where the composite plated layer 106 containing Ni and Sn on the surface of the steel sheet 103 is formed, in detail explain.
[0035]
　Composite plated layer 106 according to the present embodiment, as shown in FIG. 2A, may be formed on one surface of the steel sheet 103, as shown in Figure 2B, it may be formed on both surfaces of the steel plate 103. Composite plated layer 106 has a Fe-Ni-Sn alloy layer 105d, and Fe-Ni-Sn alloy layer 105d island Sn plated layer formed on 105e, a.
[0036]
　To form the composite plating layer 106, first Ni plating layer on the steel plate 103 (not shown) is formed. Ni plating layer (not shown) is made of Ni or Fe-Ni alloy, it is formed to ensure the corrosion resistance of the chemical conversion treated steel sheet 10.
　The effect of improving corrosion resistance of the chemical conversion treated steel sheet 10 by Ni is determined by the amount of Ni contained in the composite plating layer 106. Ni content in the composite plating layer 106, per side 2 mg / m of a metal Ni amount 2 if more than the effect of improving corrosion resistance by Ni is expressed.
[0037]
　On the other hand, the effect of improving corrosion resistance the more Ni content in the composite plating layer 106 is increased, the Ni content in the composite plating layer 106, per side 200 mg / m of a metal Ni amount 2 by weight, improved corrosion resistance Ni effect of is saturated. Moreover, since Ni is an expensive metal, the Ni content in the composite plating layer 106, per side 200 mg / m of a metal Ni amount 2 exceeds, economically undesirable.
　Therefore, the Ni content in the composite plating layer 106, per side 2.0 mg / m of a metal Ni amount 2 ~ 200 mg / m 2 and. Ni amount in the composite plated layer 106, more preferably, per side 5.0 mg / m of a metal Ni amount 2 ~ 100 mg / m 2 is. Composite plated layer 106, per side 5.0 mg / m of a metal Ni amount 2 By containing the above Ni, the effect of improving corrosion resistance due to Ni can be exhibited more effectively. Further, the Ni content in the composite plating layer 106, per side 100 mg / m of a metal Ni amount 2 is set to be lower than or equal, it is possible to further reduce the manufacturing cost.
[0038]
　After Ni plating layer described above (not shown) is formed, Sn plating layer (not shown) is formed. Incidentally, Sn-plated layer in the present embodiment (not shown) may be composed of Sn only, in addition to Sn, and may contain impurities and trace elements.
[0039]
　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, Sn alloy formed by melting溶錫process also has excellent corrosion resistance and weldability.
　By performing the melt溶錫treatment after forming the Sn plating layer (not shown), Fe-Ni-Sn alloy layer 105d is formed on the steel plate 103, island Sn plating on Fe-Ni-Sn alloy layer 105d layer 105e is formed.
[0040]
　In the island-shaped Sn plating layer 105e, Sn is present in an island shape, the underlying Fe-Ni-Sn alloy layer 105d to sea are exposed. The island Sn plating layer 105e, the film adhesion and coating adhesion of the chemical conversion treated steel sheet 10 is secured.
　The heat treatment after the film laminate or paint application, there are cases where chemical conversion treated steel sheet 10 is heated to the melting point (232 ° C.) or more Sn. Unlike this embodiment, when the entire surface of the Fe-Ni-Sn alloy layer 105d Sn is coating, Sn is melted or oxidized by the above heat treatment, the film adhesion and coating adhesion of the chemical conversion treated steel sheet 10 there is not preferable because it may not be ensured.
[0041]
　Composite plated layer 106 according to this embodiment, one surface per 0.10 ~ 10.0 g / m of a metal Sn amount 2 contains Sn of.
　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 effects described above, in the composite plating layer 106, per side 0.10 g / m of a metal Sn amount 2 it is necessary to contain Sn of.
[0042]
　Further, workability of the more chemically treated steel sheet 10 content of Sn in the composite plating layer 106 is increased, although weldability and corrosion resistance improvement, the content of Sn is, per side of a metal Sn content 10.0 g / m 2 if it exceeds, the above effect by Sn is saturated. The content of Sn is, per side 10.0 g / m of a metal Sn amount 2 if it exceeds, economically undesirable. For the foregoing reasons, the content of Sn in the composite plating layer 106, per side 10.0 g / m of a metal Sn quantity 2 or less.
　The content of Sn in the composite plating layer 106, more preferably, per side 0.30 g / m of a metal Sn amount 2 ~ 7.0 g / m 2 is. Composite plated layer 106, per side 0.30 g / m of a metal Sn amount 2 By containing the above Sn, it is possible to more reliably exhibit the above-described effects due to Sn. The composite plating layer 106, per side 7.0 g / m of a metal Sn amount 2 By containing the following Sn, it is possible to further reduce the manufacturing cost.
[0043]
　The total of the metallic Sn quantity of metal Ni amount and Sn of Ni contained in the composite plating layer 106 is more than 50 wt% of the composite plating layer 106. Preferably, the total of the metallic Sn quantity of metal Ni amount and Sn of Ni contained in the composite plating layer 106 is more than 70 wt% of the composite plating layer 106.
[0044]
　Composite plated layer 106, in addition to the above Ni and Sn, a metal Fe amount per surface 1.0 ~ 3500 mg / m 2 may contain Fe in. The composite plating layer 106 may contain inevitable impurities which would mixed in such manufacturing process.
[0045]
　When using a steel plate 103 which Ni plating layer 105 or composite plating layer 106 is formed on the surface as a container for steel, it is laminated to the film on the surface of the Ni plating layer 105 or composite plating layer 106, or paint is applied also, it is difficult to prevent the sulfide blackening. As the reason, S is contained in beverages and foods are contents were combined with Ni or Sn in the plating layer 105, black NiS, 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, and the like.
[0046]
　Also, when the Ni plating layer 105 or composite plating layer 106 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 NiS, SnS, SnS 2 , FeS, Fe 2 S 3 , Fe 2 in order to reduce the blackening caused by S, etc., heretofore mainly chromate film on the surface of the Ni plating layer 105 or composite plated layer 106 There has been formed.
[0047]
　Chemical treated steel sheet 10 according to this embodiment, in order to improve the sulfidation blackening, the upper layer of the Ni plating layer 105 or composite plating layer 106, as an alternative to conventional chromate film, Zr compounds, phosphoric acid compounds and Al compounds It is the chemical conversion coating layer 107 containing formed.
[0048]
[Chemical conversion for film layer 107 '
　as shown in FIGS. 1A ~ FIG 2B, the chemical conversion treated steel sheet 10 of the present embodiment, on the Ni plating layer 105 or composite plating layer 106, 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.
[0049]
　Zr film containing the Zr compound, when formed on the Ni plating layer 105 or composite plating layer 106 overlapping the three coating Al film containing phosphate film and Al compounds containing phosphorus acid compound, corrosion resistance and adhesion Although it obtained some effect with respect to gender, not sufficient for practical use. However, as in this embodiment, by a chemical conversion Zr compound in treated film layer 107 and the phosphoric acid compound and an Al compound is present in a mixed state partially, the overlapped three coating as described above than when it is formed Te, it is possible to obtain excellent corrosion resistance and adhesion.
[0050]
　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.
[0051]
　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, Ni plating of the chemical conversion coating layer 107 with the adhesion is reduced with respect to the layer 105 or composite plating layer 106, 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.
[0052]
　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.
[0053]
　Chemical conversion coating layer 107, in addition to the Zr compounds described above, further comprising one or more phosphorus acid compound.
[0054]
　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 and phosphate ions and the steel plate 103, Ni plating layer 105 or composite plating layer 106, and is contained in the chemical conversion film layer 107 compound 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.
[0055]
　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 Ni plating layer 105 or composite plating layer 106 of the chemical conversion coating layer 107, welding electrical resistance rises and descend. 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 .
[0056]
　Therefore, the content of phosphoric acid compound of the chemical conversion coating layer 107 according to this embodiment, one surface per 1.0 mg / m at the P content 2 ~ 100 mg / m 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 .
[0057]
　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.
[0058]
　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.
[0059]
　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.
[0060]
　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, the chemical conversion treatment solution used in forming a chemical conversion coating layer 107 It precipitates when present in large amounts, the chemical conversion treatment solution becomes cloudy.
[0061]
　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.
[0062]
　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 2.0 mg / m 2 is.
[0063]
　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.
[0064]
　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.
[0065]

　chemically treated steel sheet 10, as described above, has a Ni plating layer 105 or composite plated layer 106 on the steel plate 103, conversion on the Ni plating layer 105 or composite plated layer 106 having a treatment coating layer 107. That is, in the chemical conversion treated steel sheet 10, and in contact with the steel plate 103 and the Ni plating layer 105 or composite plating layer 106 does not have another layer between the steel plate 103 and the Ni plating layer 105 or composite plating layer 106. Another Similarly, in the chemical conversion treated steel sheet 10, between the Ni plating layer 105 or a composite plating layer 106 is in contact with the chemical conversion coating layer 107, Ni plating layer 105 or composite plated layer 106 and the chemical conversion coating layer 107 It does not have the layers.
[0066]

　metal Ni amount and the metal amount of Sn Ni plating layer 105 and the composite plating layer 106, for example, can be measured by fluorescent X-ray method. In this case, a metal Ni amount known samples, previously preparing a calibration curve for the metal Ni amount, to identify the relative metal Ni amount using a calibration curve prepared. Similarly, the metal Sn amount, using a metal Sn amount known samples, previously preparing a calibration curve for the metal Sn amount, to identify the relative metal Sn amount using a calibration curve prepared.
[0067]
　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.
[0068]
　The measurement method of each component is not limited to the above method, it is possible to apply a known measurement method.
[0069]

　Next, with reference to FIG. 3, a method for manufacturing the chemical conversion treated steel sheet 10 according to the present embodiment will be described in detail. Figure 3 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.
[0070]
　[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).
[0071]
　[Plating Step]
　Subsequently, with respect to the surface of the steel sheet 103, to form one of the Ni-plated layer 105 and the composite plating layer 106 (step S103).
　When forming a Ni plating layer 105 on the surface of the steel sheet 103, it may be a known technique such as an electroplating method or a vacuum evaporation method. Incidentally, also in order to form the Fe-Ni diffusion layer (not shown) at the interface between the steel plate 103 and the Ni plating layer 105, heat treatment may be performed after the Ni plating layer 105 formed.
[0072]
　On the surface of the steel sheet 103, in the case of forming a composite plating layer 106 having a Fe-Ni-Sn alloy layer 105d and the island-shaped Sn plating layer 105e is, Ni plating of Ni or Fe-Ni alloy on the surface of the steel sheet 103 forming a layer (not shown), after further forming the Sn-plated layer (not shown) on the Ni plating layer (not shown), is formed by performing a melting溶錫treatment (reflow treatment).
　That is, by melt溶錫process, the Fe of the steel sheet 103, Ni plating layer and the Ni (not shown), Sn-plated layer and a part of Sn (not shown), but Fe-Ni-Sn alloy layer alloyed together 105d is formed, the Sn plating layer of the balance being the islands, island Sn plating layer 105e is formed.
[0073]
　As a method of forming the Ni or Fe-Ni Ni plating layer made of an alloy (not shown), general electric plating method (e.g., cathodic electrolysis method) can be utilized.
　A method of forming a Sn-plated layer (not shown) is not particularly limited, for example, it is possible to use a method in which plating by immersing the steel plate 103 in a known electroplating method or molten Sn.
[0074]
　In the case of forming the Ni plating layer (not shown) by diffusion plating method, after subjected to Ni plating on the surface of the steel sheet 103, a diffusion treatment for forming a diffusion layer in the annealing furnace is performed. Simultaneously with longitudinal or diffusion process of the diffusion process may be performed nitriding treatment. Even when subjected to nitriding treatment, the effect of effect and nitriding treatment with the Ni in the Ni plating layer in the present embodiment (not shown) without interfering, it is possible to achieve these effects together.
[0075]
　Sn plating layer after forming the (not shown), molten 溶錫 process (reflow process) is performed. By performing the melt 溶錫 process, and Ni in Fe and Ni plating layers of the Sn and the steel plate 103 which is melted (not shown) is alloyed, formed Fe-Ni-Sn alloy layer 105d and the island-shaped forming an island-shaped Sn plating layer 105e made of Sn. The island Sn plating layer 105e may be formed by appropriately controlling the melt 溶錫 process.
[0076]
　Electrolytic treatment
　step] After one of the formation of the Ni plating layer 105 and the composite plating layer 106 by electrolytic 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.
[0077]
　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.
[0078]
　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.
[0079]
　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.
　The temperature of the chemical conversion treatment liquid, to increase the reactivity of the chemical conversion treatment solution at the interface, to improve the deposition efficiency of the chemical conversion coating layer 107, either one of the composite plating layer 106 and the Ni plating layer 105 is formed it is preferably higher than the surface temperature of the steel plate 103.
[0080]
　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.
[0081]
　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, to one of the surfaces of the Ni plating layer 105 and the composite plating layer 106 can form a chemical conversion coating layer 107 according to this embodiment.
[0082]
　Incidentally, in forming the chemical conversion coating layer according to the present 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.
[0083]
　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.
[0084]
　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.
[0085]
　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.
[0086]
　Post Processing Step]
　Subsequently, if necessary, with respect to one and the chemical conversion treated steel sheet 103 formed of the coating layer 107 and the Ni plating layer 105 and the composite plating layer 106, a known post-treatment is carried out (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.
[0087]
　In the above description, it has been described the case of forming a chemical conversion coating layer 107 on the Ni plating layer 105 or composite plating layer 106 by an electrolytic process, allowed to apply a sufficient time to form a chemical conversion film If it is, due dipping rather than electrolytic treatment, it may be formed chemical conversion film layer 107.
Example
[0088]
　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.
[0089]
(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.
[0090]
　In Example 1, a generally steel plate used as a container for steel used as the base material, to form a Ni plating layer as a plating layer. The content of Ni in the Ni plating layer, in all samples, per side 1000 mg / m of a metal Ni content 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.
[0091]
　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.
[0092]
　
　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
[0093]
　The evaluation results obtained are shown in FIG. 4, the horizontal axis indicates 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. 4, the content of the Al compound is, per side 0.1 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 0.1 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.
[0094]
(Example 2)
　Next, and the type of plating layer, the content of each component contained in the chemical conversion coating layer, whether sulfidation blackening how changes was verified. In the Examples and Comparative Examples except Comparative Example a5, plating layer is one of the Ni plating layer and the composite plating layer. On the other hand, in Comparative Example a5, on the Ni plating layer composite plated layer is formed (plating layer is formed two layers).
　In the invention Example A1 ~ A31 and Comparative Examples a1 ~ a6, as a source of Al ions (NH 4 ) 3 AlF 6 while using, in Comparative Example a7 and a8, Al as the source of Al ions 2 (SO 4 ) 3 and to form a chemical conversion coating layer using.
　Metal Ni amount contained in the plated layer and the metal Zr content in the metallic Sn quantity and the chemical conversion coating layer, P amount and metal Al content was measured by a fluorescent X-ray analysis. 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 was determined, the peak intensity ratio of the metal Al and other Al compounds . 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. 　The measurement results are shown in Table 1 below.
[0095]
[Table 1]

[0096]
　
　corrosion resistance test solution was used 3% acetic acid. Cut the steel to 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 the area where corrosion resistance test fluid touches the Ni-plated steel plate (the area of the heat-resistant bottle mouth) to evaluate the corrosion resistance at a rate of corroded area.
　More specifically, the test piece at a rate of corroded area to the area in contact with the test liquid, were scored from 1 to 10 points. Note that in the following evaluation criteria, if the rating is 5 or more, can withstand the practical use.
[0097]
　　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
[0098]
　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.
[0099]
　
　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 2 below, "Very Good" 10 points to 8 points, 7 points to 5 points below four points "Good" was labeled "Not Good".
[0100]
　The results obtained are shown in Table 2 below.
[0101]
[Table 2]

[0102]
　As shown in Table 2, the present invention Examples A1 ~ A31 are all had excellent corrosion resistance and sulfidation blackening. On the other hand, Comparative Examples a1 ~ a8 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 a7 and a8 using, Al quantity and Al 2 O 3 amount is significantly less, sulfidation blackening was also "Not Good".
[0103]
(Example 3)
　Next, and the type of plating layer, the content of each component contained in the chemical conversion coating layer, whether sulfidation blackening how changes was verified.
　For each sample with a Ni plating layer or a composite plating layer shown in Table 3, the chemical conversion treatment was carried out under the conditions shown in Table 4 (chemical conversion treatment solution conditions and electrolytic treatment conditions). Metal Zr amount with the chemical conversion coating layer formed on the plating layer of each sample, P amount, metallic Al content Al and 2 O 3 amount shown in Table 5.
　Also, for each sample having a plating layer and the chemical conversion coating layer was evaluated corrosion resistance and sulfidation blackening in the same manner as in Example 2. The results are shown in Table 5.
　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.
[0104]
[table 3]

[0105]
[Table 4]

[0106]
[table 5]

[0107]
　As shown in Table 5, 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".
[0108]
　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
[0109]
　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
[0110]
　　10 chemically treated steel sheet
　103 steel
　105 Ni plating layer
　105d Fe-Ni-Sn alloy layer
　105e island Sn plating layer
　106 composite plated layer
　107 chemical conversion coating layer

The scope of the claims
[Requested item 1]
　And the steel sheet;
　a plating layer containing Ni is formed on at least one surface of said steel sheet;
　formed on the plating layer, 1.0 ~ 150 mg / m of a metal Zr content 2 and Zr compound of 1 in P content .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;
equipped with,
　the plating layer is
　a metal 5.0 ~ 3000 mg / m of Ni amount 2 Ni plating layer containing Ni, or,
　2.0 ~ 200 mg / m of a metal Ni content 2 and Ni of 0.10 ~ 10.0 g / m of a metal Sn amount 2 and a of Sn, a composite plated layer island Sn plating layer is formed on the Fe-Ni-Sn alloy layer,
a chemical conversion treatment steel sheet, characterized in that.
[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 weight 2 Zr compound of the;
　P amount ~ 70.0 mg 2.0 / m 2 ; phosphoric acid compound and
　0.20 in Al metal content ~ 20.0 mg / m 2 and Al compound of;
containing
, characterized in that, the chemical conversion treated steel sheet according to claim 1 or 2.
[Requested item 4]
　The Ni plating layer, 10.0 ~ 2000 mg / m of a metal Ni amount 2 containing Ni of
and wherein the chemical conversion treated steel sheet according to any one of claims 1 to 3.
[Requested item 5]
　The composite plating layer,
　the metal Ni amount 5.0 ~ 100 mg / m 2 and Ni in;
　a metallic Sn quantity 0.30 ~ 7.0 g / m 2 and Sn in;
containing
, characterized in that, according conversion treated steel sheet according to any one of claim 1-3.
[Requested item 6]
　The surface of the chemical conversion coating layer is not coated with a film or coating
, wherein the chemical conversion treated steel sheet according to any one of claims 1 to 5.
[Requested item 7]
　On the surface of the steel sheet, the metal Ni amount 5.0 ~ 3000 mg / m 2 Ni plating layer containing Ni, or, 2.0 ~ 200 mg / m of a metal Ni content 2 0.10 - in Ni and Sn metal of 10.0 g / m 2 and a Sn of plating process and of forming a composite plating layer island Sn plating layer is formed on the Fe-Ni-Sn alloy
　layer; and 10 to 20000 ppm of Zr ions, 10 to and F ions 20000 ppm, and phosphate ions 10 ~ 3000 ppm, and 100 ~ 30000 ppm nitrate ions and sulfate ions in total, includes, and Al ions 500 ~ 5000 ppm, wherein the source of Al ions (NH 4 ) 3 AlF 6 is, by using the chemical conversion treatment liquid temperature is less than 5 ° C. or higher ° C. 90, 1.0 ~ 100A / dm 2 electrolysis of current density and 0.20 to 150 seconds By performing the electrolytic treatment under conditions of time, the electrolytic treatment to form a chemical conversion coating layer on said Ni plating layer or the composite plated layer;
having
, characterized in that, the production method of the chemical conversion treated steel sheet .
[Requested item 8]
　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 7.