Technical field
[0001]
　The present invention relates to a method of manufacturing a container for a steel sheet and a container for steel.
　This application, on April 16, 2015, claiming priority on Japanese Patent Application No. 2015-83984 filed in Japan, the contents of which are incorporated herein.
Background technique
[0002]
　As containers for beverage or food, Ni-plated steel sheet, a metal container that can manufacturing a plated steel sheet such as a Sn-plated steel sheet or an Sn-based alloy plated steel sheets are widely used. For such metal container surfaces, there is a case where if or film coating is applied after canning before or can manufacturing is laminated. The paint and film used for surface treatment of metal containers are collectively referred to as coating agent.
　The plated steel sheet for use in underlying coating agent, in order to ensure the adhesion and corrosion resistance of the coating agent, a surface treatment using hexavalent chromate or the like (hereinafter, referred to as chromate treatment) is performed often (e.g., see Patent Document 1 below.). Further, the plated steel sheet a chromate treatment is performed, if necessary, organic solvent resistance, fingerprint resistance, for the purpose of imparting scratch resistance or lubricity or the like, on a film formed by chromate treatment the coating layer is formed made of an organic resin.
[0003]
　However, recently, since hexavalent chromium used for the chromate treatment is detrimental environmental, there is a movement to replace surface treatment of the plated steel sheet to another surface treatment from chromate treatment.
　For example, Patent Document 2 and Patent Document 3 below, as the surface treatment of the plated steel sheet as a substitute for the chromate treatment, cathodic electrolysis treatment using the chemical conversion treatment solution containing Zr ions and F ions are disclosed.
[0004]
　Patent Document 4 below, cathodic electrolysis treatment using the chemical conversion treatment solution containing one at least one of phosphoric acid ions and Ti ions and Zr ions are disclosed.
　Patent Document 5 below, cathodic electrolysis treatment using the chemical conversion treatment solution containing Zr ions, F ions and phosphate ions is disclosed.
　Patent Document 6 below, cathodic electrolysis treatment using the chemical conversion treatment solution containing Zr ions and organic substances have been disclosed.
[0005]
　Patent Document 7 below, Zr ions, cathodic electrolysis treatment using the chemical conversion treatment solution containing phosphoric acid ions and organic substances have been disclosed.
　Patent Document 8 and Patent Document 9 below, Zr ions, cathodic electrolysis treatment using the chemical conversion treatment liquid containing a phosphoric acid ion and nitrate ion has been disclosed. In particular, Patent Document 9 below, by increasing the nitrate ion, the film formed by the cathodic electrolysis treatment (hereinafter, referred to as the chemical conversion coating layer) method for promoting the formation have been disclosed.
CITATION
Patent Literature
[0006]
Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-239855
Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-325402
Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-23422
Patent Document 4: Japanese Patent Laid-Open SHO 54- Publication No. 68734
Patent Document 5: Japanese Laid-open Patent Publication No. 2006-9047
Patent Document 6: Japanese Laid-open Patent Publication No. 2008-50641
Patent Document 7: Japanese Laid-open Patent Publication No. 2009-1851
Patent Document 8: Japanese Laid-open Publication No. 2009-84623
Patent Document 9: international Publication No. 2011/118588 Patent Publication
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　However, in the technique disclosed in Patent Documents 2 to Patent Document 8, it takes a long time to form a chemical conversion coating layer containing Zr compound, there is a problem that can not be obtained a suitable productivity. To form in a short time chemical conversion film layer using the technique disclosed in Patent Document 9 is required a high concentration of nitrate ions, there is a problem that the environment is undesirable.
[0008]
　The container steel sheet for use in food containers it is necessary to have a sulfidation blackening, in Patent Documents 2 to Patent Document 9, a method for improving sulfidation blackening is not disclosed.
　The vessel steel plate, for example, when using a high protein foods such as fish or beans in food containers and contents, the retort processing after food packing (high-temperature heat sterilization treatment in the presence of water vapor), the container at least one of the inner and contents are sometimes discolored rarely black. Such a blackening phenomenon is referred to as sulfide blackening.
　Sulfur contained in food (S) is thermally decomposed by retort treatment, hydrogen sulfide (H 2 S) and thiols (HS - ) and the like are generated. The hydrogen sulfide and thiols, undergo a structure and metal reaction vessel inner surface, the metal sulfide black is produced, sulfide blackening occurs.
　The sulfide blackening is caused, there is a case where the appearance of the container is deteriorated. Further, a metal sulfide generated black, consumers sometimes mistaken corrosion of metal corrosion or contents of the container inner surface. Therefore, particularly in the container steel sheet for use in food containers, it is necessary to avoid as much as possible to generate a sulfide blackening.
[0009]
　The present invention has been made in view of the above circumstances, and an object thereof is to provide an excellent productivity, a manufacturing method of a container for steel and container steel sheet having environmental resistance and sulfidation blackening.
Means for Solving the Problems
[0010]
　The present invention is to solve the above problems, adopts the following means in order to achieve the object.
[0011]
(1) for containers steel sheet according to one embodiment of the present invention includes a steel plate, is provided as an upper layer of the steel sheet, in terms to 560 ~ 5600 mg / m on the metal Sn amount 2 and the Sn-plated layer containing Sn of the provided as an upper layer of the Sn-plated layer, a metal Zr amount in terms of 3.0 ~ 30.0 mg / m 2 Zr compound of the metal Mg amount converted to 0.50 ~ 5.00 mg / m 2 of Mg comprising a compound, and a chemical conversion coating layer containing.
[0012]
(2) A container for steel sheet according to the above (1), the Sn plating layer, may be adopted further containing Fe-Sn alloy.
[0013]
(3) A container for steel sheet according to (1) or (2), wherein the chemical conversion coating layer, 1.5 at least one of phosphoric acid and phosphate, in total in terms of the amount of P ~ 25.0 mg / m 2 may be further employed a configuration containing.
[0014]
(4) A method of manufacturing a container for a steel sheet according to one embodiment of the present invention, on the steel sheet, in terms of 560 ~ 5600 mg / m on the metal Sn amount Sn 2 and a plating step of forming a Sn plating layer containing, the plating after step, Zr ions 100 ~ 3000 ppm, by performing cathodic electrolysis treatment using the chemical conversion treatment solution containing Mg ions F ions and 50 ~ 300 ppm of 120 ~ 4000 ppm, a chemical conversion coating layer on the Sn plated layer a chemical conversion treatment step of forming to the chemical conversion after the treatment step, the cleaning of performing the Sn plating layer and the chemical conversion coating layer and the steel sheet is formed with the cleaning process of at least 0.5 seconds using a 40 ° C. or more water and a step, a.
[0015]
(5) In the method for manufacturing a container for a steel sheet according to the above (4), wherein was melt 溶錫 processing to the steel sheet Sn plating layer is formed, in said at least a portion of the Sn steel of the Sn plated layer at least a part of the Fe may be adopted a configuration in which an alloy of.
[0016]
The method of manufacturing a container for a steel sheet according to (6) above (4) or (5), the chemical conversion treatment liquid, may be adopted further comprising the following phosphate ions 2000 ppm.
[0017]
(7) (4) In the method for manufacturing containers for steel sheet according to any one aspect to (6), wherein the chemical conversion treatment solution further configuration adopted include the following nitrate ions and ammonium ions 20000ppm total it may be.
[0018]
(8) (4) In the method for manufacturing containers for steel sheet according to any one aspect to (7), wherein prior to the washing step, the Sn plating layer with a 10 ° C. or higher 40 ° C. below the water and the chemical conversion treatment the steel sheet coating layer is formed may be adopted further comprising constituting the preliminary washing step for performing a cleaning process of at least 0.5 seconds.
Effect of the invention
[0019]
　According to the above embodiment, it is possible to provide excellent productivity, a manufacturing method of a container for steel and container steel sheet having environmental resistance and sulfidation blackening.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020]
FIG. 1 is a schematic diagram showing a configuration of a container steel sheet according to the present embodiment.
It is a flowchart showing a flow of a method of manufacturing containers for steel sheet according to [2] The present embodiment.
DESCRIPTION OF THE INVENTION
[0021]
　Hereinafter, a method for manufacturing a container for a steel sheet and a container for steel sheet according to the embodiment will be described with reference to the accompanying drawings.
(Container steel sheet)
　will be described first vessel steel plate 10.
　Figure 1 is a schematic diagram showing the structure of a vessel steel plate 10 according to the present embodiment. As shown in FIG. 1, container steel plate 10 includes a steel plate (original plate) 101 used as a base material, a Sn-plated 103 layer formed on the steel sheet 101, the chemical conversion film formed on the Sn-plated layer 103 It includes a layer 105, a.
[0022]
　Steel 101 is not particularly limited, it may be a known steel sheet 101 used as a container for steel. There is no particular limitation, such as a manufacturing method and material of these known steel 101. Hot rolling from a conventional billet manufacturing processes, pickling, cold rolling, annealing, through a known step of temper rolling or the like can be used steel sheets 101 prepared.
[0023]
　In the container for steel 10, as the upper layer of the steel sheet 101, Sn-plated layer 103 containing Sn is provided. Sn plating layer 103 of the present embodiment, in terms of metal Sn amount, per side 560 ~ 5600 mg / m 2 containing Sn of.
　Sn excellent workability has the weldability and corrosion resistance, In order to exert these effects, Sn content of the Sn-plated layer 103, per side 560 mg / m in terms of metal amount of Sn 2 above it is necessary that there is.
　While the Sn content of the Sn-plated layer 103 is above effects are improved as increases, Sn content per surface 5600 mg / m in terms of metal amount of Sn 2 in excess, the above effect is saturated. Therefore, from an economic point of view, the Sn content of the Sn-plated layer 103 per surface 5600 mg / m in terms of metal amount of Sn 2 or less.
[0024]
　Sn content of the Sn-plated layer 103 is preferably, per side 700 ~ 4500 mg / m in terms of metal amount of Sn 2 is, more preferably, 1200 ~ 4000 mg / m 2 is.
　By performing the melt溶錫treatment after formation of the Sn-plated layer 103, at least a portion of the Sn plated layer 103 forms at least a portion of the Fe and Fe-Sn alloy in the steel sheet. Thus, the appearance quality of the corrosion resistance and surface (mirror finish quality, etc.) can be further improved.
[0025]
　Sn plating layer 103 may be formed on both surfaces of the steel sheet 101, it may be formed from the viewpoint of reducing manufacturing costs on only one side of the steel plate 101. The steel plate 101 that Sn plating layer 103 only on one side are formed when the can manufacturing process, for example, it is preferable that the surface of the Sn plating layer 103 is formed is processed to become the inner surface of the container .
[0026]
　Sn content of the Sn-plated layer 103 is, for example, can be measured by fluorescent X-ray method. In this case, a Sn content known sample in advance a calibration curve relating the Sn content, measured relatively Sn content using the calibration curve.
[0027]
　By melting溶錫treatment after formation when only Sn plating layer 103 is formed (Sn plated layer 103 is performed on the surface of the steel sheet 101, a case where an alloy Sn-plated layer is formed on the surface of the steel sheet 101 including), be surface-treated with Sn plating layer 103 by coating, sulfur contained in the beverage or food or the like, through the coating, bonded to Sn, black SnS or SnS 2 may form such is there.
　Also, when the plated defective portion comprising a plurality of fine holes in the Sn-plated layer 103 is present, bonded to the Fe contained in the sulfur and the steel sheet 101, a black FeS, Fe 2 S 3 , or Fe 2 S it may but formed. In the present embodiment, SnS, SnS 2 , FeS, Fe 2 S 3 , or Fe 2 a phenomenon in which the compound of black is formed of S and the like, referred to as sulfide blackening. Further, the resistance (characteristics) for sulfide blackening, referred to as sulfidation blackening.
[0028]
　Vessel steel plate 10, in order to improve the sulfidation blackening comprises chemical conversion coating layer 105 as an upper layer of the Sn-plated layer 103.
　Chemical conversion coating layer 105, in terms of metal Zr content 3.0 ~ 30.0 mg / m 2 and Zr compounds of in terms of metal Mg content 0.50 ~ 5.00 mg / m 2 and Mg compound containing.
[0029]
　Zr compound contained in the chemical conversion film layer 105 has a function of improving sulfidation blackening, the adhesion and processability.
　The Zr compound according to the present embodiment, for example, oxidation Zr, phosphate Zr, mentioned hydroxide Zr and fluoride Zr etc. (including respective hydrates), but the chemical conversion coating layer 105 above the Zr compound a multiple content.
[0030]
　When Zr content in the chemical conversion coating layer 105 is increased, sulfidation blackening of the vessel steel plate 10, adhesion and workability are improved. Specifically, Zr content of the chemical conversion coating layer 105, 3.0 mg / m per one side in terms of metal Zr content 2 in the case described above, practically suitable sulfurization blackening is ensured.
　On the other hand, Zr content per surface 30.0 mg / m in terms of metal Zr content 2 exceeds, too thick chemical conversion coating layer 105, the adhesion of the chemical conversion film layer 105 itself is deteriorated, sulfidation blackening decreases. Further, Zr content per surface 30.0 mg / m in terms of metal Zr content 2 by weight, there are cases where the electrical resistance of the chemical conversion coating layer 105 is increased, the weldability decreases.
　Accordingly, Zr content of the chemical conversion coating layer 105, in terms of metal Zr content per surface 3.0 ~ 30.0 mg / m 2 and. The lower limit of Zr content is preferably in terms of metal Zr content per surface 5.0 mg / m 2 or more, more preferably, 8.0 mg / m 2 is at least. Upper limit of the Zr content is preferably, 20.0 mg / m per one side in terms of metal Zr content 2 or less, more preferably, 15.0 mg / m 2 or less.
[0031]
　Chemical conversion coating layer 105 contains a Mg compound in addition to the Zr compound. As described later, the chemical conversion treatment solution used in forming the chemical conversion film layer 105 is contained Mg ions, Mg ions in the chemical conversion treatment liquid, the chemical conversion in the coating layer 105 as a Mg compound with Zr compound It is captured. Mg compound in the chemical conversion coating layer 105, in the cleaning step performed after the formation of the chemical conversion coating layer 105, there is a case to be removed from the partially chemical conversion coating layer 105, the remainder being the chemical conversion coating layer 105 remaining in the.
　The present inventors have found that the chemical conversion coating layer 105 by including a Mg compound, was found that improves the sulfidation blackening.
[0032]
　Examples of Mg compound contained in the chemical conversion film layer 105, oxide Mg, hydroxide Mg, fluoride Mg, and phosphate Mg (including respective hydrates), with the chemical conversion coating layer 105 described above a Mg compound may be a plurality of content. These Mg compounds have generally transparent or white.
　Further, Mg ions, thiol ion is the subject of the sulfide blackening phenomenon (HS - ) or hydrogen sulfide (H 2 combines with S), By Mg ions bond with the thiol ion or hydrogen sulfide, it is possible to inhibit the binding of a Fe or Sn and thiol ion or hydrogen sulfide.
[0033]
　Furthermore, Mg compound in the chemical conversion coating layer 105 prevents the thiol ions and hydrogen sulphide passes through the chemical conversion film layer 105. The compounds produced by the the Mg ion and thiol ion or hydrogen sulfide reacts also prevents the thiol ions and hydrogen sulphide passes through the chemical conversion film layer 105.
　That is, by the chemical conversion coating layer 105 containing a Mg compound, it is possible that the Sn or Fe and thiol ion or hydrogen sulfide to reduce the likelihood of reaction, it is possible to suppress the sulfide blackening phenomenon.
[0034]
　To ensure the sulfidation blackening as mentioned above, the chemical conversion coating layer 105, per side 0.50 ~ 5.00 mg / m in terms of metallic Mg amount 2 containing Mg compound of.
　Chemical Mg content in the treated film layer 105, in terms of metal Mg content per surface 0.50 mg / m 2 by at least, having practically suitable sulfidation blackening.
　Moreover, the chemical conversion coating layer 105, 5.00 mg / m per one side in terms of metallic Mg amount 2 for containing a Mg compound greater than is required a large amount addition of Mg compounds in the chemical conversion treatment solution . The inclusion of a large amount of Mg compound chemical conversion treatment solution is not preferred because in some cases the formation of the chemical conversion coating layer 105 does not proceed favorably. Moreover, the chemical conversion coating layer 105 is 5.00 mg / m per one side in terms of the metal Mg amount 2 by including a Mg compound greater than, is no effect on the adhesion to the coating (primary adhesion) but adhesiveness when water vapor presence temperature sterilization treatment such as retort treatment (secondary adhesion) is not preferable because it may degrade the rust resistance or coating under corrosive. Furthermore, the chemical conversion treatment film layer 105 in terms of one-side per 5.00 mg / m and the metal Mg amount 2 when containing Mg compounds excess, when using containers steel plate 10 in food containers, taste or flavor of the contents because it may damage the unfavorable.
[0035]
　The lower limit of the content of the Mg compound of the chemical conversion coating layer 105 is preferably per side 0.80 mg / m in terms of metallic Mg amount 2 is, more preferably 1.00 mg / m 2 is. On the other hand, the upper limit of the amount of the Mg compound of the chemical conversion coating layer 105 is preferably per side 4.00 mg / m in terms of metallic Mg amount 2 is, more preferably 3.00 mg / m 2 is.
[0036]
　Zr amount of compound or Mg compound content in the chemical conversion coating layer 105 is, for example, a total content of metal Zr or metal Mg in the chemical conversion coating layer 105 which is determined by quantitative analysis, such as X-ray fluorescence analysis, It means the content of Zr compound or Mg compound remaining in the chemical conversion coating layer 105 after the washing step to be described later.
　In the case where Sn plating layer 103 contains Mg, the chemical conversion treatment step after having measured the Mg compound amount of the previous Sn plating layer 103 for, container steel plate 10 after the chemical conversion treatment step Mg the amount of compound was determined from the difference between them, it is possible to measure the Mg compound amount in the chemical conversion film layer 105.
[0037]
　Chemical conversion coating layer 105 may contain at least one of the addition to phosphoric acid and phosphate of Zr compounds and Mg compounds. Examples of phosphate contained in the chemical conversion film layer 105, and a phosphoric acid Zr and phosphate Mg (including respective hydrates). Chemical conversion coating layer 105, of the compound composed of a phosphoric acid and phosphate, may contain a plurality of compounds.
　Chemical conversion coating layer 105 by at least one of phosphoric acid and phosphate, it is possible to obtain an excellent sulfidation blackening and adhesiveness. The total content of phosphoric acid and phosphate, per side 1.5 mg / m in terms of P content 2 if more than can be obtained a practically suitable sulfurization blackening and adhesiveness.
　The total content of the phosphoric acid and phosphate are increased, but also improved sulfidation blackening and adhesion, 25 per side total content of phosphoric acid and phosphate in terms of P content. 0 mg / m 2 exceeds, by adhesion of the phosphoric acid or phosphate in the chemical conversion coating layer 105 is deteriorated, unfavorably the adhesiveness and coating film under corrosive and coating decreases. The total content of phosphoric acid and phosphate per side 25.0 mg / m in terms of P content 2 by weight, undesirably the electric resistance is deteriorated weldability increases.
[0038]
　Accordingly, chemical conversion coating layer 105, a total of phosphoric acid and phosphate, in terms of 1.5 per one surface ~ 25.0 mg / m in the amount of P 2 preferably contains.
　The lower limit of the total content of phosphoric acid and phosphates, more preferably, per side 2.5 mg / m in terms of P content 2 is, more preferably, 5.0 mg / m 2 is .
　The upper limit of the total content of phosphoric acid and phosphates, more preferably, per side 20.0 mg / m in terms of P content 2 is, more preferably, 12.5 mg / m 2 is.
[0039]
　Chemical total amount of phosphoric acid and phosphate treatment coating layer 105 is contained, the P content in the chemical conversion film layer 105 after the cleaning process, for example, quantitative analysis methods such as X-ray fluorescence analysis It can be quantified by.
[0040]
　[Method for container steel sheet for 10]
　Next, a method for manufacturing a container for a steel sheet 10 will be described with reference to FIG.
　Figure 2 is a flowchart illustrating a method of manufacturing a container for a steel sheet 10 according to this embodiment. As shown in FIG. 2, the manufacturing method of the container for the steel sheet 10 has a plating process, chemical conversion treatment and washing steps.
[0041]
　[Plating Step]
　First, plated with Sn on the surface of the steel sheet 101 to form a Sn plating layer 103 (step S101). The method of Sn plating is not particularly limited, electroplating, it may be a known technique such as vacuum deposition or sputtering. The Sn plating bath, can be used Ferrostan bath or the like.
　As described above, it may be subjected to melt溶錫treatment after the plating step.
[0042]
　[Chemical conversion treatment step]
　Next, the chemical conversion treatment step, the upper layer of the Sn-plated layer 103, to form a chemical conversion film layer 105 (step S103).
　The chemical conversion treatment step, the cathodic electrolysis treatment using the chemical conversion treatment solution.
[0043]
　When using the immersion treatment method as a method for forming the chemical conversion film layer 105, the adhesion of the chemical conversion coating layer 105 for etching the underlying becomes uneven, and, since the time of chemical conversion treatment step is longer , industrial production unfavorable.
　On the other hand, at the cathode electrolytic treatment, the hydrogen evolution at the interface between the forced charge transfer and the steel sheet 101 and the chemical conversion solution, the surface of the chemical conversion coating layer 105 to be formed is preferable to be cleaned. Further, the cathode electrolytic treatment, by the pH of the chemical conversion treatment solution is increased, preferably for attachment of the chemical conversion coating layer 105 is promoted.
[0044]
　Conditions of the cathode electrolytic treatment is not particularly limited, for example, chemical conversion treatment solution at a temperature of ° C. ~ 60 10 ° C., 0.1 ~ 20.0A / dm 2 of current density and 0.01 to 30 seconds of processing time conditions it can be carried out under.
　PH of the chemical conversion treatment solution is preferably from 3.0 to 4.5 in the case of lowering the pH after adding nitric acid or hydrofluoric acid, suitably by when raising the pH of the addition of ammonia it may be adjusted.
[0045]
　Chemical conversion treatment solution used in the chemical conversion treatment step contains Zr ions 100 ~ 3000 ppm. Zr ions in the chemical conversion treatment solution is incorporated into the chemical conversion film layer 105 as a Zr compound.
　The lower limit of Zr ions in the chemical conversion treatment liquid is preferably 500 ppm, more preferably 1000 ppm. The upper limit of Zr ions in the chemical conversion treatment liquid is preferably 2500 ppm, more preferably 2000 ppm.
[0046]
　Chemical conversion treatment solution contains F ions 120 ~ 4000 ppm. F ions by forming the Zr ions and complex ions, has a role to stabilize the Zr ions in the chemical conversion treatment solution.
　Although F ions in the chemical conversion solution also incorporated into the chemical conversion film layer 105 similar to the Zr ions, F compounds in the chemical conversion coating layer 105 is preferably removed as much as possible by washing step to be described later.
[0047]
　Chemical conversion treatment solution contains Mg ions 50 ~ 300 ppm.
　By chemical conversion treatment liquid contains a Mg ion, Mg compound is contained in the chemical conversion film layer 105, it is improved, which is preferable sulfidation blackening. Furthermore, Mg ions can promote the precipitation of Zr ions. Specifically, when the chemical conversion treatment liquid of comparison Zr compound amount in the case of not containing a case, in the chemical conversion coating layer 105 formed by the chemical conversion treatment step including a Mg ion, a Mg ion it is include Zr compound content in more chemical conversion coating layer 105 of the case.
[0048]
　Cause precipitation accelerating effect of Zr by Mg ions is considered as follows.
[0049]
[Formula 1]

[0050]
　The solution containing Zr ions and F ions, as shown in the above equation (1), Zr ions [ZrF with F ion 6 ] 2- is present stably in the form of complex ions, such as. In cathodic electrolysis process, the hydrogen generated at the interface between the forced charge transfer and the steel sheet 101 and the electrolytic treatment solution, pH is raised. By pH increases, complex ions mentioned above is hydrolyzed, as shown in the above equation (1) becomes a Zr ion and F ions, then the chemical conversion coating layer 105 containing Zr compound is precipitated.
　The reaction of the above formula (1) the equilibrium (reversible) reactions, but by F ions in the chemical conversion treatment solution is increased, the reaction of right of the above formulas (1) (complex ions decomposed reaction) , it is significantly inhibited.
[0051]
　Mg ions to function as a scavenger of F ions, to reduce the inhibitory effect of right reaction of formula (1) above by the F ion. Ie, F ions, by the presence of Mg ions, water-soluble by 'soft ionic interaction "[F - ... Mg 2+ ... F - ] to form, [F - ... Mg 2+ ... F - ] reducing the F ion concentration in the area near the deposition is believed to reduce the inhibitory effect of right reaction of the above formula (1). Incidentally, [F - ... Mg 2+ ... F - away from deposition site,] [F - ... Mg 2+ ... F - ] is such that dissociated into F ions and Mg ions, added during the chemical conversion treatment solution it is preferable to prepare a Mg ion concentration.
　As described above, by chemical conversion treatment liquid contains a Mg ion, Zr deposition is accelerated. Therefore, the manufacturing method of the container for the steel plate 10 according to the present embodiment, it is possible to shorten the time required for the chemical conversion treatment step, has excellent productivity.
[0052]
　Mg ion concentration to be added to the chemical conversion treatment solution is preferably 50 ~ 300 ppm. When Mg ion concentration is less than 50 ppm, it is not sufficient to exert a precipitation accelerating effect of Zr. On the other hand, when the Mg ion concentration is 300ppm greater, MgF sparingly soluble 2 to become easily formed, which is not preferable.
　Mg ion concentration to be added to the chemical conversion treatment liquid is more preferably 100 ~ 200 ppm.
　Incidentally, Mg ion is preferably added in readily water-soluble salt such as nitrate Mg or sulfuric Mg.
[0053]
　Chemical conversion treatment liquid may contain the following phosphoric acid ions 2000 ppm.
　By chemical conversion treatment liquid contains phosphate ions, the chemical conversion coating layer 105 contains a phosphoric acid or phosphate is preferable because of improving the sulfidation blackening and adhesiveness.
[0054]
　Chemical conversion treatment liquid may contain the following nitrate ions and ammonium ions 20000ppm in total. By chemical conversion treatment liquid contains nitrate ions and ammonium ions, it is possible to shorten the time required for the chemical conversion treatment step is preferable because the productivity is improved.
　Incidentally, the chemical conversion treatment liquid, rather than one of the nitrate ions and ammonium ions, it is preferable to include both nitrate ions and ammonium ions. The reason for this is as follows.
　In forming the chemical conversion coating layer 105 containing Zr, first, by reaction of the following formula (2), H at the cathode 2 is generated, pH is raised.
[0055]
　2H 2 O + 4e - → H 2 ↑ + 2OH - · · · (2)
[0056]
　As the reaction of the above formula (2), Zr 4+ , PO 4 3- is ZrO 2 , Zr 3 (PO 4 ) 4 precipitates as such, to form a chemical conversion film layer 105. In the film forming reaction, pH increase by reaction right when there are nitrate ions shown in the following scheme (3) and (4) is accelerated, resulting in film formation is promoted. Further, by the reaction shown in equation (3) and (4) below, H inhibits film formation by stirring action 2 generation of is suppressed. Thus, it is possible to shorten the time required for the chemical conversion treatment step. Furthermore, ammonium ions are considered to serve to promote the above-described effects due to nitrate ions.
　Incidentally, the chemical conversion treatment liquid Mg ions, is that it has a suitable effect described above by containing nitrate ions and ammonium ions, was revealed for the first time by the present invention.
[0057]
[Formula 2]

[0058]
　To further improve the characteristics of such sulfidation blackening, for example, first Daiichi Kasei treatment liquid first layer of the Sn-plated layer 103 side to the chemical conversion film layer 105 by performing cathodic electrolysis treatment using a (not shown) form, followed by performing a cathodic electrolysis treatment using a second chemical conversion treatment liquid, the second layer of the first layer upper to the chemical conversion coating layer 105 of the chemical conversion coating layer 105 (not shown) formed it may be.
　Note that contain identical components and Daiichi Kasei treatment liquid and the second chemical conversion treatment liquid, only temperature is different. Examples of the temperature of Daiichi Kasei treatment liquid include less 10 ° C. or higher 40 ° C., examples of the temperature of the second chemical conversion treatment solution include 45 ℃ ~ 60 ℃.
　First layer of chemical conversion coating layer 105 are the dense layer, it is preferable to ensure properties such sulfidation blackening. Second layer of chemical conversion coating layer 105, because it has a rough surface roughness is suitable to ensure the adhesion between the chemical conversion film layer 105 and a coating agent.
[0059]
　Washing Step]
　F ions, since aqueous ionic species such as nitrate ions and ammonium ions contained in the chemical conversion treatment solution is incorporated into the chemical conversion film layer 105 with Zr compound. The ion species in the chemical conversion coating layer 105 does not affect the adhesion between the coating (primary adhesion), and causes deterioration of the secondary adhesion, rust resistance or coating under corrosive Become. This is the ion species in the chemical conversion coating layer 105 to steam and corrosion solution is eluted, decomposed the binding of the chemical conversion coating layer 105 and the coating material, or is believed to be due to corrosion of the steel plate 101.
　Therefore, in this embodiment, after the chemical conversion treatment step, at least, cleaning of more than 0.5 seconds at 40 ° C. or more water (hereinafter referred to as the cleaning process) is performed (step S107). The upper limit of the temperature of the water used in this washing step is not particularly limited, for example, 90 ~ 100 ° C.. The upper limit of the washing time of the washing step is not particularly limited, for example, 10 seconds.
[0060]
　F ions, in order to further remove water soluble ionic species such as nitrate ions and ammonium ions from the chemical conversion coating layer 105, after performing the chemical conversion treatment step, prior to the present cleaning process, less 10 ° C. or higher 40 ° C. the cleaning process of at least 0.5 seconds with water (hereinafter, referred to as pre-washing step) is preferably performed (step S105). The upper limit of the washing time of the pre-washing step is not particularly limited, for example, 20 seconds.
　As a method for washing pre-washing step and the cleaning step include dipping or spraying process.
[0061]
　Removing the ionic species eluting at a low temperature by the preliminary washing step, to remove the ionic species eluting at high temperature by the washing step. By increasing the processing time of the pre-washing step and the washing step, the removal effect can be improved. Incidentally, the washing liquid used in the present washing process, thereby improving the removing effect higher temperatures.
　As each of the processing time is less than 0.5 seconds, it is difficult to reduce the ionic species.
[0062]
　F ions, nitrate ions and ammonium ions are preferably removed from unless the chemical conversion coating layer 105 can be the cleaning process, unable entirely removed, there may be a case that inevitably remain.
[0063]
　In the method of manufacturing a container for a steel sheet of the present embodiment, it is not used a high concentration of nitrate ions, are preferred on the environment.
Example 1
[0064]
　Described Examples and Comparative Examples of the present invention are described below. Incidentally, the embodiment described below, only one example of a manufacturing method of a container for a steel sheet and a container for steel sheet according to the embodiment of the present invention, a method of manufacturing a container for a steel sheet and a container for steel sheet according to the embodiment of the present invention It is not limited to the following examples.
[0065]
　To investigate the precipitation-promoting effect of Zr by Mg ions, the same conditions conditions other than Mg ion concentration in the chemical conversion treatment step, changing the Mg ion concentration, and the Zr compound amount of the formed chemical conversion coating layer. The results are shown in Table 1.
　The processing solution 1-1 to 3-2 in Table 1 is the same temperature and pH either, cathodic electrolysis treatment is performed under the conditions of the same current density and processing time. As shown in Table 1, by adding Mg ions, Zr content of the chemical conversion coating layer formed is increasing, Mg ions have been shown to have a deposition promoting effect of Zr .
[0066]
[Table 1]

Example 2
[0067]
　Shown in Table 2 using a chemical conversion treated steel sheet having an Sn plated layer and the chemical conversion coating layer to prepare a test material, the performance was evaluated for the items of the following (A) ~ (H). The evaluation results are shown in Table 3.
[0068]
(A) sulfidation blackening
　cut out test material to a size of 60mm × 60mmL, ends in a length of 5mm (a portion steel end face is exposed by the shearing) was masked with tape. 1 wt Na% 2 was immersed in S solution (adjusted to pH = 7 with lactic acid) was subjected for 60 minutes to retort treatment at a temperature of 125 ° C.. The appearance of each test material after the retort processing was visually evaluated.
　Specifically, if a better results than the chromate treated material "Very Good", a case was slightly better results than the chromate treated material "Good", when there is equal discoloration and chromate treated material was evaluated as "Average", a case some discoloration degree is greater than the chromate treatment material "Fair", the case than the discoloration degree is greater chromate treatment material "Poor".
[0069]
(B) processability
　on both sides of the test material, adhered at a temperature of 200 ° C. The PET film having a thickness of 20 [mu] m, was subjected to can manufacturing processing by drawing and ironing step by step. Flaw of the film, the floating and peeling was observed and evaluated workability from their area ratio.
　Specifically, defects of the film, the case where floating and peeling was observed "Very Good", flaw of the film, the case where the area ratio of the floating and peeling were less than 0% and 0.5% " Good ", flaw of the film, floating and when the area ratio of peeling was 0.5% or less than 15%" Fair ", flaw of the film, the area ratio of floating and peeling of 15 percent or broken unworkable was evaluated as "Poor" the case was.
　The area ratio, defects of the film, the area of the float and partial peeling was observed, it was determined by dividing the total area of the pasted PET film.
[0070]
(C) Weldability
　using a wire seam welder, under the conditions of the welding wire speed 80 m / min, was welded to the test material by changing the current. Comprehensively judging from the proper current range welding defects such as sufficient minimum current value and the dust and welding spatter welding strength is obtained consists of a maximum current value starts conspicuous was evaluated weldability.
　Specifically, the secondary side of the proper current range of "Very Good" in the case of more than 1500A, "Good" and when the current proper current range of the secondary side is less than or 800A 1500A, the secondary side of the current appropriate current range "Fair" in the case of less than 100A 800A, current proper current range of the secondary side is a case of less than 100A was evaluated as "Poor".
[0071]
(D) Film adhesion
　to both surfaces of the test material, baking at a temperature of 200 ° C. The PET film having a thickness of 20 [mu] m, drawing and ironing performs processing to produce a can body. Performs retorted for 30 minutes at a temperature of 125 ° C., to observe the peeling conditions of the film were evaluated film adhesion from the release area ratio.
　Specifically, if the peeling area ratio of 0% "Very Good", a case where the release area ratio is less than 0% and 2% "Good", a case where peeling area ratio of less than 2% 10% " Fair ", the peeling area ratio is a case of more than 10% was evaluated as" Poor ".
[0072]
(E) primary coating adhesion
　epoxy test material - phenolic resin was applied, was carried out for 30 minutes to baking treatment at a temperature of 200 ° C.. Put a grid cut of a depth reaching the base iron at 1mm intervals, and peeling with tape. Observing the peeling conditions were evaluated primary coating adhesion from the release area ratio.
　Specifically, if the peeling area ratio of 0% "Very Good", a case where the release area ratio is less than 0% and 5% "Good", the peeling area ratio of the case of less than 5 percent 30 percent " Fair "peeling area ratio and the case of more than 30% was evaluated as" Poor ".
[0073]
(F) Secondary coating adhesion
　epoxy test material - phenol resin was coated, it was carried out for 30 minutes to baking treatment at a temperature of 200 ° C.. Put a grid cut of a depth reaching the base iron at 1mm intervals, was followed for 30 minutes retorted at a temperature of 125 ° C.. After drying, peeling the coating film tape, to observe the peeling conditions were evaluated secondary paint adhesion from the release area ratio.
　Specifically, if the peeling area ratio of 0% "Very Good", a case where the release area ratio is less than 0% and 5% "Good", the peeling area ratio of the case of less than 5 percent 30 percent " Fair "peeling area ratio and the case of more than 30% was evaluated as" Poor ".
[0074]
(G) coating under corrosion
　epoxy test material - phenolic resin was applied, was carried out for 30 minutes to baking treatment at a temperature of 200 ° C.. Then, put the grid cut having a depth reaching the base steel, the test solution consisting of -1.5% saline mixture of 1.5% citric acid, was immersed at a temperature of 45 ° C. 72 hours. After washing and drying, it was subjected to a tape peeling. Observing the corrosion condition of the coating film corrosion under conditions and flat portion of the portion containing the cut, the evaluation of the corrosion area ratio of the width and the flat plate portion of the coating film under corrosion were evaluated coating under corrosion.
　Specifically, the coating film under corrosion width 0.2mm below and "Very Good" and when the corrosion area ratio of 0% of the flat portion, the coating film under corrosion width 0.2mm or 0.3mm below and the flat plate portion of cases corrosion area ratio is less than 0% and 1% "Good", less than the coating corrosion under wide than 0.3 mm 0.45 mm and the flat portion of the corroded area ratio of the case of less than 1 percent 5 percent " Fair ", the coating film under corrosion width than 0.45mm or flat portion of the corroded area ratio was the case of more than 5% was evaluated as" Poor ".
[0075]
(H) retort rust resistance
　was tested material for 30 minutes retorted at a temperature of 125 ° C.. Then, by observing the rust occurrence of it was evaluated retort rust resistance from rust area ratio.
　Specifically, if the rust area ratio of 0% "Very Good", a case where rust area ratio is less than 0% and 1% "Good", rust area ratio of 1 percent or less of 5% "Fair" the case, rust area ratio was the case of more than 5% was evaluated as "Poor".
[0076]
[Table 2]

[0077]
[table 3]

[0078]
　As shown in Table 3, the present invention Examples A1 ~ A20 are in any of characterization has a rating of more than "Good", was of suitable properties. On the other hand, Comparative Examples a1 ~ a6 are either characteristic is evaluated as "Poor", it had properties inferior to Inventive Examples.
Example 3
[0079]
　To produce a chemically treated steel sheet in the following manner. Production conditions are shown in Table 4.

　using the following methods (treatment 1) or (treatment 2), the Sn plating layer is formed on steel sheet having a thickness of 0.17 ~ 0.23 mm, were produced Sn plated steel sheet .
[0080]
　(Treatment 1)
　After the cold rolling, annealing and pressure-regulated steel sheet, after degreasing and pickling, on both sides, the Sn plating layer is formed by using a Ferrostan bath was prepared Sn-plated steel sheet.
　(Treatment 2)
　after cold rolling, annealing and pressure-regulated steel sheet, after degreasing and pickling, on both sides, to form a Sn plating layer with a Ferrostan bath. Thereafter, the reflow processing (melting溶錫treatment) to prepare a Sn-plated steel sheet having an Sn alloy layer.
[0081]

　against Sn-plated steel sheet manufactured by the method of the above (treatment 1) or (treatment 2), subjected to one of the following methods (treatment 3) - (treatment 7) to form a chemical conversion coating layer containing Zr compound and Mg compound on the surface of the Sn plated steel sheet by. In treatment ~ 6 3, 0.5 ~ 30.0A / dm 2 current density, temperature of the chemical conversion treatment solution of the cathodic electrolytic treatment time of 0.5-5.0 seconds and 10 ~ 60 ° C. in went the cathode electrolytic treatment. Further, the processing method 7, the temperature was immersed for 180 seconds immersion time chemical conversion treatment liquid is pH was 60 ° C. 3.5.
[0082]
　(Treatment 3)
　was dissolved fluoride Zr, by performing cathodic electrolysis treatment using the chemical conversion treatment liquid having added thereto a nitric Mg, to form a chemical conversion coating layer.
[0083]
(Treatment 4) was dissolved fluoride Zr and phosphate, by performing cathodic electrolysis treatment using the chemical conversion treatment liquid having added thereto a nitric Mg, to form a chemical conversion coating layer.
[0084]
(Treatment 5) was dissolved fluoride Zr and nitric acid ammon, by performing cathodic electrolysis treatment using the chemical conversion treatment liquid having added thereto a nitric Mg, to form a chemical conversion coating layer.
[0085]
(Treatment 6) fluoride Zr, dissolved phosphoric acid and nitric acid ammon, by performing cathodic electrolysis treatment using the chemical conversion treatment liquid having added thereto a nitric Mg, to form a chemical conversion coating layer.
[0086]
(Treatment 7) was dissolved fluoride Zr, by performing the immersion treatment using the chemical conversion treatment liquid having added thereto a nitric Mg, to form a chemical conversion coating layer.
[0087]

　After formation of the chemical conversion coating layer by the above process were subjected to preliminary cleaning by immersing the steel sheet 0.5 seconds to 5.0 seconds in distilled water at less than 10 ° C. or higher 40 ° C. The.
　After precleaning, the main cleaning was carried out by immersing time steel sheets shown in Table 4 in distilled water at a temperature shown in Table 4.
[0088]

　metal Sn amount of the plating layer was measured by X-ray fluorescence method. Further, Zr content of the chemical conversion coating layer, Mg content and the content of the phosphoric acid or phosphate (converted to P amount) was measured by quantitative analysis methods such as X-ray fluorescence analysis.
　The measurement results are shown in Table 5.
[0089]

　for the test material subjected to the above processing, the items listed in Example 2 (A) ~ (H) , the performance was evaluated for the items of the (I) described below. The evaluation results are shown in Table 6.
[0090]
(I) Mg ions Zr adhesion promoting effect of the addition
　using a chemical conversion treatment solution was removed Mg ions from the chemical conversion treatment solution used in making the test material, the container under the same conditions as the other conditions are the test material use steel (hereinafter referred to as Mg-free container steel sheet) was produced. It was then measured Zr content of Mg-free container for steel.
　The Zr content of each test material, the ratio obtained by dividing the Zr content of Mg-free container for steel plate (hereinafter, referred to as Zr adhesion promoter rate) was thus evaluated Zr adhesion promoting effect of Mg ion addition. Specifically, if the Zr adhesion promoting ratio is more than 1.3, "Very Good", "Good" in the case of ~ 1.2 to less than 1.3, the case of more than 1.2 to less than 1.1 "Fair", a case of less than 1.1 was evaluated as "Poor".
[0091]
[Table 4]

[0092]
[table 5]

[0093]
[Table 6]

[0094]
　Inventive Examples B1 ~ B26 are both together having a Zr adhesion promoting effect of Mg ion addition, excellent sulfidation blackening, workability, weldability, film adhesion, primary paint adhesion, secondary paint adhesion had a coating under corrosive and corrosion resistance.
　Furthermore, the chemical conversion coating layer is 1.5 mg / m as P amount 2 by containing the above phosphoric acid or a phosphate, the film adhesion (including processability) and the coating film under corrosive resistance was further improved.
　On the other hand, in Comparative Examples b1 ~ b8, with no Zr adhesion promoting effect, sulfidation blackening, weldability, formability, weldability, film adhesion, primary paint adhesion, secondary paint adhesion, coating film At least some of the properties of the lower corrosiveness and corrosion resistance was inferior.
[0095]
　In Comparative Example b1 and b4, small F ion content in the chemical conversion solution, Zr 4+ ions (ZrF 6 ) 2- can not exist stably in solution in the processing solution as complex ions, such as, ZrO 2 precipitated in the process liquid as an insoluble matter in the form of such, even when containing Mg ions were less Zr compound amount of the chemical conversion coating layer. Therefore, it considered precipitation accelerating effect of Zr by Mg ion was not suitable.
　In Comparative Example b2 and b3, since the F ion content in the chemical conversion treatment solution is present in excess, Mg ions can not sufficiently exhibit the function as a scavenger of F ions, preferably precipitation accelerating effect of Zr by Mg ion In is considered that there was no.
　In Comparative Example b5, since the Mg ion content in the chemical conversion treatment liquid is insufficient, believed precipitation accelerating effect of Zr by Mg ion was not suitable. Conversely, when F ions is large, (ZrF 6 ) 2- make it difficult to film forming in complex ions such as be excessively stabilized. )
[0096]
　In Comparative Example b6, since Mg ion content in the chemical conversion treatment solution was excessive, MgF sparingly soluble 2 is formed, does not function adequately Mg ions as scavengers, precipitation accelerating effect of Zr by Mg ion is preferably It considered that there was no.
　Comparative Example b8 are using dipping process rather than the cathode electrolytic treatment, chemical conversion treatment solution was less Zr compound amount of the chemical conversion coating layer even when containing Mg ions. Therefore, it considered precipitation accelerating effect of Zr by Mg ion was not suitable.
[0097]
　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 changes in form, for even such modifications are intended to fall within the technical scope of the present invention.
Industrial Applicability
[0098]
　According to the above embodiment, it is possible to provide excellent productivity, a manufacturing method of a container for steel and container steel sheet having environmental resistance and sulfidation blackening.
DESCRIPTION OF SYMBOLS
[0099]
　10 container steel sheet for
　101 steel
　103 Sn-plated layer
　105 chemical conversion coating layer

The scope of the claims
[Claim 1]
　; Steel plate and
　provided as upper layer of the steel sheet, in terms to 560 ~ 5600 mg / m on the metal Sn amount 2 Sn plating layer and containing a Sn;
　provided as an upper layer of the Sn-plated layer, in terms of metal Zr content 3.0 ~ 30.0 mg / m Te 2 and Zr compounds of in terms of metal Mg content 0.50 ~ 5.00 mg / m 2 ; and Mg compound, a chemical conversion coating layer containing
comprises
that wherein the container for steel.
[Claim 2]
　The Sn plating layer further contains Fe-Sn alloy
, wherein the container for steel sheet according to claim 1.
[Claim 3]
　The chemical conversion coating layer, at least one of phosphoric acid and phosphate, in terms of total 1.5 ~ 25.0 mg / m in in the P amount 2 further contains
, characterized in that, according to claim 1 or container for steel sheet according to 2.
[Claim 4]
　On the steel sheet, a Sn 560 ~ 5600 mg / m in terms of metal amount of Sn 2 plating process and to form a Sn plating layer comprising;
　after the plating step, Zr ions 100 ~ 3000ppm, 120 ~ F ions and 50 of 4000ppm by performing cathodic electrolysis treatment using the chemical conversion treatment solution containing Mg ion ~ 300 ppm, the chemical conversion treatment step and for forming a chemical conversion coating layer on the Sn plated layer;
　after the chemical conversion treatment step, 40 ° C. or more water wherein the main cleaning step performs Sn plating layer and the chemical conversion coating layer is formed the steel plate cleaning at least 0.5 seconds using;
having
, characterized in that, the manufacturing method of the container for the steel sheet.
[Claim 5]
　The was melt溶錫processing to the steel sheet Sn plating layer is formed, alloying and at least a portion of the Fe in said at least a part of the Sn steel of the Sn plating layer
, characterized in that, according method for producing a container for steel sheet according to claim 4.
[Claim 6]
　The chemical conversion treatment solution further comprises the following phosphate ions 2000ppm
and wherein the method of manufacturing a container for a steel sheet according to claim 4 or 5.
[Claim 7]
　The chemical conversion treatment solution further comprises the following nitrate ions and ammonium ions 20000ppm in total
and wherein the method of manufacturing a container for a steel sheet according to any one of claims 4-6.
[8.]
　Wherein prior to the washing step, the Sn plating layer and pre-cleaning step of performing the chemical conversion coating layer and the steel sheet is formed cleaning process of at least 0.5 seconds with a 10 ° C. or higher 40 ° C. below the water with further
characterized in that, the manufacturing method of the container for steel sheet according to any one of claims 4-7.