JP5157487B2 - Steel plate for containers and manufacturing method thereof - Google Patents

Description

  The present invention relates to a steel plate for containers and a method for producing the same, and particularly relates to a steel plate for containers excellent in corrosion resistance and can manufacturing processability and a method for producing the same.

  Metal containers have long been used as containers for beverages and foods. As the steel material of this metal container, nickel (Ni) plated steel sheet, tin (Sn) or Sn-based alloy plated steel sheet is mainly used. In order to enhance the rust prevention effect of these plated steel sheets, hexavalent metal has been conventionally used. Rust prevention treatment with chromate using chromate or the like is widely performed. Furthermore, a coating layer made of an organic resin has been formed on the chromate-treated film for the purpose of imparting organic solvent resistance, fingerprint resistance, scratch resistance, lubricity, etc., if necessary ( For example, see Patent Document 1.)

  On the other hand, in recent years, attention has been paid to the fact that trivalent chromium is harmless while hexavalent chromium is harmful, against the background of increasing environmental problems. Conventionally, Ni-plated steel sheets, Sn or Sn alloy-plated steel sheets have been used. There is a movement to try to omit the chromate treatment itself. Since the coating film formed by the chromate treatment itself has a high degree of corrosion resistance and paint adhesion, if such chromate treatment is not performed, these performances are expected to be significantly reduced. The

  Therefore, despite the reduction of the amount of chromium used for chromate treatment performed on the surface of Ni-plated steel sheets, Sn or Sn alloy-plated steel sheets, and good anticorrosion and coating despite the use of rust prevention treatment instead of chromate treatment It has been required to form a rust preventive layer having adhesion.

  In order to solve the above-mentioned problems, for example, a Sn-plated steel sheet is immersed in a chemical conversion treatment solution containing a phosphate ion and a silane coupling agent, or a treatment method in which the chemical conversion treatment solution is applied and dried (for example, Patent Document 2) Reference).

  Moreover, not only the surface treatment method by immersion or coating as described above, but also, for example, a method of surface-treating an Sn-plated steel sheet by an electrolytic reaction using a phosphate compound (see, for example, Patent Document 3) or Al. A method of surface-treating a material by an electrolytic reaction using a titanium-based compound (for example, see Patent Document 4) is disclosed.

  Furthermore, not only a method using an electrolytic reaction, but also an aluminum-based, zinc-based, iron-based, and magnesium-based substrate (see, for example, Patent Document 5), Sn or Sn-based alloy-plated steel (see, for example, Patent Document 6). Also disclosed is a method for cathodic electrolysis of the material with a chemical conversion treatment material containing a zirconium (Zr) -containing compound and a fluorine-containing compound.

JP 2000-239855 A Japanese Patent Laid-Open No. 2004-60052 JP 2000-234200 A JP 2002-194589 A Japanese Patent Laid-Open No. 2005-23422 JP-A-2005-325402

  However, the method described in Patent Document 2 has a problem that productivity is poor because it is a treatment such as immersion in chemical conversion solution, coating and drying.

  Moreover, although the method of patent documents 3-6 forms a surface treatment film | membrane by electrolytic reaction or cathode electrolytic treatment, even if the method as described in these literatures is used, sufficient corrosion resistance and contact | adherence It was difficult to realize the sex.

  Therefore, the present invention has been made in view of such problems, and its purpose is to achieve excellent corrosion resistance and can manufacturing processability even when surface treatment is substituted for chromate treatment. The object is to provide a new and improved container steel plate and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventor has found that a chemical conversion treatment film composed of a chemical conversion treatment film is used in order to improve the corrosion resistance and can manufacturing processability of the chemical conversion treatment film which is a surface treatment film. It came to mind that the layer structure of the layers is important.

  Therefore, as a result of earnest research on the layer structure of the chemical conversion coating layer, the present inventor obtained a chemical conversion coating having a suitable coating structure by forming the chemical conversion coating by low-temperature electrolytic treatment. It has been found that excellent corrosion resistance and canning processability can be obtained.

The present invention has been completed based on such findings, and the gist of the present invention is as follows.
(1) At least one surface of the steel sheet has a chemical conversion coating layer containing a mixture of zirconium oxide, zirconium phosphate, and phenol resin, and the chemical conversion coating layer is the entire film of the chemical conversion coating layer. The phenol resin present at least in a thickness portion within 10% from the surface layer with respect to the thickness, and the zirconium present at least in a thickness portion within 40% from the surface layer with respect to the total film thickness of the chemical conversion coating layer. A phosphate and an oxide of zirconium present at least in a thickness portion of 40% to 100% from the surface layer with respect to the total film thickness of the chemical conversion coating layer, and within 10% from the surface layer In the thickness portion, in the spectrum chart by X-ray photoelectron spectroscopy focusing on carbon (C) or nitrogen (N), the maximum noise height in the spectrum chart X-ray photoelectron spectroscopy focusing on phosphorus (P) or oxygen (O) of the phosphate of zirconium in a thickness portion within 40% of the surface layer. In the spectrum chart in the analysis, a peak having a height of 2 times or more with respect to the maximum noise height in the spectrum chart is shown, and in the thickness portion of 40% to 100% from the surface layer, oxygen of the zirconium oxide ( A steel plate for containers, characterized in that, in a spectrum chart in X-ray photoelectron spectroscopic analysis focusing on O), a peak having a height that is twice or more the maximum noise height in the spectrum chart is shown .
(2) The chemical conversion treatment film layer contains a zirconium component, a phosphoric acid component, and a phenol resin component, has a pH in the range of 3.1 to 3.7, and has a liquid temperature of 10 ° C to 40 ° C. The steel plate for containers according to (1), which is formed by cathodic electrolysis.
(3) The cathode electrolysis treatment is performed at an electrolysis current density of 0.05 A / dm ^{2 to} 50 A / dm ² and an energization time of 0.01 seconds to 5 seconds, according to (2) The steel plate for containers as described.
(4) the chemical conversion coating layer is characterized by containing a zirconium ^1mg / ^{m 2 ~9mg} / m 2 of metal zirconium content, container steel sheet according to any one of (1) to (3) .
(5) the chemical conversion coating layer is characterized by containing the phosphoric acid 0.5mg ^{/ m 2} ~8mg ^/ m 2 in phosphorus content container according to any of (1) to (4) Steel plate.
( 6 ) The container according to any one of (1) to ( 5 ), wherein the chemical conversion coating layer contains 0.1 mg / m ^{2 to} 5 mg / m ² of a phenol resin in terms of carbon content. Steel plate.
( 7 ) A base plating layer containing at least nickel or tin is formed between the steel sheet and the chemical conversion coating layer, for containers according to any one of (1) to ( 6 ) steel sheet.
(8) the lower plating layer is a nickel plating layer, the nickel plating layer is characterized in that it contains nickel 150mg ^{/ m 2} ~1000mg ^/ m 2 in metal amount of nickel, according to (7) Steel plate for containers.
(9) the lower plating layer has a tin plating layer, the tin plating layer is characterized by containing tin 560mg ^{/ m 2} ~5600mg ^/ m 2 by metal tin content, according to (7) Steel plate for containers.
( 10 ) The steel sheet has a nickel base or an iron-nickel alloy plated base nickel layer formed on the steel sheet surface, and a part of the tin plating applied on the base nickel layer and one of the base nickel layers. A plated steel sheet in which a tin plating layer containing island-shaped tin alloyed with part or all is formed. The plated steel sheet has a nickel metal content of 5 to 150 mg / m ² and a metal tin content of 300. The steel plate for containers according to any one of (1) to ( 6 ), characterized by containing ~ 3000 mg / m ² of tin.

  According to the present invention, the chemical conversion coating layer is located on the surface side of the chemical conversion coating layer, the phosphate layer in which zirconium phosphate is unevenly distributed, and the steel plate side of the chemical conversion coating layer, Since an oxide layer containing a zirconium oxide as a main component is provided, excellent corrosion resistance and can-making processability can be realized even when surface treatment instead of chromate treatment is performed.

(First embodiment)
Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

[Configuration of Steel Plate for Containers According to this Embodiment]
First, the structure of the container steel plate according to the first embodiment of the present invention will be described in detail with reference to FIG. Drawing 1 is an explanatory view for explaining composition of steel plate 10 for containers concerning this embodiment.

  The steel plate 10 for containers which concerns on this embodiment contains the steel plate 20 used as an original plate, and the chemical conversion treatment film layer 30 formed in at least one surface of this steel plate 20, as shown to Fig.1 (a). .

(About steel plate 20)
The original plate used in the present embodiment is not particularly restricted, and a steel plate that is normally used as a container material can be used. Also, the manufacturing method and material of the steel plate are not particularly restricted. For example, the steel plate is manufactured through a normal slab manufacturing process through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling. Can be used.

  Moreover, as shown in FIG.1 (b), the base plating layer 40 which consists of metals, for example may be formed in the surface of said steel plate 20. As shown in FIG. As a method for forming the base plating layer 40, a known technique can be used. For example, an electroplating method, a vacuum evaporation method, a sputtering method, or the like can be used. In addition, the method of forming the base plating layer 40 which concerns on this embodiment is not restrict | limited to said example.

(About the base plating layer 40)
<Example 1: Ni plating layer>
As the base plating layer 40 formed on the surface of the steel plate 20, for example, a Ni plating layer can be formed. The Ni plating layer is provided in order to ensure paint adhesion, film adhesion, corrosion resistance, and weldability of the steel plate 20. Since Ni is a highly corrosion-resistant metal, it is possible to improve the corrosion resistance of the steel plate for containers 10 according to this embodiment by forming a Ni plating layer on the surface of the steel plate 20 according to this embodiment. The method for forming the Ni plating layer is not particularly limited, and a known technique can be used. For example, a method such as a vacuum deposition method or a sputtering method, an electroplating method or an electroless plating method can be used. It is possible to use a wet plating method such as a method. Moreover, Ni and Fe in a steel plate may be alloyed to provide a Fe—Ni alloy plating layer.

The paint adhesion, film adhesion, corrosion resistance, and weldability improvement effect of the alloy layer by Ni is manifested when the amount of Ni to be plated, that is, the amount of metal Ni in the Ni plating layer is 10 mg / m ² or more, for example. As the amount of metallic Ni in the Ni plating layer increases, the paint adhesion, film adhesion, corrosion resistance, and weldability improving effects of the Ni plating layer increase. In addition, although the paint adhesion, film adhesion, corrosion resistance, and weldability improvement effects are manifested with a metal Ni amount of 10 mg / m ² , the Ni content in the Ni plating layer is, for example, 150 mg in order to obtain sufficient corrosion resistance. / M ² or more is more preferable.

Moreover, it is preferable that Ni content in a Ni plating layer is 1000 mg / m < ² > or less, for example. This is because when the Ni content in the Ni plating layer exceeds 1000 mg / m ² , the paint adhesion, film adhesion, corrosion resistance, and weldability improvement effects are saturated, and Ni is an expensive metal. Therefore, it is economically disadvantageous to plate more than 1000 mg / m ² of Ni.

The Ni plating layer according to this embodiment may be formed of pure Ni as long as the Ni content in the Ni plating layer is in the range of 150 mg / m ^{2 to} 1000 mg / m ^2. , Ni alloy may be used. In addition, for the purpose of improving the mechanical strength, the steel sheet may be subjected to nitriding treatment, and even in such a case, by nitriding treatment, the steel sheet is less likely to be crushed or deformed even if the thickness of the steel sheet is reduced. The effect obtained is not reduced.

  Further, after forming the Ni plating layer, a heat treatment for forming a diffusion layer may be performed for the purpose of further improving the corrosion resistance. Furthermore, for example, when forming a Ni plating layer by a diffusion plating method, after plating Ni on the steel plate surface, a diffusion treatment for forming a diffusion layer is performed in an annealing furnace. Nitriding treatment may be performed before or after or simultaneously with the diffusion treatment.

<Example 2: Composite plating layer containing Ni and Sn>
Another example of the base plating layer 40 formed on the surface of the steel plate 20 includes a composite plating layer containing Ni and Sn. This composite plating layer is formed on the surface of the steel plate 20, and is formed on the Ni plating layer made of Ni or Fe—Ni alloy having a metallic Ni amount of, for example, 5 to 150 mg / m ² , and on the Ni plating layer. Sn plating layer whose Sn amount is 300-3000 mg / m < ² >, for example is included. This Sn plating layer is formed into an island shape by being at least partially alloyed with Ni in the Ni plating layer by a molten tin treatment.

The Ni-based plating layer made of the above-described Ni or Fe—Ni alloy is formed to ensure paint adhesion, film adhesion, corrosion resistance, and weldability. Since Ni is a highly corrosion-resistant metal, it is possible to improve the corrosion resistance of the alloy layer containing Fe and Sn formed during the molten tin treatment by Ni plating. The effect of improving paint adhesion, film adhesion, corrosion resistance, and weldability of the alloy layer with Ni begins to appear when the amount of metal Ni in the Ni plating layer is 5 mg / m ² or more, and the alloy layer increases as the Ni content increases. The effect of improving the corrosion resistance is increased. Therefore, the amount of metallic Ni in the Ni plating layer is preferably 5 mg / m ² or more, for example.

Moreover, it is preferable that the amount of metallic Ni in the Ni plating layer is, for example, 150 mg / m ² or less. This is because when the amount of metallic Ni in the Ni plating layer exceeds 150 mg / m ² , the paint adhesion, film adhesion, corrosion resistance, and weldability improvement effects are saturated, and Ni is an expensive metal. Therefore, it is economically disadvantageous to plate more than 150 mg / m ² of Ni.

  In addition, when Ni diffusion plating is performed, after Ni plating, diffusion treatment is performed in an annealing furnace to form a Ni diffusion layer, but nitriding treatment may be performed before or after the Ni diffusion treatment. . Even when the nitriding treatment is performed, both the effect of Ni as the Ni plating layer and the effect of the nitriding treatment layer in this embodiment can be achieved.

  As a method of Ni plating and Fe—Ni alloy plating, for example, a publicly known method generally used in electroplating can be used.

  After the Ni-based plating, Sn plating is performed. The “tin plating” in this specification includes not only plating with metallic tin but also a mixture of metallic tin with irreversible impurities and a mixture of metallic tin with a trace element. The Sn plating method is not particularly limited, but for example, a known electroplating method is preferably used, and a method of plating by dipping a steel plate in molten Sn may be used.

  The Sn plating layer by the above Sn plating is formed to ensure corrosion resistance and weldability. Since Sn itself has high corrosion resistance, it exhibits excellent corrosion resistance and weldability both as metallic tin and as an alloy formed by the molten tin treatment described below.

The excellent corrosion resistance of Sn is remarkably improved from the amount of metal Sn of 300 mg / m ² or more, and the degree of improvement in corrosion resistance increases as the Sn content increases. Therefore, the amount of metallic Sn in the Sn plating layer is preferably 300 mg / m ² or more, for example. Moreover, since the corrosion resistance improving effect is saturated when the amount of metallic Sn exceeds 3000 mg / m ² , the Sn content is preferably, for example, 3000 mg / m ² or less from an economical viewpoint.

In addition, Sn with low electric resistance is soft and spreads by pressurizing Sn between the electrodes during welding, so that a stable energization region can be secured, and thus particularly excellent weldability is exhibited. This excellent weldability is exhibited when the amount of metal Sn is 100 mg / m ² or more. Moreover, in the range of the amount of metal Sn exhibiting excellent corrosion resistance, the weldability improving effect is not saturated. Therefore, in order to ensure excellent corrosion resistance and weldability, it is preferable that the amount of metal Sn is, for example, 300 mg / m ² or more and 3000 mg / m ² or less.

  After the Sn plating as described above, a molten tin treatment is performed. The purpose of the molten tin treatment is to melt Sn and alloy it with the underlying steel plate 20 or the underlying metal (for example, Ni plating layer) to form a Sn—Fe or Sn—Fe—Ni alloy layer, and to form an alloy layer. In addition to improving the corrosion resistance, an island-shaped Sn alloy is formed. This island-shaped Sn alloy can be formed by appropriately controlling the molten tin treatment.

  By performing the above-described treatment, a coating structure in which metallic tin is not present and a plating layer having an excellent Fe—Ni or Sn—Fe—Ni alloy plating layer with excellent film adhesion is exposed (that is, an “island” Sn alloy) , A steel sheet having a plating structure in which an Fe—Ni alloy or Sn—Fe—Ni alloy plating layer corresponding to the “sea” portion is formed can be manufactured.

<Example 3: Sn plating layer>
As yet another example of a lower plating layer 40 formed on the surface of the steel sheet 20, for example, can be metal Sn amount on the surface of the steel sheet 20 is exemplified Sn plating layer is 560mg ^{/ m 2} ~5600mg ^/ m 2 about . As described above, Sn has excellent workability, weldability, and corrosion resistance. However, in order to obtain sufficient corrosion resistance only by Sn plating, the amount of metal Sn is preferably set to, for example, 560 mg / m ² or more. Moreover, although the corrosion resistance improves as the amount of metal Sn increases, in the case of Sn plating alone, when the amount of metal Sn exceeds 5600 mg / m ² , the corrosion resistance improvement effect is saturated. Therefore, from the economical point of view, when Sn plating is used alone, the amount of metal Sn is preferably 5600 mg / m ² or less. Similarly to the above case, by performing the molten tin treatment after Sn plating, Fe and Fe—Sn alloy layers in the steel sheet can be formed, and the corrosion resistance and surface appearance can be improved (mirror appearance). Further improvement is possible.

  The base plating layer 40 such as the Ni plating layer, the composite plating layer, or the Sn plating layer may be formed on both surfaces of the steel plate 20, and only one surface (one surface) of the steel plate 20 from the viewpoint of manufacturing cost reduction. It may be formed. In addition, when forming said base plating layer 40 only in the single side | surface of the steel plate 20, if the base plating layer 40 is formed in the surface of the steel plate 20 of the side in which the chemical conversion treatment film layer 30 which concerns on this embodiment is not formed. Good. When the steel plate 20 on which the base plating layer 40 is formed only on one surface of the steel plate can be processed, for example, the surface on which the base plating layer 40 is formed is processed to be the inner surface of the container. Is preferred.

<Measurement method of each component in the base plating layer>
Here, the amount of metallic Ni and the amount of metallic Sn in the base plating layer can be measured by, for example, a fluorescent X-ray method. In this case, a calibration curve related to the amount of metal Ni is specified in advance using a sample of the amount of deposited Ni that has a known amount of metal Ni, and the amount of metal Ni is relatively specified using this calibration curve. Similarly, in the case of the amount of metal Sn, a calibration curve related to the amount of metal Sn is specified in advance using a sample of the amount of Sn deposited with a known amount of metal Sn, and the amount of metal Sn is specified relatively using this calibration curve. To do.

(About chemical conversion treatment film layer 30)
The chemical conversion treatment film layer 30 according to the present embodiment is formed on the steel plate 20 or the base plating layer 40 as described above, as shown in FIG. The chemical conversion treatment film layer 30 includes, for example, a Zr component, a phosphoric acid component, and a phenol resin component as components that form the chemical conversion treatment film layer 30.

  When the above-mentioned Zr component, phosphoric acid component and phenol resin component are each formed as a Zr film, phosphoric acid film and phenol resin film, some practical effects are observed although corrosion resistance and adhesion are recognized to some extent. I can't show it. However, like the chemical conversion treatment film layer 30 according to the present embodiment, the chemical conversion treatment film layer 30 is a composite film in which a Zr component, a phosphoric acid component, and a phenol resin component are combined to exhibit excellent practical performance. Is possible. Furthermore, since the properties of each film are complemented in a range where the amount of the film is small, the performance of the film combining the three types of Zr film, phosphoric acid film, and phenol resin film is more stably exhibited.

<About Zr component>
The Zr component contained in the chemical conversion treatment film layer 30 according to the present embodiment has a function of improving corrosion resistance and adhesion, particularly processing adhesion. The Zr component according to the present embodiment is composed of, for example, a plurality of Zr compounds such as zirconium hydroxide and zirconium fluoride in addition to zirconium oxide and zirconium phosphate. Such a Zr component is excellent in corrosion resistance and adhesion, in particular, processing adhesion. Therefore, as the amount of the Zr component contained in the chemical conversion coating layer 30 increases, the corrosion resistance and adhesion of the steel plate 10 for containers, in particular, Processing adhesion will be improved.

Specifically, when the amount of Zr component deposited on the steel plate 20 or various undercoat layers 40 as the chemical conversion coating layer 30 is 1 mg / m ² or more in terms of the amount of metal Zr, there is no practical problem. Corrosion resistance and paint adhesion are ensured. On the other hand, as the adhesion amount of the Zr component increases, the effect of improving the adhesion resistance such as corrosion resistance and coating also increases. However, when the adhesion amount of the Zr component exceeds 9 mg / m ² in terms of the metal Zr amount, Since the derived film becomes too thick, the adhesiveness of the chemical conversion film itself decreases (mainly due to cohesive failure), and the electrical resistance increases and the weldability decreases. Moreover, when the adhesion amount of a Zr component exceeds 9 mg / m < ² > by metal Zr amount, the adhesion nonuniformity of a chemical conversion treatment film may appear as an external appearance nonuniformity. Therefore, in the container steel sheet 10 according to this embodiment, the adhesion amount of Zr components (i.e., the content of Zr) is preferably set to ^1mg / ^{m 2 ~9mg} / m 2 of metal Zr content. More preferably, the adhesion amount of Zr component is ^2mg / ^{m 2 ~6mg} / m ² of metal Zr content. The adhesion amount of Zr component by the range of ^{2mg / m 2 ~6mg / m 2} , with corrosion resistance can be secured after the retort, it is possible to reduce the fine adhesion unevenness.

<About the phosphoric acid component>
In addition to the zirconium component described above, the chemical conversion coating layer 30 further includes a phosphoric acid component formed of one or more phosphoric acid compounds.

  The phosphoric acid component according to the present embodiment has a function of improving corrosion resistance and adhesion, particularly processing adhesion. The phosphoric acid component according to the present embodiment includes iron phosphate, nickel phosphate, tin phosphate, phosphoric acid formed by reacting with a base (steel plate, Ni plating layer, composite plating layer, Sn plating layer) or zirconium component. It is comprised from the composite component which consists of 1 type of phosphoric acid compounds, such as a zirconium, or these 2 or more types of phosphoric acid compounds. Since such a phosphoric acid component is excellent in corrosion resistance and adhesiveness, especially processing adhesiveness, the corrosion resistance and adhesiveness of the steel plate 10 for containers will improve, so that the quantity of the phosphoric acid component formed increases.

Specifically, when the adhesion amount of the phosphoric acid component in the chemical conversion coating layer 30 is 0.5 mg / m ² or more in terms of the P amount, a level of corrosion resistance and adhesion such as coating that are practically no problem are ensured. . On the other hand, with the increase in the adhesion amount of the phosphoric acid component, the effect of improving the corrosion resistance and adhesion such as coating is also increased. However, when the adhesion amount of the phosphoric acid component exceeds 8 mg / m ² in terms of P amount, phosphoric acid Since the coating derived from the components becomes too thick, the adhesion of the chemical conversion coating itself decreases (mainly due to cohesive failure), and the electrical resistance increases and the weldability decreases. Moreover, when the adhesion amount of a phosphoric acid component exceeds 8 mg / m < ² > by P amount, the adhesion nonuniformity of a chemical conversion treatment film may appear as an external appearance nonuniformity. Therefore, in the container steel sheet 10 according to this embodiment, the adhesion amount of the phosphate component is preferably set to ^0.5 / ^{m 2 ~8mg} / m 2 in the P content. More preferably, the adhesion amount of the phosphate component is ^1mg / ^{m 2 ~5mg} / m 2 in the P content. By setting the adhesion amount of the phosphoric acid component in the range of 1 mg / m ² to 5 mg, corrosion resistance after retorting can be ensured and minute adhesion unevenness can be reduced.

<About phenol resin component>
Moreover, said chemical conversion treatment film layer 30 further contains a phenol resin component in addition to the above-mentioned zirconium component and phosphoric acid component. The phenol resin component according to the present embodiment is, for example, a water-soluble phenol resin modified with N, N-diethanolamine as shown in the following chemical formula 1 (in the solution (in water) as an ammonium salt in the presence of phosphoric acid. Presumed to exist).

... (Chemical formula 1)

  The phenol resin component according to the present embodiment has a function of improving adhesion, particularly processing adhesion. Since the phenol resin itself is an organic substance, it has very good adhesion to paints and laminate films made from organic substances. Since the phenol resin itself is an organic substance, it has excellent adhesion to paints and laminate films. In particular, when the surface treatment layer undergoes processing that greatly deforms, the surface treatment layer itself may be coherently broken due to the processing, and adhesion may deteriorate. However, phenolic resins are processed in Zr films and phosphate films. It has the effect of significantly improving the adhesion. Therefore, the adhesiveness of the steel plate 10 for containers will improve, so that the quantity of the phenol resin component formed increases.

Specifically, when the adhesion amount of the phenol resin component in the chemical conversion coating layer 30 is 0.1 mg / m ² or more in terms of the C amount, a practically satisfactory level of adhesion is secured. On the other hand, the adhesion improvement effect increases with an increase in the adhesion amount of the phenol resin component. However, when the adhesion amount of the phenol resin component exceeds 5 mg / m ² in terms of C amount, it is derived from the phenol resin component. Since the film becomes too thick, the adhesion of the chemical conversion film itself decreases, and the electrical resistance increases and the weldability decreases. Moreover, when the adhesion amount of a phenol resin component exceeds 5 mg / m < ² > by C amount, the adhesion nonuniformity of a chemical conversion treatment film may appear as an external appearance nonuniformity. Accordingly, the container steel sheet 10 according to this embodiment, the adhesion amount of the phenolic resin component, it is necessary to 0.1mg ^{/ m 2} ~5mg ^/ m 2 in C content. Preferably the coating weight of the phenolic resin component is 0.3mg ^{/ m 2} ~4mg ^/ m 2 in C content. The adhesion amount of the phenolic resin component by a range of ^{0.3mg / m 2 ~4mg / m 2} , it is possible to reduce the fine adhesion unevenness (yellow due to adhesion odd).

<About the measuring method of each component content in a chemical conversion treatment film layer>
The amount of metal Zr and the amount of P contained in the chemical conversion film layer 30 according to the present embodiment can be measured by a quantitative analysis method such as fluorescent X-ray analysis, for example. On the other hand, the amount of C can be measured by subtracting the amount of C existing in the steel sheet using a TOC (total organic carbon meter).

<About the film structure of the chemical conversion treatment film layer 30>
Next, the film structure of the chemical conversion film layer 30 according to this embodiment will be described in detail with reference to FIG. FIG. 2 is an explanatory diagram for explaining the film structure of the chemical conversion film 30 according to the present embodiment.

  The chemical conversion treatment film layer 30 according to the present embodiment is intended to share the functions of the Zr oxide and the Zr phosphate, which are components constituting the chemical conversion treatment film layer 30, and includes the Zr oxide and Zr. The chemical conversion film layer 30 containing a mixture of a phosphate and a phenol resin is composed of an oxide layer mainly composed of an oxide of Zr, a phosphate layer in which the phosphate of Zr is unevenly distributed, and a phenol resin. A phenol resin layer that is unevenly distributed.

  As shown in FIG. 2, the film structure of the chemical conversion coating layer 30 according to the present embodiment is positioned on the surface side of the oxide layer 32 positioned on the steel plate 20 side and the oxide layer 32 of the chemical conversion coating layer 30. A phosphoric acid layer 34, a coexisting layer 36 between the oxide layer 32 and the phosphoric acid layer 34, in which a Zr oxide and a Zr phosphate coexist, and the outermost layer of the chemical conversion coating layer 30 And a phenolic resin layer 38 located on the surface.

  Here, when the thickness of the chemical conversion coating layer 30 is 100%, the surface layer is 0% deep, and the portion in contact with the steel plate 20 is 100% deep, the phenol resin layer 38 is 0% of the surface layer of the chemical conversion coating 30. The phosphor layer 34 is mainly unevenly distributed in the thickness portion within 0% depth to 40% depth of the surface layer of the chemical conversion coating 30. On the other hand, the oxide layer 32 is mainly unevenly distributed from the 40% depth of the chemical conversion coating 30 to the portion in contact with the steel plate 20, in other words, the 100% depth portion that is the lowermost portion of the thickness of the chemical conversion coating layer 30. It is preferable. The coexistence layer 36 in which the oxide of Zr and the phosphate of Zr coexist is expressed in the same notation, and a portion having a depth of 20% to 60%.

In addition, the total film thickness of the chemical conversion treatment layer, the thicknesses of the respective layers, and the ratio of the thicknesses in the present embodiment are basically equivalent to SiO ₂ values in X-ray photoelectron spectroscopy (XPS) described later. Each numerical value can be specified based on the above. That is, the method for measuring the thickness of each layer according to the present embodiment is limited to the value obtained using this method.

  From the above-mentioned meaning, each absolute value does not indicate an accurate value in a strict sense, but the film structure of the chemical conversion film layer 30 is on the steel plate 20 side as shown in FIG. The oxide layer 32 located, the phosphoric acid layer 34 located on the surface side of the chemical conversion coating layer 30, and located between the oxide layer 32 and the phosphoric acid layer 34, the oxide of Zr and the phosphoric acid of Zr In the present embodiment, the film layer forming position of each layer and the arrangement order of the film layers are constituted by a coexisting layer 36 in which salt coexists and a phenol resin layer 38 positioned as the outermost layer of the chemical conversion film layer 30. There is essentially no change.

As described above, the oxide layer 32 is a layer mainly composed of an oxide of Zr. Here, the oxide of Zr may be zirconium oxide · n hydrate represented by ZrO ₂ · nH ₂ O, or may be a zirconium oxide anhydride represented by ZrO ₂ . As shown in FIG. 2, the oxide layer 32 exists on the surface of the steel plate 20 and in the vicinity of the surface. The oxide layer 32 is presumed to form a dense matrix, and exhibits excellent corrosion resistance and adhesion between the chemical conversion coating layer 30 and the steel plate 20. It is essential that the oxide layer 32 is unevenly distributed in a thickness portion of about 40 to 100% in the depth direction from the surface layer of the chemical conversion treatment film layer 30, particularly, unevenly distributed on the surface of the steel plate 20. . When the oxide layer 32 is not unevenly distributed on the surface of the steel plate 20, excellent corrosion resistance, which is a function shared by the oxide layer 32, and adhesion between the chemical conversion coating layer 30 and the steel plate 20 are significantly impaired. Preferably, the oxide layer 32 is present from about 40% in the depth direction from the surface layer, and is reliably present on the outermost surface of the steel plate 20. In addition to the zirconium oxide, the oxide layer 32 may contain, for example, a Zr phosphate within 10%, and other compounds such as a small amount of a phenol resin component. May be.

As described above, the phosphoric acid layer 34 is a layer in which Zr phosphate is unevenly distributed, that is, a layer in which a large amount of Zr phosphate is present in the chemical conversion film 30. Here, the phosphate of Zr is zirconium phosphate · m or n hydrate represented by Zr ₃ (PO ₄ ) ₄ · mH ₂ O, Zr (HPO ₃ ) ₂ · nH ₂ O, or the like. . As shown in FIG. 2, the phosphoric acid layer 34 exists in the surface layer of the chemical conversion coating layer 30 and in the vicinity of the surface layer. The phosphoric acid layer 34 exhibits excellent corrosion resistance and adhesion between the chemical conversion treatment film layer 30 and a paint or film that can be formed on the chemical conversion treatment film layer 30, in particular, processing adhesion. The phosphoric acid layer 34 is unevenly distributed in the depth direction from the surface layer of the chemical conversion treatment film 30, and in a thickness portion of 40% from the outermost layer, in particular, unevenly distributed in the outermost layer of the chemical conversion treatment film 30. Is required. When the phosphoric acid layer 34 is not unevenly distributed on the outermost surface layer, excellent corrosion resistance, which is a function shared by the phosphoric acid layer 34, a chemical conversion coating layer 30, and a paint or film that can be formed on the chemical conversion coating layer 30, The adhesion between the two is significantly impaired. Preferably, the phosphoric acid layer 34 is present up to about 40% in the depth direction as well as the surface layer. In addition, in the phosphoric acid layer 34, for example, an oxide of Zr may exist within 10% in addition to the above-described zirconium phosphate, and other compounds may exist.

  As described above, the coexistence layer 36 is a layer located between the oxide layer 32 and the phosphoric acid layer 34, and is a layer in which the Zr oxide and the Zr phosphate coexist. is there. Here, the interface between the oxide layer 32 and the coexistence layer 36 and the interface between the coexistence layer 36 and the phosphoric acid layer 34 do not exist clearly, and are continuous from the oxide layer 32 to the coexistence layer 36. In particular, the layer structure has changed. Also, the layer structure of the interface between the coexistence layer 36 and the phosphoric acid layer 34 continuously changes from the coexistence layer 36 to the phosphoric acid layer 34. In the coexistence layer 36, in addition to the above-described zirconium oxide and zirconium phosphate, other compounds, for example, a trace amount of a phenol resin component may be present.

  The presence of the phosphoric acid layer 34 and the coexistence layer 36 as described above in the chemical conversion treatment film layer 30 according to the present embodiment means that the Zr phosphate is present in the chemical conversion treatment film layer 30 with a certain distribution. In the phosphoric acid layer 34, most of the Zr phosphate present in the chemical conversion coating layer 30 is present, and as the coexisting layer 36 becomes the oxide layer 32, the Zr It shows that the abundance of phosphate is decreasing.

  As described above, the phenol resin layer 38 is a layer located at the outermost layer of the chemical conversion treatment film layer 30, and a layer in which the phenol resin is unevenly distributed, that is, a large amount of phenol resin is present in the chemical conversion treatment film layer 30. It is a layer. This phenolic resin layer 38 is present in the outermost layer of the chemical conversion coating 30 in a film-like or interspersed manner, and has excellent corrosion resistance due to the oxidizability of the phenolic resin and is applied in a subsequent process of the can manufacturing process. , Demonstrate adhesion to film, especially processing adhesion. This phenol resin layer 38 is unevenly distributed in the depth direction from the surface layer of the chemical conversion treatment film layer 30 and within a thickness portion within 10% from the outermost layer, in particular, unevenly distributed in the outermost surface layer of the chemical conversion treatment film layer 30. It is essential to be. When the phenol resin layer 38 is not unevenly distributed in the outermost layer, excellent corrosion resistance, which is a function shared by the phenol resin layer 38, and a coating or film that can be formed on the chemical conversion coating layer 30 and the chemical conversion coating layer 30, The adhesion between the two is impaired. Preferably, the phenol resin layer 38 is present up to about 10% in the depth direction as well as the surface layer. In addition to the above-described phenol resin, for example, an oxide of Zr or a phosphate of Zr may exist in the phenol resin layer 38, or another compound may exist.

  The chemical conversion treatment film layer 30 according to the present embodiment has a layer structure composed of approximately three layers as described above. For example, the chemical conversion treatment film layer by X-ray photoelectron spectroscopy (XPS) is used. It is clear from the result of the composition state analysis including the depth direction analysis.

3A to 3E are examples of measurement results of XPS spectra of the chemical conversion treatment film layer 30 according to the present embodiment. 3A shows Zr in the chemical conversion coating layer 30, FIG. 3B shows phosphorus (P) in the chemical conversion coating layer 30, FIG. 3C shows carbon (C) in the chemical conversion coating layer 30, and FIG. FIG. 3E is a measurement result of XPS spectrum focusing on oxygen (O) in the chemical conversion coating layer 30 and FIG. 3E focusing on nitrogen (N) in the chemical conversion coating layer 30. The numbers from 1 nm to 22 nm described in FIG. 3A to FIG. 3E indicate the depth (SiO ₂ ) of the chemical conversion film 30 to which the XPS spectrum is focused when the surface layer of the chemical conversion film 30 is 0 nm. (Converted value). 3A to 3E are XPS spectra when the chemical conversion film layer 30 is formed with a thickness of about 17 nm (actually measured value by TEM observation).

The XPS spectrum was measured using the measurement apparatus and measurement conditions shown in Table 1 below. For analysis of the obtained XPS spectrum, MultiPak V. 8.0 (manufactured by Ulvac-phi) was used. In addition, the XPS spectrum was corrected for energy so that the binding energy was C1s = 284.8 eV. Hereinafter, the depths indicated by XPS data are all converted to SiO ₂ .

  Here, in the present embodiment, “existing” means that the maximum noise height existing in the spectrum chart with respect to the spectrum chart obtained by XPS analysis (the baseline is set by the shirley method, narrow scan). On the other hand, the element showing a peak having a height of 1.5 times or more is defined as “existing”.

  In the present embodiment, “unevenly distributed” means that the maximum noise height existing in the spectrum chart is compared with the spectrum chart obtained by XPS analysis (baseline correction by the Shirley method, narrow scan). Thus, it is defined that a corresponding element species is “unevenly distributed” for a peak having a height of twice or more.

  Here, referring to FIG. 3A which is an XPS spectrum focusing on Zr, from a spectrum measuring 0 nm (that is, a surface layer of the chemical conversion coating layer 30) to a spectrum observing a depth of about 14 nm. , Peaks due to Zr are clearly observed. This indicates that Zr is present from the surface layer of the chemical conversion coating layer 30 to about 14 nm, and Zr exists only at a concentration below the XPS measurement limit at a depth deeper than about 14 nm. Indicates that it is not. This shows that the thickness of the film is about 14 nm.

  Referring to FIG. 3C, which is an XPS spectrum focusing on carbon (C), from the spectrum observing 0 nm (that is, the surface layer of the chemical conversion coating layer 30) to the spectrum observing a depth of about 1 nm. , C peaks are observed. This indicates that most of the phenolic resin is present on the outermost surface of the chemical conversion coating layer 30 (the outermost layer includes organic contaminants on the coating surface), and C is deeper than about 2 nm. It shows that it exists only at a concentration below the measurement limit of XPS.

  Next, referring to FIG. 3E, which is an XPS spectrum focusing on nitrogen (N), a spectrum in which a depth of about 1 nm is observed from a spectrum in which 0 nm (that is, the surface layer of the chemical conversion coating layer 30) is observed. Up to now, peaks due to N derived from phenolic resin have been observed. This indicates that most of the phenolic resin is present on the outermost surface of the chemical conversion coating layer 30 (the outermost layer contains organic dirt on the coating surface), and N is deeper than about 2 nm. It shows that it exists only at a concentration below the measurement limit of XPS.

  3B, which is an XPS spectrum focusing on phosphorus (P), from a spectrum observing 0 nm (that is, a surface layer of the chemical conversion coating layer 30) to a spectrum observing a depth of about 4 nm. A clear peak representing a phosphate ion is observed. However, in the spectrum observing the depth of about 6 nm, the intensity of the peak due to the phosphate ion is almost the same as the intensity of the background, and the peak due to the phosphate ion is observed. Not. In the chemical conversion coating layer 30 shown in FIG. 3B, phosphate ions are present from the surface layer to about 4 nm, and the phosphate ions are below the XPS measurement limit at a depth deeper than about 6 nm. Is present only at a concentration of.

  Further, when attention is paid to FIG. 3D, which is an XPS spectrum focusing on oxygen (O), there is no change in the O of Zr phosphate from the spectrum measuring 0 nm to the spectrum observing a depth of about 4 nm. The resulting peak is clearly observed. On the other hand, a peak derived from O of the Zr oxide is observed from around 2 to 4 nm to around 14 nm. This indicates that Zr phosphate exists from the surface layer of the chemical conversion coating layer 30 to about 4 nm, and at a depth deeper than about 4 nm, the Zr phosphate is XPS. It indicates that it exists only at concentrations below the measurement limit. Further, it is shown that an oxide of Zr is present from about 4 nm to about 14 nm from the surface layer of the chemical conversion coating layer 30, and at a depth deeper than about 14 nm, the Zr oxide is XPS. It indicates that it exists only at concentrations below the measurement limit.

  The XPS spectrum measurement results shown in FIGS. 3 (a), 3 (b), 3 (c), 3 (d) and 3 (e) are the chemical conversion coating layer 30 of this measurement example. In this case, most of the phenolic resin is present up to about 1 nm from the surface layer (in other words, in the case of this sample, about 7% from the surface layer of the film), and about 4 nm from the surface layer (in other words, from this sample) In this case, a large amount of phosphate of Zr exists up to about 28% from the surface layer of the film, and the oxide of Zr is mainly located at about 4 nm to 14 nm (in other words, about 28% to 100%). It is present as a component.

  Thus, in the chemical conversion treatment film layer 30 according to the present embodiment, the Zr oxide, the Zr phosphate, and the phenol resin are not uniformly present, and most of the phenol resin is the chemical conversion treatment film layer 30. The Zr phosphate is present in the chemical conversion treatment film layer 30 with a specific distribution, and is unevenly distributed in the surface of the chemical conversion treatment film layer 30 and in the vicinity of the surface layer. By having such a film configuration, the steel plate for containers 10 according to the present embodiment has excellent corrosion resistance and can manufacturing processability.

[Method for producing chemical conversion coating layer]
As mentioned above, although the structure of the steel plate 10 for containers which concerns on this embodiment was demonstrated, the manufacturing method for manufacturing this steel plate 10 for containers is demonstrated in detail.

  The manufacturing method of the steel plate 10 for containers which concerns on this embodiment performs the low-temperature cathodic electrolysis process with respect to the steel plate 20, and forms the above-mentioned chemical conversion treatment film layer 30 on the at least single side | surface of a steel plate.

  As described above, the chemical conversion treatment film layer 30 according to this embodiment is composed of approximately three film layers of the oxide layer 32 / coexistence layer 36 / phosphoric acid layer 34 / phenol resin layer 38 in order from the steel plate 20 side. It has the layer structure which becomes. In order to form such a film structure, cathodic electrolysis treatment is performed on the steel plate 20 and the steel plate 20 on which the base plating layer 40 is formed using an acidic solution in which Zr ions, phosphate ions and a phenol resin are dissolved. Do. By using the cathodic electrolysis treatment, the chemical conversion treatment film layer 30 having the layer structure as described above can be formed in one step.

  Here, as a method of forming the chemical conversion treatment film layer 30 on the steel plate 20, a method of immersing the steel plate 20 in the chemical conversion treatment solution may be considered in addition to the above-described cathodic electrolytic treatment. However, in this method by immersion treatment, the steel sheet and the underlayer that are the foundation of the chemical conversion coating layer are etched and various coatings are formed. The chemical conversion film layer 30 having the layer structure as described above is difficult to form. Moreover, since the processing time required for formation of the chemical conversion treatment film layer 30 becomes long, it is disadvantageous for industrial production.

  On the other hand, in the method using cathodic electrolysis, a uniform film is formed for 0.01 seconds or more, together with forced charge transfer and surface normalization due to hydrogen generation at the steel plate interface and adhesion promoting effect due to an increase in hydrogen ion concentration (pH). It is formed in a short time of about several seconds. Therefore, the method by cathodic electrolysis is a very advantageous method industrially. Therefore, in order to form the chemical conversion film layer 30 according to the present embodiment, it is necessary to use a method based on cathodic electrolysis.

  In order to form the chemical conversion treatment film layer 30 by cathodic electrolytic treatment, it is necessary to prepare a chemical conversion treatment solution in which the Zr component, the phosphoric acid component, and the phenol resin component are dissolved at a predetermined ratio. Specifically, as the chemical conversion treatment solution, the acidic solution contains 10 ppm to 1500 ppm of a low molecular weight phenol resin having a zirconium ion of 100 ppm to 7500 ppm, a phosphate ion of 50 ppm to 5000 ppm, and a mass average molecular weight of about 5000. What is necessary is just to use. Moreover, you may add another component in a chemical conversion liquid as needed.

  Moreover, the pH of the chemical conversion treatment liquid for forming the chemical conversion treatment film layer 30 is preferably in the range of 3.1 to 3.7, more preferably around 3.5. In addition, nitric acid, ammonia, or the like may be added as necessary to adjust the pH of the chemical conversion treatment solution.

(Concerning conditions for cathodic electrolysis)
In the cathodic electrolysis treatment according to the present embodiment, it is necessary to perform the electrolysis treatment (low temperature cathodic electrolysis treatment) with the liquid temperature of the chemical conversion treatment solution used for the cathodic electrolysis treatment being, for example, 10 ° C. to 40 ° C. Thus, by performing the cathodic electrolytic treatment at a low temperature of 40 ° C. or less, it is possible to form a dense and uniform film structure formed of particles having a very small particle diameter. Moreover, when the liquid temperature is less than 10 ° C., the film formation efficiency is poor, and when the outside air temperature is high such as in summer, the chemical conversion liquid needs to be cooled, which is not economical. In addition, when the liquid temperature exceeds 40 ° C., the formed film structure is non-uniform, and defects, cracks, microcracks, etc. are generated, making it difficult to form a dense film, which is a starting point for corrosion and the like. Therefore, it is not preferable.

Moreover, in forming the chemical conversion treatment film layer 30 by cathodic electrolysis, the electrolysis current density is preferably set to 0.05 A / dm ² to 50 A / dm ² , for example. When the current density is less than 0.05 A / dm ² , the adhesion amount of the chemical conversion coating layer 30 is reduced, and it becomes difficult to form a stable coating, and the corrosion resistance and can manufacturing processability are reduced. It is not preferable. In addition, when the current density exceeds 50 A / dm ² , the amount of the chemical conversion coating layer deposited exceeds the required amount and becomes saturated, and in some cases, in a washing process such as water washing after the electrolytic chemical conversion treatment. It is not economical, for example, a film with insufficient adhesion is washed away (peeled). Moreover, since the liquid temperature of the chemical conversion treatment liquid used for the cathodic electrolysis treatment is increased, the chemical conversion treatment liquid needs to be cooled in order to maintain the low temperature cathode electrolysis according to the present embodiment, which is not preferable.

  Moreover, it is preferable that the said cathodic electrolysis process is performed by the energization time of 0.01 second-5 second. If the energization time is less than 0.01 seconds, the amount of film adhesion may be reduced, and corrosion resistance, paint adhesion, and the like may be reduced. On the other hand, when the energization time exceeds 5 seconds, the coating amount exceeds the required amount and the amount of deposition becomes saturated, and in some cases, the coating process is insufficient in the washing process such as water washing after the electrolytic conversion treatment. It is not economical such as washing (peeling) a thin film, and also causes an increase in the temperature of the electrolytic treatment solution, and an extra treatment of cooling the electrolytic treatment solution in order to maintain the temperature conditions of the low-temperature cathodic electrolysis described above May be required.

By performing cathodic electrolysis with the electrolytic current density and energization time as described above, a film with an appropriate amount of adhesion can be formed on the surface of the steel plate 20. Thus, for example, if it contains a predetermined concentration or more of Zr ions in the chemical conversion treatment solution, to form a chemical conversion film containing Zr adhesion amount of ^1mg / ^{m 2 ~9mg} / m 2 of metal Zr content can, chemical when in the treatment liquid if contains a predetermined concentration or more of phosphate ions, to form a chemical conversion film containing phosphoric acid deposition amount of 0.5mg ^/ m ² ~8mg / m 2 in the amount of P it is possible, to form a chemical conversion film containing a conversion if in the treatment liquid if contains a predetermined concentration or more phenolic resins, C amount 0.1mg ^/ m ² ~5mg / m 2 of coating weight of the phenolic resin Can do.

  Moreover, you may perform the above-mentioned low-temperature cathodic electrolysis process with respect to the steel plate 20 in which the base plating layer 40 was formed in at least one side. In this case, the chemical conversion treatment film layer 30 is formed on the base plating layer 40.

  In addition, in forming the chemical conversion treatment film layer 30 according to the present embodiment, tannic acid may be further added to the acidic solution used for the low-temperature cathode electrolytic treatment. By adding tannic acid to the acidic solution, tannic acid reacts with iron (Fe) of the steel plate during the above treatment, and a film of iron tannate is formed on the surface of the steel plate. Since this iron tannate film improves rust resistance and adhesion, the chemical conversion film layer 30 may be formed in an acidic solution to which tannic acid is added, if necessary.

  Further, as the solvent of the acidic solution used for forming the chemical conversion coating layer 30, for example, water (distilled water) or the like can be used, but the solvent of the acidic solution according to the present embodiment is the same as that described above. It is not regulated and can be appropriately selected according to the material to be dissolved, the forming method, the forming conditions of the chemical conversion coating layer 30, and the like.

In the chemical conversion solution, for example, a Zr complex such as H ₂ ZrF ₆ can be used as a Zr supply source. Zr in the Zr complex as described above is present in the chemical conversion solution as Zr ⁴⁺ due to the increase in pH at the cathode electrode interface. Such Zr ions further react in the chemical conversion solution, and become a compound such as ZrO ₂ , Zr ₃ (PO ₄ ) ₄ , Zr (HPO ₃ ) _2, etc., and can form a Zr film. . Furthermore, in order to adjust the pH of the chemical conversion treatment solution, for example, nitric acid or ammonia may be added.

  In addition, the layer structure of the chemical conversion treatment film layer 30 which concerns on this embodiment is not only the case where a steel plate is passed between electrodes once in the processing tank which performs a cathodic electrolytic treatment (one pass process), but multiple times ( Even in the case of electrolytic treatment) (multi-pass treatment), it is formed similarly.

  As described above, the steel plate for containers 10 according to the present embodiment has the chemical conversion treatment film layer 30 containing a mixture of a Zr oxide, a Zr phosphate, and a phenol resin on at least one surface of the steel plate 20. The chemical conversion coating layer 30 is located on the outermost surface of the chemical conversion coating layer 30 and the phenolic resin layer 38 in which the phenol resin is unevenly distributed, and the zirconium phosphate is unevenly positioned in the steel plate 20 side of the phenolic resin layer 38. It has the phosphoric acid layer 34 and the oxide layer 32 which is located in the steel plate 20 side of the phosphoric acid layer 34, and has a zirconium oxide as a main component. The chemical conversion treatment film layer 30 according to this embodiment forms a layer structure of an oxide layer 32 / coexistence layer 36 / phosphoric acid layer 34 / phenolic resin layer 38 in order from the steel sheet 20 side by low-temperature cathodic electrolysis. Excellent corrosion resistance and adhesion are exhibited, and as a result, excellent can-making processability can be exhibited. Moreover, since the chemical conversion treatment film layer 30 according to the present embodiment is formed by a low-temperature cathodic electrolysis method, it is possible to form a dense and uniform film, and the appearance of the steel plate 10 for containers is good.

  Below, the steel plate 10 for containers which concerns on this invention is demonstrated further, showing an Example and a comparative example. The following embodiment is merely a specific example of the present invention, and the present invention is not limited to the embodiment described below.

<Production of steel plate>
First, the steel plate 20 on which the chemical conversion film layer 30 was formed was produced by the method described below.

(A1) Manufacturing method of steel plate without base plating layer Steel plate obtained by degreasing and pickling both surfaces of steel substrate (steel plate) having a thickness of 0.17 to 0.23 mm after annealing and pressure adjustment after cold rolling Was made.

(A2) Manufacturing method of steel plate with Ni plating layer present After cold rolling, the steel substrate (steel plate) having a thickness of 0.17 to 0.23 mm annealed and regulated is degreased and pickled, and then Ni plating was performed on both sides using a Watt bath to prepare a Ni-plated steel sheet.

(A3) Manufacturing method of steel sheet having Ni plating layer After performing Ni plating on both surfaces of a cold-rolled steel substrate (steel sheet) having a thickness of 0.17 to 0.23 mm using a Watt bath An Ni diffusion layer was formed by annealing, and degreasing and pickling were further performed to prepare a Ni-plated steel sheet.

  In addition, the adhesion amount of the metallic nickel of the obtained Ni plating steel plate was measured by the fluorescent X ray method.

(A4) Manufacturing method of steel plate having Ni plating + Sn plating layer (island-like Sn alloy layer) (I)
After cold rolling, after annealing and adjusting a steel base (steel plate) having a thickness of 0.17 to 0.23 mm, degreased and pickled, Fe-Ni using a sulfuric acid-hydrochloric acid bath on both sides Alloy plating was performed, followed by Sn plating using a ferrostan bath, followed by molten tin treatment, and Ni and Sn plated steel sheets having island-shaped Sn alloy layers were produced.

(A5) Manufacturing method (II) of steel plate having Ni plating + Sn plating layer (island-like Sn alloy layer)
Cold-rolled steel base (steel plate) with a thickness of 0.17 to 0.23 mm is plated with Ni on both sides using a Watt bath to form a Ni diffusion layer during annealing, degreasing, pickling Then, Sn plating was performed using a ferrostan bath, and then a molten tin treatment was performed to prepare a Ni and Sn plated steel sheet having an island-shaped Sn alloy layer.

(A6) Manufacturing method of steel plate having Sn plating layer After cold rolling, after degreasing and pickling a steel substrate (steel plate) having a thickness of 0.17-0. Then, Sn was plated using a ferrostan bath, and then a molten tin treatment was performed to produce a Sn-plated steel sheet having a Sn alloy layer.

  In addition, the adhesion amount of metallic nickel and metallic tin of the obtained steel plate was measured by the fluorescent X-ray method.

<Formation of chemical conversion treatment film layer>
Next, on the surface (both sides) of the steel sheet produced by the above-described methods (A1) to (A6), the chemical conversion treatment film layer 30 is formed by cathodic electrolytic treatment using a chemical conversion treatment liquid having the components shown in Table 2 below. Formed. In addition, the liquid temperature of the chemical conversion liquid was 30 degreeC, pH was 3.5, and the electrolysis current density was 1.0-3.0 A / dm < ² > (refer following (B1)-(B3)).

  (B1): Cathodic electrolysis by immersing the platingless steel sheet and the plated steel sheet prepared by the methods (A1) to (A6) in a treatment solution in which Zr fluoride, phosphoric acid and phenol resin are dissolved in distilled water. After the treatment, it was washed with water and dried.

  (B2): Cathodic electrolysis by immersing the platingless steel sheet and the plated steel sheet prepared by the methods (A1) to (A6) above in a treatment solution in which Zr fluoride, phosphoric acid and tannic acid are dissolved in distilled water. After the treatment, it was washed with water and dried.

  (B3): A plating-less steel sheet and a plated steel sheet prepared by the methods (A1) to (A6) above are immersed in a processing solution in which Zr fluoride is dissolved in distilled water, and then subjected to cathodic electrolytic treatment, followed by washing with water. And dried (comparative example).

  About each steel plate 10 for containers produced by the above-mentioned method, the amount of metal Zr, the amount of P, and the amount of C in chemical conversion treatment film layer 30 were measured by the quantitative analysis method using fluorescent X-rays.

<Performance evaluation method>
Subsequently, each container steel plate 10 produced by the method described above was used as a test material, and each test material was evaluated for corrosion resistance, rust resistance, workability, weldability, paint adhesion, film adhesion, and appearance. It was. Hereinafter, specific evaluation methods and evaluation criteria will be described.

(1) Corrosion resistance After applying an epoxy-phenol resin to one surface of each of the test materials of Examples and Comparative Examples, baking was carried out by holding at 200 ° C. for 30 minutes. A test solution comprising a mixed solution of citric acid (1.5% by mass) -salt (1.5% by mass) obtained by adding a crosscut having a depth reaching the steel substrate to the portion coated with the resin. The film was immersed for 72 hours at 45 ° C., washed and dried, and then subjected to a tape peeling test. Under the coating film (epoxy-phenol resin film) in the cross-cut portion, the corrosion state of the flat plate portion. It was evaluated with. As a result, the case where no corrosion was observed under the coating film was ◎, the case where slight corrosion was observed under the coating film to the extent that there was no practical problem, and the minute corrosion was recognized under the coating film. The case where a slight corrosion was observed on the flat plate part or the case where a significant corrosion was observed under the coating film or the case where the plate part was found to be corrosive was rated as x.

(2) Rust resistance For each test material of the example and comparative example, a cycle test in which the humidity is maintained for 2 hours in an environment of 90% and the cycle test in which the humidity is maintained for 2 hours in an environment of 40% for 2 months. And the occurrence of rust was evaluated. As a result, it was ◎ that there was no rusting, ◯ that there was very little rusting to the extent that there was no practical problem, △ that there was slight rusting, and rusting mostly. The thing was set as x.

(3) Workability After laminating a PET film having a thickness of 20 μm on both surfaces of each test material of the examples and comparative examples at 200 ° C., a can-making process by drawing and ironing is performed in stages, and the molding is performed. It was evaluated by sex. As a result, it was found that there was no breakage or generation of wrinkles and the moldability was very good. X.

(4) Weldability The minimum that can obtain sufficient welding strength by welding each test material of the example and the comparative example by using a wire seam welding machine and changing the current at a welding wire speed of 80 m / min. The evaluation was comprehensively based on the width of an appropriate current range consisting of a current value (4000 A or less) and a maximum current value (5000 A or more) at which welding defects such as dust and welding spatter start to stand out. As a result, the case where the weldability was wider than that of the current value range and the weldability was extremely good was evaluated as ◯, the case where the weldability was narrower than the above range, and the case where welding was impossible.

(5) Paint adhesion After applying an epoxy-phenolic resin to one surface of each test material of Examples and Comparative Examples, baking was carried out by holding at 200 ° C. for 30 minutes. And after forming notches with a depth reaching the steel substrate in a grid pattern at intervals of 1 mm in the part where the resin was applied, a cross-cut peel test was performed in which an adhesive tape was applied to the part and peeled off. . As a result, ◎ indicates that there was no peeling at all, ○ indicates that there was a slight peeling that does not cause a problem in practice, △ indicates that there was a slight peeling, and × indicates that most of the peeling has occurred.

(6) Film adhesion After laminating a PET film having a thickness of 20 μm on both surfaces of each of the test materials of Examples and Comparative Examples at 200 ° C., a squeezing and ironing process was performed to produce a can body. On the other hand, the retort process for 30 minutes was performed at 125 degreeC, and the peeling condition of the film in that case evaluated. As a result, ◎ indicates that there was no peeling, ◯ indicates that there was a slight peeling with no practical problem, △ indicates that there was a slight peeling, and most of the peeling occurred. The thing was set as x.

(7) Appearance Each test material of Examples and Comparative Examples was visually observed and evaluated in terms of unevenness generated in the Zr film, phosphoric acid film and phenol resin film. As a result, it was ◎ that there was no unevenness at all, ◯ that had slight unevenness to the extent that there was no practical problem, △ that had slight unevenness, and × that had extremely unevenness × It was.

(8) Island-like Sn situation The surface of the island-like Sn situation when Sn plating was performed after Ni-based plating was observed with an optical microscope, and the island-like Sn situation was evaluated. A case where an island is formed as a whole is indicated by ◯, a case where a part of the island is not formed is indicated by Δ, and a case where an island is not formed is indicated by ×.

(9) Uneven distribution of phosphate layer of Zr After the formation of the chemical conversion treatment, XPS analysis is performed, and the phosphate layer of Zr is unevenly distributed in the thickness portion within 40% from the surface layer with respect to the total thickness of the chemical conversion treatment film. In the case of the coating composition, it was marked as ◯, and when the same layer was not unevenly distributed, it was marked as x.

(10) Zr oxide layer uneven distribution situation After the chemical conversion treatment skin formation, XPS analysis is performed, and the Zr oxide layer is unevenly distributed in a portion of 40% to 100% from the surface layer with respect to the total thickness of the chemical conversion treatment film. ◯ when the film structure is, and × when the same layer is not unevenly distributed.

(11) Situation of uneven distribution of phenolic resin layer After XPS analysis, XPS analysis is performed, and the phenolic resin layer is unevenly distributed in the thickness portion within 10% from the surface layer with respect to the total thickness of the chemical conversion coating. If there was no ubiquitous layer, it was marked as x.

  The amount of coating was determined by quantitative analysis with X-ray fluorescence for the amounts of Zr and P, and the amount of C was determined by the total carbon content measurement method. In addition, about the amount of C adhesion, about the sample obtained by carrying out the electrolytic treatment by B2 in the said Table 2, the C amount derived from phenol resin and C derived from a tannic acid was described, and the total C amount was described. .

  The above results are shown in Table 3 below. Table 3 below also shows the amount of metallic Ni, the amount of metallic Sn, and the content of each coating in each test material of the examples and comparative examples. Moreover, the amount of metallic Ni and the amount of metallic Sn shown in Table 3 below are values obtained by a fluorescent X-ray measurement method, and the content of each film is a value obtained by quantitative analysis with fluorescent X-rays.

  As shown in Table 3 above, uneven distribution of the phosphoric acid layer, the oxide layer, and the phenol resin layer was confirmed, and Examples 1 to 29 in which the Zr content, the P content, and the C content belong to the scope of the present invention. The above evaluations (1) to (11) showed good results.

  On the other hand, as shown in Comparative Examples 1 to 11 in Table 3 above, a phosphoric acid layer, an oxide layer or a phenol resin layer in which uneven distribution was not confirmed, or a Zr content, a P content, or a C content However, the evaluation of the above (1) to (11) was inferior to those of Examples 1 to 29.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

It is explanatory drawing for demonstrating the structure of the steel plate for containers which concerns on suitable embodiment of this invention. It is explanatory drawing for demonstrating the chemical conversion treatment film layer which concerns on the same embodiment. It is a measurement result of an XPS spectrum of a chemical conversion treatment film layer concerning the embodiment. It is a measurement result of an XPS spectrum of a chemical conversion treatment film layer concerning the embodiment. It is a measurement result of an XPS spectrum of a chemical conversion treatment film layer concerning the embodiment. It is a measurement result of an XPS spectrum of a chemical conversion treatment film layer concerning the embodiment. It is a measurement result of an XPS spectrum of a chemical conversion treatment film layer concerning the embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Steel plate for containers 20 Steel plate 30 Chemical conversion coating layer 32 Oxide layer 34 Phosphoric acid layer 36 Coexistence layer 40 Undercoat layer

Claims (10)

At least one surface of the steel sheet has a chemical conversion coating layer containing a mixture of zirconium oxide, zirconium phosphate, and phenol resin,
The chemical conversion coating layer is
With respect to the total film thickness of the chemical conversion coating layer, the phenol resin present at least in a thickness portion within 10% from the surface layer;
The zirconium phosphate present at least in a thickness portion within 40% of the surface layer with respect to the total film thickness of the chemical conversion coating layer,
With respect to the total film thickness of the chemical conversion coating layer, the zirconium oxide present at least in a thickness portion of 40% to 100% from the surface layer; and
Have
In the thickness portion within 10% from the surface layer, in the spectrum chart by X-ray photoelectron spectroscopy focusing on carbon (C) or nitrogen (N), the height is twice or more the maximum noise height in the spectrum chart. Showing a peak with
In the spectrum portion in the X-ray photoelectron spectroscopic analysis focusing on oxygen (O) of phosphorus (P) or the phosphate of zirconium in the thickness portion within 40% from the surface layer, the maximum noise height in the spectrum chart Showing peaks that are more than twice as high,
In the thickness portion of 40% to 100% from the surface layer, in the spectrum chart in the X-ray photoelectron spectroscopic analysis focusing on the oxygen (O) of the zirconium oxide, it is at least twice the maximum noise height in the spectrum chart. A steel plate for containers, characterized by exhibiting a peak having a height of . The chemical conversion coating layer contains a zirconium component, a phosphoric acid component, and a phenol resin component, has a pH in the range of 3.1 to 3.7, and has a liquid temperature of 10 ° C to 40 ° C. Formed by electrolytic treatment
The steel plate for containers according to claim 1, wherein The cathodic electrolysis treatment is 0.05 A / dm ² ~ 50A / dm ² At an electrolysis current density of 0.01 sec to 5 sec.
The steel plate for containers according to claim 2, wherein The chemical conversion coating layer is characterized by containing a zirconium ^1mg / ^{m 2 ~9mg} / m 2 of metal zirconium content, container steel sheet according to any one of claims 1-3. The chemical conversion coating layer is characterized by containing the phosphoric acid 0.5mg ^{/ m 2} ~8mg ^/ m 2 in phosphorus content, container steel sheet according to any one of claims 1-4. The chemical conversion coating layer is characterized by containing a 0.1mg ^{/ m 2} ~5mg ^/ m 2 of phenol resin in the carbon content, container steel sheet according to any one of claims 1-5. The steel plate for containers according to any one of claims 1 to 6 , wherein a base plating layer containing at least nickel or tin is formed between the steel plate and the chemical conversion coating layer. The base plating layer is a nickel plating layer,
It said nickel plating layer is characterized in that it contains nickel 150mg ^{/ m 2} ~1000mg ^/ m 2 of metal nickel content, container steel sheet according to claim 7. The base plating layer is a tin plating layer,
The tin plating layer is characterized by containing tin 560mg ^{/ m 2} ~5600mg ^/ m 2 by metal tin content, container steel sheet according to claim 7. The steel plate
A nickel base or iron-nickel alloy plating base nickel layer is formed on the steel plate surface, and a part of the tin nickel layer applied to the base nickel layer and a part or all of the base nickel layer are alloyed. Is a plated steel sheet on which a tin plating layer containing island-shaped tin is formed,
The plated steel sheet, a nickel 5 to 150 mg / ^{m 2} of metal nickel content, characterized by containing a tin 300~3000mg / ^{m 2} by metal tin content, claim 1-6 The steel plate for containers as described in 4.