JP2016060925A - Steel sheet for vessel, and production therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a steel sheet for a vessel, which is excellent in corrosion resistance, and a manufacturing method therefor.SOLUTION: A steel sheet for a vessel comprises, in at least a portion of the surface of the steel sheet: a plated sheet steel having a plated layer composed of, at least one layer selected from the group composed of a Ni layer, a Sn layer, a Ni-Fe alloy layer, a Fe-Sn-Ni alloy layer and a Fe-Sn alloy layer; and a membrane arranged on the surface of said plated sheet steel on the side of said plating layer, wherein said membrane contains Ti and has a coating weight of Ti conversion of 1.0 mg/mor more and less than 60.0 mg/min the Ti conversion for one side of said plated sheet metal, and wherein said membrane contains in total at least one kind selected from the group consisting of K, Na, Mg and Ca at a mass ratio of 1.0×10to 1.0×10as a mass ratio to Ti in total.SELECTED DRAWING: None

Description

  The present invention relates to a steel plate for containers and a method for producing the same.

  As a steel plate (container steel plate) used for a container such as a can, for example, Patent Document 1 discloses that “at least one surface of a steel plate is Ni layer, Sn layer, Fe—Ni alloy layer, Fe—Sn alloy layer and Fe— It has a corrosion-resistant film composed of at least one layer selected from Ni-Sn alloy layers, contains Ti on the corrosion-resistant film, and is further selected from Co, Fe, Ni, V, Cu, Mn and Zn. A surface-treated steel sheet having an adhesive film containing 0.01 to 10 as a total mass ratio of at least one of the above-described materials is disclosed ([Claim 1]).

JP 2010-31348 A

  As a result of studying the steel plate for containers (surface-treated steel plate) described in Patent Document 1, the present inventors have found that the corrosion resistance may be inferior. Specifically, with the PET film laminated and the paint applied, the corrosion resistance of the scratches (scratches reaching the ground iron (steel plate)) when the steel plate for containers is immersed in an acidic aqueous solution (each “film”) It was found that “corrosion resistance after application” and “corrosion resistance after painting”) may be insufficient.

  This invention is made | formed in view of the above point, and it aims at providing the steel plate for containers which is excellent in corrosion resistance, and its manufacturing method.

The present inventors have found that the above object can be achieved by adopting the following configuration.
That is, the present invention provides the following (1) to (7).
(1) A plating layer including at least one layer selected from the group consisting of a Ni layer, a Sn layer, a Ni—Fe alloy layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer on at least a part of the surface of the steel plate. And a coating disposed on the surface of the plated steel sheet on the plating layer side, wherein the coating contains Ti, and Ti per side of the plated steel sheet adhesion amount conversion is less than 1.0 mg / m ² or more 60.0 mg / m ^2, the coating mass K, Na, at least one selected from the group consisting of Mg and Ca, for Ti in the total Steel plate for containers containing 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻² as a ratio.
(2) The film according to (1), further containing at least one selected from the group consisting of Ni, Co, and Mn in a total mass ratio of 0.01 to 0.10 with respect to Ti. Steel plate for containers.
(3) A method for producing a steel plate for containers according to (1) above, wherein a Ni layer, a Sn layer, a Ni—Fe alloy layer, Fe—Sn is formed on at least a part of the surface of the steel plate. A plated steel sheet having a plating layer including at least one layer selected from the group consisting of a Ni alloy layer and a Fe—Sn alloy layer is selected from the group consisting of a Ti component, a K component, a Na component, a Mg component, and a Ca component. by performing cathodic electrolysis treatment in the processing solution containing the M ¹ component is at least one, to form the coating method for producing a container for steel.
The amount (4) The content of the Ti component in the processing liquid, in the amounts terms of Ti, a 0.01~0.10mol / L, the content of the M ¹ component in the processing liquid, that is in terms of metal in a molar ratio to the content of the Ti component in (M ¹ / Ti), is from 2.0 to 30.0, a manufacturing method of a container for a steel sheet according to (3).
(5) A method for producing a container steel plate according to the above (2), wherein a Ni layer, a Sn layer, a Ni-Fe alloy layer, Fe-Sn is formed on at least a part of the surface of the steel plate. A plated steel sheet having a plating layer including at least one layer selected from the group consisting of a Ni alloy layer and a Fe—Sn alloy layer is selected from the group consisting of a Ti component, a K component, a Na component, a Mg component, and a Ca component. By performing cathodic electrolysis treatment in a treatment liquid containing at least one M ¹ component and at least one M ² component selected from the group consisting of a Ni component, a Co component, and a Mn component, The manufacturing method of the steel plate for containers which forms.
(6) The content of the Ti component in the treatment liquid is an amount in terms of Ti and is 0.01 to 0.10 mol / L, and the content of the M ¹ component in the treatment liquid is an amount in terms of metal. The molar ratio (M ¹ / Ti) to the content of the Ti component is 2.0 to 30.0, and the content of the M ² component in the treatment liquid is an amount in terms of metal, and the Ti in a molar ratio with respect to the content of the component (M ² / Ti), 0.1 to 1.0, the manufacturing method of the container for steel sheet according to (5).
(7) The method for producing a steel plate for a container according to any one of (3) to (6), wherein an electrolytic current density at the time of performing the cathodic electrolysis treatment is 20.0 A / dm ² or more.

  ADVANTAGE OF THE INVENTION According to this invention, the steel plate for containers excellent in corrosion resistance and its manufacturing method can be provided.

[Steel plate for containers]
The steel plate for containers of the present invention schematically has a plated steel plate and a specific film disposed on the surface of the plated steel plate on the plating layer side. The container steel plate of the present invention is excellent in corrosion resistance (corrosion resistance after film application and corrosion resistance after coating).
First, specific embodiments of the plated steel sheet and the coating will be described in detail below.

[Plated steel sheet]
The plated steel sheet has a plating layer that covers at least a part of the surface of the steel sheet.
As a raw steel plate, a general steel plate for cans can be used. The plating layer may be a continuous layer or a discontinuous island shape. Moreover, the plating layer should just be provided in the at least single side | surface of the steel plate, and may be provided in both surfaces. The plating layer can be formed by a known method according to the contained metal element.
Below, the suitable aspect of a steel plate and a plating layer is explained in full detail.

<steel sheet>
The kind of steel plate is not particularly limited, and a steel plate (for example, a low carbon steel plate or an extremely low carbon steel plate) that is usually used as a container material can be used. The manufacturing method and material of the steel plate are not particularly limited, and the steel plate is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, temper rolling, etc. from a normal slab manufacturing process.
If necessary, a steel sheet having a nickel (Ni) -containing layer formed on the surface thereof may be used, and a plated layer including an Sn layer described later may be formed on the Ni-containing layer. By performing Sn plating using a steel sheet having a Ni-containing layer, a plating layer containing island-shaped Sn can be formed, and weldability is improved.
The Ni-containing layer only needs to contain nickel, and examples thereof include a Ni plating layer (Ni layer) and a Ni—Fe alloy layer.
The method for applying the Ni-containing layer to the steel sheet is not particularly limited, and examples thereof include a known method such as electroplating. Moreover, when providing a Ni-Fe alloy layer as a Ni containing layer, a Ni diffused layer can be coordinated by forming Ni on a steel plate surface by electroplating etc., and annealing, thereby forming a Ni-Fe alloy layer.
The amount of Ni in the Ni-containing layer is not particularly limited, and is preferably 50 to 2000 mg / m ² as the Ni conversion amount per one side.

<Plating layer>
The plated steel sheet includes a plated layer including at least one layer selected from the group consisting of a Ni layer, a Sn layer, a Ni—Fe alloy layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer on at least a part of the surface of the steel plate. Have The plating layer only needs to be provided on at least one side of the steel plate, and may be provided on both sides. Moreover, a plating layer is a layer which covers at least one part on the steel plate surface, A continuous layer may be sufficient and a discontinuous island shape may be sufficient as it.

0.1-15.0 g / m < ² > is preferable, as for Sn adhesion amount per one side of the steel plate of a plating layer, 0.2-15.0 g / m < ² > is more preferable, and 1.0-15.0 g / m < ² > is. Further preferred.
In addition, Sn adhesion amount can be measured by surface analysis by coulometric method or fluorescent X-ray. In the case of fluorescent X-rays, a calibration curve relating to the Sn amount is specified in advance using a Sn adhesion amount sample with a known Sn amount, and the Sn amount is relatively specified using the calibration curve.

As a plating layer, in addition to a plating layer composed of an Sn layer obtained by plating Sn, the lowermost layer (Sn layer / steel plate interface) of the Sn layer obtained by heating and melting Sn by energization heating after Sn plating, etc. A plating layer in which a part of the Fe—Sn alloy layer is formed is also included.
Moreover, as a plating layer, Sn plating is performed on a steel sheet having a Ni-containing layer on the surface, and Sn is heated and melted by current heating or the like, and is formed on the lowermost layer (Sn layer / steel sheet interface) of the Sn layer. Examples thereof include a plating layer in which an Fe—Sn—Ni alloy layer, an Fe—Sn alloy layer, etc. are partially formed.
In the present invention, the aforementioned Ni-containing layer (Ni layer, Ni—Fe alloy layer) is also included in the plated layer of the plated steel sheet.

Examples of the method for producing the plating layer include a known method (for example, an electroplating method or a method of plating by immersing in molten Sn).
For example, a phenol sulfonic acid Sn plating bath, a methane sulfonic acid Sn plating bath, or a halogen-based Sn plating bath is used, and the adhesion amount per one surface is set to a predetermined amount (for example, 2.8 g / m ² ). After Sn is electroplated, it is heated and melted at a temperature equal to or higher than the melting point of Sn (231.9 ° C.), and Fe—Sn is applied to the bottom layer (Sn layer / steel plate interface) of the Sn single layer. A plating layer on which an alloy layer is formed can be manufactured. When the heat melting treatment is omitted, a Sn single plating layer (Sn layer) can be manufactured.
In addition, when the steel sheet has a Ni-containing layer on its surface, the lowermost layer (Sn layer / steel sheet interface) of the plating layer (Sn layer) of Sn alone is obtained by performing a heat melting treatment after Sn plating on the Ni-containing layer. An Fe—Sn—Ni alloy layer, an Fe—Sn alloy layer, and the like are formed.

[Coating]
Next, the film | membrane arrange | positioned on the surface by the side of the plating layer of the plated steel plate mentioned above is demonstrated. The coating generally contains Ti (titanium element) as a main component, and is further selected from the group consisting of K (potassium element), Na (sodium element), Mg (magnesium element), and Ca (calcium element). It is a film containing at least one selected from the above, and is formed using a treatment liquid described later.

The coating has a Ti equivalent adhesion amount (hereinafter also referred to as “Ti adhesion amount”) per side of a plated steel sheet of 1.0 mg / m ² or more and less than 60 mg / m ² . If the Ti adhesion amount is less than 1.0 mg / m ² or 60 mg / m ² or more, the corrosion resistance is inferior, but if it is within this range, the corrosion resistance is excellent. Ti adhesion amount, for the reason that corrosion resistance more excellent, preferably ^{3~30mg / m 2, 5~20mg / m} 2 is more preferable.

In addition, the coating is composed of at least one selected from the group consisting of K, Na, Mg, and Ca (hereinafter also referred to as “M ¹ ”) with respect to the total mass ratio of Ti (hereinafter referred to as “mass ratio (M ^1)”. / Ti) ”) is contained in the range of 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻² .
Thereby, the steel plate for containers of this invention is excellent in corrosion resistance. The reason is not clear, but is presumed as follows. That is, when the coating contains at least one of a trace amount of K, Na, Mg, and Ca, the coverage with respect to the plating layer is improved, and there is a scratch reaching the base iron (steel plate) in an acidic aqueous solution. Furthermore, it is considered that the supply of H ⁺ ions to the plating layer surface can be suppressed, and the cathodic reaction rate of corrosion can be reduced. However, this mechanism is speculation, and even if the mechanism is different, it is within the scope of the present invention.
The mass ratio (M ¹ / Ti) is preferably 3.0 × 10 ^{−4 to} 9.0 × 10 ^{−3 and} more preferably 9.0 × 10 ^{−4 to} 5.0 × 10 because the corrosion resistance is more excellent. ^-3 is more preferable.

Further, the film is made of at least one selected from the group consisting of Ni, Co, and Mn (hereinafter also referred to as “M ² ”) with respect to the total mass ratio to Ti (hereinafter referred to as “mass ratio (M ² / Ti). ) ”)), It is preferable to contain 0.01 to 0.10.
Thereby, the steel plate for containers of this invention is more excellent in corrosion resistance. The reason is not clear, but is presumed as follows. That is, it contained at least either in the coating Ni, Co and Mn are increased strength of the film itself, suppressing cohesive failure of the coating, for improving the adhesion between the coating and the plating layer, H ⁺ This is probably because the permeation of ions and the like can be suppressed, and the cathodic reaction rate of corrosion can be reduced. However, this mechanism is speculation, and even if the mechanism is different, it is within the scope of the present invention.
The mass ratio (M ² / Ti) is more preferably 0.02 to 0.09, and further preferably 0.04 to 0.08.

The amount of Ti adhesion is measured by surface analysis using fluorescent X-rays.
On the other hand, for K, Na, Mg and Ca, and Ni, Co and Mn, the amount contained in the film is extremely small. Therefore, the steel sheet on which the film is formed is 100 cm ² on one side in 100 mL of water. After immersing to an area and boiling for 30 minutes, the amount of element eluted in water is quantified using ICP mass spectrometry and ion chromatography.

  Ti, K, Na, Mg, Ca, Ni, Co, Mn, and the like in the film are included as various compounds, and the types and aspects of the compounds are not particularly limited.

[Manufacturing method of steel plate for containers]
Next, a method for producing the above-described container steel plate of the present invention (hereinafter also referred to as “the production method of the present invention”) will be described. The production method of the present invention includes at least a film forming step of forming the above-described film using a treatment liquid described later (hereinafter also referred to as “treatment liquid of the present invention”).

[Film formation process]
The film forming step is a step of forming the above-described film on the surface of the plated steel plate on the plating layer side, and is a step of subjecting the plated steel plate immersed in the treatment liquid of the present invention described later to cathodic electrolysis. In addition, you may implement the alternating electrolysis which performs a cathode electrolytic treatment and an anodic electrolytic treatment alternately.
Hereinafter, the treatment liquid of the present invention used, conditions for the cathodic electrolysis, and the like will be described in detail.

<Processing liquid>
The treatment liquid of the present invention contains a Ti component (Ti compound) for supplying Ti (titanium element) to the film.
The Ti component is not particularly limited. For example, titanium alkoxide, titanyl ammonium oxalate, potassium titanyl oxalate dihydrate, titanium sulfate, titanium lactate, titanium hydrofluoric acid (H ₂ TiF ₆ ) and / or its Salt. Specific examples of the salt of titanium hydrofluoric acid include potassium hexafluorotitanate (K ₂ TiF ₆ ), sodium hexafluorotitanate (Na ₂ TiF ₆ ), and ammonium hexafluorotitanate ((NH ₄ ) ₂ TiF ₆ ) and the like.
Of these, titanium hydrofluoric acid and / or a salt thereof is preferable from the viewpoints of stability of the treatment liquid, availability, and the like.

The content of the Ti component in the treatment liquid of the present invention is an amount in terms of Ti, preferably 0.01 to 0.10 mol / L, more preferably 0.03 to 0.07 mol / L.
In addition, as “amount converted to Ti”, for example, when using titanium hydrofluoric acid and / or a salt thereof, the amount converted to hexafluorotitanate ion (TiF ₆ ²⁻ ) corresponds, Specifically, when 1 mol / L of potassium hexafluorotitanate (K ₂ TiF ₆ ) is present, the amount in terms of Ti is 1 mol / L.

Furthermore, the treatment liquid of the present invention provides a K component (K compound), a Na component (Na compound) for supplying at least one (M ¹ ) selected from the group consisting of K, Na, Mg and Ca to the film. ), Mg component (Mg compound), and Ca component (Ca compound) at least one selected from the group consisting of Ca (Ca compound) (hereinafter also referred to as “M ¹ component”).
Examples of the M ¹ component include, but are not limited to, sulfates such as potassium sulfate, sodium sulfate, magnesium sulfate, and calcium sulfate; nitrates such as potassium nitrate, sodium nitrate, magnesium nitrate, and calcium nitrate; potassium chloride, sodium chloride, and chloride. And chlorides such as magnesium and calcium chloride.
The content of the M ¹ component in the treatment liquid of the present invention is a metal-converted amount, and the molar ratio (M ¹ / Ti) to the content of the Ti component is preferably 2.0 to 30.0, preferably 5.0 to 20.0 is more preferable.

Further, when the coating containing Ni, at least one selected from the group consisting of Co and Mn and (M ^2), the processing liquid of the present invention, further, Ni component (Ni compounds), Co component (Co compound And at least one selected from the group consisting of Mn components (Mn compounds) (hereinafter also referred to as “M ² component”).
The M ² component is not particularly limited, but for example, sulfates such as nickel sulfate, cobalt sulfate and manganese sulfate; nitrates such as nickel nitrate, cobalt nitrate and manganese nitrate; chlorides such as nickel chloride, cobalt chloride and manganese chloride And the like.
The content of the M ² component in the treatment liquid of the present invention is a metal-converted amount and is a molar ratio (M ² / Ti) to the content of the Ti component, preferably 0.1 to 1.0, 0.3 to 0.8 is more preferable.

The “amount in terms of metal” in the contents of the M ¹ component and the M ² component is an amount in which these components are converted into metals (metal ions). For example, potassium sulfate (K ₂ SO ₄ ) and magnesium sulfate ( In the case where both MgSO ₄ ) and 1 mol / L are present, the amount in terms of metal is 2 mol / L for the former and 1 mol / L for the latter.

When the Ti component is, for example, potassium hexafluorotitanate (K ₂ TiF ₆ ) or sodium hexafluorotitanate (Na ₂ TiF ₆ ), the Ti component is potassium ion (K ⁺ ) or sodium ion. Since it contains (Na ⁺ ), it also serves as the M ¹ component.
As described above, the Ti component, the M ¹ component, and the M ² component may also serve as other components, but even such a case is within the scope of the present invention.

As the solvent in the treatment liquid of the present invention, water is usually used, and an organic solvent may be used in combination.
The pH of the treatment liquid of the present invention is not particularly limited, but is preferably 2.0 to 5.0 because the treatment time can be shortened and the stability of the treatment liquid is excellent. For adjusting the pH, a known acid component (for example, phosphoric acid, sulfuric acid) or an alkali component (for example, sodium hydroxide, aqueous ammonia) can be used.
Further, the treatment liquid of the present invention may contain a surfactant such as sodium lauryl sulfate or acetylene glycol as necessary. Further, from the viewpoint of the stability of the adhesion behavior over time, the treatment liquid may contain a condensed phosphate such as pyrophosphate.
20-80 degreeC is preferable and, as for the liquid temperature of a process liquid, 40-60 degreeC is more preferable.

<Cathode electrolysis treatment>
In the film forming step, the electrolytic current density when performing the cathodic electrolysis treatment is 10 for the reason that Ti, M ¹ and M ² in the formed film are appropriate, and the corrosion resistance of the steel plate for containers of the present invention is more excellent. 0.0 A / dm ² or more is preferable, 20.0 A / dm ² or more is more preferable, and 30.0 A / dm ² or more is more preferable. In addition, although the upper limit of an electrolysis current density is not specifically limited, 120.0 A / dm < ² > or less is mentioned, and 100.0 A / dm < ² > or less is preferable.
Moreover, for the same reason, the energization time of the cathodic electrolysis treatment is preferably 0.1 to 5 seconds, and more preferably 0.3 to 2 seconds. The quantity of electricity at the time of cathodic electrolysis is the product of the current density and the energization time, and is appropriately set.

In addition, it is preferable to perform the water-washing process of the obtained steel plate after a cathodic electrolysis process from a viewpoint of removing the impurity of the membrane | film | coat surface.
The method of the water washing treatment is not particularly limited. For example, when the production is performed on a continuous line, a method of providing a water washing tank after the film treatment tank and continuously immersing in water after the film treatment is exemplified. The temperature of the water used for the water washing treatment is preferably 40 to 90 ° C.
At this time, the washing time is preferably more than 0.5 seconds, and more preferably 1.0 to 5.0 seconds, because the effect of the washing treatment is more excellent.
Further, drying may be performed instead of or after the washing process. The temperature and method during drying are not particularly limited, and for example, a normal dryer or an electric furnace drying method can be applied. The temperature during the drying treatment is preferably 100 ° C. or lower. If it is in the said range, the oxidation of a film | membrane can be suppressed and stability of a film | membrane composition is maintained. The lower limit is not particularly limited, but is usually about room temperature.

[Pretreatment process]
The manufacturing method of this invention may be equipped with the pre-processing process before the membrane | film | coat formation process mentioned above. The pretreatment step is a step of subjecting the plated steel plate to cathodic electrolysis in an alkaline aqueous solution (for example, a sodium carbonate aqueous solution).
When forming a plating layer containing an Sn layer or the like, the surface may be oxidized to form tin oxide. However, by performing cathodic electrolysis treatment, unnecessary tin oxide is removed and tin is formed. The amount of oxide can be adjusted.
Examples of the solution used for the cathodic electrolysis in the pretreatment step include an alkaline aqueous solution (for example, an aqueous sodium carbonate solution). Although content of the alkali component (for example, sodium carbonate) in alkaline aqueous solution is not specifically limited, For example, 5-15 g / L is preferable and 8-12 g / L is more preferable.
The temperature of the alkaline aqueous solution during the cathodic electrolysis is not particularly limited, but is preferably 40 to 60 ° C. The electrolysis conditions (current density, electrolysis time) of the cathodic electrolysis are appropriately adjusted. In addition, you may perform a water washing process after a cathode electrolytic process as needed.

  The steel plate for containers of the present invention obtained by the production method of the present invention is used for manufacturing various containers such as DI cans, food cans, and beverage cans.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Manufacture of plated steel sheets>
A plated steel sheet was produced by the following method.
First, a steel plate (T4 original plate) having a thickness of 0.22 mm was electrolytically degreased, and a nickel plating layer was formed on both sides with a Ni adhesion amount per one side shown in Table 3 using a Watt bath. After that, Ni—Fe alloy layer (Ni-containing layer) (the Ni adhesion amount is shown in Table 3) by annealing at 700 ° C. in an atmosphere of 10 vol.% H ₂ +90 vol.% N ₂ to diffuse and infiltrate nickel plating. ) Was formed on both sides.
Subsequently, the Sn layer was formed on both surfaces of the steel sheet having the Ni-containing layer as the surface layer, using an Sn plating bath, with the Sn adhesion amount per one side shown in Table 3. Thereafter, a heat melting treatment was performed at a melting point of Sn or higher, and plating layers were formed on both surfaces of the T4 original plate. In this way, a plating layer composed of Ni—Fe alloy layer / Fe—Sn—Ni alloy layer / Sn layer was formed in order from the lower layer side.

<Production of test materials for steel plates for containers>
The test material of the steel plate for containers was produced as follows.
<< Pretreatment process >>
The manufactured plated steel sheet was immersed in an aqueous sodium carbonate solution having a bath temperature of 50 ° C. and 10 g / L, and was subjected to cathodic electrolysis under the conditions shown in Table 2.
<< Film formation process >>
Next, the plated steel sheet that had undergone the pretreatment step was washed with water, and using the treatment liquid (solvent: water) having the composition shown in Table 1 whose pH was adjusted to 4.0, the treatment temperature and electrolysis conditions (current) shown in Table 2 were used. The cathode electrolysis treatment was performed at a density, a current-carrying time and a quantity of electricity). Then, it washed with the water washing | cleaning time shown in Table 2, and dried at room temperature using the blower, and formed the film | membrane on both surfaces. Thereby, the test material of the steel plate for containers was produced.

<Evaluation>
Then, the corrosion resistance after film sticking and the corrosion resistance after painting were evaluated by the following methods for the test materials of the produced steel plates for containers. In addition, about each component amount in a film | membrane, it measured or calculated by the method mentioned above. The results are summarized in Table 3 below.

<Corrosion resistance after film application>
A commercially available PET film (Melinex 850, manufactured by DuPont) is applied to the surface of the produced steel plate for containers under the conditions that the roll pressure is 4 kg / cm ² , the plate feed speed is 40 mpm, and the surface temperature of the plate after passing through the roll is 160 ° C. Then, heat-sealing was performed, followed by post-heating in a batch furnace (holding at a final plate temperature of 210 ° C. for 120 seconds) to produce a laminated steel plate.
Next, a cross cut having a depth reaching the ground iron (steel plate) was put on the film surface of the produced laminated steel plate (width 70 mm × length 40 mm) using a cutter. The laminated steel sheet with the cross cut was immersed in a test solution at 55 ° C. composed of a mixed aqueous solution containing 1.5 mass% citric acid and 1.5 mass% sodium chloride for 96 hours. After dipping, washing and drying, a cellophane adhesive tape was applied to the film surface, and the tape was peeled off. The film peeling width (total width on the left and right extending from the cut portion) was measured at any four locations at the center of the cross cut portion, and the average value of the four locations was determined. The average value of the film peeling width was regarded as the corrosion width and evaluated according to the following criteria. Practically, if the result is ま た は or ◯, it can be evaluated as having excellent corrosion resistance.
◎: Corrosion width less than 0.5 mm ○: Corrosion width 0.5 mm or more and less than 1.0 mm △: Corrosion width 1.0 mm or more and less than 2.0 mm ×: Corrosion width 2.0 mm or more

<Corrosion resistance after painting>
An epoxy phenol-based paint was applied to the surface of the produced steel plate for containers (width 70 mm × length 40 mm), and then baked at 210 ° C. for 10 minutes to give a coating amount of 50 mg / dm ² .
Next, a cross-cut having a depth reaching the ground iron (steel plate) was put on the coated surface of the coated steel plate (painted steel plate) using a cutter. The coated steel sheet with the cross cut was immersed in a test solution at 55 ° C. composed of a mixed aqueous solution containing 1.5% by mass citric acid and 1.5% by mass sodium chloride for 96 hours. After immersion, after washing and drying, a cellophane adhesive tape was applied to the coating film, and the tape was peeled off. The film peeling width (total width on the left and right extending from the cut portion) was measured at any four locations at the center of the cross cut portion, and the average value of the four locations was determined. The average value of the film peeling width was regarded as the corrosion width and evaluated according to the following criteria. Practically, if the result is ま た は or ◯, it can be evaluated as having excellent corrosion resistance.
◎: Corrosion width less than 0.2 mm ○: Corrosion width 0.2 mm or more and less than 0.6 mm △: Corrosion width 0.6 mm or more and less than 1.0 mm ×: Corrosion width 1.0 mm or more

As is clear from the results shown in Tables 1 to 3 above, all of the inventive examples (test materials Nos. 4 to 9 and 13 to 30) were excellent in corrosion resistance.
In addition, among the inventive examples (test materials No. 4 to 9 and 13 to 21) containing only M ¹ but not M ² in the film, the mass ratio (M ¹ / Ti) is 3.0 × 10 ^−. Invention examples (test materials No. 4 to 6 and 16 to 21) which are within the range of ^{4 to} 9.0 × 10 ⁻³ but outside the range of 9.0 × 10 ^{−4 to} 5.0 × 10 ⁻³ ) In contrast, the inventive examples (test materials No. 5, 6, 17, 18, 20, and 21) having a current density of 50.0 A / dm ² m or 100.0 A / dm ² have a current density of 10 Corrosion resistance was superior to that of the inventive examples (test materials Nos. 4, 16 and 19) of 0.0 A / dm ² .
However, among the inventive examples (test materials No. 4 to 9 and 13 to 21) containing only M ¹ without containing M ² in the film, the mass ratio (M ¹ / Ti) is 9.0 × 10 ^−. Invention examples (test materials No. 7 to 9 and 13 to 15) within the range of ^{4 to} 5.0 × 10 ⁻³ are invention examples (test material No. 7) having a current density of 10.0 A / dm ^2. And 13), the corrosion resistance is as excellent as the invention examples (test materials Nos. 8, 9, 14, and 15) having a current density of 50.0 A / dm ² m or 100.0 A / dm ^2. It was.
In the invention examples containing a combination of the M ¹ and M ² in the film (test material Nanba22～30) are invention examples current density of 10.0A / dm ² (test material No.22, 25 and 28) have excellent corrosion resistance to the same extent as the inventive examples (23, 24, 26, 27, 29 and 30) having a current density of 50.0 A / dm ² m or 100.0 A / dm ^2. It was.

In contrast, Comparative Example weight ratio (M ¹ / Ti) is less than 1.0 × 10 ^-4 (test material Nanba1～3), and the mass ratio (M ¹ / Ti) of 1.0 The comparative example (test material No. 10-12 and 31-33) larger than * 10 ^<-2 > was inferior in corrosion resistance.

Claims (7)

Plating having a plating layer including at least one layer selected from the group consisting of a Ni layer, a Sn layer, a Ni—Fe alloy layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer on at least a part of the surface of the steel plate A steel plate for containers having a steel plate and a coating disposed on the surface of the plated steel plate on the plating layer side,
The coating contains a Ti, the amount of deposition of Ti in terms of per side of the plated steel sheet is less than 1.0 mg / m ² or more 60.0 mg / m ^2,
The film contains at least one selected from the group consisting of K, Na, Mg, and Ca in a total mass ratio of 1.0 × 10 ^{−4 to} 1.0 × 10 ^{−2 with} respect to Ti. Steel plate.   The steel sheet for containers according to claim 1, wherein the coating further contains at least one selected from the group consisting of Ni, Co, and Mn in a total mass ratio of 0.01 to 0.10 with respect to Ti. . It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers according to claim 1,
Plating having a plating layer including at least one layer selected from the group consisting of a Ni layer, a Sn layer, a Ni—Fe alloy layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer on at least a part of the surface of the steel plate The coating film is obtained by subjecting the steel sheet to cathodic electrolysis in a treatment liquid containing a Ti component and at least one M ¹ component selected from the group consisting of a K component, a Na component, a Mg component, and a Ca component. The manufacturing method of the steel plate for containers which forms. The content of the Ti component in the treatment liquid is 0.01 to 0.10 mol / L in terms of Ti,
The content of the M ¹ component in the treatment liquid is a metal-converted amount and is a molar ratio (M ¹ / Ti) to the content of the Ti component, and is 2.0 to 30.0. The manufacturing method of the steel plate for containers of description. It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers according to claim 2,
Plating having a plating layer including at least one layer selected from the group consisting of a Ni layer, a Sn layer, a Ni—Fe alloy layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer on at least a part of the surface of the steel plate The steel sheet is at least one selected from the group consisting of a Ti component, a M ¹ component selected from the group consisting of a K component, a Na component, a Mg component and a Ca component, and a Ni component, a Co component and a Mn component. by performing cathodic electrolysis treatment in the processing solution containing the M ² component is a species, to form the coating method for producing a container for steel. The content of the Ti component in the treatment liquid is 0.01 to 0.10 mol / L in terms of Ti,
The content of the M ¹ component in the treatment liquid is a metal-converted amount, and a molar ratio (M ¹ / Ti) to the content of the Ti component is 2.0 to 30.0,
The content of the M ² component in the treatment liquid, in the amounts in terms of metal, the molar ratio of the content of the Ti component (M ² / Ti), 0.1 to 1.0, in claim 5 The manufacturing method of the steel plate for containers of description. The manufacturing method of the steel plate for containers of any one of Claims 3-6 whose electrolytic current density at the time of performing the said cathodic electrolysis process is 20.0 A / dm < ² > or more.