JP5214437B2 - Steel plate for containers - Google Patents

Description

The present invention relates to a steel plate for containers excellent in drawing ironing, weldability, corrosion resistance, paint adhesion, and film adhesion as a material for can manufacturing.
This application is based on Japanese Patent Application No. 2006-091353 and Japanese Patent Application No. 2007-069262 and incorporates the contents thereof.

Metal containers used for beverages and foods are roughly classified into two-piece cans and three-piece cans. In a two-piece can represented by a DI can, after squeezing and ironing, painting is performed on the inner surface of the can and painting and printing are performed on the outer surface of the can. In the three-piece can, the surface corresponding to the inner surface of the can is coated and the surface corresponding to the outer surface of the can is printed, and then the can body is welded.
In any can type, it is indispensable to perform a coating process before and after making the can. For coating, a solvent-based or water-based paint is used, and then baking is performed. In this painting process, waste (such as waste solvent) resulting from the paint is discharged as industrial waste, and exhaust gas (mainly carbon dioxide) is released to the atmosphere. In recent years, efforts have been made to reduce these industrial waste and exhaust gas for the purpose of protecting the global environment. Among these, as an alternative to painting, the technology of laminating films has attracted attention and has spread rapidly.

So far, in a two-piece can, many methods for manufacturing a can in which a film is laminated to make a can and related inventions have been provided. For example, Patent Document 1 discloses a method for manufacturing a squeezed iron cake. Further, for example, Patent Document 2 discloses a squeezing iron. Further, for example, Patent Document 3 discloses a manufacturing method of a thinned deep-drawn can. Moreover, it is disclosed by patent document 4 about the coated steel plate for drawn ironing irons.
In a three-piece can, a film laminated steel strip for a three-piece can and a manufacturing method thereof are disclosed in, for example, Patent Document 5. Further, for example, Patent Document 6 discloses a three-piece can steel plate having a multilayer organic film on the outer surface of the can. Further, a steel plate for a three-piece can having a striped multilayer organic film is disclosed in, for example, Patent Document 7. Further, for example, Patent Document 8 discloses a method for producing a three-piece can-stripe laminated steel sheet.

  On the other hand, in many cases, a chromate film subjected to an electrolytic chromate treatment is used for a steel sheet used as a base of a laminate film. The chromate film has a two-layer structure, and a hydrated Cr oxide layer is present on the metal Cr layer. Therefore, the laminate film (adhesive layer in the case of a film with an adhesive) ensures adhesion to the steel sheet through the hydrated Cr oxide layer of the chromate film. Although details about the mechanism of the adhesion development have not been clarified, it is said to be a hydrogen bond between a hydroxyl group of hydrated Cr oxide and a functional group such as a carbonyl group or an ester group of a laminate film.

The above-mentioned invention certainly has the effect of greatly advancing the conservation of the global environment. On the other hand, in recent years, in the beverage container market, the cost and quality between materials such as PET bottles, bottles, paper, etc. The competition for steel sheets for laminated containers has been intensifying, and with respect to coating applications, which are conventional techniques, with excellent adhesion and corrosion resistance, more excellent can-making processability, especially , Film adhesion, processed film adhesion, corrosion resistance, and the like have come to be required.
Japanese Patent No. 1571783 Japanese Patent No. 1670957 JP-A-2-263523 Japanese Patent No. 1601937 Japanese Patent Laid-Open No. 3-236554 JP-A-3-113494 JP-A-5-111979 JP-A-5-147181

  The present invention has been devised in view of the above-mentioned problems, and its object is to provide excellent can-making processability while ensuring excellent adhesion, corrosion resistance, and weldability. Another object of the present invention is to provide a steel plate for containers excellent in weldability, can manufacturing processability and appearance.

  As a result of intensive studies on the use of the Zr film as a new film that replaces the chromate film, the present inventors have found that a Zr film or a Zr film obtained by combining a Zr film with a phosphoric acid film or a phenolic resin film is very different from a painted or laminated film. It was found that a strong covalent bond was formed, and excellent can-making processability higher than that of the conventional chromate film was obtained, and the present invention shown below was reached.

(1) on the surface of the steel sheet, Ni-plated layer containing 5mg / m ² ~150mg / m ² of Ni, or Ni Fe-Ni alloy plating layer containing 5mg / m ² ~150mg / m ² is formed; the Ni plating layer , or Sn plating of 300mg / m ² ~3000mg / m ² over the Fe-Ni alloy plating layer is applied; melted by溶錫process, the Ni plating layer or a portion or all of the Fe-Ni alloy plating layer, immersing the phosphate ions, the acidic solution obtained by dissolving the one or more of Zr ions and phenol resins; part of the Sn plating is alloyed metal Sn plating layer remains partially with by or an electrolytic treatment with the acidic solution, it, the composite film on an upper layer of the alloy Sn plating and residual metal Sn plating layer is formed, the composite coating is, 0.1 mg / m ² ~ a P amount A phosphoric acid compound of 200 mg / m ^2, and a metallic Zr amount 1 mg / m ² to 500 mg / in Zr and C of ^{m 2 0.1mg / m 2 ~100mg /} m 1 or more of ² phenolic resin A steel plate for containers, characterized by comprising:

(2) the surface of the steel sheet, Ni-plated layer containing 5mg / m ² ~150mg / m ² of Ni, or Ni Fe-Ni alloy plating layer containing 5mg / m ² ~150mg / m ² is formed; the Ni plating layer , or Sn plating of 300mg / m ² ~3000mg / m ² over the Fe-Ni alloy plating layer is applied; melted by溶錫process, the Ni plating layer or a portion or all of the Fe-Ni alloy plating layer, immersing the phosphate ions, the acidic solution obtained by dissolving the one or more of Zr ions and phenol resins; part of the Sn plating is alloyed metal Sn plating layer remains partially with by or an electrolytic treatment with the acidic solution, it, the composite film on an upper layer of the alloy Sn plating and residual metal Sn plating layer is formed, the composite coating is, 0.1 mg / m ² ~ a P amount A phosphoric acid compound of 5 mg / m ^2, and a metallic Zr amount 1 mg / m ² to 15 mg / in Zr and C of ^{m 2 0.1mg / m 2 ~15mg /} m 1 or more of ² phenolic resin A steel plate for containers, characterized by comprising:

(3) on the surface of the steel sheet, Ni-plated layer containing 5mg / m ² ~150mg / m ² of Ni, or Ni Fe-Ni alloy plating layer containing 5mg / m ² ~150mg / m ² is formed; the Ni plating layer , or Sn plating of 300mg / m ² ~3000mg / m ² over the Fe-Ni alloy plating layer is applied; melted by溶錫process, the Ni plating layer or a portion or all of the Fe-Ni alloy plating layer, immersing the phosphate ions, the acidic solution obtained by dissolving the one or more of Zr ions and phenol resins; part of the Sn plating is alloyed metal Sn plating layer remains partially with by or an electrolytic treatment with the acidic solution, it, the composite film on an upper layer of the alloy Sn plating and residual metal Sn plating layer is formed, the composite coating is, 0.1 mg / m ² ~ a P amount a phosphoric acid compound of mg / m ^2, and a metallic Zr amount 1mg / m ² ~9mg / in Zr and C of ^{m 2 0.1mg / m 2 ~8mg /} m 1 or more of ² phenolic resin A steel plate for containers, characterized by comprising:

(4) An Sn plating layer of 560 mg / m ^{2 to} 5600 mg / m ² is applied to the surface of the steel sheet; a part of the Sn plating layer is alloyed by molten tin treatment; phosphate ions, Zr ions immersed in an acidic solution prepared by dissolving the one or more of the emissions and phenol resin, or an electrolytic treatment with the acidic solution, by the composite film on an upper layer of the alloy Sn plating and residual metal Sn plating layer There is formed, the composite film is 0 with phosphoric acid compound and, Zr and C content of 1mg / m ² ~500mg / m ² of metal Zr content of 0.1mg / m ² ~100mg / m ² in the P content. container steel sheet, characterized in that; and a least one of 1mg / m ² ~100mg / m ² of phenol resin.

(5) A Sn plating layer of 560 mg / m ^{2 to} 5600 mg / m ² is applied to the surface of the steel sheet; a part of the Sn plating layer is alloyed by the molten tin treatment; phosphate ions, Zr ions immersed in an acidic solution prepared by dissolving the one or more of the emissions and phenol resin, or an electrolytic treatment with the acidic solution, by the composite film on an upper layer of the alloy Sn plating and residual metal Sn plating layer There is formed, the composite film is 0 with phosphoric acid compound and, Zr and C content of 1mg / m ² ~15mg / m ² of metal Zr content of 0.1mg / m ² ~15mg / m ² in the P content. container steel sheet, characterized in that; and a least one of 1mg / m ² ~15mg / m ² of phenol resin.

(6) An Sn plating layer of 560 mg / m ^{2 to} 5600 mg / m ² is applied to the surface of the steel sheet; a part of the Sn plating layer is alloyed by molten tin treatment; phosphate ions, Zr ions immersed in an acidic solution prepared by dissolving the one or more of the emissions and phenol resin, or an electrolytic treatment with the acidic solution, by the composite film on an upper layer of the alloy Sn plating and residual metal Sn plating layer There is formed, the composite film is 0 with phosphoric acid compound and, Zr and C content of 1mg / m ² ~9mg / m ² of metal Zr content of 0.1mg / m ² ~8mg / m ² in the P content. container steel sheet, characterized in that; and a least one of 1mg / m ² ~8mg / m ² of phenol resin.

(7) A container for steel sheet according to any one of the above (1) to (6), wherein the electrolytic treatment may be met cathode electrolytic treatment.

(8) A container for steel sheet according to any one of the above (1) to (6), wherein the electrolytic treatment is a cathodic electrolysis treatment, Zr ion, phosphate ion, the及Beauty phenol resin 3 The composite film may be formed by electrolytic treatment in the acidic solution in which seeds are dissolved.

(9) A container for steel sheet according to the above (7) or (8), wherein the cathodic electrolysis treatment may be performed by including the acidic solution or tannic acid the acidic solution.

  The steel plate for containers of the present invention has excellent drawing ironing, weldability, corrosion resistance, paint adhesion, film adhesion, and appearance.

Embodiments of the steel plate for containers according to the present invention excellent in weldability, can manufacturing process and appearance will be described in detail below.
The original plate used in the present invention is not particularly limited, and a steel plate usually used as a container material is used. The production method and material of the original plate are not particularly limited, and the original plate is produced through a normal slab production process through processes such as hot rolling, acid tip, cold rolling, annealing, and temper rolling. The surface of the steel sheet is provided with a metal surface treatment layer, but the application method is not particularly limited, and for example, a known technique such as electroplating, vacuum deposition, or sputtering may be used. Furthermore, you may combine with the heat processing for providing a diffused layer.

In the present embodiment, as a form of metal surface treatment layer, Ni plating layer containing 5mg / m ² ~150mg / m ² of Ni on the surface of the steel sheet, or Fe-Ni alloy plating layer containing 5 mg / m ² to 150 mg Ni are is formed, further Sn plating 300mg / m ² ~3000mg / m ² is applied thereon, by melt溶錫process, a portion of some or all of the underlying Ni layer and the Sn plating layer is made to alloying A part of the metal Sn plating layer remains.
The purpose of performing Ni-based plating of Ni or Fe—Ni alloy plating on the steel sheet and providing the Ni-based plating layer is to ensure corrosion resistance. Since Ni is a highly corrosion-resistant metal, the corrosion resistance of the alloy layer formed during the molten tin treatment can be improved by plating Ni on the surface of the steel sheet. The effect of improving the corrosion resistance of the alloy layer by Ni starts to appear when the amount of Ni to be plated starts from 5 mg / m ² or more, so the Ni amount needs to be 5 mg / m ² or more. As the amount of Ni increases, the effect of improving the corrosion resistance of the alloy layer increases. However, when the amount of Ni exceeds 150 mg / m ² , the improvement effect is saturated. Further, since Ni is an expensive metal, it is economically disadvantageous to plate 150 mg / m ² or more of Ni. Therefore, Ni amount is required to ^{5mg / m 2 ~150mg / m 2} .

  In the case of forming the Ni diffusion layer, after Ni plating, the diffusion treatment is performed in an annealing furnace to form the Ni diffusion layer. In the invention, the effect of Ni as the Ni-based plating layer and the effect of the nitriding layer can be achieved. About the method of Ni plating and Fe-Ni alloy plating, you may make it use the well-known method generally performed by the electroplating method.

After the Ni-based plating, Sn plating is performed. Sn plating here is plating using metal Sn, but inevitable impurities may be mixed, and trace elements may be added. The Sn plating method is not particularly limited, and a known electroplating method, a method of plating by immersing in molten Sn, or the like may be used. The purpose of Sn plating is to ensure corrosion resistance and weldability. Since Sn itself has high corrosion resistance, it exhibits excellent corrosion resistance both as metal Sn and as an alloy Sn formed by the molten tin treatment described below. The excellent corrosion resistance of Sn is remarkably improved from 300 mg / m ² or more, and the corrosion resistance is improved as the Sn plating amount is increased, but the effect is saturated at 3000 mg / m ² or more. Therefore, the Sn plating amount is desirably 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 if the amount of metal Sn is 100 mg / m ² or more. Moreover, if it is the range of Sn plating amount of this invention, it is not necessary to prescribe | regulate the upper limit of metal Sn amount. Therefore, considering the two points described above, with limited Sn coating weight in the range of ^{300mg / m 2 ~3000mg / m 2} .

After Sn plating, molten tin treatment is performed. The purpose of the molten tin treatment is to melt Sn and alloy it with a base steel plate or a base metal to form a Sn—Fe or Sn—Fe—Ni alloy layer to improve the corrosion resistance of the alloy layer, and to add metal Sn Is to leave a part of it. As the remaining form of metal tin, there are various forms such as an island shape, a pool shape, and a stripe shape. By controlling this molten tin treatment, a part of the metal Sn is left, and a steel sheet having a plating structure in which the Sn—Ni or Fe—Ni—Sn alloy plating layer having excellent paint and film adhesion is partially exposed is obtained. be able to.
Further, as another form in the metal surface treatment layer of the present invention, plated with Sn in 560mg / m ² ~5600mg / m ² on the surface of the steel sheet, by a melt溶錫treatment to alloy a part of the Sn plating layer There is something. Sn has excellent workability, excellent weldability, and corrosion resistance, but Sn plating alone requires 560 mg / m ² or more from the viewpoint of corrosion resistance. The corrosion resistance improves as the Sn plating amount increases, but the effect is saturated when the Sn plating amount is 5600 mg / m ² or more. Therefore, the Sn plating amount is desirably 5600 mg / m ² or less from an economical viewpoint. Moreover, by performing the molten tin treatment after Sn plating, a Sn alloy layer is formed and the corrosion resistance is further improved.

Two or more kinds of Zr film, phosphoric acid film, and phenol resin film are applied to the upper layer of these metal surface treatment layers.
A Zr film, a phosphoric acid film, and a phenol resin film, although having some effects even when used alone, do not have sufficient practical performance. However, a film in which two or more of Zr film, phosphoric acid film, and phenol resin film are combined exhibits excellent practical performance. In addition, when the Zr film is combined with one or more of a phosphoric acid film or a phenol film, even more practical performance is exhibited. Furthermore, in a range where the amount of the film is small, in order to complement each characteristic, a film composed of three kinds of Zr film, phosphoric acid film, and phenol resin film has more stable practical performance. In addition, the film in which two or more of Zr, phosphoric acid compound, phenol, etc. are mixed in the same film, compared to the case where two or more of Zr film, phosphoric acid film and phenol resin film are separately formed, Inferior to practical performance such as corrosion resistance and adhesion. The reason for this is not clear, but it is thought that the performance of individual components is inhibited by mixing Zr, phosphoric acid, and phenol in the same film.

The role of the Zr film is to ensure corrosion resistance and adhesion. The Zr film is composed of a Zr compound such as Zr oxide, hydroxide Zr, Zr fluoride, Zr phosphate, or a composite film thereof. These Zr compounds have excellent corrosion resistance and adhesion. Therefore, when the Zr film increases, the corrosion resistance and adhesion begin to improve, and when the amount of metal Zr is 1 mg / m ² or more, practically satisfactory levels of corrosion resistance and adhesion are secured. As the amount of Zr film further increases, the effect of improving corrosion resistance and adhesion also increases. However, when the amount of Zr film exceeds 500 mg / m ^{2 in} terms of metal Zr, the Zr film becomes too thick and the adhesion of the Zr film itself is reduced. In addition to deterioration, the electrical resistance increases and the weldability deteriorates. Accordingly, Zr coating weight, it is necessary to 1mg / m ² ~500mg / m ² of metal Zr content.

Further, if the amount of Zr film exceeds 15 mg / m ² in terms of metal Zr, uneven adhesion of the film may appear as appearance unevenness, and therefore, the amount of Zr film is more preferably 1 mg / m ^{2 in} terms of metal Zr. it is a ~15mg / m ^2. Furthermore, in order to better stabilize the more uneven appearance is preferably 0.1mg / m ² ~9mg / m ² weight Zr coating in amounts metallic Zr.

The role of the phosphate film is to ensure corrosion resistance and adhesion. The phosphoric acid film is formed of a film such as phosphoric acid Fe, phosphoric acid Sn, phosphoric acid Ni, phosphoric acid Zr, phosphoric acid-phenolic resin film, or a composite film thereof formed by reacting with the base. These phosphoric acid films have excellent corrosion resistance and adhesion. Therefore, when the phosphoric acid film increases, the corrosion resistance and adhesion begin to improve, and when the P amount is 0.1 mg / m ² or more, a practically satisfactory level of corrosion resistance and adhesion are secured. Furthermore, when the amount of phosphoric acid film increases, the effect of improving corrosion resistance and adhesion also increases. However, when the amount of phosphoric acid film exceeds 100 mg / m ² in terms of P amount, the phosphoric acid film becomes too thick and adhesion of the phosphoric acid film itself is increased. As a result, the electrical resistance increases and the weldability deteriorates. Therefore, phosphoric acid coating amount is required to 0.1mg / m ² ~100mg / m ² in the P content.

Further, when the amount of the phosphoric acid film exceeds 15 mg / m ^{2 in} terms of the amount of P, uneven adhesion of the film may appear as appearance unevenness, and therefore the amount of phosphoric acid film is more preferably 0.1 mg / m in terms of the amount of P. ^{2 to} 15 mg / m ² . Furthermore, in order to better stabilize the more uneven appearance is preferably 0.1mg / m ² ~8mg / m ² weight phosphate film is in P content.

The role of the phenolic resin film is to ensure adhesion. Since the phenol resin itself is an organic substance, it has excellent adhesion to paints and laminate films. Therefore, when the phenol resin film increases, the adhesiveness starts to improve, and when the C amount is 0.1 mg / m ² or more, a practically satisfactory level of adhesiveness is secured. Furthermore, when the amount of the phenol resin film increases, the effect of improving the adhesion also increases. However, when the amount of the phenol resin film exceeds 100 mg / m ² in terms of C amount, the electrical resistance increases and the weldability deteriorates. Therefore, phenolic resin coating amount, it is necessary to 0.1mg / m ² ~100mg / m ² in C content.

Further, when the amount of phenol resin film exceeds 15 mg / m ² in terms of C amount, uneven adhesion of the film may appear as appearance unevenness. Therefore, the amount of phenol resin film is more preferably 0.1 mg / m in terms of C amount. preferably set to ^{2 ~15mg} / m ^2. Furthermore, in order to better stabilize reduced more appearance unevenness, and it is preferably a 0.1mg / m ² ~8mg / m ² phenolic resin film amount C content.

Methods for applying these films include a method of immersing a steel sheet in an acidic solution in which Zr ions, phosphate ions and low molecular weight phenol resins are dissolved, and a method of performing cathodic electrolysis. In the immersion treatment, various films are formed by etching the base, so that the adhesion becomes uneven and the treatment time becomes long, which is disadvantageous for industrial production. On the other hand, in the cathodic electrolysis treatment, a uniform film can be formed in a few seconds to several tens of seconds in combination with forced charge transfer, surface cleaning by hydrogen generation at the steel plate interface, and adhesion promotion effect by pH increase. Since it can be processed, it is extremely advantageous industrially. Therefore, cathodic electrolysis is desirable for the application of the Zr film, phosphoric acid film, and phenol resin film of the present invention.
In addition, when tannic acid is added to an acidic solution used for immersion treatment or cathodic electrolysis treatment, tannic acid binds to Fe and forms a film of tannic acid Fe on the surface, thereby improving rust resistance and adhesion. Since it is effective, it may be processed in a solution to which tannic acid is added depending on the application.

  Below, the Example and comparative example of this invention are described, and the result is shown in Tables 1-3. First, a surface treatment layer was formed on a steel sheet having a thickness of 0.17 mm to 0.23 mm using the following methods (1) to (3).

  (1) After cold rolling, the annealed and pressure-controlled original sheet is degreased and pickled, and then Sn is plated using a ferrostan bath. Then, the molten tin process was performed and the Sn plating steel plate which has a Sn alloy layer was produced.

  (2) After cold rolling, the annealed and pressure-adjusted original plate was degreased and pickled, and then Fe-Ni alloy plating was performed using a sulfuric acid-hydrochloric acid bath, followed by Sn plating using a ferrostan bath. Then, the molten tin process was performed and the Ni and Sn plating steel plate which has a Sn alloy layer was produced.

  (3) After cold rolling, Ni plating is performed using a watt bath, a Ni diffusion layer is formed during annealing, degreasing, pickling, Sn plating using a ferrostan bath, and then molten tin treatment. A Ni, Sn plated steel sheet having a Sn alloy layer was prepared.

  After the surface treatment layer was formed by the above treatment, a Zr film, a phosphoric acid film, and a phenol resin film were formed by the following treatments (4) to (11).

  (4) The steel sheet was immersed in a treatment solution in which fluorinated Zr, phosphoric acid and phenol resin were dissolved, and after cathodic electrolysis, dried to form a Zr film, a phosphoric acid film and a phenol resin film.

  (5) The steel sheet was immersed in a treatment solution in which phosphoric acid and a phenol resin were dissolved, and after cathodic electrolysis, it was dried to form a phosphoric acid film and a phenol resin film.

  (6) The steel sheet was immersed in a treatment solution in which Zr fluoride and phosphoric acid were dissolved, and after cathodic electrolysis, it was dried to form a Zr film and a phosphoric acid film.

  (7) The steel sheet was immersed in a treatment solution in which Zr fluoride and a phenol resin were dissolved, and after cathodic electrolysis, dried to form a Zr film and a phenol resin film.

  (8) The steel sheet was immersed in a treatment solution in which fluorinated Zr, phosphoric acid, and tannic acid were dissolved, and after cathodic electrolysis, dried to form a Zr film and a phosphoric acid film.

  (9) The steel sheet was immersed in a treatment solution in which fluorinated Zr, phosphoric acid, and phenol resin were dissolved, and dried to form a Zr film, a phosphoric acid film, and a phenol resin film.

  (10) The steel sheet was immersed in a treatment solution in which phosphoric acid and a phenol resin were dissolved, and dried to form a phosphoric acid film and a phenol resin film.

  (11) The steel sheet was immersed in a treatment solution in which Zr fluoride and phosphoric acid were dissolved and dried to form a Zr film and a phosphoric acid film.

  About the test material which performed said process, performance evaluation was performed about each evaluation item of (A)-(H) shown below. A PET film having a thickness of 20 μm was laminated at 200 ° C. to prepare a test material, and performance evaluation was performed for each item (A) to (D) shown below.

(A) Workability A PET film having a thickness of 20 μm is laminated on both surfaces of the test material at 200 ° C., and canning is performed in stages by drawing and ironing, and molding is performed in four stages (◎: very good, ○ : Good, Δ: wrinkles were observed, x: fractured and unworkable).
(B) Weldability Using a wire seam welder, the current is changed under the conditions of a welding wire speed of 80 m / min, and the test material is welded. Judging comprehensively from the range of the appropriate current range consisting of the maximum current value at which welding defects begin to become conspicuous, weldability is improved in four stages (◎: very good, ○: good, △: inferior, ×: unweldable) evaluated.

(C) Film adhesion A 20 μm thick PET film is laminated on both sides of the test material at 200 ° C., drawn and ironed to produce a can, and subjected to a retort treatment at 125 ° C. for 30 min. Was evaluated in four stages (◎: no peeling at all, ○: very slight peeling with no practical problem, Δ: slight peeling, x: peeling at most).
(D) Paint adhesion After applying epoxy-phenolic resin to the test material and baking it at 200 ° C for 30 minutes, put a goblet with a depth reaching the iron core at intervals of 1 mm, peel it off with tape, Evaluation was made at the stage (（: no peeling at all, ○: slight peeling at a practical level, Δ: slight peeling, ×: peeling at most).
(E) Corrosion resistance After applying an epoxy-phenol resin to the test material and baking it at 200 ° C. for 30 minutes, a cross cut with a depth reaching the base iron is added, and a 1.5% citric acid-1.5% salt mixed solution In a test solution consisting of: 45 ° C for 72 hours, washed, dried, and then peeled off from the tape. There are 4 levels of cross-cut corrosion under the coating and flat corrosion (◎: under-corrosion corrosion) Not recognized, ○: Slight under-coating corrosion to the extent that there is no practical problem is observed, Δ: Slight under-coating corrosion and slight corrosion is observed in the flat plate part, ×: Severe under-coating corrosion and flat plate The corrosion was recognized in the part) and evaluated.

(F) Rust resistance The test material is left in an atmosphere of repeated drying and wetting (humidity 90%, 2hr <=> humidity 40%, 2hr) for 2 months, and the rust generation status is 4 levels (◎: no rusting) , ○: Slight rusting to the extent that there is no practical problem, △: Slight rusting, ×: Mostly rusting).
(G) Appearance Visual observation of test material, Zr film, phosphoric acid film, phenol resin film unevenness occurrence in 5 stages (◎: No unevenness, ◎: Very slight unevenness to the extent that there is no practical problem , ○: slight unevenness, Δ: unevenness, x: significant unevenness).
(H) Metal Sn situation When Sn plating is performed after Ni-based plating and the molten tin treatment is controlled, the remaining state of metal Sn is observed with an optical microscope, and the metal Sn situation is classified into three stages (○: surface) It was evaluated as follows: △: there is a portion that does not remain, ×: there is no portion remaining).
The amount of coating was determined by quantitative analysis with X-ray fluorescence for the amount of Zr and P, and the amount of C was determined by the total carbon measurement method.

In Tables 1 to 3, Examples 1 to 42 satisfy the conditions defined in the present invention. On the other hand, Comparative Examples 1-5 all deviate from the conditions defined in the present invention. In Examples 1-42, good evaluation results were obtained for all the evaluation items (A) to (H). In particular, Example No. 31-No. 42, the Zr film adhesion amount is 0.1 to 9 mg / m ² in terms of Zr amount, the phosphoric acid film adhesion amount is 0.1 to 8 mg / m ² in terms of P amount, Two or more kinds of phenol resin films having an adhesion amount of 0.1 to 8 mg / m ² in terms of C amount are applied. For this reason, the characteristic outstanding in the external appearance was acquired. On the other hand, Comparative Examples 1 to 5 could not obtain good evaluation results for all the evaluation items (A) to (H).

  According to the present invention, a steel plate for containers having excellent drawing ironing, weldability, corrosion resistance, paint adhesion, film adhesion, and appearance can be obtained.

Claims (9)

The surface of the steel sheet, Ni-plated layer containing 5mg / m ² ~150mg / m ² of Ni, or Ni Fe-Ni alloy plating layer containing 5mg / m ² ~150mg / m ² is formed;
300 mg / m ^{2 to} 3000 mg / m ² of Sn plating is applied on the Ni plating layer or the Fe—Ni alloy plating layer;
By molten tin treatment, a part or all of the Ni plating layer or Fe—Ni alloy plating layer and a part of the Sn plating are alloyed, and a part of the metal Sn plating layer remains;
And phosphate ions, immersed in an acidic solution prepared by dissolving and one or more of Zr ions and phenol resin, or an electrolytic treatment with the acidic solution, by the alloy Sn plating and residual metal Sn A composite film is formed on the plating layer,
The composite film is
A phosphoric acid compound of 0.1mg / m ² ~100mg / m ² in the amount of P,
In Zr and C content of 1mg / m ² ~500mg / m ² of metal Zr content and a least one of 0.1mg / m ² ~100mg / m ² of phenol resin;
A steel plate for containers characterized by that. The surface of the steel sheet, Ni a 5mg / m ² ~150mg / m ² containing Ni plating layer, or Ni and the Fe-Ni alloy plating layer formed comprises ^{5mg / m 2 ~150mg / m 2} ;
300 mg / m ^{2 to} 3000 mg / m ² of Sn plating is applied on the Ni plating layer or the Fe—Ni alloy plating layer;
By molten tin treatment, a part or all of the Ni plating layer or Fe—Ni alloy plating layer and a part of the Sn plating are alloyed, and a part of the metal Sn plating layer remains;
And phosphate ions, immersed in an acidic solution prepared by dissolving and one or more of Zr ions and phenol resin, or an electrolytic treatment with the acidic solution, by the alloy Sn plating and residual metal Sn A composite film is formed on the plating layer,
The composite film is
A phosphoric acid compound of 0.1mg / m ² ~15mg / m ² in the amount of P,
In Zr and C content of 1mg / m ² ~15mg / m ² of metal Zr content and a least one of 0.1mg / m ² ~15mg / m ² of phenol resin;
A steel plate for containers characterized by that. The surface of the steel sheet, Ni-plated layer containing 5mg / m ² ~150mg / m ² of Ni, or Ni Fe-Ni alloy plating layer containing 5mg / m ² ~150mg / m ² is formed;
300 mg / m ^{2 to} 3000 mg / m ² of Sn plating is applied on the Ni plating layer or the Fe—Ni alloy plating layer;
By molten tin treatment, a part or all of the Ni plating layer or Fe—Ni alloy plating layer and a part of the Sn plating are alloyed, and a part of the metal Sn plating layer remains;
And phosphate ions, immersed in an acidic solution prepared by dissolving and one or more of Zr ions and phenol resin, or an electrolytic treatment with the acidic solution, by the alloy Sn plating and residual metal Sn A composite film is formed on the plating layer,
The composite film is
A phosphoric acid compound of 0.1mg / m ² ~8mg / m ² in the amount of P,
In Zr and C content of 1mg / m ² ~9mg / m ² of metal Zr content and a least one of 0.1mg / m ² ~8mg / m ² of phenol resin;
A steel plate for containers characterized by that. An Sn plating layer of 560 mg / m ^{2 to} 5600 mg / m ² is applied to the steel sheet surface;
A part of the Sn plating layer is alloyed by molten tin treatment;
And phosphate ions, immersed in an acidic solution prepared by dissolving and one or more of Zr ions and phenol resin, or an electrolytic treatment with the acidic solution, by the alloy Sn plating and residual metal Sn A composite film is formed on the plating layer,
The composite film is
A phosphoric acid compound of 0.1mg / m ² ~100mg / m ² in the amount of P,
In Zr and C content of 1mg / m ² ~500mg / m ² of metal Zr content and a least one of 0.1mg / m ² ~100mg / m ² of phenol resin;
A steel plate for containers characterized by that. An Sn plating layer of 560 mg / m ^{2 to} 5600 mg / m ² is applied to the steel sheet surface;
A part of the Sn plating layer is alloyed by molten tin treatment;
And phosphate ions, immersed in an acidic solution prepared by dissolving and one or more of Zr ions and phenol resin, or an electrolytic treatment with the acidic solution, by the alloy Sn plating and residual metal Sn A composite film is formed on the plating layer,
The composite film is
A phosphoric acid compound of 0.1mg / m ² ~15mg / m ² in the amount of P,
In Zr and C content of 1mg / m ² ~15mg / m ² of metal Zr content and a least one of 0.1mg / m ² ~15mg / m ² of phenol resin;
A steel plate for containers characterized by that. An Sn plating layer of 560 mg / m ^{2 to} 5600 mg / m ² is applied to the steel sheet surface;
A part of the Sn plating layer is alloyed by molten tin treatment;
And phosphate ions, immersed in an acidic solution prepared by dissolving and one or more of Zr ions and phenol resin, or an electrolytic treatment with the acidic solution, by the alloy Sn plating and residual metal Sn A composite film is formed on the plating layer,
The composite film is
A phosphoric acid compound of 0.1mg / m ² ~8mg / m ² in the amount of P,
In Zr and C content of 1mg / m ² ~9mg / m ² of metal Zr content and a least one of 0.1mg / m ² ~8mg / m ² of phenol resin;
A steel plate for containers characterized by that. It is a steel plate for containers given in any 1 paragraph of Claims 1-6,
The electrolytic treatment is cathodic electrolytic treatment. It is a steel plate for containers given in any 1 paragraph of Claims 1-6,
The electrolytic treatment is a cathodic electrolysis treatment, Zr ion, phosphate ion, by being electrolytically treated three in the acid solution obtained by dissolving the及beauty phenol resin, wherein the composite film is formed . The steel plate for containers according to claim 7 or 8,
The cathodic electrolysis is performed in an acidic solution or the acidic solution containing tannic acid.