KR100993431B1 - Steel sheet for containers - Google Patents

Abstract

The container steel sheet is formed with a Ni plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni or a Fe—Ni alloy plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni on the surface of the steel sheet. Sn plating of 300 mg / m 2 to 3000 mg / m 2 is performed on the plating layer or the Fe—Ni alloy plating layer, and a part or all of the Ni plating layer or the Fe—Ni alloy plating layer and the Sn plating are formed by molten tin treatment. A part is alloyed, and a part of metal Sn plating layer remains, and the upper part of the alloy Sn plating and the remaining metal Sn plating layer has a Zr film of 1 mg / m 2 to 500 mg / m 2 in the amount of metal Zr, and 0.1 mg / m 2 to 100 in the amount of P. Two or more types are provided in the phenol resin film of 0.1 mg / m <2>-100 mg / m <2> in the phosphate film of mg / m <2> and C amount.

Steel plate for container, Molten tin treatment, Phosphate film, Phenolic resin film, Laminate film

Description

Steel Sheet for Containers {STEEL SHEET FOR CONTAINERS}

BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates to a steel sheet for containers which is excellent in drawing and ironing processing, weldability, corrosion resistance, paint adhesion, and film adhesion, as a raw material for can manufacturing.

This application introduces the content based on Japanese Patent Application No. 2006-091353 and Japanese Patent Application No. 2007-069262 as a basic application.

Metal containers used for beverages or foods are largely divided into two-piece cans and three-piece cans. In a two-piece can represented by a DI can, after drawing and ironing processing is performed, painting is performed on the inner surface of the can, and painting and printing are performed on the outer surface of the can. In addition, in the three-piece can, painting is performed on the surface corresponding to the inner surface of the can, and printing is performed on the surface corresponding to the outer surface of the can, followed by welding of the trunk portion of the can.

Regardless of the type of can, it is essential to perform a coating step before and after can production. A solvent type or water-based paint is used for painting, and baking is performed after that. In this coating process, waste (waste solvent, etc.) resulting from paint is discharged as industrial waste, and exhaust gas (mainly carbon dioxide) is discharged to the atmosphere. In recent years, for the purpose of global environmental conservation, there has been a campaign to reduce these industrial wastes and exhaust gases. Among these, the technique of laminating a film attracts attention as a substitute for painting, and has rapidly spread widely.

Until now, in a two-piece can, the manufacturing method of the can which laminates a film and manufactures, and the invention which concerns on this are provided. For example, Patent Document 1 discloses a method for producing a drawing and ironing can. Moreover, about the drawing and ironing can, it is disclosed by patent document 2, for example. Moreover, about the manufacturing method of a thinned deep drawing can, it is disclosed by patent document 3, for example. In addition, Patent Document 4 discloses a coated steel sheet for drawing and ironing cans.

In addition, in a three-piece can, the film laminated steel belt for a three-piece can and its manufacturing method are disclosed by patent document 5, for example. Moreover, about the steel plate for three-piece cans which has a multilayer organic film on a can outer surface, it is disclosed by patent document 6, for example. Moreover, about the steel plate for three-piece cans which has a stripe-shaped multilayer organic film, it is disclosed by patent document 7, for example. Moreover, about the manufacturing method of a 3-piece can stripe laminated steel sheet, it is disclosed by patent document 8, for example.

On the other hand, in most cases, the chromate film which electrolytically chromated was used for the steel plate used for the base of a laminated film. The chromate film has a two-layer structure, and a hydrated Cr layer is present on the upper layer of the metal Cr layer. Therefore, the laminated film (adhesive layer if it is a film with adhesive) secures adhesiveness with a steel plate via the hydration Cr layer of a chromate film. Although the detail of this adhesive expression mechanism is not made clear, it is called hydrogen bonding of the hydroxyl group of hydrous oxidized Cr, and functional groups, such as a carbonyl group or ester group, of a laminated film.

While the above invention can certainly achieve the effect of greatly advancing the preservation of the global environment, on the other hand, in the beverage container market recently, competition in cost and quality between materials such as PET bottles, bottles, and papers has intensified. Also for the above-described laminated container steel sheet, after securing excellent adhesiveness and corrosion resistance with respect to the coating application which is a prior art, more excellent can manufacturing processability, especially film adhesiveness, processed film adhesiveness, corrosion resistance, etc. became required.

Patent Document 1: Japanese Patent No. 1571383

Patent Document 2: Japanese Patent No. 1670957

Patent Document 3: Japanese Patent Laid-Open No. 2-263523

Patent Document 4: Japanese Patent No. 1601937

Patent Document 5: Japanese Patent Application Laid-Open No. 3-236954

Patent Document 6: Japanese Patent Application Laid-Open No. 3-113494

Patent Document 7: Japanese Patent Application Laid-Open No. 5-111979

Patent Document 8: Japanese Patent Application Laid-Open No. 5-147181

The present invention has been made in view of the above-described problems, and its object is to obtain excellent adhesiveness, corrosion resistance, and weldability, and then to provide excellent can manufacturing processability, which is excellent in weldability, can manufacturing processability, and container steel sheet having excellent appearance. Is to provide.

The present inventors have intensively studied the use of the Zr film as a new film instead of the chromate film, and as a result, a Zr film in which a phosphate film or a phenol resin film is combined with the Zr film or Zr film forms a very strong covalent bond with a coating or a laminate film. The inventors of the present invention have found that excellent can manufacturing processability of conventional chromate coatings or more can be obtained, and the present invention shown below has been achieved.

(1) A Ni plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni or a Fe—Ni alloy plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni is formed on the surface of a steel sheet, and the Ni plating layer is Or Sn plating of 300 mg / m 2 to 3000 mg / m 2 on the Fe-Ni alloy plating layer, and part or all of the Ni plating layer, or the Fe-Ni alloy plating layer by the tin melting treatment, and the A portion of the Sn plating is alloyed so that a portion of the metal Sn plating layer remains, and an upper portion of the alloy Sn plating and the remaining metal Sn plating layer has a Zr film of 1 mg / m 2 to 500 mg / m 2 in the amount of metal Zr, and 0.1 mg / m in the amount of P. The steel plate for containers which is provided with 2 or more types of the phenol resin film of 0.1 mg / m <2> -100 mg / m <2> by the phosphoric acid film of m <2> -100 mg / m <2> and C amount.

(2) A Ni plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni or a Fe-Ni alloy plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni is formed on the surface of the steel sheet, and the Ni plating layer is Or Sn plating of 300 mg / m 2 to 3000 mg / m 2 on the Fe-Ni alloy plating layer, and part or all of the Ni plating layer or the Fe-Ni alloy plating layer and part of the Sn plating are formed by molten tin treatment. The alloyed part of the metal Sn plating layer remains, and on the upper layer of the alloy Sn plating and the remaining metal Sn plating layer, a Zr film of 1 mg / m 2 to 15 mg / m 2 in the amount of metal Zr and 0.1 mg / m 2 to 15 mg in the amount of P The steel plate for containers which is provided with 2 or more types from the phenol resin film of 0.1 mg / m <2> -15 mg / m <2> in phosphoric acid film of / m <2> and C amount.

(3) A Ni plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni or a Fe—Ni alloy plating layer containing 5 mg / m 2 to 150 mg / m 2 of Ni is formed on the surface of the steel sheet, and the Ni plating layer is Or Sn plating of 300 mg / m 2 to 3000 mg / m 2 on the Fe-Ni alloy plating layer, and part or all of the Ni plating layer or the Fe-Ni alloy plating layer and part of the Sn plating are formed by molten tin treatment. The metal Sn plating layer remains partially alloyed, and a Zr film of 1 mg / m 2 to 9 mg / m 2 in an amount of metal Zr and P in an amount of 0.1 mg / m 2 to 8 mg / is deposited on the upper layer of the alloy Sn plating and the remaining metal Sn plating layer. The steel plate for containers with which two or more types are provided in the phosphate film of 2 m <2> and the phenol resin film of 0.1 mg / m <2> -8 mg / m <2> by C amount.

(4) A Sn plating layer of 560 mg / m 2 to 5600 mg / m 2 is applied to the surface of the steel sheet, and a part of the Sn plating layer is alloyed by molten tin treatment, and the metal Zr amount is formed on the upper layer of the alloyed Sn plating layer. 2 or more types of Zr film of 1 mg / m <2> -500 mg / m <2>, phosphoric acid film of 0.1 mg / m <2> -100 mg / m <2> in P amount, and phenolic resin film of 0.1 mg / m <2> -100 mg / m <2> in C amount Steel plate for containers provided with this.

(5) A Sn plating layer of 560 mg / m 2 to 5600 mg / m 2 is applied to the surface of the steel sheet, and a part of the Sn plating layer is alloyed by molten tin treatment, and the metal Zr amount is formed on the upper layer of the alloyed Sn plating layer. 2 or more types of 1 mg / m <2> -15 mg / m <2> Zr film, P amount of 0.1 mg / m <2> -15 mg / m <2> phosphoric acid film, C amount of 0.1 mg / m <2> -15 mg / m <2> phenolic resin film Steel plate for containers provided with this.

(6) A Sn plating layer of 560 mg / m 2 to 5600 mg / m 2 is applied to the surface of the steel sheet, and a part of the Sn plating layer is alloyed by molten tin treatment, and the metal Zr amount is formed on the upper layer of the alloyed Sn plating layer. 2 or more types of Zr film of 1 mg / m <2>-9 mg / m <2>, the phosphate film of 0.1 mg / m <2> -8 mg / m <2> in P amount, and the phenol resin film of 0.1 mg / m <2> -8 mg / m <2> in C amount Steel plate for containers provided with this.

(7) In the steel plate for containers in any one of said (1)-(6), 2 or more types may be formed among a Zr film, a phosphate film, and a phenol resin film by a cathode electrolytic treatment.

(8) In the steel sheet for containers according to any one of (1) to (6), three kinds of Zr coatings, phosphate coatings and phenol resin coatings may be formed by cathodic electrolytic treatment.

(9) In the steel sheet for containers according to (7) or (8), the cathodic electrolytic treatment may be performed in an acidic solution or an acidic solution containing tannic acid.

The steel plate for containers of this invention has the outstanding drawing and ironing process, weldability, corrosion resistance, paint adhesiveness, film adhesiveness, and external appearance.

Embodiment of the steel plate for containers of this invention excellent in weldability, can manufacturing processability, and an external appearance is demonstrated in detail below.

The disc used in this invention is not specifically limited, Usually, the steel plate used as a container material is used. The manufacturing method, material, etc. of this original plate are not specifically limited, either, It manufactures from normal steel plate manufacturing process via processes, such as hot rolling, pickling, cold rolling, annealing, and temper rolling. Although the metal surface treatment layer is provided on the surface of a steel plate, it does not specifically limit about the provision method, For example, well-known techniques, such as an electroplating method, a vacuum evaporation method, a sputtering method, may be used, or the heating for providing a diffusion layer. You may combine with a process.

In this embodiment, as one form of a metal surface treatment layer, the Ni plating layer which contains Ni 5 mg / m <2> -150 mg / m <2> or the Fe-Ni alloy plating layer which contains Ni 5 mg / m <2> -150 mg is provided in the steel plate surface. Sn plating of 300 mg / m 2 to 3000 mg / m 2 is formed thereon, and a part or all of the underlying Ni layer and a part of the Sn plating layer are alloyed by molten tin treatment, and a part of the metal Sn plating layer remains. .

The purpose of performing Ni-based plating of Ni or Fe-Ni alloy plating on a steel sheet and providing a Ni-based plating layer is to secure corrosion resistance. Since Ni is a highly corrosion-resistant metal, corrosion resistance of the alloy layer formed at the time of molten tin process can be improved by plating Ni on the steel plate surface. Since the corrosion resistance improvement effect of the alloy layer by Ni starts to express Ni from 5 mg / m <2> or more, Ni amount is 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 this Ni amount exceeds 150 mg / m <2>, the improvement effect will be saturated. In addition, since Ni is an expensive metal, plating of Ni of 150 mg / m 2 or more is economically disadvantageous. Therefore, it is necessary to make Ni amount into 5 mg / m <2> -150 mg / m <2>.

In the case of forming a Ni diffusion layer, after Ni plating, a diffusion treatment is performed in the annealing furnace to form a Ni diffusion layer. However, even if the Ni diffusion treatment is performed before or after the Ni diffusion treatment, or at the same time, the Ni system in the present invention is used. The effect of Ni as a plating layer and the effect of a nitride treatment layer can be exhibited. As for the method of Ni plating and Fe-Ni alloy plating, a known method generally carried out by the electroplating method may be used.

After Ni-based plating, Sn plating is performed. Sn plating here is plating using metal Sn, but an unavoidable impurity may mix, and a trace element may be added. The method of Sn plating is not particularly limited, and a known electroplating method or a method of immersion and plating of molten Sn may be used. The purpose of Sn plating is to secure corrosion resistance and weldability. Since Sn itself has high corrosion resistance, it exhibits excellent corrosion resistance not only as metal Sn but also as alloy Sn formed by the molten tin process described next. The corrosion resistance of Sn is remarkably improved from 300 mg / m 2 or more, and the corrosion resistance improves as the amount of Sn plating increases, but the effect saturates when it is 3000 mg / m 2 or more. Therefore, from the viewpoint of economics, the plating amount of Sn is preferably set to 3000 mg / m 2 or less.

In addition, Sn having low electrical resistance is soft and spreads by being pressed by Sn between electrodes during welding, so that a stable energization region can be ensured, thereby exhibiting particularly excellent weldability. This excellent weldability is exhibited when the amount of metal Sn is 100 mg / m 2 or more. In addition, if it is a range of Sn plating amount of this invention, it is not necessary to define the upper limit of metal Sn amount. Therefore, in consideration of the above two points, the Sn plating amount was limited to the range of 300 mg / m 2 to 3000 mg / m 2.

After Sn plating, molten tin treatment is performed. The purpose of the molten tin treatment is to melt Sn, alloy it with a base steel sheet or a base metal, form a Sn-Fe or Sn-Fe-Ni alloy layer to improve the corrosion resistance of the alloy layer, and partially retain metal Sn. It is to let. As the remaining form of the metal tin, there are various forms such as island shape, grass shape and stripe shape. By controlling this molten tin treatment, a metal sheet can be partially left to obtain a steel sheet having a plating structure in which a Sn-Ni or Fe-Ni-Sn alloy plating layer having excellent coating and film adhesion properties is partially exposed.

Moreover, as another form in the metal surface treatment layer of this invention, Sn plating of 560 mg / m <2> -5600 mg / m <2> is given to the steel plate surface, and some Sn plating layers are alloyed by the molten tin process. Sn has excellent workability, excellent weldability and corrosion resistance, but only Sn plating requires 560 mg / m 2 or more from the viewpoint of corrosion resistance. Corrosion resistance improves as Sn plating amount increases, but when it becomes 5600 mg / m <2> or more, the effect will be saturated. Therefore, from the viewpoint of economics, the plating amount of Sn is preferably 5600 mg / m 2 or less. Further, by performing molten tin treatment after Sn plating, a Sn alloy layer is formed and the corrosion resistance is further improved.

Two or more types are provided to the upper layer of these metal surface treatment layers among a Zr film, a phosphate film, and a phenol resin film.

Although the Zr film, the phosphate film, and the phenol resin film are used alone, some effects are recognized, but they do not have sufficient practical performance. However, excellent practical performance is exhibited by the film which combined 2 or more types of a Zr film, a phosphate film, and a phenol resin film. Moreover, when 1 or more types of a phosphate film or a phenolic film are compound | combined with a Zr film, the outstanding practical performance is exhibited. Moreover, in the range with a small film amount, in order to complement each characteristic, the film which combined three types of Zr film, a phosphate film, and a phenol resin film has more stable practical performance. Moreover, the film which mixes 2 or more types of Zr, a phosphate type compound, a phenol, etc. in the same film is compared with the case where 2 or more types of a Zr film, a phosphate film, and a phenol resin film are formed separately, and it is practical of corrosion resistance, adhesiveness, etc. Poor performance Although this reason is not clear, it is thought that the performance which an individual component exhibits is impaired by mixing Zr, phosphoric acid, and a phenol in the same film.

The role of the Zr film is to secure corrosion resistance and adhesion. The Zr film is composed of a Zr compound such as Zr oxide, Zr hydroxide, Zr fluoride, Zr phosphate, or a composite film thereof. These Zr compounds have excellent corrosion resistance and adhesiveness. Therefore, when Zr film increases, corrosion resistance and adhesiveness begin to improve, and when it becomes 1 mg / m <2> or more by metal Zr amount, corrosion resistance and adhesiveness of a level which is satisfactory practically is ensured. In addition, when the amount of Zr coating increases, the effect of improving corrosion resistance and adhesion also increases. However, when the amount of Zr coating exceeds 500 mg / m 2 in terms of the amount of metal Zr, the Zr coating becomes too thick, resulting in deterioration of the adhesion of the Zr coating itself and electrical resistance. It rises and deteriorates weldability. Therefore, the amount of Zr film needs to be 1 mg / m <2>-500 mg / m <2> in the amount of metal Zr.

In addition, when the amount of Zr coating exceeds 15 mg / m <2> by the amount of metal Zr, since the adhesion nonuniformity of a film may become an external appearance nonuniformity, More preferably, the amount of Zr coating is 1 mg / m <2> -15 mg by the amount of metal Zr. / M 2. In addition, in order to stabilize the appearance irregularity more favorably, the amount of Zr coating is preferably 0.1 mg / m 2 to 9 mg / m 2 as the amount of metal Zr.

The role of the phosphate coating is to ensure corrosion resistance and adhesion. The phosphate film is composed of a film such as Fe phosphate, Sn phosphate, Ni phosphate, Zr phosphate, or phosphate-phenol resin film formed by reacting with the base or a composite film thereof. These phosphate coatings have excellent corrosion resistance and adhesiveness. Therefore, when the phosphate film increases, corrosion resistance and adhesiveness begin to improve, and when P amount becomes 0.1 mg / m <2> or more, the corrosion resistance and adhesiveness of the level which is satisfactory practically is ensured. In addition, when the amount of phosphate coating increases, the effect of improving corrosion resistance and adhesion also increases. However, when the amount of phosphate coating exceeds 100 mg / m 2 in P amount, the phosphate coating becomes excessively thick, resulting in deterioration of the adhesion of the phosphate coating itself and an increase in electrical resistance. Weldability deteriorates. Therefore, the amount of phosphate coating needs to be 0.1 mg / m 2 to 100 mg / m 2 in terms of P amount.

When the amount of the phosphate film exceeds 15 mg / m 2 in the amount of P, the adhesion irregularity of the film may be expressed as the appearance unevenness, so the amount of the phosphate film is more preferably 0.1 mg / m 2 to 15 mg / m 2 as the amount of P. . In addition, in order to stabilize the appearance irregularity more favorably, the amount of the phosphate film is preferably 0.1 mg / m 2 to 8 mg / m 2 in terms of P amount.

The role of the phenol resin film is to secure adhesion. Since phenol resin itself is an organic substance, it has very good adhesion with paints and laminate films. Therefore, when phenol resin film increases, adhesiveness will begin to improve and when C amount becomes 0.1 mg / m <2> or more, practically good level of adhesiveness will be ensured. In addition, when the amount of the phenolic resin film is increased, the effect of improving adhesion is also increased. However, when the amount of the phenolic resin film is more than 100 mg / m 2 in the amount of C, the electrical resistance increases and the weldability is deteriorated. Therefore, the amount of phenol resin films needs to be 0.1 mg / m <2> -100 mg / m <2> by C amount.

When the amount of the phenol resin film exceeds 15 mg / m 2 in the amount of C, the adhesion unevenness of the film may be expressed as the appearance unevenness, and more preferably the amount of the phenol resin film in the amount of C is 0.1 mg / m 2 to 15 mg. It is good to set it as / m <2>. In addition, in order to further reduce the appearance unevenness and stabilize it satisfactorily, it is preferable to make the amount of the phenol resin film into the amount of C from 0.1 mg / m 2 to 8 mg / m 2.

These coating methods include a method of immersing a steel plate in an acid solution in which Zr ions, phosphate ions, and a low molecular weight phenol resin are dissolved, or a method performed by cathodic electrolytic treatment. In the immersion treatment, since various substrates are formed by etching the substrate, adhesion becomes uneven and the treatment time becomes long, which is disadvantageous in industrial production. On the other hand, in the cathodic electrolytic treatment, the surface cleansing caused by the forced charge transfer and the hydrogen generation at the steel plate interface and the adhesion promoting effect due to the pH increase are good, and the uniform coating can be treated in a short time of several seconds to several tens of seconds. Very advantageous. Therefore, cathodic electrolytic treatment is preferable for the provision of the Zr film, the phosphate film and the phenol resin film of the present invention.

In addition, when tannic acid is added to the acidic solution used for the immersion treatment and the cathodic electrolytic treatment, tannic acid is combined with Fe to form a film of Fe tannin acid on the surface, thereby improving the rust resistance and adhesion. Therefore, you may process in the solution which added tannic acid.

Below, the Example and comparative example of this invention are described, and the result is shown to Tables 1-3. First, the surface treatment layer was formed on the steel plate of 0.17 mm-0.23 mm of plate | board thickness using the method of the following processes (1)-(3).

(1) After cold rolling, the annealed and quenched disc is degreased and pickled, and then Sn is plated using a phenol sulfonic acid 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 quenched discs were degreased and pickled, followed by Fe-Ni alloy plating using a sulfuric acid hydrochloric acid bath, followed by Sn plating using a phenol sulfonic acid 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, and after degreasing and pickling, Sn plating is performed using a phenol sulfonic acid bath, followed by molten tin treatment. To produce a Ni and Sn-plated steel sheet having a Sn alloy layer.

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

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

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

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

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

(8) The steel plate was immersed in a treatment solution in which Zr fluoride, phosphoric acid, and tannic acid were dissolved, and dried after cathode electrolysis to form a Zr film and a phosphate film.

(9) The steel plate was immersed in a treatment solution in which Zr fluoride, phosphoric acid and phenol resin were dissolved, followed by drying to form a Zr film, a phosphate film and a phenol resin film.

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

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

About the test material which performed the said process, performance evaluation was performed about each evaluation item of (A)-(H) shown below. The PET film of 20 micrometers in thickness was laminated at 200 degreeC, the test material was produced, and performance evaluation was performed about each item of (A)-(D) shown below.

(A) processability

A PET film having a thickness of 20 μm was laminated at 200 ° C. on both sides of the test material, and the can manufacturing process by drawing processing and ironing was performed step by step, and molding was performed in four stages (◎: very good, ○: good, △ : Damage was recognized, x: fractured and impossible to process).

(B) weldability

Using a wire seam welder, at a welding wire speed of 80 m / min, change the current to weld the test specimen to obtain a minimum weld current, welding dust, welding spatter, etc. It is judged comprehensively from the area of the appropriate current range consisting of the maximum current value at which the welding defects start to stand out, and in four steps (◎: very good, ○: good, △: inferior, ×: impossible to weld). Weldability was evaluated.

(C) film adhesion

A PET film having a thickness of 20 μm was laminated at 200 ° C. on both surfaces of the test material, a drawing and ironing process was performed, a can body was prepared, and a retort treatment was performed at 125 ° C. for 30 min. No peeling at all, (circle): Very slight peeling with which there is no problem practically, (triangle | delta): There exists a slight peeling, and X: peeling in most).

(D) paint adhesion

Epoxy phenolic resin was applied to the test material and baked at 200 ° C. for 30 min. Then, a checkerboard scale having a depth of about 1 mm was reached at intervals of 1 mm, peeled off with a tape, and the peeling was carried out in four steps. No peeling, (circle): Very slight peeling with which there is no problem practically, (triangle | delta): There exists a slight peeling, and X: peeling in most).

(E) corrosion resistance

Epoxy phenolic resin was applied to the test material and baked at 200 ° C. for 30 min. Then, a crosscut having a depth reaching the ground iron was placed therein, and then immersed at 45 ° C. for 72 hours in a test solution composed of 1.5% citric acid-1.5% saline solution. After washing and drying, the tape was peeled off, and the coating film was subjected to the corrosion of the crosscut portion and the corrosion of the flat plate at four stages (◎: corrosion was not recognized under the coating; ○: very slight coating with no problems in practical use. Under corrosion was recognized, △: slight under-coating corrosion and slight corrosion on the flat plate, ×: severe under-coating and flat plate corrosion).

(F) hearing resistance

The test material was repeatedly wet and dry (humidity 90%, 2hr <=> humidity 40%, 2hr) and left for 2 months in an atmosphere of rust. Very little of rust, △: little of rust, ×: most of it).

(G) appearance

Observation of the test material visually, 5 stages of occurrence of non-uniformity of Zr film, phosphate film, and phenolic resin film (◎◎: No non-uniformity at all, ◎: Very slight non-uniformity with no practical problem, ○: Slight nonuniformity, Δ: nonuniformity, ×: significant nonuniformity).

(H) metal Sn situation

The surface of the metal Sn in the case of performing Sn plating after Ni plating and controlling molten tin treatment was observed on the surface with an optical microscope, and the metal Sn situation was observed in three steps (○: remaining on the entire surface, △: remaining There was a part which was not made, and x: not remaining). The coating amount was quantitatively analyzed by fluorescent X-ray for the amount of Zr and P, and the total amount of C was determined by the total carbon content measurement method.

In these Tables 1-3, the 1st-42nd Example satisfy | fills the conditions prescribed | regulated by this invention. On the other hand, all the 1st-5th comparative examples deviate from the conditions prescribed | regulated by this invention. In all the evaluation items of said (A)-(H), the favorable evaluation result was obtained for the 1st-42nd Example. Particularly, in Examples Nos. 31 to 42, the amount of Zr film deposited was 0.1 to 9 mg / m 2 in the amount of Zr, the amount of the phosphoric acid film deposited was 0.1 to 8 mg / m 2 in the amount of P, and the amount of C phenol resin was deposited. 2 or more types are given in the phenol resin film which is 0.1-8 mg / m <2>. For this reason, the outstanding characteristic was acquired especially in external appearance. On the other hand, the 1st-5th comparative example was unable to acquire favorable evaluation result in all the evaluation items of said (A)-(H).

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

Claims (10)

On the surface of the steel sheet, a Ni plating layer containing Ni 5 mg / m 2 to 150 mg / m 2 or a Fe—Ni alloy plating layer containing Ni 5 mg / m 2 to 150 mg / m 2 is formed. Sn plating of 300 mg / m 2 to 3000 mg / m 2 is performed on the Ni plating layer or the Fe—Ni alloy plating layer. By the molten tin treatment, a part or all of the Ni plating layer or the Fe—Ni alloy plating layer and a part of the Sn plating are alloyed to partially leave a metal Sn plating layer, The Zr film of 1 mg / m 2 to 500 mg / m 2 in the amount of metal Zr, the phosphoric acid film of 0.1 mg / m 2 to 100 mg / m 2 in the amount of P and 0.1 mg of C in the upper portion of the alloy Sn plating and the remaining metal Sn plating layer 2 or more types are provided in the phenol resin film of / m <2> -100mg / m <2>, The steel plate for containers characterized by the above-mentioned. On the surface of the steel sheet, a Ni plating layer containing Ni 5 mg / m 2 to 150 mg / m 2 or a Fe—Ni alloy plating layer containing Ni 5 mg / m 2 to 150 mg / m 2 is formed. Sn plating of 300 mg / m 2 to 3000 mg / m 2 is performed on the Ni plating layer or the Fe—Ni alloy plating layer. By the molten tin treatment, a part or all of the Ni plating layer or the Fe—Ni alloy plating layer and a part of the Sn plating are alloyed to partially leave a metal Sn plating layer, The Zr film of 1 mg / m 2 to 15 mg / m 2 in the amount of metal Zr, the phosphoric acid film of 0.1 mg / m 2 to 15 mg / m 2 in the amount of P and 0.1 mg of C in the upper layer of the alloy Sn plating and the remaining metal Sn plating layer 2 or more types are provided in the phenol resin film of / m <2> -15mg / m <2>, The steel plate for containers characterized by the above-mentioned. On the surface of the steel sheet, a Ni plating layer containing Ni 5 mg / m 2 to 150 mg / m 2 or a Fe—Ni alloy plating layer containing Ni 5 mg / m 2 to 150 mg / m 2 is formed. Sn plating of 300 mg / m 2 to 3000 mg / m 2 is performed on the Ni plating layer or the Fe—Ni alloy plating layer.  By the molten tin treatment, a part or all of the Ni plating layer or the Fe—Ni alloy plating layer and a part of the Sn plating are alloyed to partially leave a metal Sn plating layer, The Zr film of 1 mg / m 2 to 9 mg / m 2 in the amount of metal Zr, the phosphoric acid film of 0.1 mg / m 2 to 8 mg / m 2 in the amount of P and 0.1 mg of C in the upper portion of the alloy Sn plating and the remaining metal Sn plating layer 2 or more types are provided in the phenol resin film of / m <2> -8mg / m <2>, The steel plate for containers characterized by the above-mentioned. Sn plating layer of 560 mg / m <2> -5600 mg / m <2> is given to the steel plate surface, A part of the Sn plating layer is alloyed by molten tin treatment, On the upper layer of the alloyed Sn plating layer, a Zr film of 1 mg / m 2 to 500 mg / m 2 in a metal Zr amount, a phosphoric acid film of 0.1 mg / m 2 to 100 mg / m 2 in a P amount, and 0.1 mg / m 2 to a C amount 2 or more types are provided in the phenol resin film of 100 mg / m <2>, The steel plate for containers characterized by the above-mentioned. Sn plating layer of 560 mg / m <2> -5600 mg / m <2> is given to the steel plate surface, A part of the Sn plating layer is alloyed by molten tin treatment, On the upper layer of the alloyed Sn plating layer, a Zr film of 1 mg / m 2 to 15 mg / m 2 in an amount of metal Zr, a phosphoric acid film of 0.1 mg / m 2 to 15 mg / m 2 in an amount of P and 0.1 mg / m 2 in an amount of C 2 or more types are provided in the phenol resin film of 15 mg / m <2>, The steel plate for containers characterized by the above-mentioned. Sn plating layer of 560 mg / m <2> -5600 mg / m <2> is given to the steel plate surface, A part of the Sn plating layer is alloyed by molten tin treatment, On the upper layer of the Sn plating layer alloyed, a Zr film of 1 mg / m 2 to 9 mg / m 2 in a metal Zr amount, a phosphoric acid film of 0.1 mg / m 2 to 8 mg / m 2 in a P amount, and 0.1 mg / m 2 to a C amount 2 or more types are provided in the phenol resin film of 8 mg / m <2>, The steel plate for containers characterized by the above-mentioned. The steel sheet for containers according to any one of claims 1 to 6, wherein two or more kinds of Zr films, phosphate coatings, and phenolic resin coatings are formed by cathodic electrolytic treatment. The steel sheet for containers according to any one of claims 1 to 6, wherein three kinds of a Zr film, a phosphate film, and a phenol resin film are formed by a cathode electrolytic treatment. The steel sheet for containers according to claim 7, wherein the cathodic electrolytic treatment is performed in an acidic solution or an acidic solution containing tannic acid. The steel sheet for containers according to claim 8, wherein the cathodic electrolytic treatment is performed in an acidic solution or an acidic solution containing tannic acid.