TWI394658B - Steel sheet for containers - Google Patents

Description

Steel plate for containers Technical field

The present invention relates to a steel sheet for containers which can be used as a raw material for can processing, and particularly relates to a drawing and ironing process, weldability, corrosion resistance, paint adhesion, and film adhesion. Steel plate for containers.

Background technique

Metal containers for beverages or foods can be roughly divided into two-piece cans and three-piece cans. A two-piece can represented by a DI can is subjected to press drawing processing, and then coated on the inner surface side of the can, and coated and printed on the outer side of the can. Further, the three-piece can was coated on the surface corresponding to the inner surface of the can, and printed on the surface corresponding to the outer surface of the can, and then the can body was welded.

Regardless of the type of can, the coating step must be performed before and after canning. A solvent-based or water-based paint can be used for the coating, followed by baking. In the coating step, waste (dissolved solvent, etc.) generated by the paint is discharged as industrial waste, and exhaust gas (mainly carbonic acid gas) is released into the atmosphere. In recent years, measures are being taken to reduce such industrial wastes or exhaust gases for the purpose of protecting the global environment. Among them, the technology of replacing the coating with film bonding is attracting attention and rapidly expanding.

Heretofore, regarding the two-piece can, a number of methods for forming a can to form a can or a related invention have been provided. For example, a manufacturing method of a press-drawn can is disclosed as in Patent Document 1. Further, a drawn and ironed can is disclosed as in Patent Document 2. Further, a method of manufacturing a deep drawn can is disclosed in Patent Document 3, for example. Moreover, the coated steel sheet for a press-drawn can is disclosed in Patent Document 4, for example.

Further, in the case of a 3-piece can, a film-layered steel strip for a three-piece can and a method for producing the same are disclosed in Patent Document 5. Further, a steel sheet for a three-piece can having a multilayer organic film on the outside of the can is disclosed in Patent Document 6. Further, a steel sheet for a three-piece can having a strip-shaped multilayer organic film is disclosed in Patent Document 7. Further, a method for producing a three-piece can-shaped laminated steel sheet is disclosed in Patent Document 8.

On the other hand, a chromic acid film treated with electrolytic chromic acid is often used on the steel sheet used for the substrate of the laminated film. The chromic acid film has a two-layer structure, and the upper layer of the metal Cr layer has a hydrated oxidized Cr layer. Therefore, the laminated film (in the case of a film having an adhesive agent, it is an adhesive layer) can be oxidized by the chromic acid film to oxidize the Cr layer to ensure adhesion to the steel sheet. Although the details of the mechanism for exhibiting the adhesion are not clear, it can be said that the hydroxyl group of the hydrated oxidized Cr is bonded to the hydrogen of a functional group such as a carbonyl group or an ester group of the laminate film.

The above invention can indeed achieve the effect of greatly improving the protection of the global environment. On the other hand, in recent years, in the beverage container market, the competition between the cost and quality of raw materials such as PET bottles, bottles, and papers has intensified, and the above-mentioned laminated containers are used. In the steel sheet, it is necessary to ensure excellent adhesion to the coating application of the prior art and corrosion resistance, and further excellent can processing properties, particularly film adhesion, film adhesion, corrosion resistance, and the like.

[Patent Document 1] Patent No. 1 571 783 [Patent Document 3] Patent Publication No. 1670957 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Invention

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a weldability and a can processability which are excellent in not only excellent adhesion, corrosion resistance, weldability, but also excellent potability. Steel plate for containers with excellent appearance.

The present inventors have focused on the use of a Zr film as a substitute for a new film of a chromic acid film, and found that a Zr film or a Zr film and a coated or laminated film formed by compounding a phosphoric acid film or a phenol resin film on a Zr film can be formed. The very strong covalent bond gives excellent processability on a conventional chromic acid film, and the present invention shown below is completed.

(1) A steel sheet for containers, formed ² ~ 150mg / m Ni containing 5mg / m ² of Ni-plating layer on the steel sheet surface, or containing ^{5mg / m 2 ~ 150mg / m} Ni 2 of the Fe-Ni alloy plating layer; And the Sn plating of 300 mg/m ² to 3000 mg/m ² is formed on the Ni plating layer or the Fe-Ni alloy plating layer; part or all of the Ni plating layer or the Fe-Ni alloy plating layer and a part of the Sn plating layer are melted. It is alloyed by tin-melting treatment, and a part of the metal Sn plating layer remains. The upper layer of the Sn-plated alloy and the residual metal Sn plating layer is coated with a Zr film having a metal Zr amount of 1 mg/m ² to 500 mg/m ² , and the amount of P is 0.1mg / m ² ~ 100mg / m ² of phosphate films, C in an amount of 0.1mg / m ² ~ 100mg / m ² of phenol resin film of two kinds or more.

(2) A steel sheet for container, formed with Ni containing ^{5mg / m 2 ~ 150mg / m} 2 of Ni-plating layer on the steel sheet surface, or containing ^{5mg / m 2 ~ 150mg m Ni} 2 of the Fe-Ni alloy plating layer /; And the Sn plating of 300 mg/m ² to 3000 mg/m ² is formed on the Ni plating layer or the Fe-Ni alloy plating layer; part or all of the Ni plating layer or the Fe-Ni alloy plating layer and a part of the Sn plating layer are melted. The tin alloy is alloyed and a part of the metal Sn plating layer remains; and the upper layer of the Sn alloy and the residual metal Sn plating layer is coated with a Zr film having a metal Zr amount of 1 mg/m ² to 15 mg/m ² , P in an amount of 0.1mg / m ² ~ 15mg / m ² of phosphate films, C in an amount of 0.1mg / m ² ~ 15mg / m ² of phenol resin film of two kinds or more.

(3) A steel sheet for containers, formed ² ~ 150mg / m Ni containing 5mg / m ² of Ni-plating layer on the steel sheet surface, or containing ^{5mg / m 2 ~ 150mg / m} Ni 2 of the Fe-Ni alloy plating layer; And the Sn plating of 300 mg/m ² to 3000 mg/m ² is formed on the Ni plating layer or the Fe-Ni alloy plating layer; part or all of the Ni plating layer or the Fe-Ni alloy plating layer and a part of the Sn plating layer are melted. The tin is treated and alloyed, and a part of the metal Sn plating layer remains; and the upper layer of the Sn alloy and the residual metal Sn plating layer is coated with a Zr film having a metal Zr amount of 1 mg/m ² to 9 mg/m ² , P in an amount of 0.1mg / m ² ~ 8mg / m ² of phosphate films, C in an amount of 0.1mg / m ² ~ 8mg / m ² of phenol resin film of two kinds or more.

(4) A steel sheet for containers, formed ² ~ 5600mg / m of the Sn plating layer containing 560mg / m ² on the steel sheet surface; part by the Department of the Sn-plated tin melting alloying treatment; and by alloying after the upper cladding of the Sn plating of a metal Zr in an amount of ^{1mg / m 2 ~ 500mg / m} Zr film of ^2, P in an amount of 0.1mg / m ² ~ 100mg / m ² of phosphate films, C in an amount of 0.1mg / m ² Two or more of the phenol resin films of ~100 mg/m ² .

Based portion of the Sn plating tin melting treatment by alloying;; and by the alloying (5) A steel sheet for containers with ² ~ 5600mg / m Sn ² of the plating layer containing 560mg / m is formed on the surface of the steel sheet upper cladding of the Sn plating of a metal Zr in an amount of ^{1mg / m 2 ~ 15mg / m} Zr film of ^2, P in an amount of 0.1mg / m ² ~ 15mg / m ² of phosphate films, C in an amount of 0.1mg / m ² Two or more of the phenol resin films of ~15 mg/m ² .

(6) A steel sheet for container, the steel sheet has a surface coating containing ^{560mg / m 2 ~ 5600mg / m} Sn plating layer of ^2; a portion of the Sn-based plating layer of tin melting treatment by alloying; and by the alloying upper cladding of the Sn plating of a metal Zr in an amount of ^{1mg / m 2 ~ 9mg / m} Zr film of ^2, P in an amount of 0.1mg / m ² ~ 8mg / m ² of phosphate films, C in an amount of 0.1mg / m ^Two or more kinds of phenol resin films of ² to 8 mg/m ² .

(7) In the steel sheet for a container according to any one of the items (1) to (6), two or more of the Zr film, the phosphoric acid film, and the phenol resin film may be formed by cathodic electrolysis.

(8) The steel sheet for a container according to any one of the items (1) to (6), wherein the three types of films of the Zr film, the phosphoric acid film, and the phenol resin film are formed by cathodic electrolysis.

(9) The steel sheet for containers according to the above item (7) or (8), wherein the cathodic electrolysis treatment is carried out in an acidic solution or an acidic solution containing citric acid.

The steel sheet for containers of the present invention has excellent press workability, weldability, corrosion resistance, paint adhesion, film adhesion, and appearance.

Best form for implementing the invention

Hereinafter, an embodiment of the steel sheet for a container of the present invention excellent in weldability, potability, and appearance will be described in detail.

The original sheet used in the present invention is not particularly limited, and a steel sheet which can be used as a container material is usually used. The method for producing the original sheet, the material, and the like are not particularly limited, and can be produced from a general steel sheet manufacturing step by hot rolling, pickling, cold rolling, annealing, and flattening. The surface of the steel sheet is coated with a metal surface treatment layer, and the coating method is not particularly limited. For example, a known technique such as an electroplating method, a vacuum evaporation method, or a sputtering method, or a heating method for coating the diffusion layer may be used. Process the combination.

In this embodiment, Ni is formed containing ^{5mg / m 2 ~ 150mg / m} 2 of Ni plating or the containing ^{Fe- 5mg / m 2 ~ 150mg /} m Ni on the steel sheet surface ² of the metal surface treatment layer forms one line a Ni alloy plating layer on which 300 mg/m ² to 3000 mg/m ² of Sn plating is formed; part or all of the substrate Ni layer and one part of the Sn plating layer are alloyed by melt-melting treatment, and a part remains. Metal Sn plating.

A Ni-plated Ni or Fe-Ni alloy-plated Ni-based system is applied to the steel sheet to coat the Ni-based plating layer for the purpose of ensuring corrosion resistance. Since Ni is a high-resistance metal, by plating Ni on the surface of the steel sheet, the corrosion resistance of the alloy layer formed during the molten tin-melting treatment can be improved. Since the effect of improving the corrosion resistance of the alloy layer by Ni is not started until the amount of Ni plated is 5 mg/m ² or more, the amount of Ni must be 5 mg/m ² or more. The effect of improving the corrosion resistance of the alloy layer increases as the amount of Ni increases, but when the amount of Ni is more than 150 mg/m ² , the effect of the improvement is saturated. Further, it is not economically economical to plate Ni with a high-valent Ni-based metal of 150 mg/m ² or more. Therefore, the amount of Ni must be controlled at 5 mg/m ² to 150 mg/m ² .

Further, when the Ni diffusion layer is formed, Ni plating is performed in an annealing furnace after Ni plating, and a Ni diffusion layer is formed, and the Ni system of the present invention can be exhibited even before or after the Ni diffusion treatment. The effect of Ni on the plating layer and the effect of the nitrided treatment layer. In general, a method of plating Ni and plating an Fe-Ni alloy can use a known method by electroplating.

Next, Sn plating is performed after Ni plating. The term "Sn plating" as used herein refers to a case where plating is performed using metal Sn, and inevitably, impurities may be mixed, and a trace element may be added. The method of plating Sn is not particularly limited, and any known plating method or a method of immersing in molten Sn and plating it may be used. The purpose of plating Sn is to ensure corrosion resistance and weldability. Since Sn itself has high corrosion resistance, excellent corrosion resistance can be exhibited regardless of the metal Sn or the alloy Sn formed by the molten tin treatment described below. The excellent corrosion resistance of such Sn is remarkably improved after 300 mg/m ² or more, and the corrosion resistance increases as the amount of Sn plating increases, but when it is 3000 mg/m ² or more, the effect is saturated. Therefore, from the economic point of view, the amount of Sn plating is preferably controlled to be 3000 mg/m ² or less.

Further, Sn having a low electric resistance is soft, and Sn can be extended by pressurizing between the electrodes during welding to ensure a stable energization region, and particularly excellent weldability can be exhibited. As long as the amount of the metal Sn is 100 mg/m ² or more, such excellent weldability can be exhibited. Further, as long as it is in the range of the Sn plating amount of the present invention, it is not necessary to define the upper limit amount of the amount of metal Sn. Therefore, considering the above two points, the amount of Sn plating is limited to the range of 300 mg/m ² to 3000 mg/m ² .

After the Sn plating, a molten tinning treatment is performed. The purpose of performing the molten tinning treatment is to melt Sn and alloy it with a substrate steel plate or a substrate metal to form a Sn-Fe or Sn-Fe-Ni alloy layer to improve the corrosion resistance of the alloy layer and to partially The metal Sn remains. The residual form of the metallic tin has various forms such as an island shape, a pool shape, and a strip shape. By controlling the molten tin treatment, a steel sheet having a plating structure in which a part of the metal Sn remains and a part of the coating and the Sn-Ni or Fe-Ni-Sn alloy plating layer having excellent film adhesion is exposed can be obtained.

Further, another aspect of the present invention a metal surface treated with a layer of Ownership containing 560mg / m ² ~ 5600mg / m of plated Sn ^2, Sn-based plating layer portion of the tin melting treatment by alloying the steel sheet surface is formed. Sn has excellent workability, excellent weldability, and corrosion resistance. However, when Sn is only plated, it is necessary to be 560 mg/m ² or more from the viewpoint of corrosion resistance. Although the corrosion resistance increases as the amount of plating Sn increases, the effect is saturated at 5600 mg/m ² or more. Therefore, from the economical point of view, the amount of Sn plating is preferably controlled to be 5600 mg/m ² or less. Further, by performing a molten tinning treatment after Sn plating, a Sn alloy layer can be formed, and corrosion resistance can be further improved.

The upper surface of the metal surface treatment layer is coated with two or more of a Zr film, a phosphoric acid film, and a phenol resin film.

Although the Zr film, the phosphoric acid film, and the phenol resin film have a certain effect even when used alone, they do not have sufficient practical properties. However, two or more types of films of a Zr film, a phosphoric acid film, and a phenol resin film are combined to exhibit excellent practical properties. In addition, when one or more types of Zr film composite phosphoric acid film or phenol resin film are used, more excellent practical performance can be exhibited. Further, in the range where the amount of the film is small, three types of films in which a Zr film, a phosphoric acid film, and a phenol resin film are combined have a more stable practical performance due to the complementary characteristics. In addition, two or more kinds of films of Zr, a phosphoric acid compound, and a phenol are mixed in the same film, and corrosion resistance and adhesion are compared with those of two or more types of Zr film, phosphoric acid film, and phenol resin film. Such practical performance is not good. Although the reason for this is not clear, it is considered that the Zr, the phosphate compound, and the phenol are mixed in the same film, and the performance of each component is hindered.

The function of the Zr film is to ensure corrosion resistance and adhesion. The Zr film is composed of a Zr compound such as Zr oxide, Zr hydroxide, fluorinated Zr or phosphoric acid Zr or a composite film thereof. These Zr compounds have excellent corrosion resistance and adhesion. Therefore, when the Zr film is increased, the corrosion resistance, the adhesion, and the like are started to increase. When the amount of the metal Zr is 1 mg/m ² or more, the corrosion resistance and the adhesion property to the extent that there is no practical problem can be ensured. However, when the Zr film is further increased, the effect of improving the corrosion resistance or the adhesion is also increased. However, when the amount of the Zr film of the Zr film is more than 500 mg/m ² , the Zr film is too thick, so that the Zr film body is closely connected. The property is deteriorated, and the electric resistance is increased to deteriorate the weldability. Therefore, the amount of metal Zr of the Zr film amount needs to be controlled to be 1 mg/m ² to 500 mg/m ² .

In addition, when the amount of the metal Zr of the Zr film amount is more than 15 mg/m ² , the uneven adhesion of the film (mura) appears to be uneven in appearance, so the amount of the metal Zr of the Zr film amount is 1 mg/m ² to 15 mg. /m ^{2 is} preferred. Further, in order to make the appearance unevenness more stable, the amount of the metal Zr in the amount of the Zr film is preferably from 0.1 mg/m ² to 9 mg/m ² .

The function of the phosphoric acid film is to ensure corrosion resistance and adhesion. The phosphoric acid film is formed of a film of phosphoric acid Fe, phosphoric acid Sn, phosphoric acid Ni, phosphoric acid Zr or a phosphate phenol resin film or a composite film formed by reaction with a substrate. These phosphoric acid films have excellent corrosion resistance and adhesion. Therefore, when the phosphoric acid film is increased, the corrosion resistance, the adhesion, and the like are started to increase. When the amount of P is 0.1 mg/m ² or more, the corrosion resistance and the adhesion property to the extent that there is no practical problem can be ensured. On the other hand, when the phosphoric acid film is further increased, the effect of improving the corrosion resistance or the adhesion is also increased. However, when the amount of the phosphoric acid film is more than 100 mg/m ² , the phosphoric acid film is too thick to make the phosphoric acid film body adhere. Deterioration, and the resistance rises, and the weldability is deteriorated. Therefore, the amount of P in the phosphoric acid film amount needs to be controlled to be 0.1 mg/m ² to 100 mg/m ² .

Further, when the amount of P of the phosphoric acid film is more than 15 mg/m ² , the uneven adhesion of the film appears to be uneven in appearance, so the amount of P of the phosphoric acid film is 0.1 mg/m ² to 15 mg/m ^{2 .} good. Further, in order to make the appearance unevenness more stable, the amount of P in the phosphoric acid film amount is more preferably 0.1 mg/m ² to 8 mg/m ² .

The function of the phenol resin film is to ensure adhesion. Since the phenol resin itself is an organic substance, it has excellent adhesion to a coating material or a laminated film. Therefore, when the phenol resin film is increased, the adhesion and the like are started to increase, and when the amount of C is 0.1 mg/m ² or more, the adhesion to the extent that there is no practical problem can be ensured. On the other hand, when the phenol resin film is further increased, the effect of improving the adhesion is also increased. However, when the amount of C of the phenol resin film is more than 100 mg/m ² , the electric resistance is increased and the weldability is deteriorated. Therefore, the amount of C of the phenol resin film amount needs to be controlled to be 0.1 mg/m ² to 100 mg/m ² .

Further, when the amount of C of the phenol resin film is more than 15 mg/m ² , the uneven adhesion of the film appears to be uneven in appearance, so the amount of C of the phenol resin film is 0.1 mg/m ² to 15 mg/m. ^{2 is} preferred. Further, in order to further reduce the unevenness in appearance and to make it stable, the amount of C of the phenol resin film is preferably from 0.1 mg/m ² to 8 mg/m ² .

The method of coating the films is a method of immersing the steel sheet in an acidic solution in which Zr ions, phosphate ions, and low molecular phenol resins are dissolved, or a method of performing cathodic electrolysis. Since the immersion treatment etches the substrate to form various films, adhesion may be uneven. In addition, because of the long processing time, it is disadvantageous in industrial production. On the other hand, the cathodic electrolysis treatment is complementary to the surface cleaning caused by the forced charge movement and the hydrogen generated at the interface of the steel sheet, and the accelerated adhesion effect due to the pH rise, and can be in the range of several seconds to several tens A uniform film is handled in a short time of about seconds, so it is extremely advantageous industrially. Therefore, it is preferable to coat the Zr film, the phosphoric acid film, and the phenol resin film of the present invention by cathodic electrolysis treatment.

Further, when citric acid is added to an acidic solution used for immersion treatment or cathodic electrolysis treatment, tannic acid is bonded to Fe to form a film of bismuth citrate on the surface, which has an effect of improving rust resistance, adhesion, and the like. Therefore, it can also be carried out in a solution to which citric acid is added depending on the application.

Hereinafter, examples and comparative examples of the present invention will be described, and the results thereof will be shown in the first to third tables. First, a surface treatment layer is formed on a steel sheet having a thickness of 0.17 mm to 0.23 mm by the following methods (1) to (3).

(1) The original plate which was annealed and smoothed after cold rolling was degreased and pickled, and then Sn was plated using a plating ferrostan bath. Thereafter, a molten tinning treatment was performed to prepare a Sn-plated steel sheet having a Sn alloy layer.

(2) The original plate after annealing and flattening after cold rolling is degreased and pickled, and then a Fe-Ni alloy is formed by a sulfuric acid-hydrochloric acid bath, and then a plating tinplate bath is used to plate Sn. Thereafter, a molten tinning treatment was performed to prepare a Ni-plated or Sn-coated steel sheet having a Sn alloy layer.

(3) After cold rolling, Ni plating was performed using a watts bath, a Ni diffusion layer was formed during annealing, and after degreasing and pickling, Sn was plated using an electroplated tinplate bath. Thereafter, a molten tinning treatment was performed to prepare a Ni-plated or Sn-coated steel sheet having a Sn alloy layer.

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

(4) The steel sheet is immersed in a treatment liquid in which fluorinated Zr, phosphoric acid, or phenol resin is dissolved, and subjected to cathodic electrolysis, followed by drying to form a Zr film, a phosphoric acid film, and a phenol resin film.

(5) The steel sheet is immersed in a treatment liquid in which phosphoric acid or phenol resin is dissolved, and subjected to cathodic electrolysis, followed by drying to form a phosphoric acid film or a phenol resin film.

(6) The steel sheet is immersed in a treatment liquid in which fluorinated Zr or phosphoric acid is dissolved, subjected to cathodic electrolysis, and then dried to form a Zr film or a phosphoric acid film.

(7) The steel sheet is immersed in a treatment liquid in which fluorinated Zr or a phenol resin is dissolved, and subjected to cathodic electrolysis, followed by drying to form a Zr film or a phenol resin film.

(8) The steel sheet is immersed in a treatment liquid in which fluorinated Zr, phosphoric acid, and citric acid are dissolved, and then dried to form a Zr film or a phosphoric acid film.

(9) The steel sheet is immersed in a treatment liquid in which fluorinated Zr, phosphoric acid, or phenol resin is dissolved, and then dried to form a Zr film, a phosphoric acid film, or a phenol resin film.

(10) The steel sheet is immersed in a treatment liquid in which phosphoric acid or a phenol resin is dissolved, and then dried to form a phosphoric acid film or a phenol resin film.

(11) The steel sheet is immersed in a treatment liquid in which fluorinated Zr or phosphoric acid is dissolved, and then dried to form a Zr film or a phosphoric acid film.

The performance evaluation of each of the evaluation items (A) to (H) shown below was performed on the test material subjected to the above treatment. A PET film having a thickness of 20 μm was bonded at 200 ° C to prepare a test material, and performance evaluations of the respective evaluation items (A) to (H) shown below were performed.

(A) Processability A PET film having a thickness of 20 μm was bonded to both sides of a test material at 200 ° C, and can be subjected to canning processing by press working and drawing processing in stages, and then formed into four stages (◎: pole Good, ○: good, △: It can be confirmed that 瑕疵, ╳: broken and cannot be processed).

(B) Weldability Using a wire seam melder, the current is changed to weld the test material under the condition of a wire speed of 80 m/min, based on the minimum current at which sufficient weld strength can be obtained, and dust and welding. The welding defects such as splashes begin to show the magnitude of the appropriate current range by the significant maximum current value, and the comprehensive judgment is made, and the weldability is further in four stages (◎: excellent, ○: good, △: inferior, ×: impossible) Soldering) for evaluation.

(C) Film Adhesiveness A PET film having a thickness of 20 μm was bonded to both sides of a test material at 200 ° C, and subjected to press drawing processing to prepare a can body, which was further subjected to a distillation treatment at 125 ° C for 30 minutes, and then the film was peeled off. Four stages (?: no peeling at all, ○: there was a slight peeling to the extent that there was no practical problem, Δ: some peeling, ×: a large part of peeling) was evaluated.

(D) Coating adhesion The epoxy phenol resin was applied to the test material, dried at 200 ° C for 30 min, and then divided into squares of deep iron at intervals of 1 mm, and then peeled off with a tape, and then peeled off to 4 The stage (?: no peeling at all, ○: there was a slight peeling to the extent that there was no practical problem, Δ: some peeling, ×: a large part of peeling) was evaluated.

(E) Corrosion resistance The epoxy phenol resin was coated on a test material, dried at 200 ° C for 30 min, and then crossed into a cross-cut of a deep iron, and then mixed in 1.5% citric acid-1.5% salt. The test liquid of the liquid composition was immersed at 45 ° C for 72 hours, and then peeled off after washing and drying, and the corrosion state under the coating film of the cross section and the corrosion state of the flat plate portion were in four stages (◎: Unable to see Corrosion under the coating film, ○: Corrosion under the coating film to the extent that there is no practical problem, △: corrosion under the fine coating film and slight corrosion of the flat portion can be seen, ×: severe coating can be seen Evaluation of under-film corrosion and flat plate corrosion).

(F) Rust resistance The test material was placed in an atmospheric environment of dry and wet repetitive (humidity 90%, 2 hr <=> humidity 40%, 2 hr) for 2 months, and then the rust condition was 4 stages (◎: no at all Rusting, ○: There is a slight rust, Δ: some rust, ×: a large part of rust, which is not practically problematic.

(G) Appearance: The test material was visually observed, and the unevenness of the Zr film, the phosphoric acid film, and the phenol resin film was changed to five stages (◎: ◎ there was no unevenness at all, ◎: there was no practical problem. Some unevenness, ○: some slight unevenness, △: unevenness, ×: significant unevenness were evaluated).

(H) The state of the metal Sn is observed by an optical microscope after the Ni plating is performed, and Sn is controlled, and then the residual state of the metal Sn after the molten tin treatment is controlled, and the state of the metal Sn is again in three stages (○: residual on the entire surface) , △: there was a portion that did not remain, and ×: no residue) was evaluated.

Among the film adhesion amounts, the Zr and P amounts were quantitatively analyzed by fluorescent X-rays, and the C adhesion amount was determined by the total carbon amount measurement method.

In the first to third tables, Examples 1 to 42 satisfy the conditions specified in the present invention. In contrast, Comparative Examples 1 to 5 were all out of the conditions specified in the present invention. Among all the evaluation items of the above (A) to (H), Examples 1 to 42 gave good evaluation results. In particular, in Examples No. 31 to No. 42, the Zr amount of the Zr film adhesion amount was 0.1 mg/m ² to 9 mg/m ² , and the P amount of the phosphoric acid film adhesion amount was 0.1 mg/m ² to 8 mg. /m ² , and the C amount of the phenol resin film adhesion amount is two or more kinds of phenol resin films of 0.1 mg/m ² to 8 mg/m ² . Therefore, excellent characteristics can be obtained particularly in appearance. In contrast, Comparative Examples 1 to 5 failed to obtain good evaluation results in all of the evaluation items (A) to (H) described above.

Industrial use possibility

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

Claims (10)

A container with a sheet, is formed on the steel sheet surface of the Ni containing ^{5mg / m 2 ~ 150mg / m} 2 of the Ni plating layer, or containing ^{5mg / m 2 ~ 150mg / Fe} -Ni alloy plating m Ni ² of; and the Ni a plating layer of 300 mg/m ² to 3000 mg/m ² is formed on the plating layer or the Fe-Ni alloy plating layer; a part or all of the Ni plating layer or the Fe-Ni alloy plating layer and a part of the Sn plating layer are treated by molten tin melting And alloyed, and a part of the metal Sn plating layer remains; and the metal Zr amount is 1 mg/m ² to 500 mg/m ² of the Zr film containing oxidized Zr, and the P content is 0.1 mg/m ² to 100 mg/m ² of the phosphoric acid A phosphoric acid film of Zr or phosphoric acid, and a film of two or more kinds of phenol resin films having a C content of 0.1 mg/m ² to 100 mg/m ² are individually coated on the above-mentioned Sn-plated alloy and residual metal Sn plating layer. A container steel sheet, is formed on the steel sheet surface of the Ni containing ^{5mg / m 2 ~ 150mg / m} 2 of the Ni plating layer, or containing ^{5mg / m 2 ~ 150mg / Fe} -Ni alloy plating m Ni ² of; and the Ni a plating layer of 300 mg/m ² to 3000 mg/m ² is formed on the plating layer or the Fe-Ni alloy plating layer; a part or all of the Ni plating layer or the Fe-Ni alloy plating layer and a part of the Sn plating layer are treated by molten tin melting And alloyed, and a part of the metal Sn plating layer remains; and the metal Zr amount is 1 mg/m ² to 15 mg/m ² of the Zr film containing oxidized Zr, and the amount of P is 0.1 mg/m ² to 15 mg/m ² A phosphoric acid film containing phosphoric acid Zr or phosphoric acid, and a film of two or more kinds of phenol resin films having a C content of 0.1 mg/m ² to 15 mg/m ² are individually coated on the above-mentioned Sn-plated Sn alloy and residual metal Sn plating layer. . A container with a sheet, is formed on the steel sheet surface of the Ni containing ^{5mg / m 2 ~ 150mg / m} 2 of the Ni plating layer, or containing ^{5mg / m 2 ~ 150mg / Fe} -Ni alloy plating m Ni ² of; and the Ni a plating layer of 300 mg/m ² to 3000 mg/m ² is formed on the plating layer or the Fe-Ni alloy plating layer; a part or all of the Ni plating layer or the Fe-Ni alloy plating layer and a part of the Sn plating layer are treated by molten tin melting And alloyed, and a part of the metal Sn plating layer remains; and the metal Zr amount is 1 mg/m ² to 9 mg/m ² of the Zr film containing oxidized Zr, and the amount of P is 0.1 mg/m ² to 8 mg/m ² A phosphoric acid film containing phosphoric acid Zr or phosphoric acid, and a film of two or more kinds of phenol resin films having a C content of 0.1 mg/m ² to 8 mg/m ² are individually coated on the above-mentioned Sn-plated Sn alloy and residual metal Sn plating layer. . Steel sheet for a container, is formed on the steel sheet surface ² ~ 5600mg / m Sn ² of the plating layer containing 560mg / m; the Sn-based plating layer portion of the tin melting treatment by alloying; and the metal Zr in an amount of 1mg / m ² ~500 mg/m ² of a Zr thin film containing Zr oxide and a phosphoric acid film containing a phosphoric acid Zr or a phosphoric acid Sn having a P content of 0.1 mg/m ² to 100 mg/m ² and a C amount of 0.1 mg/m ² to 100 mg/m ² Two or more kinds of the film of the phenol resin film are individually coated on the above-mentioned alloyed Sn plating layer. Steel sheet for a container, is formed on the steel sheet surface ² ~ 5600mg / m Sn ² of the plating layer containing 560mg / m; the Sn-based plating layer portion of the tin melting treatment by alloying; and the metal Zr in an amount of 1mg / m ² ~ 15mg / m ² of the Zr oxide film containing Zr, P in an amount of ^{0.1mg / m 2 ~ 15mg / m} 2 of a film containing phosphoric acid or phosphoric acid Sn, Zr, C in an amount of ^{0.1mg / m 2 ~ 15mg / m} 2 Two or more kinds of the film of the phenol resin film are individually coated on the above-mentioned alloyed Sn plating layer. A container steel sheet, the steel sheet coated with a surface containing ^{560mg / m 2 ~ 5600mg / m} Sn 2 of the plating layer; the train part of the Sn plating layer by tin melting alloying treatment; and the metal Zr in an amount of 1mg / m ² to 9 mg/m ² of Zr thin film containing Zr oxide and a phosphoric acid film containing phosphoric acid Zr or phosphoric acid having a P content of 0.1 mg/m ² to 8 mg/m ² , and the amount of C is 0.1 mg/m ² to 8 mg/m. ^Two or more kinds of the film of the phenol resin film of 2 are individually coated on the above-mentioned alloyed Sn plating layer. The steel sheet for a container according to any one of the first to sixth aspects of the invention is formed by a cathodic electrolytic treatment to form two or more of the Zr film, the phosphoric acid film, and the phenol resin film. The steel sheet for containers according to claim 7, wherein the cathodic electrolysis treatment is carried out in an acidic solution or an acidic solution containing citric acid. The steel sheet for a container according to any one of the first to sixth aspects of the invention is formed by forming a film of the Zr film, a phosphoric acid film, or a phenol resin film by cathodic electrolysis. The steel sheet for containers according to claim 9, wherein the cathodic electrolysis treatment is carried out in an acidic solution or an acidic solution containing citric acid.