WO2001004380A1 - Steel plate for laminated container, and method for producing can using the same and can - Google Patents

Abstract

A steel plate for a laminated container which has a surface treating layer containing one or more of Sn, Ni, Fe, Cr and a hydrated Cr oxide on at least one surface of a steel plate and, formed on the layer, a coating comprising an organic resin or an inorganic-organic resin comprising a phosphoric acid-based compound, an organic silicon compound, or Ti, Zr or a compound thereof and having a thickness of 1 to 500 nm exhibits excellent workability in manufacturing cans, and also is excellent in film adhesion, corrosion resistance and weldability. In particular, a steel plate for a laminated container which has, in the following order from the surface of the steel plate, a Ni-based plating layer in an amount of 5 to 500 mg/m2 in terms of metallic Ni, a Sn-based alloy layer and a metallic Sn plating layer in the form of islands in an amount of 100 to 1500 mg/m2, and on these metal-based layers, a coating layer comprising a phenol-based resin having a thickness of 1 to 500 nm and containing a phosphoric acid-based compound in an amount of 0.1 mg/m2 in terms of P is useful for applications involving welding.

Description

 Description Steel plate for laminated container, method for manufacturing can using it, and can

 The present invention provides, as a material for can manufacturing, a steel plate for a laminate container which is particularly excellent in drawing and ironing, weldability, corrosion resistance, and film adhesion, and a method for manufacturing a can using the same. And the resulting cans. Background art

 Metal containers used for beverages and food are roughly classified into two-piece and three-piece cans. Two-piece cans, such as DI cans, are drawn and ironed and then painted on the inner surface of the can and painted and printed on the outer surface of the can. For three-piece cans, the surface corresponding to the inner surface of the can is painted, the surface corresponding to the outer surface of the can is printed, and then the body of the can is welded. The coating process is indispensable for all types of cans before and after can making. Solvent-based or water-based paint is used for painting, and baking is performed afterwards. In this painting process, waste (waste solvent, etc.) derived from paint is discharged as industrial waste, and exhaust gas is emitted. (Mainly carbon dioxide) is released into the atmosphere. In recent years, efforts have been made to reduce these industrial wastes and exhaust gases for the purpose of preserving the global environment. Among them, the technology of laminating films as an alternative to painting has attracted attention and has spread rapidly.

To date, in the case of two-piece cans, there have been provided a large number of can manufacturing methods for laminating and manufacturing films and related inventions. For example, "Method of manufacturing drawn iron cans (Patent No. 1571783)", "Stretched iron cans (Patent No. 1670957)", "Method of manufacturing thinned deep drawn cans" (Japanese Unexamined Patent Publication No. 2-263523) and "Coated steel sheet for drawing and ironing can (Patent No. 1 601937)".

 Further, in the case of three-piece cans, there are described “film laminated steel strip for three-piece can and method for producing the same (JP-A-3-236954)”, “three-layer cans having a strip-shaped multilayer organic coating”. Steel sheet for one-piece cans (Japanese Patent Laid-Open No. 5-111980) and a method for producing a three-piece can striped laminate steel sheet (Japanese Patent Laid-Open No. 5-147181).

 In many cases, a chromate film that has been subjected to electrolytic chromate treatment is used for the steel sheet used as the base of the film of the laminating can. The chromate coating has a two-layer structure, and a hydrated oxidized Cr layer exists above the metallic Cr layer. Therefore, the laminate film (adhesive layer in the case of a film with an adhesive) secures adhesion to the steel sheet through the hydrated oxidized Cr layer of the chromatized film. The mechanism of this adhesion development is not known in detail, but it is a hydrogen bond between the hydroxyl group of the hydrated oxidized Cr and a functional group such as a carbonyl group or an ester group of the laminate film. It is said that.

 Further, as a film not subjected to electrolytic chromate treatment, a coated metal material having a film-forming undercoat film formed on the surface of a metal material and a method for producing the same (Japanese Patent Application Laid-Open No. H10-4611). No. 01 publication)].

 Although the above-mentioned invention certainly has the effect of greatly advancing the preservation of the global environment, on the other hand, in the beverage container market in recent years, the cost of materials such as PET bottles, bottles, and paper has been increasing. And competition for quality are intensifying, and even with the above-mentioned steel sheets for laminated containers, better can-making processability than before, especially film adhesion, processed film adhesion, and corrosion resistance , Weldability, etc. have been required.

In other words, in the case of a laminated steel sheet that secures adhesion to the laminated film through the hydrated oxidized Cr layer of the chromate film, the drawing or ironing is performed. Since the film was damaged due to severe processing, the film adhesion after processing was deteriorated and the corrosion resistance was also reduced, further improvement of the film adhesion at the processed part is required. .

 In addition, as a coating which is not subjected to electrolytic chromate treatment, a coated metal material having a film-forming undercoat formed on the surface of a metal material and a method for producing the same are disclosed in Japanese Patent Application Laid-Open No. H10-46101. However, due to severe processing by drawing and ironing, the film became a starting point of corrosion at the damaged part and the corrosion resistance of the processed part was significantly deteriorated, so further film adhesion in the severely processed part It is required to improve resistance and corrosion resistance. Summary of the Invention

 The present inventors have conducted intensive studies on a film using an inorganic substance or an organic resin as a new film instead of a chromate film, and as a result, a film using an inorganic substance or an organic resin was applied on the film. The present invention was found to form a very strong covalent bond with the laminating film to be obtained, and to obtain excellent can-making processability superior to conventional chromatized coatings, and led to the present invention. is there.

 That is, in the first aspect, the present invention provides the following.

 (1) At least one surface of the steel sheet has a surface treatment layer containing at least one of Sn, Ni, Fe, Cr, and hydrated Cr oxide, and a coating made of organic resin or inorganic organic resin Characterized by having a thickness of 1 to 500 nm.

(2) a steel sheet one surface to small, Sn, Ni, Fe, Cr, having a surface treatment layer containing one or more hydrated oxide Cr, thereon, and the P 0.1 mg / m ² or more on of-phosphate-based compound, La characterized and. 1 to 500 nm giving the child a coating made of an organic resin containing one or more of the Si 0.1 mg / m ² or more organic Gay containing compounds Mi Ne Sheet steel for containers. (3) At least one surface of the steel sheet has a surface treatment layer containing at least one of Sn, Ni, Fe, Cr, and hydrated Cr oxide, and P is O. lmg nom ² or more. It is characterized in that a coating of a phenolic resin containing at least one of an organic gay compound of 0.1 mg / m ² or more as a phosphoric acid compound and 0.1% or more as Si is applied for 1 to 500 runs. Steel plates for laminate containers.

(4) and the steel sheet one surface to small, Sn, Ni, Fe, Cr, having a surface treatment layer containing one or more hydrated oxides, thereon, a metal of 0.2~300 mg / m ² Ti Or a steel sheet for a laminate container, which is provided with a coating of 1 to 500 nm made of an inorganic organic resin containing at least one of Zr or a compound thereof.

(5) with the steel sheet one side less, Sn, Ni, Fe, Cr, having a surface treatment layer containing one or more hydrated oxide Cr, thereon, a metal of 0.2~300 mg / m ² Ti Or a steel sheet for a laminate container, which is provided with a coating of a phenolic resin containing at least one of Zr and one or more of these compounds in a thickness of 1 to 500 nm.

(6) with the steel sheet one side less, Sn, Ni, Fe, Cr, having a surface treatment layer containing one or more hydrated oxide Cr, thereon, a metal of 0.2 ~ 300 mg / m ² Ti or include one or more Zr or their compounds, further, as a P 0. lmg / m ² or more-phosphate-based compound, of the Si 0. lmg / m 2 or more organic Gay-containing compound A steel sheet for a laminate container, wherein a coating made of an organic resin containing at least one kind is applied in a thickness of 1 to 500 nm.

(7) to at least the steel sheet one surface has Sn, Ni, Fe, Cr, a surface treatment layer containing one or more hydrated oxides, thereon, a metal of 0.2~300 mg / m ² Ti or comprise one or more of Zr or their compounds, further, of the P 0. lmg / m ² or more-phosphate-based compound, 0. lmg / m 2 or more organic Gay-containing compound as a Si 1 For laminating containers, characterized in that a coating made of phenolic resin containing at least one or more species is applied in a thickness of 1 to 500 nm. steel sheet.

 (8) The laminate container according to (3), (5) or (7), wherein the phenolic resin content in the phenolic resin coating is 70% or more. For steel plate.

(9) In the above (1) to (8), the surface treatment layer characterized in that it contains at least one of Sn, Ni, Fe, Cr and hydrated oxidized Cr, wherein Sn is 80 to 80%. 6000mg ^/ / m ^2, N i is 10~ 800 mg / m ^2, Fe as a metal Ni is 10~800 mg / m ^2, Cr and hydrated Cr oxide as the metallic Fe as the metal Cr La Mi Ne one sampling container steel plate, wherein the Dearuko ² ~200 mg / m 2. Similarly, the present inventors have proposed that a steel-based plating layer, an island-shaped Sn-plated layer, and an upper layer of a chrome-based layer be provided on the steel sheet surface in order to achieve even higher weldability, film adhesion, and corrosion resistance. As a new film that replaces the gall film, we have intensively studied a film that uses organic resin. As a result, the coating using organic resin forms a very strong covalent bond with the laminating film applied on top of the coating, and exhibits excellent adhesion over conventional chromatographic coatings. Further, they have found that the presence of a chromate treatment layer can provide more excellent adhesion and corrosion resistance, and as a preferred embodiment of the present invention, have led to the invention of the second aspect.

 Thus, the present invention provides the following in a second aspect.

(10) and the steel sheet one surface to small, in order from a side close to the steel sheet, a metal Ni content 5 - 500 mg / m ² has a Ni-based plated layer has a Sn-based alloy layer, 100 ~ 1500 mg / it has a metal Sn plating layer m ^2, having a coating layer composed of 1 to 500 nm of Funino Lumpur based resin containing as a P thereon 0. lmg / m ² or more-phosphate compound A steel plate for a laminate container characterized by the following.

(11) and the steel sheet one surface to small, in order from a side close to the steel sheet has a Ni-based plated layer of 5~ 500 mg7m ² of metal Ni amount having a Sn-based alloy layer, 100 ~ 1500mg / m ² With an island-shaped metal Sn plating layer of A steel sheet for a laminate container, characterized by having a coating layer of a 1-500 nm phenolic resin containing lmg / m ² or more of a phosphoric acid compound.

(12) and the steel sheet one surface to small, in order from a side close to the steel sheet, a metal Ni amount having a Ni-based plated layer of 5 to 500 mg / m ^2, having a Sn-based alloy layer, 100 ~ 1500mgZm ² has the island-like metallic Sn plating layer, thereon, a metal Cr content, 4~40g Zm ² of grants chromate layer, further 0. 1 to 200 mg as a P thereon / A steel sheet for a laminate container, characterized in that it has a coating of 1 to 500 nm made of a phenolic resin containing m ² of a phosphoric acid compound.

(13) the at rather low in the steel sheet one side, in order from a side close to the steel sheet, a metal Ni amount having a Ni-based plated layer of 5 to 500 mg / m ^2, having a Sn-based alloy layer, 100 ~ 1500nig / m ² island-shaped metal Sn plating layer, and P on it

It includes 0. lmg / m ² or more-phosphate compounds, further, 1 to 500 nm of the full node on containing one or more Ti or Zr or their compounds of 0.2~ 300 mg / m ² by metal weight A steel sheet for a laminate container, characterized by having a coating layer made of a resin.

(14) least for a steel plate one side also, in order from a side close to the steel sheet, a metal Ni content 5 - 500 mg / m ² of having a Ni-based plated layer has a Sn-based alloy layer, 100 ~ 1500mgZm subjecting an island-shaped metal Sn plating layer ^2, thereon, a metal amount having a click Lome over coat layer of 4～40G Zm ^2, as a P thereon 0 .1-200 mg / m include ^{2-phosphate-based} compound, further having 1 to 500 nm a film consisting of full Nord resin containing one or more Ti, or Zr or a compound thereof of 0.2 ~ 300 mg / m ² by metal weight A steel sheet for laminated containers characterized by the following characteristics.

(15) The steel plate for a laminated welded can described in the above (11) to (14), wherein the area ratio of the island-shaped Sn is 40 to 95%. (16) The laminate container according to (12) or (14), wherein the chromate layer contains at least 2 mg / m ^{2 of} hydrated oxidized Cr in terms of the amount of metallic Cr. For steel plate.

 Further, according to the present invention, there is also provided a can-making method using these steel plates for a laminated container, and a can obtained by the method.

 (17) A can using a laminated steel sheet, characterized in that the steel sheet for a laminated container according to any one of (1) to (9) is made by a drawing or ironing process. Manufacturing method.

 (18) A method for producing a can using a laminated steel sheet, wherein the can is produced by a welding process using the laminated steel sheet according to (10) to (16).

 (19) A can made of a laminated steel sheet, which is manufactured by drawing or ironing using the steel sheet for a laminated container according to any one of (1) to (9).

 (20) A can made of a laminated steel sheet having a welded portion, using the laminated steel sheet for a laminate container according to any one of (10) to (16). BRIEF DESCRIPTION OF THE FIGURES

 Fig. 1 is a schematic sectional view of a steel sheet for a laminate container of the present invention.

 FIG. 2 is a schematic cross-sectional view of another steel plate for a laminate container of the present invention, and FIG. 3 is a schematic longitudinal sectional view of a laminate container of the present invention.

 FIG. 4 is a schematic cross-sectional view of another steel plate for a laminate container of the present invention, and FIG. 5 is a schematic cross-sectional view of still another steel plate for a laminate container of the present invention.

FIG. 6 is a schematic view of another laminate container of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION (First aspect)

 Hereinafter, the steel sheet for a laminated container according to the first aspect of the present invention will be described in detail.

 Original plate

 The original sheet used in the present invention is not particularly limited, and a steel sheet usually used as a container material is used. The production method and material of the original sheet are not particularly limited, and the original sheet is produced through a normal billet production process through hot rolling, pickling, cold rolling and the like.

 Surface treatment layer

 In the first aspect of the present invention, by providing a surface treatment layer containing Sn, Ni, Fe, Cr, and hydrated Cr to the original sheet, it is excellent in can workability, weldability, and corrosion resistance. Thus, a laminated container steel sheet having excellent film adhesion can be obtained.

 The method of applying a surface treatment layer containing Sn, Ni, Fe, Cr, and hydrated Cr oxide to the original sheet is not particularly limited, and examples thereof include an electroplating method, a vacuum evaporation method, and a sputtering method. Any known technique may be used, and heat treatment for providing a diffusion layer may be combined.

In the surface treatment layer containing one or more of Sn, Ni, Fe, Cr and hydrated oxidized Cr thus provided, Sn is 80 to 6000 mg / m ² as metallic Sn, and Ni is metallic Ni. 10~800 mg / m ^2, Fe is 10~800 mg / m ^2, Cr and hydrated Cr oxide as a metal Fe is correct preferred is ² ~ 200 mg / m 2 as a metal Cr Te

Sn layer

Sn exhibits excellent workability and weldability. In particular, when it is necessary to perform severe processing (drawing, ironing, etc.) to reduce the plate thickness to 1Z2 or less, and even 13 or less, the Sn layer has very excellent characteristics. It is suitable because it can be given. This effect is particularly noticeable when the Sn layer is used alone. However, it is also effective when combined with other plating in consideration of other characteristics. It is desirable that 80 nigZm ² or more of the metal Sn exhibit this effect. In order to ensure sufficient weldability, it is more desirable to provide ZOOmgZm ² or more, and in order to ensure sufficient workability, it is more desirable to provide lOOOOmgZm ² or more. , improvement on the effect of weldability is increased, the 6000Mg7m ² or more is because economically disadvantageous saturates its improving effect. Therefore, it is desirable that the amount of Sn attached is not more than 600 mg / m ² as metal Sn.

 Ni, FeS

Ni and Fe exert their effects on film adhesion, corrosion resistance, and weldability. To achieve this, Ni or Fe of lOmgZm ² or more as metal Ni or Fe must be adhered. Desirable. As the amount of Ni and Fe deposited increases, the excellent effects of Ni and Fe on improving film adhesion, corrosion resistance and weldability increase. However, when the amount exceeds 800 mg nom ² , the effect is saturated. Disadvantageously. Accordingly, Ni, deposition amount of Fe is LOmgZm ² or more as a metal Ni or Fe, arbitrary desired 800MgZm ² or less.

 Cr and hydrated oxide Cr layer

Further, Cr and hydrated oxidized Cr exhibiting excellent film adhesion and corrosion resistance are desirably ² to 200 mg / m ² as Cr metal. That is, when the amount of Cr and hydrated Cr oxide attached is less than 2 mg / m ² as metallic Cr, the adhesion is insufficient. Therefore, it is desirable that the amount of Cr and hydrated Cr oxide be 2 mgZm ² or more as Cr metal. As the amount of deposition of Cr and hydrated Cr oxide is increased, off I Lum adhesion, although the corrosion resistance improvement effect of increase, since it exceeds ² OOmg / m 2 and weldability tend to deteriorate, and water It is desirable that the amount of oxidized Cr be 200 mgZm ² or less as a metal.

Organic resin or inorganic single organic resin layer After providing a surface treatment layer containing at least one of Sn, Ni, Fe, Cr, and hydrated Cr oxide, the organic resin or the inorganic monoorganic resin as the essence of the present invention is provided. By adding an organic resin or inorganic monoorganic resin in combination with a surface treatment layer containing at least one of Sn, Ni, Fe, Cr, and hydrated oxidized Cr, steel sheets for laminated containers are more With excellent can processability, it can be particularly excellent in film adhesion, processed film adhesion and corrosion resistance.

 Organic resin layer

 As described above, the organic resin film provided in the present invention produces a covalent bond with a laminated film or an adhesive layer, and exhibits an effect of ensuring high adhesion. Examples of resins that can achieve this effect include epoxy resins, phenolic resins, urethane resins, vinyl resins, ester resins, and styrene resins. A phenolic resin is an example of a resin exhibiting performance. The phenolic resin can be produced by a conventional method. For example, it is produced by polycondensing a phenolic compound, a naphthol compound or a bisphenol with formaldehyde.

 The organic resin of the present invention exerts its effect even when mixed with various resins, but in order to exhibit the excellent properties of phenolic resin, the phenolic resin content should be 70% or more. It is desirable to do it.

 Inorganic-organic resin layer

 In addition, the inorganic compound contained in this resin has an effect of greatly improving film adhesion and corrosion resistance. Examples of the inorganic compound include a phosphoric acid compound, an organic gay compound, a sulfuric acid compound, a halogen compound, a chloric acid compound, a nitric acid compound, and the like. As a product that has an effect of improving corrosion resistance

, A phosphoric acid compound and an organic gay compound. Phosphoric acid compounds, organic gay compounds

 Examples of the phosphoric acid-based compound having these improving effects include phosphoric acid or a salt thereof, condensed phosphoric acid or a salt thereof, zirconium phosphate, and titanium phosphate. Examples of the salt include alkali metal salts such as ammonium salt, sodium salt and potassium salt.

 Examples of the organic gay compound include vinyl ethoxysilane, amino propyl triethoxy silane, melcapto propyl trimethoxy silane, melacryloxy propyl triethoxy silane, and α-methyl propyl triethoxy silane. Monoglycidoxyprovir trimethoxysilane and the like.

The presence of at least one of a phosphoric acid compound or an organic gay compound in the organic resin enables the film to exhibit high film adhesion and corrosion resistance. It is desirable that a phosphoric acid compound having a concentration of 0.1 mg / m ² or more or an organic gay compound having a concentration of 0.1 mg Zm ² or more as Si exists. However, if the content of a phosphoric acid compound or an organic gay compound in the resin is increased, it is disadvantageous economically, so that the content of the phosphoric acid compound or the organic gay compound in the resin is increased. Is preferably 200 mgZm ² or less as P or Si.

 Ti or Zr compound

Furthermore, in the present invention, by including Ti or Zr or one or more of these compounds in the inorganic-organic resin, more excellent film adhesion and corrosion resistance can be exhibited. The effect of the present invention is not lost even if Ti and Zr combine with P or Si in the coating. The content of Ti or Zr or a compound thereof contained in the inorganic organic resin is desirably 0.2 to 300 mg / m ² as Ti or Zr. If the content of Ti or Zr is less than 0.2 nig Zm ² , the effect of improving film adhesion and corrosion resistance is small, and if it exceeds 300 mg Zm ² , it is economically disadvantageous. The content of Ti or Zr or a compound thereof in the inorganic-organic resin is desirably 0.2 to 300 mg / m ² as Ti or Zr. The method for incorporating Ti or Zr or a compound thereof into an inorganic-organic resin is not particularly limited. This can be achieved by including a Ti compound or a Zr compound in the treatment solution described below, and immersing the steel sheet in the compound.

Although there are no particular restrictions on Ti compounds, Ti salts are desirable for practical and performance reasons. Examples of the Ti salt include titanium phosphate, titanium hydrofluoric acid and salts thereof such as lithium, sodium, and ammonium, titanium sulfate, titanyl sulfate, and the like.

 The Zr compound is not particularly limited, but a Zr salt is desirable from the viewpoint of practicality or performance. Examples of the Zr salt include zirconium phosphate, zirconium hydrofluoric acid and salts thereof such as lithium, sodium and ammonium, zirconium sulfate, zirconyl sulfate and zirconyl nitrate.

 Method of forming resin layer

 The method for applying the inorganic-organic resin described above is not particularly limited. For example, the above-mentioned organic resin (epoxy resin, phenol resin, urethane resin, vinyl resin, ester resin, styrene resin) and the above-mentioned phosphoric acid compound, organic resin It can be obtained by immersing in a treatment solution in which a gayne compound, a Ti compound, or a Zr compound is mixed, squeezing with a ringer roll or the like, and drying.

 Laminate foi Norem

The film for laminating is not particularly limited, and may be a known laminating film. For example, polyethylene, polycarbonate, polyester, and the like can be used. The thickness of the film is not particularly limited. Generally, a film with a thickness in the range of 5 to 40 m is used. The lamination method is also particularly limited. A method of heating and softening to laminate coating is suitable, but an adhesive may be used.

 Steel plate for laminated container

 FIG. 1 and FIG. 2 schematically show the steel sheet for a laminated container of the present invention obtained as described above.

 Fig. 1 shows an example of a laminated steel sheet having a Ni plating layer 2 formed on the surface of a steel sheet 1 and an organic resin layer 4 formed thereon. Fig. 2 shows another example, in which a steel plating layer 2 is formed on the surface of a steel sheet 1, a chromate plating layer 3 is formed thereon, and an inorganic-organic resin layer 4 is formed thereon. An example of a steel sheet for a laminated container formed with is shown below. Although the number of plating layers is one and two in FIGS. 1 and 2, the number and combination of the plating layers are not particularly limited. However, it is strongly preferred to include Sn plating for particularly severe forming processes.

 Laminated steel plate container

 FIG. 3 shows an example of a can using the steel sheet for a laminated container of the present invention. The laminated steel sheet container of the present invention can be applied to any of a two-piece can and a three-piece can, and is not limited to the example shown in FIG. A laminating film 5 is laminated and coated on the surface treatment layer and the organic resin layer or the inorganic organic resin layers 2 to 4 of the steel sheet for a laminate container shown in FIG. Using the steel sheet for laminate container thus obtained, a bottomed can 6 is formed by deep drawing as shown in FIG. The bottomed can 6 is subjected to net processing and flange processing as necessary, and a steel or A1 lid (not shown) is wound around to complete the sealed can.

 In FIG. 3, the laminated film 5 of the present invention is on the inner surface 7 of the can. Usually, a laminate film is also formed or painted on the outer surface of the can, but the constitution is not a problem in the present invention.

In the laminate container using the steel plate for a laminate container of the present invention, Even when subjected to severe forming such as drawing, the adhesion of the laminated film to the steel sheet is not impaired, and it is also excellent in corrosion resistance and weldability, and can be used as a beverage can and stored for a long time. However, there is no unpleasant smell or taste caused by organic matter in the drink inside.

 (Second side)

 Hereinafter, the second aspect, which is a preferred embodiment of the first aspect of the present invention, that is, a steel sheet for a laminate container having particularly excellent weldability will be described in detail.

 Original plate

 The original plate used may be the same as that described above.

 Plating layer

 The base sheet is provided with a Ni-based plating layer, a Sn-based alloy layer, and a Sn-plated layer in order from the side closer to the steel sheet, preferably a chromate layer, and an organic resin layer thereon. By providing a layer or an inorganic-organic resin layer, the second aspect of the present invention, a steel sheet for a laminated container, which is particularly excellent in weldability and excellent in film adhesion and corrosion resistance is provided.

 Ni-based plating

 Examples of the Ni-based plating applied to the original sheet include Ni plating, Fe—Ni alloy plating, and Νίdiffusion plating. Ni plating and Fe—Ni alloy plating are known electric plating. It may be performed by the plating method. Ni plating can be performed by performing a heat treatment at 600 to 1000 ° C. after Ni plating to provide a Ni diffusion layer. Further, even after the application of the Ni diffusion layer, temper rolling is performed without departing from the essence of the present invention.

The role of the Ni-based plating layer is to ensure the corrosion resistance of the steel sheet of the present invention by utilizing the excellent corrosion resistance of Ni metal itself. If the Ni plating amount is less than 5 mg / m ² , the excellent corrosion resistance of the Ni metal itself will not be exhibited, so the Ni plating amount must be 5 mgZm ² or more. Corrosion resistance when Ni plating increases However, if the amount of Ni plating exceeds 500 mg / m ² , the effect of the improvement is saturated, which is economically disadvantageous. Therefore, Ni deposition amount is 5 MGZ m ² or more, is regulated to 500 mg / m ² or less.

 Sn

 Next, Sn plating is applied to ensure weldability. Since Sn is a soft metal, when it is sandwiched between electrodes by seam welding, a mouth contact layer or a finole resin layer, which will be described later, is broken, and a good current-carrying area can be secured. Therefore, the steel sheet of the present invention ensures good welding (especially resistance welding). The method of plating Sn may be a known method such as electroplating of Sn, and is not particularly limited.

In order to exhibit excellent weldability, the amount of Sn must be 100 mg / m ² or more. This is because if the Sn plating amount is less than 100 mg / m ² , the high-speed weldability required for industrial production deteriorates, so the Sn plating amount is required to be 100 mgZm ² or more. Weldability of the steel sheet of the present invention is improved with Sn plating amount increases, the Sn plating weight exceeds 1500MgZm ^2, since the improving effect is saturated, more, Sn to plated is in economic unsaturated Profit. Therefore, Sn-plating amount is restricted to 100~ 1500mgZm ^2.

 Molten tin treatment (alloying, islanding)

Subsequent to the Sn plating, a molten tin treatment is performed to provide a Sn-based alloy layer and an island-shaped Sn plated layer thereon. There are two purposes for performing the molten tin treatment. One is to improve the corrosion resistance by alloying the previously deposited Ni-based plating layer with Sn, and the other is to form the island-shaped Sn and improve the high-temperature adhesion of the film. That is. In the vicinity of the weld, the temperature rises above the melting point of Sn, so that Sn liquefies and the film adhesion on Sn becomes extremely low. Therefore, in order to secure film adhesion even at high temperatures, Sn is formed into islands, and the surface of the high melting point Ni-based plating layer and the alloy layer of Sn are exposed. Need to be done.

 Therefore, in order to ensure film adhesion at high temperatures, the area ratio of the islanded Sn is regulated to 95% or less. If the Sn area ratio exceeds 95%, the Sn exposure becomes excessive and the film adhesion at high temperatures deteriorates. Therefore, the Sn area ratio must be 95% or less. If the area ratio of Sn is reduced, the effect of improving film adhesion at high temperatures increases, but if the area ratio of Sn is less than 40%, the excellent weldability of Sn metal deteriorates. Area ratio must be 40% or more.

 There is no particular restriction on the method of turning Sn into islands, and the steel sheet coated with Sn may be heated to a temperature equal to or higher than the melting point of Sn by electric heating or induction heating. At this time, the use of extremely low-concentration flux or water instead of the flux promotes island formation, so the flux concentration is controlled and the desired area ratio of island-like Sn Can be produced.

 Chromate

Subsequent to the Sn plating, it is desirable that a chromate layer be provided in order to exhibit more excellent film adhesion and corrosion resistance. Configuration hydrated Cr oxide of click Lome over coat layer or a hydrated Cr oxide and the metal or Ranaru comprises the deposition amount as a metal, an oxide hydrate Cr ² mgZm 2 or more at least, also, As the entire chromatographic layer, as metal

It needs to be 4 ~ 40mg / m ² . This is due to the fact that hydrated Cr oxide is indispensable to ensure excellent adhesion. The adhesion amount of hydrated Cr oxide is 2 mg / m ² or more for metallic Cr, and the effect of improving adhesion is exhibited. In addition, in order to ensure excellent corrosion resistance, it is desirable that a chromate layer of 4 mg / m ² or more be present as a metal. This is because if the chromate layer is less than 4 mg / m ² , excellent corrosion resistance of Cr will not be exhibited, and it will be difficult to secure sufficient corrosion resistance.

As the amount of chromate attached increases, the effect of improving corrosion resistance also increases. On the other hand, since the chromate layer is an electrically insulating film, when the amount of metallic Cr exceeds 40 mg / m ² , the weldability rapidly deteriorates. Therefore, the chromate layer is desirably 4 to 40 mg / m ² as metallic Cr.

 The method for providing the chromate layer is not particularly limited.For example, the electrolytic treatment or the immersion treatment may be performed in a Cr acid solution, a Cr acid monosulfuric acid solution, or a Cr acid-hydrofluoric acid solution. .

 Phenolic resin coating

After applying a Sn plating layer or click Lome over coat layer, although the film is 1 to 500 nm imparts consisting Fueno Lumpur resin containing 0.1 mg / m ² or more-phosphate-based compound is P, This layer may be the same as described above.

 Laminate Fai Norem

 This may be a laminate film similar to that described above.

 Steel plate for laminated container

 Figs. 4 and 5 schematically show examples of the steel sheet for a laminated container according to the second aspect of the present invention manufactured as described above. In FIG. 4, 11 indicates a base steel sheet, 12 indicates a metal Ni-based plating layer, 13 indicates a Sn-based alloy layer, 15 indicates a metal Sn plating layer, and 16 indicates an organic resin layer. In FIG. 5, 11 is a base steel sheet, 12 is a Ni-based metal plating layer, 13 is a Sn-based alloy layer, 14 is an island-shaped metal Sn plating layer, 15 is a mouth mate layer, and 16 is an inorganic-organic layer. 3 shows a resin layer. After laminating film 17 is laminated and coated on these organic resin layers or inorganic mono-organic resin layers 16, cans are manufactured.

The surface treatment and lamination of this steel sheet for a laminating container including the metal Ni plating layer 12, the Sn alloy layer 13, the metal Sn plating layer 15, the organic resin layer or the inorganic-organic resin layer 16 The first film side was developed especially for use inside containers (beverage cans). Therefore, the surface printing layer or the like may be arbitrarily formed on the opposite side. Manufacture of laminated containers

 Referring to FIG. 6, an example of a can manufactured by welding using a steel plate for a laminate container as shown in FIG. 4 or FIG. 5 is shown. Of course, the container according to the second aspect of the present invention is not limited to this.

 After laminating the laminated film on the organic resin layer or inorganic organic resin layer of the laminated steel plate by a known method, it is formed into a predetermined shape for a can. After the cutting process, the obtained laminated steel sheet for can 18 is formed into a cylindrical shape, and the edge 19 of the cylindrical portion is welded by a known welding process, preferably by resistance welding. In addition, the space between the thus-formed cylindrical can and the lid is usually sealed through a sealing window.

Example

 Examples of the present invention and comparative examples are described below, and the results are shown in the table.

 Example 1

 A surface treatment layer was provided on the steel sheet by using the following treatment methods (1) to (7).

 (Treatment method 1)

 After cold rolling, the annealed and pressurized original plate is plated with Sn using a frost bath, and then electrolytically treated in a chromic acid / monosulfuric acid solution as necessary, and then Cr or hydrated Cr is oxidized. Was given.

 (Treatment method 2)

 After cold rolling, the annealed and pressure-regulated original plate is subjected to Ni plating using a hot water bath, and then electrolytically treated in a chromic acid monosulfuric acid solution as necessary, followed by Cr or hydrated oxidation Cr was added.

 (Treatment method 3)

After cold rolling, Ni plating is performed using a hot water bath to form a Ni diffusion layer during annealing, and then, if necessary, in a chromic acid monosulfuric acid solution. Solution treatment was performed or hydrated oxidation Cr was added.

 (Treatment method 4)

 After cold rolling, the annealed and pressure-regulated original sheet is subjected to Fe plating using a sulfuric acid-hydrochloric acid bath, and then subjected to electrolytic treatment in chromic acid-monosulfuric acid solution or hydration if necessary. Oxidized Cr was applied.

 (Treatment method 5)

 After cold rolling, the annealed and pressure-regulated original plate was subjected to electrolytic treatment in a chromate monosulfuric acid solution to give Cr or hydrated oxidized Cr.

 (Treatment method 6)

 After cold rolling, the annealed and pressure-regulated base plate is coated with a Fe--Ni alloy using a sulfuric acid-hydrochloric acid bath, and then subjected to Sn plating using a ferrostan bath, followed by heat treatment to obtain Sn plating The layer was partially alloyed, and then subjected to electrolytic treatment in a chromic acid / monosulfuric acid solution as needed to give Cr or hydrated Cr oxide.

 (Treatment method 7)

 After cold rolling, the annealed and pressure-regulated original sheet is coated with Sn-Ni alloy using a sulfuric acid-hydrochloric acid bath, and then electrolytically treated or hydrated in a chromic acid-sulfuric acid solution if necessary. Cr oxide was applied.

 After the surface treatment layer was applied by the above-described treatment, a film composed of an inorganic-organic resin was applied by the following treatment methods (8) to (13).

 (Treatment method 8)

 The steel sheet was immersed in a treatment solution in which a vinyl resin, phosphoric acid, and, if necessary, titanium ammonium phosphate were dissolved, dried, and a coating made of an inorganic-organic resin was applied. .

 (Treatment method 9)

The steel sheet is immersed in a treatment solution in which urethane resin, monopropyl triethoxysilane and, if necessary, zirconium sulfate are dissolved, and then dried. A coating composed of an inorganic-organic resin was provided.

 (Treatment method 10)

 The above steel sheet is immersed in a treatment solution in which 85% phenol resin, 15% epoxy resin, sodium phosphate and, if necessary, titanium sulfate or zirconium sulfate are dissolved, dried, and made of inorganic-organic resin. A coating was applied.

 (Treatment method 1 1)

 The steel sheet was immersed in a treatment solution in which a phenol resin and titanium fluoride were dissolved, and then dried to form a coating made of an inorganic-organic resin.

 (Treatment method 12)

 The steel plate was immersed in a treatment solution in which 85% phenol resin and 15% epoxy resin were dissolved, and then dried to form a coating made of an organic resin.

 With respect to the above treated materials, a 20 nm thick polyethylene film was laminated at 200 ° C to prepare test materials, and the performance of each of the following items (A) to (D) was evaluated.

 (A) Formability

 Normal butyl stearate is applied to the test material as a lubricant, a cup is punched out at ø140 mm, and drawing and ironing are performed stepwise at a drawing ratio of 2.1 (hereinafter referred to as “drawing and ironing”). The formability was evaluated on a 4-point scale (◎: very good, Δ: good, △: flaws recognized, X: broken and unworkable).

 (B) Weldability

Welding is performed using the wire seam weldability at a welding wire speed of 80 mZ min and the current is changed, and the minimum current value and dust and welding spatter that provide sufficient welding strength are obtained. Judging comprehensively from the appropriate current range consisting of the maximum current value at which welding defects begin to stand out, there are four levels (◎: very wide, 〇: good, Δ: poor, X: not weldable) The weldability was evaluated.

 (C) Film adhesion

Normal butyl stearate is applied as a lubricant to the test piece, punched out at ø140 mm, and retorted at 125 ° C for 30 min on a test material that has been drawn and ironed at a drawing ratio of 2.1. Then, the film separation condition is evaluated in four stages (◎ _: no separation, 〇 _: very slight peeling that is practically acceptable, Δ: slight peeling, X: most peeling) did.

 (D) Corrosion resistance

Normal butyl stearate is applied to the test material as a lubricant, punched out at ø140mm, squeezed and ironed at a squeezing ratio of 2.1, and a can is made. Fill the test solution consisting of the mixed solution, attach the lid, leave it in a constant temperature room at 55 ° C for 1 month, and evaluate the corrosion state of the inner surface of the can in 4 stages. (◎ _{: No} corrosion, 〇: Practical problem The evaluation was evaluated as follows: slight slight corrosion was observed, Δ: minute corrosion was observed, and X: severe corrosion was observed.

Table 1 shows the results. As shown in Table 1, it is clear that the laminated container steel sheet manufactured by this patent and having excellent workability in lamination has excellent formability, weldability, film adhesion, and corrosion resistance. is there.

Example 2

 After applying a surface treatment layer on a steel sheet using the following treatment methods (21) to (22), a phenolic resin was applied by treatment method (23).

 ① Test material preparation method

 (Processing method 21)

 After cold rolling, the annealed and pressurized base plate is electroplated with Fe-Ni alloy, and Sn is plated using a Plostan bath, resulting in low-concentration flux. Then, heat treatment was carried out to produce island-shaped Sn, and then, if necessary, electrolytic treatment was carried out in a chromic acid monosulfuric acid solution to give a chromate layer.

 (Treatment method 22)

 After cold rolling, Ni plating is applied by electroplating, annealing, pressure regulation, Sn plating using a halogen bath, and heat treatment to produce island-shaped Sn, and then, if necessary. Electrolytic treatment was performed in a chromate-monosulfuric acid solution to give a chromate layer.

 (Treatment method 23)

 The steel sheet was immersed in a treatment solution in which a phenolic resin, phosphoric acid, and, if necessary, titanium ammonium phosphate were dissolved, and then dried to give a phenolic resin.

 ② Test material evaluation method

 With respect to the above treated materials, a 20 nm thick polyethylene film was laminated at 200 ° C to prepare test materials, and the following items were evaluated for performance.

 (A) Weldability

 It was the same as the weldability test in Example 1.

 (B ') Film adhesion

10% elongation test material at 125 ° C, 30 min retorting And evaluated the film peeling status in four stages (◎ _: no peeling at all, Δ: very slight peeling at practically no problem, △: slight peeling, X: peeling at most) did.

 (D ') Corrosion resistance

 As shown in Fig. 6, the joints of the cylinders were welded, A1 E0E (easy open end) made of A1 was attached to one side, and a welding can was prepared. And put the lid on, leave it in a constant temperature room at 55 ° C for one month, and check the corrosion condition of the inner surface of the can in 4 stages Severe corrosion, Δ: minute corrosion, X: severe corrosion).

 (E) High temperature film adhesion

 The test material is filled with a crosscut that reaches the depth of the steel, heated rapidly to 250 ° C, and air at 5 atm is blown into the center of the crosscut to check the separation of the film. The evaluation was made in four steps (◎: no peeling at all, 〇: very slight peeling of practically no problem, Δ: slight peeling, X: peeling mostly).

Table 2 shows the results. As shown in Table 2, it is clear that the steel sheet for a laminated container manufactured by the present invention and having excellent workability in lamination has excellent formability, weldability, film adhesion, and corrosion resistance. is there.

Table 2 Examples and comparative examples

Note) Underline is outside of the present invention.

Industrial applications

 The steel sheet for a laminated container of the present invention and the container using the same have excellent adaptability to severe canning, and are excellent in film adhesion, corrosion resistance, and weldability. Particularly useful as beverage containers (cans) and their materials.

Claims

The scope of the claims 1. At least one surface of the steel sheet has a surface treatment layer containing at least one of Sn, Ni, Fe, Cr and hydrated oxidized Cr, on which a coating made of organic resin or inorganic organic resin is applied A steel sheet for laminated containers with excellent can-making properties characterized by a thickness of 1 to 500 nm. 2. coating comprising said organic resin is composed of an organic resin containing one or more of the P O. lmgZm ² or more-phosphate-based compound, as a Si O. lmgZm ² or more organic Gay-containing compound The steel sheet for a laminate container according to claim 1, which is a coating. 3. A phenolic resin in which the coating made of the organic resin contains at least one of O. lmgZm ² or more of a phosphoric acid compound as P and Si as at least 0.1 mg / m ² of an organic gay compound. The steel sheet for a laminate container according to claim 1, which is a coating comprising: 4. The coating according to claim 1, wherein the coating composed of an inorganic-organic resin is a coating composed of an inorganic-organic resin containing one or more of Ti or Zr or a compound thereof in a metal amount of 0.2 to 300 mg / m ² . Steel plates for laminate containers. 5. The coating comprising an inorganic-organic resin is a coating comprising a phenolic resin containing at least one of Ti or Zr or a compound thereof at a metal amount of 0.2 to 300 mg / m ^2. Steel plate for laminating containers. 6. The coating composed of the inorganic-organic resin contains one or more of Ti or Zr or a compound thereof in a metal amount of 0.2 to 300 mg / m ² , and further has a P of 0.1 mg / m ² or more. 2. A coating for a laminate container according to claim 1, wherein the coating is made of an inorganic mono-organic resin containing one or more organic silicon compounds of 0.1 mg / m ² or more as Si. steel sheet. 7. The coating consisting of inorganic-organic resin is 0.2-300 mg in metal amount / m ² of Ti or Zr or one or more of these compounds, and further, P is 0.1 mg / m ² or more of a phosphoric acid compound, and Si is 0.1 mg / m ² or more. The steel sheet for a laminate container according to claim 1, which is a coating made of a phenolic resin containing at least one kind of an organic gay compound.  8. The steel sheet for a laminate container according to claim 3, 5 or 7, wherein the content of the phenolic resin in the coating made of the phenolic resin is 70% or more. 9. The surface treatment layer containing one or more of Sn, Ni, Fe, Cr and hydrated oxidized Cr is as follows: Sn is 80 to 6000 mg / m ² as metallic Sn, and Ni is 10 to 800 mg as metallic Ni. 9.The product according to claim 1, wherein mg / m ² and Fe are 10 to 800 mg / m ² as metal Fe, and Cr and hydrated oxide are 2 to 200 mg / m ² as metal Cr. Steel plate for laminate containers with excellent can processability. 10. the steel sheet one surface to small, in order from a side close to the steel sheet, a metal Ni amount having a Ni-based plated layer of 5 to 500 mg / m ^2, having a Sn-based alloy layer, 100 ~ 1500 mg / m having a ^second metal Sn plating layer has a coating layer made of. 1 to 500 nm of the full E Roh Lumpur based resin containing as a P thereon 0. lmg / m ² or more-phosphate compound A steel sheet for a laminate container, characterized in that:  11. The steel sheet for a laminate container according to claim 10, wherein the metal Sn plating layer is an island-shaped metal Sn plating layer. 12. On the island-shaped metal Sn plating layer, a chroma layer having a metal Cr content of 4 to 40 g Zm ² is provided, and the phenol resin coating layer is formed on the metal layer. 12. The laminate according to claim 11, wherein the phenolic resin coating layer is a coating composed of a phenolic resin containing a phosphate compound of 0.1 to 200 rag / m ² as Ρ. Steel plate for containers. 13. The full Nord resin coating layer, and a P comprises 0. lmgZm ² or more-phosphate compounds, further, a metal of 0.2~300 mg / m ² of Ti or Zr or a compound thereof The steel sheet for a laminate container according to claim 11, which is a coating layer made of a phenolic resin containing at least one kind. 14. The Fuyunoru resin coating layer, in addition to the-phosphate-based compound, a phenol-based resin comprising one or more Ti, or Zr or a compound thereof of 0.2 to 300 mg / m ² by metal weight 13. The steel sheet for a laminate container according to claim 12, which is a coating comprising:  15. The steel sheet for a laminate container according to claim 11, wherein an area ratio of the island-like Sn in the island-like metal Sn plating layer is 40 to 95%. 16. The steel sheet for a laminate container according to claim 12, wherein the chromate layer contains at least 2 mg / m ^{2 of} hydrated oxidized Cr in terms of the amount of metallic Cr. 17. A method for producing a can using a laminated steel sheet, wherein the can is produced by a drawing or ironing process using the laminated steel sheet according to any one of claims 1 to 9.  18. A method for producing a can using a laminated steel sheet, wherein the can is produced by a welding process using the laminated sheet steel sheet according to claim 10.  19. A laminated steel sheet can manufactured by using the steel sheet for laminated containers according to claim 1 by drawing or ironing.  20. A laminated steel sheet can having a welded portion, using the laminated container steel sheet according to any one of claims 1 to 9.