JP2000234181A - Steel sheet for laminated vessel excellent in can making workability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart excellent drawing and ironing workability, weldability, corrosion resistance and film adhesion to the steel sheet by providing the surface of steel with a surface treated layer contg. one or more kinds among Sn, Ni, Fe, Cr and hydrated Cr oxide and forming a resin coating film of a specified thickness thereon. SOLUTION: At least one side of a steel sheet is provided with a surface treated layer contg. one or more kinds among Sn, Ni, Fe, Cr and hydrated Cr oxide. The surface is applied with a coating film composed of an organic resin or an inorganic-organic resin to a thickness of 1 to 500 nm. As the organic resin in the coating film, a phenol resin contg. one or more kinds of a phosphoric compd. of >=0.1 mg/m2 as P and an organosilicic compd. of >=0.1 mg/m2 as Si are preferable. The inorganic matter in the inorganic-organic resin is preferably composed of Ti, Zr or their compds. of 0.2 to 300 mg/m2 by metallic quantity. Moreover, the content of the phenol resin in the resin coating film is preferably controlled to >=70%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a steel plate for a laminated container which is excellent in draw ironing, weldability, corrosion resistance and film adhesion, as a material for can processing.

[0002]

2. Description of the Related Art Metal containers used for beverages and foods have two types.
It is roughly divided into a piece can and a three piece can. After drawing and ironing, a two-piece can represented by a DI can is painted on the inner surface of the can and painted and printed on the outer surface of the can. 3
In the piece can, the surface corresponding to the inner surface of the can is painted, and the surface corresponding to the outer surface of the can is printed, and then the body of the can is welded. In any of the can types, a painting step is an essential step before and after can making. Solvent-based or water-based paints are used for painting, and then baking is performed. In this painting process, waste (waste solvents, etc.) resulting from the paint is discharged as industrial waste, and exhaust gas (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, a technique of laminating a film as an alternative to painting has attracted attention and has rapidly spread.

Hitherto, in the case of two-piece cans, there have been provided a large number of can manufacturing methods for laminating a film and making cans and related inventions. For example, "a method for producing a drawn ironing can (Patent No. 1571783)", "a drawn ironing can (patent No. 1670957)", a "method for producing a thinned deep drawn can (Japanese Patent Application Laid-Open No. 2-263523)",
"Coated steel sheet for drawing and ironing can (Patent No. 1601937)
No.) ”. In a three-piece can,
"Film-laminated steel strip for three-piece cans and method for producing the same (JP-A-3-236954)", "Steel sheet for three-piece cans having a stripe-shaped multilayer organic coating (JP-A-5-111979)", "3-piece" Method for manufacturing can striped laminated steel sheet (Japanese Patent Laid-Open No. 147181/1993)
Publication).

In many cases, a steel plate used as a base material of a film of a laminated can uses a chromate film subjected to electrolytic chromate treatment. The chromate film has a two-layer structure, and a hydrated chromium oxide layer is present on the metal Cr layer. Therefore, the laminate film (the adhesive layer in the case of a film with an adhesive) secures the adhesion to the steel sheet via the hydrated chromium oxide layer of the chromate film. Although the mechanism of this adhesion development has not been clarified in detail, it is said that the mechanism is a hydrogen bond between a hydroxyl group of the hydrated oxidized Cr and a functional group such as a carbonyl group or an ester group of the laminate film. Further, as a film not subjected to the electrolytic chromate treatment, there may be mentioned "a coated metal material in which a base film for film lamination is formed on the surface of a metal material and a method for producing the same (Japanese Patent Laid-Open No. 10-46101)".

[0005]

The above-mentioned invention certainly has the effect of greatly advancing the preservation of the global environment, but on the other hand, in recent years, in the beverage container market, PET bottles, bottles, papers and the like have been obtained. Cost and quality competition with raw materials are intensifying, and even for the above-mentioned steel sheets for laminated containers, more excellent can-making processability than before, especially film adhesion,
Processed film adhesion, corrosion resistance, etc. have been required.

[0006]

Means for Solving the Problems The present inventors have intensively studied a film using an inorganic substance or an organic resin as a new film instead of a chromate film. The present invention was found to form a very strong covalent bond with the laminated film applied to the upper layer, and to obtain excellent can-making workability more than that of the conventional chromate film. That is, the present invention provides: (1) Sn, Ni, Fe, C
r, having a surface treatment layer containing at least one hydrated oxidized Cr,
A steel sheet for a laminated container having excellent workability in can making, characterized in that a coating made of an organic resin is applied thereon in a thickness of 1 to 500 nm.

(2) Sn, N on at least one side of the steel plate
i, Fe, Cr, a surface treatment layer containing at least one kind of hydrated Cr oxide, on which a coating made of an inorganic-organic resin is applied in a thickness of 1 to 500 nm to provide a workability in can making. Excellent steel sheet for laminated containers. (3) Sn, Ni, Fe, C on at least one side of the steel plate
r, having a surface treatment layer containing at least one hydrated oxidized Cr,
On top of this, a coating made of an organic resin containing at least 0.1 mg / m ² of a phosphoric acid compound as P and at least 0.1 mg / m ² of an organosilicon compound as Si is 1 to 50.
A steel sheet for a laminate container excellent in can workability, characterized in that it is provided with 0 nm.

(4) Sn, N on at least one side of the steel plate
i, Fe, Cr, having a surface treatment layer containing one or more hydrated oxide Cr, thereon, 0.1 mg / m ² or more phosphoric acid compound as P, 0.1mg / m ² as a Si A steel sheet for a laminate container having excellent workability in can making, characterized in that a coating made of a phenolic resin containing at least one of the above organosilicon compounds is applied in a thickness of 1 to 500 nm.

(5) Sn, N on at least one side of the steel plate
i, Fe, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and a metal amount of 0.2 to 300 mg /
laminated containers for steel sheet having excellent can-processability was characterized by 1~500nm imparting coating of organic resin - inorganic comprising one or more Ti, or Zr or a compound thereof in m ^2.

(6) At least Sn, N
i, Fe, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and a metal amount of 0.2 to 300 mg /
1 to 500 nm of a phenolic resin containing m ² of Ti or Zr or one or more of these compounds.
A steel sheet for laminated containers that is excellent in workability for cans, characterized by being imparted.

(7) At least Sn, N on one side of the steel plate
i, Fe, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and a metal amount of 0.2 to 300 mg /
comprise one or more of Ti or Zr or a compound thereof in m ^2, and more, 0.1 mg / m ² or more phosphoric acid compound as P, one of 0.1 mg / m ² or more organic silicon compounds as Si A coating made of an organic resin containing
A steel sheet for a laminated container having excellent workability in can-making, characterized by being provided with a thickness of 500 nm.

(8) Sn, N on at least one side of the steel plate
i, Fe, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and a metal amount of 0.2 to 300 mg /
comprise one or more of Ti or Zr or a compound thereof in m ^2, and more, 0.1 mg / m ² or more phosphoric acid compound as P, one of 0.1 mg / m ² or more organic silicon compounds as Si A steel sheet for a laminated container having excellent workability in can making, characterized in that a coating comprising a phenolic resin containing the above is applied in a thickness of 1 to 500 nm. (9) In the above (4), (6), and (8), the phenolic resin content in the phenolic resin coating is 70%.
A steel sheet for a laminated container excellent in workability in can making, characterized by the above.

(10) In the above (1) to (8),
The surface treatment layer characterized by containing at least one of Sn, Ni, Fe, Cr and hydrated oxidized Cr, wherein Sn is 80 to 6000 mg / m ² as metal Sn and Ni is 10 as metal Ni
８００800 mg / m ² , Fe is 10 to 80 as metal Fe
0 mg / m ^2, Cr and hydrated Cr oxide is in the laminated container steel sheet excellent in can-processability was characterized by a 2 to 200 mg / m ² as metallic Cr.

Hereinafter, a steel sheet for a laminate container having excellent workability in can making, which is an effect of the present invention, will be described in detail.
The original plate used in the present invention is not particularly limited, and a steel plate usually used as a container material is used. The production method, material, and the like of the original sheet are not particularly limited, and the original sheet is produced through the steps of hot rolling, pickling, cold rolling, and the like from a normal slab production step. Sn, Ni,
There is no particular limitation on the method of providing the surface treatment layer containing Fe, Cr, and hydrated Cr oxide. For example, a known technique such as an electroplating method, a vacuum evaporation method, or a sputtering method may be used. You may combine the heat processing for giving.

The Sn, Ni, Fe, C thus added
r, in the surface treatment layer containing at least one kind of hydrated oxidized Cr, Sn is 80 to 6000 mg / m ² as metal Sn;
Ni is preferably 10 to 800 mg / m ² as metal Ni, Fe is preferably 10 to 800 mg / m ² as metal Fe, and Cr and hydrated Cr oxide are preferably ² to 200 mg / m ² as metal Cr.

Sn exhibits excellent workability and weldability.
This effect appears only when the metal Sn is 80 mg / m ^2.
The above is desirable. 20 to ensure sufficient weldability
0 mg / m ² or more, in order to ensure sufficient workability,
It is more desirable to give 1000 mg / m ² or more.
With an increase in the amount of adhered n, the effect of improving the excellent workability and weldability of Sn increases, but if the amount is 6000 mg / m ² or more, the effect is saturated, which is economically disadvantageous. Therefore,
The amount of Sn deposited is desirably 6000 mg / m ² or less as metal Sn.

Ni and Fe represent film adhesion, corrosion resistance,
It exerts its effect on weldability, and for that, Ni or F of 10 mg / m ² or more as metal Ni or Fe
It is desirable that e is attached. As the amounts of Ni and Fe attached increase, the effects of improving the film adhesion, corrosion resistance, and weldability of Ni and Fe increase, but 800 mg / m2.
^If it is ² or more, the improvement effect is saturated, which is economically disadvantageous. Therefore, it is desirable that the amount of Ni or Fe deposited is 10 mg / m ² or more and 800 mg / m ² or less as metal Ni or Fe.

Further, Cr exhibiting excellent film adhesion and corrosion resistance and hydrated Cr oxide are 2 to 20 as metallic Cr.
0 mg / m ² is desirable. That is, Cr and hydrated Cr oxide
Is inadequate in terms of adhesiveness, in which the amount of adhering is less than ² mg / m ² as metallic Cr. Therefore, it is desirable that the adhesion amount of Cr and hydrated Cr oxide be 2 mg / m ² or more as metal Cr.
As the amount of Cr and the hydrated Cr oxide increases, the effect of improving film adhesion and corrosion resistance increases, but 200 mg /
From that weldability exceeds m ² tend to deteriorate, C
r and the amount of hydrated oxidized Cr are 200 m as metal Cr.
g / m ² or less. Sn, Ni, Fe,
After applying a surface treatment layer containing at least one of Cr and hydrated oxidized Cr, the organic resin or the inorganic-organic resin as the essence of the present invention is applied.

As described above, the organic resin film provided in the present invention produces a covalent bond with a film or an adhesive layer to be laminated, and exhibits an effect of securing high adhesion. Epoxy resins,
Phenol-based resins, urethane-based resins, vinyl-based resins, ester-based resins, styrene-based resins and the like can be mentioned, and phenol-based resins are exemplified as resins exhibiting particularly excellent performance. Phenolic resins can be manufactured in the usual way,
For example, it is produced by polycondensing a phenol compound, a naphthol compound or a bisphenol with formaldehyde.

The organic resin of the present invention exhibits its effect even when mixed with various resins, but in order to exhibit the excellent properties of the phenolic resin, it is necessary that the phenolic resin content is 70% or more. Is desirable. In addition, the inorganic compound contained in the resin has an effect of greatly improving film adhesion and corrosion resistance. Examples of the inorganic compound include a phosphoric acid compound, an organosilicon compound, a sulfuric acid compound, a halogen compound, a chloric acid compound, and a nitric acid compound. Examples include phosphoric acid compounds and organosilicon 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. As salts, ammonium salts, sodium salts,
And alkali metal salts such as potassium salts. Examples of the organosilicon compound include vinylethoxysilane, aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, meracryloxypropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

The presence of at least one of a phosphoric acid compound and an organosilicon compound in the organic resin exhibits high film adhesion and high corrosion resistance. It is desirable that a phosphoric acid compound of 1 mg / m ² or more, or an organic silicon compound of 0.1 mg / m ² or more as Si exists. However, if the content of the phosphoric acid compound or the organosilicon compound in the resin is increased, it is disadvantageous economically. Therefore, the content of the phosphoric acid compound or the organosilicon compound in the resin is P
Alternatively, the content of Si is preferably 200 mg / m ² or less.

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 0.1 or less as Ti or Zr.
A range of ² to 300 mg / m ² is desirable. When the content of Ti or Zr is less than 0.2 mg / m ² , the effect of improving film adhesion and corrosion resistance is small, and when the content exceeds 300 mg / m ² , it is economically disadvantageous. The content of Ti or Zr or a compound thereof 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 the inorganic-organic resin is not particularly limited.
This can be achieved by including a Ti compound or a Zr compound in a treatment liquid described below and immersing the steel sheet in the Ti compound or the Zr compound. T
The i-compound is not particularly limited, but a Ti salt is desirable from a practical or performance standpoint. 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 a practical or performance standpoint. 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. The method for providing the above-mentioned inorganic-organic resin is not particularly limited. For example, the above-mentioned organic resins (epoxy resin, phenol resin, urethane resin, vinyl resin, ester resin, styrene resin)
And the above-mentioned phosphoric acid compound, organosilicon compound or T
It can be obtained by immersing in a treatment liquid in which the i compound and the Zr compound are mixed, squeezing with a ringer roll or the like, and drying.

[0026]

EXAMPLES Examples and comparative examples of the present invention are described below, and the results are shown in Table 1. The following processing methods (1)-
The surface treatment layer was provided on the steel plate by using the method (7). (Treatment method 1) After the cold rolling, the annealed and pressure-regulated original plate is subjected to Sn plating using a ferrostan bath, and electrolytic treatment is performed thereon in a chromic acid-sulfuric acid solution as necessary to Cr or hydrate. Cr oxide was applied. (Treatment method 2) After cold rolling, the annealed and pressure-regulated original plate is subjected to Ni plating using a Watt bath, and then, if necessary, electrolytic treatment in a chromic acid-sulfuric acid solution to perform Cr or hydration. Cr oxide was applied.

(Treatment method 3) After cold rolling, Ni plating is performed using a Watt bath to form a Ni diffusion layer during annealing.
Thereafter, if necessary, electrolytic treatment was performed in a chromic acid-sulfuric acid solution to give Cr or hydrated Cr oxide. (Treatment method 4) After cold rolling, the annealed and pressure-regulated original plate is subjected to Fe plating using a sulfuric acid-hydrochloric acid bath, and then, if necessary, electrolytically treated in a chromic acid-sulfuric acid solution to obtain Cr or Hydrated oxidized Cr was provided.

(Treatment method 5) After cold rolling, the annealed and pressure-regulated original plate was subjected to electrolytic treatment in a chromic acid-sulfuric acid solution to obtain Cr.
Alternatively, hydrated oxidized Cr was provided. (Treatment method 6) After cold rolling, the annealed and pressure-regulated original plate was subjected to Fe-Ni alloy plating using a sulfuric acid-hydrochloric acid bath, followed by Sn plating using a ferrostan bath, and then subjected to a heat treatment to obtain Sn. The plating layer is partially alloyed, and if necessary, electrolytically treated in a chromic acid-sulfuric acid solution to perform Cr treatment.
Alternatively, hydrated oxidized Cr was provided.

(Processing Method 7) After cold rolling, the annealed and pressure-regulated original plate is subjected to a Sn—Ni alloy using a sulfuric acid-hydrochloric acid bath,
If necessary, electrolytic treatment was performed in a chromic acid-sulfuric acid solution to give Cr or hydrated Cr oxide. After applying the surface treatment layer by the above treatment, the following treatment methods (8) to
In (13), a coating composed of an inorganic-organic resin was provided. (Treatment method 8) The steel sheet was immersed in a treatment liquid in which a phenol resin, phosphoric acid and, if necessary, titanium ammonium phosphate were dissolved, and then dried to give a coating composed of an inorganic-organic resin.

(Processing Method 9) The above steel sheet is immersed in a processing solution in which a urethane resin, minopropyltriethoxysilane and, if necessary, zirconium sulfate are dissolved, dried, and dried.
A coating made of an organic resin was provided. (Treatment method 10) The above steel sheet is immersed in a treatment liquid in which 85% phenolic resin-15% epoxy resin, sodium phosphate, and titanium sulfate or zirconium sulfate as necessary are dissolved, dried, and made of an inorganic-organic resin. A coating was applied.

(Treatment method 11) The above steel sheet is immersed in a treatment liquid in which a phenol resin and titanium fluoride are dissolved, and then dried,
A coating composed of an inorganic-organic resin was applied. (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,
A coating made of an organic resin was provided.

With respect to the above treated materials, a polyethylene film having a thickness of 20 nm 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 The test material is subjected to drawing and ironing stepwise, and molding is evaluated in four stages (◎: very good, △: good, △: flaws recognized, ×: broken and unworkable) did.

(B) Weldability Using the wire seam weldability, welding is performed under the conditions of a welding wire speed of 80 m / min while changing the current, and the minimum current value, dust, and welding sufficient to obtain sufficient welding strength are obtained. Judging comprehensively from the appropriate current range consisting of the maximum current value at which welding defects such as spatter begin to stand out, welding is performed in four stages (◎: very wide, △: good, △: poor, ×: not weldable) The sex was evaluated.

(C) Film adhesion The test material subjected to the drawing and ironing process is 125 ° C. for 30 minutes.
And the film was peeled in four stages (（: no peeling at all, Δ: very slight peeling at practically no problem, Δ: slight peeling, ×: peeling at most)
Was evaluated.

(D) Corrosion resistance The test material was squeezed and ironed to form a can.
A test solution consisting of a citric acid-1.5% salt mixture was filled, a lid was attached, and the container was placed in a constant temperature room at 55 ° C. for one month.
Four levels of corrosion of the inner surface of the can (◎: no corrosion was observed,
〇: Slight corrosion is observed to the extent that there is no practical problem.
Δ: slight corrosion is observed, x: severe corrosion is observed).

[0036]

[Table 1]

[0037]

As shown in Table 1, it is clear that the steel sheet for laminated containers manufactured by the present patent and having excellent workability in can manufacturing has excellent formability, weldability, film adhesion and corrosion resistance. became.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazunari Hasegawa 1-1-1, Hibata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka F-term in Nippon Steel Corporation Yawata Works (reference) 3E061 AB05 AB06 AB07 AB13 AC01 AD01 BA01 4K044 AA02 AB02 BA02 BA06 BA10 BA15 BA19 BA21 BB03 BB11 BC02 BC05 BC08 CA02 CA17 CA18 CA53

Claims (10)

[Claims] 1. At least one side of a steel plate has Sn, Ni, F
e, a surface treatment layer containing at least one of Cr and hydrated oxidized Cr, on which a coating made of an organic resin is applied in a thickness of 1 to 500 n.
A steel sheet for a laminate container having excellent workability in can making, characterized by adding m. 2. Sn, Ni, F at least on one side of a steel plate.
e, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and a coating made of an inorganic-organic resin having a thickness of 1 to 5
A steel sheet for a laminated container having excellent workability in can-making, characterized by giving a thickness of 00 nm. 3. Sn, Ni, F on at least one side of the steel plate.
e, Cr, having a surface treatment layer containing one or more hydrated oxide Cr, thereon, P as 0.1 mg / m ² or more phosphoric acid compound, as a Si 0.1 mg / m ² or more A coating comprising an organic resin containing at least one organic silicon compound;
A steel sheet for a laminate container having excellent workability in can making, characterized by having a thickness of from 500 to 500 nm. 4. Sn, Ni, F on at least one side of the steel plate
e, Cr, having a surface treatment layer containing one or more hydrated oxide Cr, thereon, P as 0.1 mg / m ² or more phosphoric acid compound, as a Si 0.1 mg / m ² or more A steel sheet for a laminated container having excellent workability in can making, characterized in that a coating made of a phenolic resin containing at least one kind of an organosilicon compound is applied in a thickness of 1 to 500 nm. 5. Sn, Ni, F on at least one side of the steel plate
e, Cr, having a surface treatment layer containing at least one of hydrated Cr oxides, and further containing at least one of Ti or Zr or a compound thereof at a metal amount of 0.2 to 300 mg / m ^2. A steel sheet for a laminated container having excellent workability in can making, characterized in that a coating made of an inorganic-organic resin is applied in a thickness of 1 to 500 nm. 6. Sn, Ni, F at least on one side of a steel plate.
e, Cr, having a surface treatment layer containing at least one of hydrated Cr oxides, and further containing at least one of Ti or Zr or a compound thereof at a metal amount of 0.2 to 300 mg / m ^2. A steel sheet for a laminate container having excellent workability in can making, characterized in that a coating made of a phenolic resin is applied in a thickness of 1 to 500 nm. 7. Sn, Ni, F on at least one side of the steel plate.
e, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and further containing at least one of Ti or Zr or a compound thereof at a metal amount of 0.2 to 300 mg / m ^2. further, 50 a coating made of an organic resin containing one or more P as 0.1 mg / m ² or more phosphoric acid compound, 0.1 mg / m ² or more organic silicon compounds as Si
A steel sheet for a laminate container excellent in can workability, characterized in that it is provided with 0 nm. 8. Sn, Ni, F on at least one side of the steel plate.
e, Cr, a surface treatment layer containing at least one of hydrated Cr oxides, and further containing at least one of Ti or Zr or a compound thereof at a metal amount of 0.2 to 300 mg / m ^2. Further, a coating of a phenolic resin containing at least one of a phosphoric acid compound of 0.1 mg / m ² or more as P and at least one organic silicon compound of 0.1 mg / m ² or more as Si is applied in a thickness of 1 to 500 nm. A steel sheet for laminated containers with excellent processability. 9. The steel sheet for a laminate container excellent in can-making workability according to claim 4, wherein the phenolic resin content in the coating made of a phenolic resin is 70% or more. 10. Sn, Ni, Fe, Cr, hydrated C oxide
r is a surface treatment layer characterized by containing at least one of Sn
Is 80 to 6000 mg / m as metal Sn^Two, Ni is gold
10 to 800 mg / m as genus Ni^Two , Fe is metal Fe
10 to 800 mg / m^Two , Cr and hydrated Cr oxide
Is 2-200 mg / m as metallic Cr ^Two Specially
9. Lamine having excellent processability in can making according to claim 1.
Steel plate for container.