JPH07126806A - Steel sheet for can excellent in corrosion resistance and its production - Google Patents
Steel sheet for can excellent in corrosion resistance and its productionInfo
- Publication number
- JPH07126806A JPH07126806A JP27562093A JP27562093A JPH07126806A JP H07126806 A JPH07126806 A JP H07126806A JP 27562093 A JP27562093 A JP 27562093A JP 27562093 A JP27562093 A JP 27562093A JP H07126806 A JPH07126806 A JP H07126806A
- Authority
- JP
- Japan
- Prior art keywords
- steel
- inclusions
- corrosion resistance
- cans
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、めっき,塗装あるいは
フィルムラミネートなどの表面処理を施してプレス加工
で製缶する缶用鋼板に係り、特に、プレス加工でめっ
き,塗装,フィルムラミネートが破断されることによる
腐食を防止する耐食性に優れた缶用鋼板とその製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a steel plate for a can which is subjected to a surface treatment such as plating, painting or film laminating and is subjected to press working, and particularly, the plating, painting and film laminating are broken by the press working. TECHNICAL FIELD The present invention relates to a steel plate for a can having excellent corrosion resistance for preventing corrosion due to corrosion and a method for manufacturing the same.
【0002】[0002]
【従来の技術】食缶や飲料缶などの製缶材料として、冷
延薄鋼板にスズめっきしたぶりきや、スズの代わりにク
ロム等を用いたティンフリースチール(tin free stee
l,TFS)等の耐食性を有する表面処理鋼板が一般的
に使用されている。これらの缶用鋼板の主なものはぶり
きで、その機械的性質はロックウエル硬さ(試験荷重30
kg,HR30T),引張強さ,降伏点,伸び等で表示さ
れるが、最も一般的には硬さを規定する調質度で示され
る。ぶりき原板の調質度はJISG 3303に次のよ
うに規定されている。( )内は製造の際の目標HR3
0Tを表し、軟質なものから硬質なものへ、順に、T−
1(49±3),T−2(53±3),T−3(57±
3),T−4(61±3),T−5(65±3),T−
6(69±3),DR−8(73),DR−9(7
6),DR−9M(77),DR−10(80)に区分
されている。このうちのT−1〜T−3はいわゆる軟質
ぶりき原板、T−4〜T−6は硬質ぶりき原板で、いず
れも一回圧延製品(シングルレデュース,SR材)であ
る。このSR材を焼鈍後更に圧延してDR(ダブルレデ
ュース)材が得られる。2. Description of the Related Art Tin cans, which are tin-plated cold-rolled thin steel sheets, or tin-free steel (chromium, etc.) instead of tin, are used as can-making materials for food and beverage cans.
Generally, a surface-treated steel sheet having corrosion resistance such as l, TFS) is used. The main of these steel sheets for cans is tinplate, and their mechanical properties are Rockwell hardness (test load 30
kg, HR30T), tensile strength, yield point, elongation, etc., but most commonly it is indicated by the tempering degree that defines hardness. The tempering degree of the tin plate is specified in JIS G 3303 as follows. () Indicates target HR3 for manufacturing
Represents 0T, T-in order from soft to hard
1 (49 ± 3), T-2 (53 ± 3), T-3 (57 ±
3), T-4 (61 ± 3), T-5 (65 ± 3), T-
6 (69 ± 3), DR-8 (73), DR-9 (7
6), DR-9M (77), and DR-10 (80). Of these, T-1 to T-3 are so-called soft tin plate and T-4 to T-6 are hard tin plates, all of which are single-rolled products (single reduce, SR material). This SR material is annealed and further rolled to obtain a DR (double reduce) material.
【0003】SR材のうち、軟質ぶりき原板は低炭素A
lキルド鋼を素材として箱焼鈍法により製造され、絞り
加工等の成形性が良好なことから2ピース缶用の缶用鋼
板として多用されている。一方、硬質ぶりき原板は、
C,N,Mn含有量を調整した低炭素Alキルド鋼を素
材として連続焼鈍法(CAL法)により製造され、生産
性が高い。Among the SR materials, the soft tin plate is a low carbon A
It is manufactured by a box annealing method using l-killed steel as a raw material, and is often used as a can steel plate for two-piece cans because it has good formability such as drawing. On the other hand, the hard tin plate is
It is manufactured by the continuous annealing method (CAL method) using low carbon Al killed steel whose C, N and Mn contents are adjusted, and has high productivity.
【0004】DR材は、上記のSR材ぶりき原板に対し
て焼鈍後に再度冷間圧延を施して製造され、加工硬化も
加えてより硬質なものになる。ところで、最近の食缶,
飲料缶には、胴部と底部が一体になった缶本体と蓋との
二部品からなるいわゆる2ピース缶が多くなっている。
このものは、スズめっきされた冷延鋼帯を所定寸法のシ
ートに切断してぶりきシートとし、そのシート面に熱硬
化性樹脂を塗布して焼付炉で焼付け、次に缶外面に相当
する面に印刷・焼付けを施し、その後プレス加工,ドロ
ーイング加工などの成形加工により缶胴と缶底が一体の
缶本体を形成する。これに内容物を充填して、別途製造
された蓋を取り付けるものである。このように缶胴部と
底部を一体成形する用途に向けられる缶用鋼板として
は、SR材でもプレス加工性の良いT−1〜T−3の軟
質ぶりき原板の方がT−4〜T−6の硬質ぶりき原板よ
り適している。[0004] The DR material is manufactured by annealing the above SR material tin plate and then cold rolling it again, and becomes harder by work hardening. By the way, recent food cans,
BACKGROUND OF THE INVENTION Many beverage cans are so-called two-piece cans that are composed of two parts, a can body having a body and a bottom integrated with a lid.
In this product, tin-plated cold-rolled steel strip is cut into sheets of specified dimensions to form tinplate sheets, the surface of which is coated with a thermosetting resin and baked in a baking oven, and then the outer surface of the can. The surface of the can is printed and baked, and then the press body and drawing process are used to form the can body with the can body and bottom. The contents are filled in this, and a lid manufactured separately is attached. As a steel plate for a can, which is used for integrally forming the can body and the bottom in this way, the soft tin plate of T-1 to T-3, which has good press workability even with the SR material, is T-4 to T. It is more suitable than -6 hard tin plate.
【0005】こうした食缶や飲料缶等に用いられる缶用
鋼板は、必然的に耐食性が大切な品質要素とされてお
り、その向上のためには原板の清浄度を改善することが
重要であることが認識されてはいるが、その具体策はま
だ提案されていない。そこで、箱焼鈍法より優れた耐食
性が得易い連続焼鈍のCAL法を利用して加工性の良い
T−1〜T−3の軟質ぶりき原板を製造するにおいて耐
食性に優れた缶用鋼板の製造方法の開発が望まれてい
た。Steel plates for cans used for such food cans and beverage cans are inevitably the important quality factor of corrosion resistance, and in order to improve them, it is important to improve the cleanliness of the original plate. However, the concrete measures have not been proposed yet. Therefore, in the production of T-1 to T-3 soft tin plate having good workability using the CAL method of continuous annealing, which is easier to obtain corrosion resistance superior to the box annealing method, the production of a steel sheet for cans having excellent corrosion resistance Development of a method was desired.
【0006】また、最近は、空缶コストの削減が重要な
課題となってきており、その対応策の一つとしてぶりき
のスズ目付量を低減したLTS(Lightly tin coated s
teel)が使用されるようになっている。また他の対応策
として空缶の軽量化が急速に進んでいる。しかし、スズ
目付量を低減すればその分スズによる耐食性が低下する
し、また空缶の軽量化を進めれば缶強度の低下は避けら
れない。Recently, reduction of the cost of empty cans has become an important issue, and as one of the countermeasures against this, LTS (Lightly tin coated s) which reduces the tin weight per unit area of tinplate.
teel) is being used. As another measure, the weight reduction of empty cans is rapidly progressing. However, if the weight per unit area of tin is reduced, the corrosion resistance due to tin is reduced accordingly, and if the weight reduction of empty cans is promoted, the reduction of can strength is inevitable.
【0007】そこで、スズ減量による耐食性の低下を補
えるような原板が求められるようになっている。また、
軽量化による缶強度の低下については、缶デザインを工
夫して缶強度を確保する方策が取られており、複雑な缶
形状のものが出現するようになっている。図1は缶強度
を向上させる缶デザインの例を示したものである。同図
(a)は缶上下のコーナ部にネックイン加工を施して1
段ネックイン1を形成したシングルネックイン缶、同図
(b)は缶上下のコーナ部に2段ネックイン2を形成し
たダブルネックイン缶、同図(c)は缶上下のコーナ部
に3段ネックイン3を形成したトリプルネックイン缶で
ある。更に4段,5段のネックインの段数を増やし、口
径を小さくして缶強度の増加が図られている。また、い
ずれも缶胴部の強度を向上させるビード4を形成してい
る。このようにして、同図(d)の在来のストレート缶
に比べて缶形状は次第に複雑化する傾向が認められる。Therefore, there has been a demand for a master plate that can compensate for the deterioration of corrosion resistance due to the weight loss of tin. Also,
Regarding the reduction in can strength due to weight reduction, measures have been taken to ensure can strength by devising a can design, and complex can shapes are emerging. FIG. 1 shows an example of a can design that improves can strength. In the same figure (a), neck-in processing is applied to the top and bottom corners of the can.
A single-neck-in can with a stepped neck-in 1 is shown, (b) is a double-necked-in can with two stepped-in necks 2 at the top and bottom corners of the can, and (c) is a three-sided can at the top and bottom corners of the can. It is a triple neck-in can in which a stepped neck-in 3 is formed. Further, the number of stages of neck-in of 4 steps and 5 steps is increased and the diameter is reduced to increase the strength of the can. Further, in each case, the bead 4 is formed to improve the strength of the can body. In this way, it is recognized that the shape of the can gradually becomes more complicated than that of the conventional straight can shown in FIG.
【0008】こうした缶デザインによる補強とは別に、
更に、同様の目的で、缶用鋼板として極薄・高強度鋼板
が要求され、JIS規格に規定されていない例えばDR
−11,DR−12に相当する程の超硬質材も必要とさ
れるようになってきている。Apart from reinforcement by such a can design,
Furthermore, for the same purpose, ultra-thin and high-strength steel plates are required as steel plates for cans, and are not specified in JIS standards, such as DR.
Ultra hard materials corresponding to -11 and DR-12 are also required.
【0009】[0009]
【発明が解決しようとする課題】最近の缶用鋼板は、上
述のように、空缶コストの低減等を目的として、 薄スズ目付鋼板(LTS)の採用、 極薄・高強度鋼板の採用、 肉薄化による強度低下を補う複雑な缶デザインの採用 等の傾向が進みつつあり、そのため、比較的厚肉な鋼板
を用いて単純な形状に成形する在来のストレート缶の時
代に比べると、成形加工の条件が複雑化・過酷化してい
る。こうした傾向に伴って缶加工部からの耐食性の劣化
という問題が生じてきている。この現象は、缶本体ばか
りではなく極薄・高強度鋼板が採用されはじめている缶
蓋についても同様に認められ、缶蓋のパネリング加工部
における耐食性劣化が問題視され始めている。As described above, the recent steel plates for cans are thin tinted steel plates (LTS), ultra-thin and high-strength steel plates for the purpose of reducing the cost of empty cans, as described above. There is an increasing trend towards the adoption of complex can designs that compensate for the reduction in strength due to thinning.Therefore, compared with the era of conventional straight cans, where relatively thick steel plates are used to form simple shapes, Processing conditions are becoming more complicated and severe. Along with this tendency, the problem of deterioration of corrosion resistance from the can processing part has arisen. This phenomenon is similarly observed not only in the main body of the can, but also in the can lid that is beginning to employ ultra-thin high-strength steel sheets, and deterioration of corrosion resistance in the paneling portion of the can lid is beginning to be considered a problem.
【0010】また、環境改善を目的として2ピース缶に
対するコイルコート鋼板の採用や、フィルムラミネート
鋼板の採用が進んでいるが、これら鋼板素材に極薄・高
強度鋼板が採用されて厳しい加工が行われはじめると共
に、プレス加工において塗膜が破れたり、フィルムラミ
ネート膜が破断して耐食性が損なわれてしまうトラブル
が見られ始めている。In addition, for the purpose of improving the environment, coil-coated steel sheets for two-piece cans and film-laminated steel sheets are being adopted, but ultra-thin and high-strength steel sheets are used for these steel sheet materials, and severe processing is performed. At the same time, problems such as tearing of the coating film in the pressing process and tearing of the film laminate film to impair the corrosion resistance are beginning to be seen.
【0011】このような耐食性劣化のトラブルを回避す
るためには、耐食性に優れた缶用鋼板を得て原板自体の
耐食性を向上させることが一つの重要な解決策になる。
そのような耐食性の良好な鋼板は、連続焼鈍のCAL法
で製造することにより得られ易いことは既に分かってい
た。しかし、従来、CAL法では箱焼鈍法で得られる鋼
板と同等の軟質性を得ることはできなかった。In order to avoid such troubles of deterioration of corrosion resistance, one important solution is to obtain a steel sheet for cans having excellent corrosion resistance and improve the corrosion resistance of the original plate itself.
It has already been known that such a steel sheet having good corrosion resistance can be easily obtained by manufacturing by the CAL method of continuous annealing. However, conventionally, the CAL method has not been able to obtain the same softness as the steel sheet obtained by the box annealing method.
【0012】すなわち、CAL法で軟質な原板を製造す
るには、冶金学的には、(1)結晶粒径を大きくし、
(2)時効硬化成分(固溶C,固溶N等)の含有量を少
なくすれば可能であると考えられる。しかし実際には、
結晶粒径を大きくするにはC量を少なくすれば良いが、
C量を少なくする(0.01%程度)ことによって逆に固溶
C量が多く残存し、これと相殺されてしまうため軟質に
はならなかった。That is, in order to manufacture a soft original plate by the CAL method, metallurgically, (1) the crystal grain size is increased,
(2) It is considered possible if the content of the age hardening component (solid solution C, solid solution N, etc.) is reduced. But in reality,
To increase the crystal grain size, the amount of C should be reduced,
On the contrary, when the amount of C is reduced (about 0.01%), the amount of dissolved C remains large, which is offset by the amount, so that the C does not become soft.
【0013】そこで、CAL法で軟質な原板を得ようと
するにあたって生じていた従来のこのような相反する問
題点を解決して、(A)固溶C量が激減できると共に結
晶粒径も粗大化できる耐食性に優れた軟質缶用鋼板並び
にその製造方法が要望されていた。他方、プレス加工法
で製造される2ピース缶用の原板は、プレス加工性に優
れた箱焼鈍法で製造される軟質ぶりき原板が採用されて
いたが、近年のプレス加工技術の向上により、従来は困
難とされてきた硬質ぶりき原板の採用が可能になってき
た。これに加えて更に、塗装鋼板或いはフィルムラミネ
ート鋼板の採用により、皮膜,フィルムの潤滑効果を利
用して深絞り加工性を大幅に改善することが可能になっ
ている。そのため、二回圧延材(DR材)、さらにはJ
ISにはないその上の超硬質材も缶用鋼材として使用さ
れ出したが、そのような超硬質の缶用鋼板材は、従来の
低炭素Alキルド鋼のCAL法焼鈍,二回圧延の工程で
は得られない。Therefore, by solving the conventional contradictory problems that have occurred when trying to obtain a soft original plate by the CAL method, (A) the amount of solid solution C can be drastically reduced and the crystal grain size is large. There has been a demand for a steel plate for soft cans that has excellent corrosion resistance and a manufacturing method thereof. On the other hand, as the original plate for a two-piece can manufactured by the press working method, the soft tin plate manufactured by the box annealing method having excellent press workability was adopted, but due to the improvement of the press working technology in recent years, It has become possible to use hard tin plate, which has been difficult in the past. In addition to this, by adopting a coated steel sheet or a film laminated steel sheet, it is possible to significantly improve the deep drawing workability by utilizing the lubrication effect of the coating and film. Therefore, double rolled material (DR material) and even J
Although an ultra-hard material, which is not in IS, has been used as a steel material for cans, such an ultra-hard steel sheet material for a can is manufactured by the conventional CAL annealing and double rolling process of low carbon Al killed steel. Can't get it.
【0014】そこで、このような最近のプレス加工技術
の進展に呼応して、(B)耐食性に優れた硬質の缶用鋼
板並びにその製造方法も要望されるようになってきた。
本発明は、このような要望に鑑みてなされたもので、そ
の目的は耐食性に優れた軟質の缶用鋼板及びその製造方
法を提供することにある。また、本発明の他の目的は、
耐食性に優れた硬質の缶用鋼板並びにその製造方法を提
供することにある。Accordingly, in response to such recent progress in press working technology, there has been a demand for (B) a hard steel sheet for cans having excellent corrosion resistance and a manufacturing method thereof.
The present invention has been made in view of such a demand, and an object thereof is to provide a soft can steel sheet having excellent corrosion resistance and a method for manufacturing the same. Further, another object of the present invention is to
It is intended to provide a hard can steel plate having excellent corrosion resistance and a manufacturing method thereof.
【0015】[0015]
【課題を解決するための手段】上記の目的を達成する本
発明の請求項1の缶用鋼板は、成分組成が重量比で、
C:0.08%以下、Si:0.03%以下、Mn:0.1 〜0.60
%、P:0.02%以下、S:0.02%以下、N:0.02%以
下、Al:0.03〜0.20%、残部は不可避的不純物を除き
Feよりなる炭素鋼であって、鋼中の全酸素量を30pp
m以下、鋼中のAl 2 O3 系介在物の最大径を5 μm以
下としたものである。[Means for Solving the Problems] A book that achieves the above object.
In the steel sheet for a can according to claim 1 of the invention, the component composition is a weight ratio,
C: 0.08% or less, Si: 0.03% or less, Mn: 0.1 to 0.60
%, P: 0.02% or less, S: 0.02% or less, N: 0.02% or less
Bottom, Al: 0.03 to 0.20%, the balance except inevitable impurities
A carbon steel made of Fe with a total oxygen content of 30 pp
m or less, Al in steel 2O3Maximum diameter of system inclusions is 5 μm or less
The one below.
【0016】また、本発明の請求項2の缶用鋼板は、請
求項1の成分組成において炭素量が0.02%以下の極低炭
素鋼としたものである。また、本発明の請求項3の缶用
鋼板は、請求項1の成分組成中の炭素量が0.09〜0.2 %
の炭素鋼としたものである。本発明の請求項4の缶用鋼
板は、上記の請求項1ないし請求項3の何れかの成分組
成中にNb:0.1 〜0.001 %、B:0.005 〜0.0001%を
含有させたものである。The steel sheet for a can according to claim 2 of the present invention is an ultra-low carbon steel having a carbon content of 0.02% or less in the composition of claim 1. Further, according to the steel plate for cans of claim 3 of the present invention, the carbon content in the component composition of claim 1 is 0.09 to 0.2%.
It is made of carbon steel. A steel sheet for a can according to claim 4 of the present invention is one in which Nb: 0.1 to 0.001% and B: 0.005 to 0.0001% are contained in the composition of any of the above claims 1 to 3.
【0017】本発明の請求項5の缶用鋼板は、上記請求
項1ないし請求項4の何れかの成分組成で示される鋼中
の介在物の組成を、CaO−Al2 O3 系としたもので
ある。更に、本発明の缶用鋼板の製造方法は、溶鋼を脱
ガス,脱炭,脱酸した後タンディッシュに移して旋回流
により非金属介在物を凝集浮上分離せしめ、かくして得
られた高清浄度の鋼片を熱延,酸洗,冷延したものを連
続焼鈍し、その後調質圧延するものである。In the steel sheet for cans according to claim 5 of the present invention, the composition of inclusions in the steel represented by any of the component compositions according to any one of claims 1 to 4 is CaO-Al 2 O 3 system. It is a thing. Further, the method for producing a steel sheet for a can of the present invention is such that the molten steel is degassed, decarburized and deoxidized and then transferred to a tundish to cause non-metallic inclusions to flocculate and separate by a swirling flow. The hot rolled, pickled and cold rolled steel slab of No. 2 is continuously annealed and then temper rolled.
【0018】[0018]
【作用】缶用鋼板の腐食発生には、鋼中の非金属介在物
のうち、原板表面に露出しているAl2 O3 系介在物の
影響が大きい。Al2 O3 系介在物の大きさが5μmを
超えると腐食液に接した場合に介在物周囲の地金が溶解
したり、スズめっきにおけるピンホールの発生が生じ
る。5μm以下であれば腐食因子として作用しない。[Function] Among the non-metallic inclusions in the steel, Al 2 O 3 -based inclusions exposed on the surface of the original plate have a great influence on the occurrence of corrosion of the steel plate for a can. If the size of the Al 2 O 3 -based inclusions exceeds 5 μm, the base metal around the inclusions will be dissolved or pinholes will be generated in the tin plating when they come into contact with the corrosive liquid. If it is 5 μm or less, it does not act as a corrosion factor.
【0019】鋼中のAl量が0.03%以上になると鋼中の
酸素量が急激に低下して30ppm以下になり、同時に
Al2 O3 系介在物の大きさも5μm以下になる。缶用
鋼板の耐食性を向上させるには、5μmを超える大きさ
のAl2 O3 系介在物の存在を規制する他に、Al2 O
3 系介在物の形態を制御することも有効である。すなわ
ち、溶鋼中へ金属Alを投入して脱酸する代わりに、A
l−Ca線を使用して脱酸すると、硬いAl2 O3 系介
在物が軟質のAl2 O3 −CaOの形態に変化し、腐食
が防止される。When the amount of Al in the steel is 0.03% or more, the amount of oxygen in the steel sharply decreases to 30 ppm or less, and at the same time, the size of Al 2 O 3 type inclusions also becomes 5 μm or less. In order to improve the corrosion resistance of the steel sheet for cans, in addition to controlling the presence of Al 2 O 3 -based inclusions having a size of more than 5 μm, Al 2 O
It is also effective to control the morphology of 3 type inclusions. That is, instead of introducing metallic Al into molten steel to deoxidize it, A
When deoxidized using the 1-Ca wire, the hard Al 2 O 3 -based inclusions change into a soft Al 2 O 3 -CaO form, and corrosion is prevented.
【0020】また、缶用鋼板の出発材である連鋳鋼片製
造用の溶鋼中のC量を極端に少なくすると、焼鈍後の固
溶C量が少なくなって、時効性に優れた製品が得られ
る。また、炭化物も激減するので、耐食性にも優れた製
品が得られる。本発明によれば、C量を極微量にするこ
とにより、連続焼鈍法(CAL法)による調質度T−1
相当の軟質原板が製造可能になる。更に、連鋳鋼片製造
に際して、鋼中に炭化物及び窒化物形成元素であるN
b,Bを添加すると、固溶C,固溶Nの量が安定的に低
減して、より優れた機械的性質,深絞り加工性を有する
T−1相当の軟質原板が製造可能になる。When the amount of C in the molten steel for producing the continuously cast steel billet, which is the starting material for the steel sheet for cans, is extremely reduced, the amount of solid solution C after annealing is reduced, and a product excellent in aging is obtained. To be Further, since carbides are also drastically reduced, a product excellent in corrosion resistance can be obtained. According to the present invention, the refining degree T-1 obtained by the continuous annealing method (CAL method) is controlled by making the amount of C extremely small.
A considerable amount of soft original plate can be manufactured. Furthermore, N is a carbide and nitride forming element in the steel during continuous cast steel production.
When b and B are added, the amounts of solid solution C and solid solution N are stably reduced, and it becomes possible to manufacture a T-1 equivalent soft original plate having more excellent mechanical properties and deep drawing workability.
【0021】また、本発明によれば、調質圧延の圧下率
を調整して調質度T−1ないしT−6、更にはDR材相
当に及ぶ任意の硬さの耐食性に優れた缶用鋼板をつくり
わけることも可能である。また、本発明によれば、逆
に、C量を通常より多く添加した鋼片を用いてCAL法
を行うと、二回圧延の圧下率が低くても硬質になり、従
来より圧延時間を短縮した二回圧延製品(DR製品)が
耐食性にも優れた缶用鋼板として製造できることがわか
った。圧下率を幾分大きくすることにより、二回圧延製
品以上の超硬質原板も得られる。Further, according to the present invention, the reduction ratio of the temper rolling is adjusted so that the tempers T-1 to T-6 and further the corrosion resistance of arbitrary hardness equivalent to the DR material are excellent. It is also possible to make steel sheets. Further, according to the present invention, conversely, when the CAL method is performed using a steel slab added with a larger amount of C than usual, it becomes hard even if the rolling reduction of the double rolling is low, and the rolling time is shortened as compared with the conventional one. It was found that the double-rolled product (DR product) can be manufactured as a steel sheet for cans having excellent corrosion resistance. By increasing the rolling reduction to some extent, an ultra-hard original plate that is more than a double rolled product can be obtained.
【0022】以下、本発明をさらに詳細に説明する。 〔1〕まず、軟質ぶりき原板をCAL法で製造するため
の手段について述べる。本発明者らは、製鋼時に真空脱
ガス処理を有効に駆使して、C量を極微量にしたAlキ
ルド鋼スラブを使用することにより、CAL法によって
も調質度T−1の軟質原板を製造することができ、ま
た、上記Alキルド鋼中に炭化物及び窒化物形成元素で
あるNb,Bを含有させたスラブを使用することによ
り、従来の箱焼鈍法で得られていたものと同等以上の機
械的性質,深絞り加工性を有する原板を製造することが
できることを見いだした。The present invention will be described in more detail below. [1] First, the means for producing a soft tin plate by the CAL method will be described. The present inventors effectively utilize vacuum degassing treatment during steel making and use an Al-killed steel slab with a very small amount of C, so that a soft original plate having a temper T-1 can be obtained by the CAL method as well. By using a slab that can be manufactured and contains Nb and B which are carbide and nitride forming elements in the above Al killed steel, it is equal to or more than that obtained by the conventional box annealing method. It has been found that it is possible to manufacture an original plate having mechanical properties and deep drawing workability.
【0023】すなわち、本発明者らは、ぶりきの硬さに
及ぼす固溶C,固溶Nの影響及び結晶粒径との関係を系
統的に調べた結果、固溶C,固溶Nが少なく、且つ結晶
粒径が大きくなると軟質になるとの知見が得られた。こ
の知見に基づいて、焼鈍後に固溶C,固溶Nを少なくす
るため、出発材である連鋳鋼片製造用溶鋼中のC量を極
端に少なくすればよいと考えた。また、NはAlNとし
てできるだけ多く析出させれば軟質になる。That is, the present inventors systematically investigated the influence of solid solution C and solid solution N on the hardness of tinplate and the relationship with the crystal grain size. It was found that the amount becomes small and the crystal grain size becomes large, the material becomes soft. Based on this finding, in order to reduce the amount of solid solution C and the amount of solid solution N after annealing, it was considered that the amount of C in the molten steel for producing a continuous cast steel slab, which is a starting material, should be extremely reduced. Also, N becomes soft as it is deposited as AlN as much as possible.
【0024】こうした見地に基づいて研究を重ねた結
果、CAL法でも調質度T−1相当の原板が得られるこ
と、さらに調質圧延の圧下率をそれぞれ変えることによ
り、T−1〜T−6さらにはDRの二回圧延製品の原板
をも作りわけることができるとの知見を得た。なお、上
記鋼片を製造するに際して、Nb,Bを添加することに
より、固溶C,固溶N量を安定して低減できるので、よ
り優れたT−1原板を製造できることも見いだした。 〔2〕次に、二回圧延製品及びそれ以上の硬さが要求さ
れる原板の製造法について述べる。As a result of repeated studies based on these viewpoints, it is possible to obtain a base plate having a temper degree T-1 even by the CAL method, and by changing the reduction ratio of temper rolling, T-1 to T- 6 Furthermore, it was found that it is possible to manufacture a master plate of a double-rolled DR product. In addition, when manufacturing the said steel slab, since the amount of solid solution C and the amount of solid solution N can be reduced stably by adding Nb and B, it was also discovered that the more excellent T-1 original plate can be manufactured. [2] Next, a method for manufacturing a double-rolled product and an original plate required to have a hardness higher than that will be described.
【0025】上記〔1〕の方法により二回圧延製品まで
製造できるようになった。この方式の鋼板は、結晶粒径
の大きくる極低炭素鋼を基にするために、深絞り加工性
に優れた特性をもったものになるが、硬質にするために
は、二回圧延の圧下率が高くならざるを得ず、圧延時間
が長くなる。そこで、本発明者らは、二回圧延性に優れ
効率良く製造できる鋼板の研究開発を進めた結果、極低
炭素鋼の場合とは全く逆に、C量を通常に比べて多く添
加して微細粒鋼板とする鋼片を用いてCAL法を行う
と、二回圧延圧下率が低くても硬質になるし、圧下率を
若干大きくすると二回圧延超えの硬さを有する原板も製
造できることを見いだした。By the method [1] described above, a double rolled product can be manufactured. The steel sheet of this system is based on an ultra-low carbon steel having a large crystal grain size, and therefore has a property of excellent deep drawability. The reduction rate is inevitably high and the rolling time is long. Therefore, as a result of the research and development of a steel sheet having excellent double-rollability and capable of being efficiently manufactured, the present inventors have added a larger amount of C than usual, which is completely opposite to the case of an ultra-low carbon steel. When the CAL method is performed using a steel piece that is a fine-grained steel plate, it becomes hard even if the reduction ratio of the double rolling is low, and if the reduction ratio is slightly increased, it is possible to manufacture a base plate having a hardness exceeding the double rolling. I found it.
【0026】一方、板厚の薄い極薄.高強度鋼板を用い
て、複雑な缶形状を有する食缶や飲料缶に仕上げたもの
についても、耐食性に起因するトラブルが生じた。そこ
で本発明者らは、特に薄スズ目付け鋼板で生じる耐食性
劣化の発生原因を素材との関連において大規模かつ詳細
に調査を行ったところ、以下のような重大な結果を得
た。On the other hand, an extremely thin plate. Trouble due to corrosion resistance also occurred in the finished food cans and beverage cans having a complicated can shape using the high-strength steel plate. Therefore, the present inventors have conducted a large-scale and detailed investigation on the cause of the deterioration of corrosion resistance that occurs particularly in the thin tinned steel sheet, in relation to the material, and obtained the following serious results.
【0027】先ず、缶内面が腐食していた缶について、
その腐食部の鋼板表面を電子顕微鏡で観察した。その結
果、塗膜が破壊されていて、その直下のスズ層にピンホ
ールが形成されていることが判明し、これに着目して更
に以下の調査を進めた。すなわち、製鋼工程で鋼を作る
に際して、溶鋼の脱酸法を(A)Mn単独脱酸−真空脱
ガス,脱炭,脱酸法、(B)Al少量添加弱脱酸−真空
脱ガス,脱炭,脱酸法、(C)Al強脱酸−真空脱ガ
ス,脱炭,脱酸法の3種類で行い、連続鋳造機で鋼片を
作り、以下常法で薄物目付(スズ目付No.10)ぶりき
を製造した。First, regarding the can whose inner surface is corroded,
The steel plate surface of the corroded part was observed with an electron microscope. As a result, it was found that the coating film was destroyed and pinholes were formed in the tin layer directly under the coating film, and the following investigation was further focused on this. That is, when making steel in the steelmaking process, the deoxidation method of molten steel is (A) Mn alone deoxidation-vacuum degassing, decarburization, deoxidation method, (B) Al small amount addition weak deoxidation-vacuum degassing, degassing Carbide, deoxidation method, (C) Al strong deoxidation-vacuum degassing, decarburization, deoxidation method are used to make steel pieces with a continuous casting machine. 10) A tin plate was produced.
【0028】このぶりきを用い、DRD缶(Drawn
& Redrawn Can)をつくり、腐食性の強
い魚肉の味付液を缶に充填し、恒温室に75℃で保管す
るという方法で、腐食促進試験を行った。その結果は次
の通りであった。 1)1年経過した時点から缶内面に腐食が生じ始めるも
のがみられた。Using this tin plate, a DRD can (Drawn
& Redlawn Can) was prepared, a can was filled with a highly corrosive seasoning liquid of fish meat, and the mixture was stored at 75 ° C. in a temperature-controlled room to carry out a corrosion acceleration test. The results were as follows. 1) Some ones began to corrode after one year had passed.
【0029】2)製鋼時の脱酸法の相違によって、その
腐食程度に差が認められた。このことから、腐食の発生
原因はプレス加工で製缶されるDRD加工にも起因して
いるが、その原点は素材原板に由来することが推定され
た。表1はこの腐食試験における腐食缶と鋼種との関係
を示したものであるが、腐食缶は鋼Bで最も多く認めら
れ、鋼C,鋼Aの順であった。2) A difference in the degree of corrosion was recognized due to the difference in the deoxidizing method during steelmaking. From this, it is estimated that the cause of corrosion is also caused by the DRD processing in which cans are manufactured by press working, but the origin thereof is derived from the raw material plate. Table 1 shows the relationship between the corrosive can and the steel type in this corrosion test. The corrosive can was most often found in steel B, followed by steel C and steel A in that order.
【0030】[0030]
【表1】 [Table 1]
【0031】腐食缶発生が鋼種(脱酸法)によって差を
生じることから、その冶金学的原因を追求するために、
上記調査に供したものと同じ薄スズ目付(No.10目
付)ぶりきについて、ぶりき表面を電子顕微鏡で詳細に
観察した。その結果、図2のスケッチ図に示したような
スズ層のピンホール5が認められ、その原板(地金)に
は非金属介在物の存在が確認された。Since the generation of corrosive can differs depending on the steel type (deoxidizing method), in order to pursue the metallurgical cause,
With respect to the tin tint (No. 10 basis weight) tin plate, which was the same as that used in the above-mentioned investigation, the tin plate surface was observed in detail with an electron microscope. As a result, the pinhole 5 in the tin layer as shown in the sketch of FIG. 2 was recognized, and the existence of non-metallic inclusions in the original plate (metal) was confirmed.
【0032】そこで、同じぶりきについて、表面のスズ
層を電解剥離法で剥離させた後、再度電子顕微鏡にて原
板表面を観察したところ、原板(地金)表面に非金属介
在物が存在していること、及び脱酸法によって非金属介
在物の組成が異なることも判明した。表2に鋼製造法と
非金属介在物組成別に、その非金属介在物の検出個数を
示した。Then, when the tin layer on the surface of the same tin plate was peeled by the electrolytic peeling method and the surface of the original plate was observed again with an electron microscope, nonmetallic inclusions were found on the surface of the original plate (bare metal). It was also found that the composition of the non-metallic inclusions differs depending on the deoxidation method. Table 2 shows the number of non-metallic inclusions detected for each steel manufacturing method and composition of non-metallic inclusions.
【0033】[0033]
【表2】 [Table 2]
【0034】Mn単独脱酸−真空脱ガス,脱炭,脱酸処
理した鋼Aは、介在物の個数は多いが、Al2 O3 系の
ものは検出されなかった。Al弱脱酸−真空脱ガス,脱
炭,脱酸処理した鋼Bでは、Al2 O3 系の介在物だけ
が多く検出された。その粒径は後記の鋼Cに比べて12
〜35μmと大きいものであった。In the steel A which was deoxidized by Mn alone-vacuum degassing, decarburized and deoxidized, the number of inclusions was large, but no Al 2 O 3 type was detected. In Steel B, which was Al weakly deoxidized-vacuum degassed, decarburized, and deoxidized, many Al 2 O 3 -based inclusions were detected. Its grain size is 12 compared to Steel C described later.
It was as large as ˜35 μm.
【0035】Al強脱酸−真空脱ガス,脱炭,脱酸処理
した鋼Cの場合は、Al2 O3 系介在物の個数は極めて
少なく、粒径も3〜11μmと小さかった。図3に、非
金属介在物のうちのAl2 O3 系介在物の個数と腐食缶
発生指数との関係を示す。このグラフから、両者の間に
非常に良い相関があることがわかった。しかし、非金属
介在物総個数と腐食缶発生指数との間には相関が認めら
れなかった。In the case of steel C that had undergone strong Al deoxidation-vacuum degassing, decarburization, and deoxidation, the number of Al 2 O 3 -based inclusions was extremely small, and the grain size was small, 3 to 11 μm. FIG. 3 shows the relationship between the number of Al 2 O 3 -based inclusions among the nonmetallic inclusions and the corrosion can generation index. From this graph, it was found that there is a very good correlation between the two. However, no correlation was found between the total number of non-metallic inclusions and the corrosive can generation index.
【0036】以上の結果から、腐食缶の発生原因として
悪影響を与えるものは、鋼中の非金属介在物のうち原板
表面に露出しているAl2 O3 系介在物であることが推
定できた。次に、Al2 O3 系介在物及びMnO,Mn
S等の成分の異なる介在物が原板表面に露出しているも
のを検出し、その原板を腐食液で直接腐食させた後、同
様に電子顕微鏡で観察した。図4に、粒径が16μmの
Al2 O3 系介在物の腐食後を、図5にMnO,MnS
系介在物の腐食後を、いずれも観察視野のスケッチで示
す。From the above results, it can be presumed that it is the Al 2 O 3 type inclusions exposed on the surface of the original plate which are the non-metallic inclusions in the steel that have a bad influence as the cause of the corrosion can. . Next, Al 2 O 3 system inclusions and MnO, Mn
It was detected that inclusions having different components such as S were exposed on the surface of the original plate, and the original plate was directly corroded with a corrosive liquid, and then similarly observed with an electron microscope. FIG. 4 shows the state after corrosion of Al 2 O 3 -based inclusions having a grain size of 16 μm, and FIG. 5 shows MnO and MnS.
After the corrosion of the system inclusions, a sketch of the observation field is shown.
【0037】この観察により、Al2 O3 系介在物の周
囲のFe(地金)が大きく溶解しているのに対して、M
nO,MnS系介在物の周囲のFeはほとんど溶解して
いないことがわかった。更に、Al2 O3 −CaO介在
物では、周囲のFeが溶解していないこともわかった。
これらのことから、缶詰の腐食に関係する介在物はAl
2 O3 系介在物であると断定できた。From this observation, Fe (metal) around the Al 2 O 3 -based inclusions was largely dissolved, whereas M
It was found that Fe around the nO and MnS inclusions was hardly dissolved. Further, it was also found that the surrounding Fe was not dissolved in the Al 2 O 3 —CaO inclusions.
From these facts, the inclusions related to the corrosion of canned goods are Al
It could be concluded that it was a 2 O 3 type inclusion.
【0038】次に、Alキルド鋼であればAl2 O3 系
介在物を工業的に無くすことが難しく、更に電子顕微鏡
の倍率で発見されていない極微小のものも露出している
筈であり、露出しているAl2 O3 系介在物が全て腐食
缶につながるのなら、もっと腐食缶が多く発生してもよ
い筈であるとの予測ができた。この腐食缶発生数の予測
と実際との差は、Al2 O3 系介在物でもその大きさに
よって実用上腐食缶になるものと、ならないものすなわ
ち害を及ぼさないものがあるということを表していると
考えられた。そこで、Al2 O3 系介在物について、大
きさで5μm程度のもの、10μmのもの、15μmの
ものを電子顕微鏡で検出して選び出し、それらの試料に
対して前述の腐食試験を行った。Next, in the case of Al-killed steel, it is difficult to eliminate Al 2 O 3 -based inclusions industrially, and extremely minute ones that have not been found by electron microscope magnification should be exposed. However, if all of the exposed Al 2 O 3 -based inclusions lead to corrosive cans, it could be predicted that more corrosive cans may be generated. The difference between the predicted number of corrosive cans and the actual number indicates that there are some Al 2 O 3 -based inclusions that can actually become corrosive cans, and some do not, that is, do not cause harm. Thought to be Therefore, Al 2 O 3 -based inclusions having a size of about 5 μm, 10 μm, and 15 μm were detected and selected by an electron microscope, and the above-described corrosion test was performed on these samples.
【0039】その結果、Al2 O3 系介在物の周囲の地
金が大きく溶解するためには、当該介在物に一定以上の
大きさが必要であり、5μm以下の大きさのAl2 O3
系介在物が原板に露出していても溶解には影響しないこ
とも判明した。同様に、スズ目付1.12g/m2 のぶりき
にして、Al2 O3 系介在物の大きさとスズ層のピンホ
ールとの関係を観察した結果、腐食試験と同様に5μm
を超える大きさのAl2 O3 系介在物が存在していた場
所からはスズ層のピンホールが発生していることも明ら
かにすることができた。As a result, in order for the metal around the Al 2 O 3 -based inclusions to be largely dissolved, the inclusions must have a certain size or more, and the Al 2 O 3 having a size of 5 μm or less is required.
It was also found that even if the system inclusions were exposed on the original plate, dissolution was not affected. Similarly, as a result of observing the relationship between the size of the Al 2 O 3 -based inclusions and the pinhole of the tin layer by tinting the basis weight of 1.12 g / m 2 , the result was 5 μm as in the corrosion test.
It was also clarified that the pinholes in the tin layer were generated from the places where the Al 2 O 3 -based inclusions having a size larger than the above were present.
【0040】大きなAl2 O3 系介在物の周囲の地金が
溶解する原因は、Al2 O3 系介在物は融点が高く、超
硬質のため圧延時に分断されることがなく、焼鈍後の調
質圧延において地金に亀裂が生じ、そこから腐食が進む
ためと考えられた。これに対して、MnO,MnS系介
在物の場合は、融点が低く軟質なため、熱間圧延,冷間
圧延で圧延方向に長く分断して伸ばされて一個一個にば
らばらになるので、地金には腐食の起点になるような亀
裂が生じることが激減する。The reason why the metal around the large Al 2 O 3 -based inclusions is dissolved is that the Al 2 O 3 -based inclusions have a high melting point and are not divided during rolling because they are superhard. It was considered that cracks occurred in the base metal during temper rolling and corrosion proceeded from there. On the other hand, in the case of MnO and MnS inclusions, since they have a low melting point and are soft, they are elongated in the rolling direction by hot rolling and cold rolling, and are elongated into individual pieces. The number of cracks that can become the starting point of corrosion is drastically reduced.
【0041】以上のことから、大きなAl2 O3 系介在
物が原板表面に露出していると、ぶりきのスズ層のピン
ホールになり、腐食液に接すると周囲の地金が大きく溶
解して腐食缶になることが容易に推測できる。一方、鋼
Aに存在する非金属介在物の個数は非常に多いが、その
大きさは10数μm程度のものの連続した形で存在して
おり、これにスズめっきを施すとスズで十分に覆い隠さ
れるため、なんら問題にならないと考えられる。From the above, if a large Al 2 O 3 -based inclusion is exposed on the surface of the original plate, it becomes a pinhole in the tin layer of tinplate, and when it comes into contact with the corrosive liquid, the surrounding metal is largely dissolved. It can be easily guessed that it will become a corrosion can. On the other hand, the number of non-metallic inclusions present in Steel A is very large, but the size thereof is present in a continuous form with a size of about several tens of μm, and if this is plated with tin, it is sufficiently covered with tin. Because it is hidden, it is unlikely to cause any problems.
【0042】そして、非金属介在物組成がMnO,Mn
S主体のため、周囲の地金の溶解程度も小さい鋼Cは、
小さなAl2 O3 系介在物が少量存在しているが、5μ
mを超えるものもあり、それらの周囲の地金が溶解さ
れ、腐食缶になるものと考えられる。以上のようなこと
から、耐食性に優れた缶用鋼板としては、腐食缶につな
がらない清浄度を有するものが要望されるといえる。The composition of non-metallic inclusions is MnO, Mn.
Steel C, which is mainly S, has a low degree of melting of the surrounding metal,
There is a small amount of small Al 2 O 3 inclusions, but 5μ
Some of them exceed m, and it is considered that the metal around them melts to form a corrosion can. From the above, it can be said that a can steel sheet having excellent corrosion resistance is required to have cleanliness that does not lead to a corrosive can.
【0043】もっとも、Mnで脱酸すると多量のMnが
必要となるために製品コストが高くなると共に、硬質と
なって加工性も悪くなるという別の問題点が生じること
になる。以上述べたような調査結果に基づいて、Al2
O3 系介在物の個数と大きさは鋼中Al量と関係すると
推定されたので、本発明者らは、次に鋼中Al量と鋼中
酸素(介在物の総量に相当する)及びAl2 O3 系介在
物の大きさとの関係を調べた。However, deoxidation with Mn causes another problem that a large amount of Mn is required and thus the product cost becomes high, and the work becomes hard and the workability deteriorates. Based on the investigation results as described above, Al 2
Since the number and size of O 3 -based inclusions were estimated to be related to the amount of Al in steel, the present inventors next examined the amount of Al in steel, oxygen in steel (corresponding to the total amount of inclusions) and Al. The relationship with the size of 2 O 3 -based inclusions was investigated.
【0044】その結果、鋼中Al量を0.03%以上に多く
し真空脱ガス,脱炭,脱酸処理を施すと、図6に示すよ
うに、鋼中酸素量も少なくなることがわかった。しか
し、介在物の大きさは5μm以下にはならなかった。こ
の酸素はAl強脱酸鋼においてはAl2 O3 クラスター
を生成し易くなるので、見掛け上大きな介在物となって
ストークスの法則で浮上分離することから、鋼中酸素量
が減少したと考えられる。これに対応して鋼中のAl2
O3 系介在物の量も減少する。As a result, it was found that when the amount of Al in the steel was increased to 0.03% or more and vacuum degassing, decarburization, and deoxidation treatment were performed, the amount of oxygen in the steel also decreased. However, the size of the inclusions did not fall below 5 μm. Since this oxygen easily forms Al 2 O 3 clusters in the Al strong deoxidized steel, it becomes apparently large inclusions and floats and separates according to Stokes' law, and it is considered that the oxygen content in the steel has decreased. . Correspondingly, Al 2 in steel
The amount of O 3 -based inclusions is also reduced.
【0045】本発明者らは、以上のようにして得られた
知見を基に、鋼中に残存する介在物の大きさを5μm以
下にすることを研究した。すなわち、連続鋳造法におい
て、例えば本出願人が先に出願した「溶融金属中の非金
属介在物の除去装置(特開平1−312024号)」を
利用して、該装置内に取鍋の溶鋼をタンディッシュに流
入し、そのタンディッシュ内の溶鋼を旋回流とすること
を試みた。その結果、旋回流とした後に鋳込むと、鋼中
の酸素が30ppm以下となると同時に露出介在物も5
μm以下なることが判明した。こうして得られた鋼を使
用して、常法で薄目付ぶりきを製造し、そのぶりきを用
い、先に述べたと同様にDRD缶をつくると共に、腐食
性の強い魚肉の味付液による腐食促進試験を行った所、
腐食缶は発生しないことを新規に見いだすことができ
た。The present inventors have studied to reduce the size of inclusions remaining in steel to 5 μm or less based on the findings obtained as described above. That is, in the continuous casting method, for example, by utilizing the “apparatus for removing non-metallic inclusions in molten metal (Japanese Patent Laid-Open No. 1-312024)” previously filed by the present applicant, the molten steel of the ladle is placed in the apparatus. Was introduced into the tundish, and an attempt was made to make molten steel in the tundish into a swirl flow. As a result, when the steel is cast after the swirling flow, the oxygen content in the steel is reduced to 30 ppm or less, and at the same time, the amount of exposed inclusions becomes 5
It was found to be less than μm. Using the steel thus obtained, a tinted tin plate is manufactured by a conventional method, and using the tin plate, a DRD can is formed in the same manner as described above, and the corrosive fish meat is corroded by a seasoning liquid. The place where the acceleration test was done,
It was newly found that no corrosion cans were generated.
【0046】更に、本発明者らは、以上の知見を利用し
て、Al2 O3 系介在物の形態を制御するべく鋭意研究
を進めた。Al2 O3 系介在物の形態制御法としては、
従来、溶鋼中へ金属Al棒を投入して脱酸する方法が行
われていたが、本発明者らは金属Al棒の代わりにAl
−Ca線を使用して脱酸する方法を採用した。これによ
り、介在物をAl2 O3 −CaOの形態に変化させるこ
とが可能と考えたためである。こうして得られた鋼を常
法でぶりきに仕上げ、スズ層中のピンホール検査及び原
板での非金属介在物検査を行った。その結果、2000
倍の拡大倍率で検出可能な約1μm以上のAl2 O3 系
介在物は皆無であり、5μm以上の介在物が検出されて
も、それは全てAl2 O3 −CaOに形態制御されてい
ることが確認された。Furthermore, the present inventors have made extensive studies based on the above findings in order to control the morphology of Al 2 O 3 type inclusions. A method for controlling the morphology of Al 2 O 3 -based inclusions includes
Conventionally, a method of deoxidizing a metal Al rod by inserting it into molten steel has been carried out. However, the present inventors used Al instead of the metal Al rod.
-The method of deoxidizing using Ca wire was adopted. This is because it is considered that the inclusions can be changed to the form of Al 2 O 3 —CaO. The steel thus obtained was tinted by a conventional method, and a pinhole inspection in the tin layer and a non-metallic inclusion inspection in the original plate were performed. As a result, 2000
There is no Al 2 O 3 type inclusion of about 1 μm or more that can be detected at a magnification of 2 times, and even if an inclusion of 5 μm or more is detected, it is all controlled by Al 2 O 3 -CaO. Was confirmed.
【0047】また、このぶりきを用いてDRD缶を製造
し、前述の腐食促進試験で腐食評価を行ったところ、腐
食缶は皆無であった。以上のことから、極薄・高強度鋼
板を使い、複雑な缶デザインにして缶強度を維持し、そ
の上、空缶コスト削減のためスズ目付量を減少したぶり
きを用いても腐食缶が発生しない耐食性に優れた缶用鋼
板をつくるには、5μm以上の超硬質のAl2 O3 系介
在物を皆無とし、その目安として鋼中の酸素量を30p
pm以下にすることが効果的であり、そのためには以下
の手段が有効であることが新規に明らかになった。A DRD can was manufactured using this tin plate, and corrosion was evaluated by the above-described corrosion acceleration test. As a result, no corrosive can was found. From the above, ultra-thin high-strength steel sheets are used to maintain a strong can with a complicated can design, and in addition, tin can reduce the weight of tin to reduce the cost of empty cans, but corrosive cans do not corrode. In order to produce a steel sheet for cans that does not generate corrosion and has excellent corrosion resistance, there is no super hard Al 2 O 3 inclusions of 5 μm or more.
It has been newly revealed that the pm or less is effective, and the following means are effective for that.
【0048】鋼中のAl量を0.03%以上に多くして全
酸素量の少ない鋼にする。 介在物をAl2 O3 −CaOに形態制御する。 タンディッシュ内の溶鋼流を旋回流として介在物を分
離除去し、鋼中の全酸素量を30ppm以下にした鋼を
つくり、これを原板にする。 本発明者らは、以上の研究で得られた諸知見に基づいて
本発明を完成するに至ったものである。The Al content in the steel is increased to 0.03% or more to obtain a steel having a low total oxygen content. The inclusions are controlled to form Al 2 O 3 —CaO. Inclusions are separated and removed by using the molten steel flow in the tundish as a swirling flow to produce steel in which the total oxygen content in the steel is 30 ppm or less, and this is used as a base plate. The present inventors have completed the present invention based on the findings obtained in the above research.
【0049】以下に、本発明の耐食性に優れた缶用鋼板
の各成分元素含有量の臨界的意義を説明する。 C:0.08(重量)%以下の低炭素鋼の場合 炭素(C)は硬度に及ぼす影響が大きい。T−1〜T−
6,DR−8〜DR−10の硬度製品を得るためには、
炭素量が0.08%以下であればよく、その限定条件を満た
し目標硬度に応じた含有量とすることで所要製品を製造
することができる。しかし、図7に示すように、C量が
0.004 以下の極微量になると軟質化し、一方、C量が増
加すると約0.01%において最も硬さが高くなる。したが
って、CAL法によって調質度T−3以下の軟質ぶりき
原板を製造するためには、C量0.004 以下にする必要が
ある。極微量炭素でT−3以上の調質度を得るには、調
質圧延の圧下率を必要硬度に応じた値とする。或いは2
回圧延で得ることができる。 C:0.09〜0.2 %の炭素鋼の場合 上記とは全く逆に2回圧延製品以上の超硬質材を得るに
は、C含有量を0.09%以上にして低圧下率で調質圧延す
ればよい。しかし、C量が0.20%を超えると硬質になり
フランジ加工性が悪くなるため0.20%以下とする。 Si:0.03%以下 Siはぶりきの耐食性を劣化させるほか、さらに材質を
極端に硬化させる元素であるから、Siを過剰に含有さ
せることは避けるべきであり、したがってSiは0.03%
以下とする必要がある。 Mn:0.1 〜0.60% Mnは、一般には熱延コイルの耳割れ発生を防止するた
めに添加されている。耳割れ発生を防止に必要な量とし
てはMnが0.05%以上であればよいが、しかし、本発明
はMnの脱酸力も利用するため下限を0.1 %とした。一
方、Mnは置換型固溶強化元素でもあるため、超硬質材
をつくるのに有効な成分であって必要に応じて添加する
が、多く添加しても経済的でないので、その上限を0.60
%とする。The critical significance of the content of each component element of the steel sheet for cans excellent in corrosion resistance of the present invention will be described below. C: 0.08 (wt)% or less of low carbon steel Carbon (C) has a great influence on hardness. T-1 to T-
In order to obtain hardness products of 6, DR-8 to DR-10,
The carbon content may be 0.08% or less, and the required product can be manufactured by satisfying the limiting conditions and adjusting the content according to the target hardness. However, as shown in FIG.
When the amount is 0.004 or less, it becomes soft, while when the amount of C increases, the hardness becomes highest at about 0.01%. Therefore, in order to manufacture a soft tin plate having a temper of T-3 or less by the CAL method, the C content needs to be 0.004 or less. In order to obtain a temper of T-3 or more with an extremely small amount of carbon, the rolling reduction of the temper rolling is set to a value according to the required hardness. Or 2
It can be obtained by rolling twice. In the case of carbon steel of C: 0.09 to 0.2% In order to obtain a superhard material having a product rolled twice or more, contrary to the above, the C content should be 0.09% or more and temper rolling at a low pressure reduction ratio. . However, if the amount of C exceeds 0.20%, it becomes hard and the flange formability deteriorates, so it is made 0.20% or less. Si: 0.03% or less Since Si is an element that deteriorates the corrosion resistance of tinplate and further hardens the material extremely, it should be avoided that Si is excessively contained. Therefore, Si is 0.03%.
Must be: Mn: 0.1 to 0.60% Mn is generally added to prevent the occurrence of ear cracks in the hot rolled coil. The amount necessary for preventing the occurrence of ear cracks is 0.05% or more of Mn, but in the present invention, the lower limit is set to 0.1% because the deoxidizing power of Mn is also utilized. On the other hand, Mn is also a substitutional solid solution strengthening element, so it is an effective component for forming a superhard material and is added as necessary. However, even if it is added in large amounts, it is not economical, so its upper limit is 0.60.
%.
【0050】S:0.02%以下 Sは、Mn量との関係において過剰に含有すると熱延コ
イルの耳割れを生成する。そのためその含有量は0.02%
以下とする。 P:0.02%以下 Pは、材料を硬化させ、且つぶりきの耐食性を劣化させ
る元素なので過剰の含有は好ましくなく、その含有量を
0.02%以下とする必要がある。S: 0.02% or less If S is contained excessively in relation to the amount of Mn, it will cause edge cracking of the hot rolled coil. Therefore, its content is 0.02%
Below. P: 0.02% or less P is an element that hardens the material and deteriorates the corrosion resistance of tinplate, so excessive content is not preferable and its content is
It should be 0.02% or less.
【0051】Al:0.03〜0.20% Alは、Al2 O3 系介在物を激減させるのに有効な成
分であり、真空脱ガス処理を組み合わせるにしてもその
下限は0.03%にする必要がある。上限は経済的な理由か
ら0.20%とする。 N:0.02%以下 Nは、鋼中に固溶していると軟質な鋼板が得られにくく
不必要な元素であるから、その含有量を0.02%以下とす
る必要がある。Al: 0.03 to 0.20% Al is an effective component for drastically reducing Al 2 O 3 inclusions, and the lower limit must be 0.03% even if vacuum degassing treatment is combined. The upper limit is 0.20% for economic reasons. N: 0.02% or less N is an unnecessary element that makes it difficult to obtain a soft steel sheet when it is in solid solution in steel, so its content must be 0.02% or less.
【0052】Nb:0.001 〜0.1 % Nbは、炭化物形成元素であって、固溶Cの残存を少な
くするとともに加工性を向上させる機能を有し、これら
の効果を得るには0.001 %以上の添加が必要である。一
方、多量に添加すると製造コストを上昇させるので必要
最低限にすることが好ましい。また、Nb系析出物によ
る結晶粒界のピン止め効果により、再結晶温度が高温に
なって連続焼鈍炉の通板作業性が悪くなるのでNbは0.
1 %以下とする。Nb: 0.001 to 0.1% Nb is a carbide forming element and has the function of reducing the amount of solid solution C remaining and improving the workability. To obtain these effects, 0.001% or more is added. is necessary. On the other hand, if added in a large amount, the production cost rises, so it is preferable to make it the necessary minimum. Further, due to the pinning effect of the crystal grain boundaries by the Nb-based precipitates, the recrystallization temperature becomes high and the workability of the continuous annealing furnace during striping deteriorates.
1% or less.
【0053】B:0.0001〜0.005 % Bは、Nbとともに存在することにより、結晶粒の過剰
な粗大化を防ぐ効果がある。また、二次加工脆性の防止
にも有用である。Bは窒化物形成元素なので軟質化に有
効であるが、連続焼鈍時に再結晶粒界にBが偏析して再
結晶を遅らせるので含有量0.005 %以下とし、下限は上
記効果を発揮するのに必要な0.0001%以上にする。B: 0.0001 to 0.005% B, together with Nb, has an effect of preventing excessive coarsening of crystal grains. It is also useful for preventing secondary processing brittleness. Since B is a nitride-forming element, it is effective for softening, but B segregates at the recrystallization grain boundaries during continuous annealing and delays recrystallization, so the content is made 0.005% or less, and the lower limit is necessary to exert the above effect. It should be 0.0001% or more.
【0054】O:30ppm以下 Oは、前述したようにAl2 O3 系介在物を少なくする
ために30ppm以下にする必要がある。これを超えて
多く含まれると、鋼中のAl,Mnあるいは耐火物中の
Si、フラックス中のCa,Na,F等と酸化物を形成
して缶の耐食性を劣化させる原因となる。O: 30 ppm or less O must be 30 ppm or less in order to reduce Al 2 O 3 type inclusions as described above. If it is contained in excess of this amount, it forms an oxide with Al, Mn in steel, Si in refractory, Ca, Na, F, etc. in flux, which causes deterioration of the corrosion resistance of the can.
【0055】[0055]
【実施例】以下、本発明を実施例により詳細に説明す
る。表3,表4に示す成分組成の鋼250tを底吹き転
炉により溶製した。表5,表6に製鋼条件及び圧延条件
を示した。表3は、本発明鋼の成分組成である。EXAMPLES The present invention will be described in detail below with reference to examples. Steel 250t having the composition shown in Tables 3 and 4 was melted by a bottom blowing converter. Tables 5 and 6 show steel making conditions and rolling conditions. Table 3 shows the composition of the steel of the present invention.
【0056】[0056]
【表3】 [Table 3]
【0057】表4は、比較鋼の成分組成である。Table 4 shows the composition of the comparative steels.
【0058】[0058]
【表4】 [Table 4]
【0059】表5は、本発明鋼の製鋼及び圧延条件であ
る。Table 5 shows the steel making and rolling conditions of the steel of the present invention.
【0060】[0060]
【表5】 [Table 5]
【0061】表6は、比較鋼の製鋼及び圧延条件であ
る。Table 6 shows the steel making and rolling conditions for the comparative steels.
【0062】[0062]
【表6】 [Table 6]
【0063】C量が0.03%以下となるように仕上げる
もの(本発明鋼No. 1〜7及び比較鋼の全部)は、溶製
でC量0.03%となして出鋼し、続いてR−H真空脱ガス
処理を施してC量を0.03%未満に脱炭,脱酸した後、A
l線を投入してAl脱酸を行い、続いて炭化物,窒化物
形成元素であるNb,Ti,Bを必要に応じて添加し、
連続鋳造へ進めた。なお、本発明鋼では、介在物を形態
制御する目的でAl棒に代えてAl−Ca線(事前にC
aを混入したもの)を使用したものもある。Those finished so as to have a C content of 0.03% or less (inventive steel Nos. 1 to 7 and all of the comparative steels) were smelted to have a C content of 0.03%, and then tapped, followed by R- H After vacuum degassing treatment to decarburize and deoxidize C to less than 0.03%,
l wire is introduced to deoxidize Al, and then Nb, Ti and B which are carbide and nitride forming elements are added if necessary,
We proceeded to continuous casting. In the steel of the present invention, in order to control the morphology of inclusions, instead of the Al bar, Al-Ca wire (C
(mixed with a) is also used.
【0064】C量が0.03%超になるように仕上げるも
の(本発明鋼No. 8〜15)は、溶製でC量0.03%とな
して出鋼し、続いてR−H真空脱ガス処理で脱酸を施し
た後、Cを必要に応じて添加し、その後Al,炭化物,
窒化物形成元素を必要に応じて添加し、同じく連続鋳造
へと進めた。なお、比較鋼No. 17,18は、比較のた
めAl添加量を本発明鋼の下限値である0.03%より少な
くして製造した。また、比較鋼の表4中の下線を施した
各成分量については、本発明鋼の範囲外の含有量にして
ある。Those finished so that the C content exceeds 0.03% (steel Nos. 8 to 15 of the present invention) were smelted to have a C content of 0.03%, and then tapped, followed by RH vacuum degassing treatment. After deoxidizing with C, C is added if necessary, and then Al, carbide,
A nitride-forming element was added if necessary, and the process was similarly advanced to continuous casting. For comparison, Comparative Steel Nos. 17 and 18 were manufactured with the amount of Al added less than the lower limit of 0.03% of the steel of the present invention. In addition, the amount of each component underlined in Table 4 of the comparative steel is a content outside the range of the steel of the present invention.
【0065】Al脱酸で生じたAl2 O3 系介在物を凝
集合体浮上分離除去するために、適切な時間、脱ガス処
理を施した。そのためにも出鋼温度は高温にした。鋼中
に非金属介在物が残留しないように、転炉でノロ切り
し、取鍋内に持ち込まれたノロに凝固剤を投入して不活
性とした。続いて、連続鋳造においては、取鍋からタン
ディッシュに移す際に空気が侵入しないように工夫した
耐火物ノズルを取り付け、さらに取鍋内のノロがタンデ
ィッシュに持ち込まれないようにも工夫して注湯を行っ
た。In order to remove the Al 2 O 3 -based inclusions generated by Al deoxidation by flocculation and separation by aggregation, degassing was performed for an appropriate time. Therefore, the tapping temperature was set high. In order to prevent non-metallic inclusions from remaining in the steel, the steel was cut into pieces with a converter and a coagulant was added to the pieces brought into the ladle to make it inert. Next, in continuous casting, a refractory nozzle was installed to prevent air from entering the ladle when transferring it from the ladle to the tundish. Poured.
【0066】タンディッシュ(T/D)は大型(75
t)のものを使用し、本発明鋼の場合及び比較鋼No. 1
8については、T/D内の溶鋼を電磁攪拌装置を用いて
旋回流とした後、鋳型に注入した。その他の比較鋼につ
いては、電磁攪拌装置による旋回流方式に代えて、比較
のためにT/D内で介在物が凝集合体浮上分離できるよ
うに工夫した従来の堰を築く方式で鋳込んだ。Tundish (T / D) is large (75
In the case of the present invention steel and comparative steel No. 1
Regarding No. 8, molten steel in T / D was swirled using an electromagnetic stirrer and then poured into a mold. For other comparative steels, instead of the swirl flow method using an electromagnetic stirrer, casting was performed by a method of constructing a conventional weir, which was devised so that inclusions could be flocculated and aggregated in the T / D for comparison.
【0067】一方、T/Dから鋳型への注入の際のイマ
ージョンノズルは、介在物が鋳型内に深く運ばれないよ
うに水平に近い角度を有するノズルを用いた。また、連
続鋳造機は垂直曲げ型連続鋳造機であり、やはり微量で
あっても混入した介在物が深く運ばれて粘調層に捕捉さ
れないような工夫をして、介在物の少ない清浄度の高い
超高清浄度鋼片を製造するように留意した。On the other hand, as the immersion nozzle at the time of injecting from the T / D into the mold, a nozzle having a nearly horizontal angle was used so that inclusions were not carried deep into the mold. In addition, the continuous casting machine is a vertical bending type continuous casting machine, and even if it is a small amount, it is devised so that the mixed inclusions are not deeply carried and trapped in the viscous layer, and the cleanliness of the inclusions is small. Care was taken to produce high ultra-cleanliness billets.
【0068】次に、上記連続鋳造によって得られたスラ
ブ鋳片を、熱間圧延,酸洗,冷間圧延,連続焼鈍,調質
圧延(ここで圧延率を1〜50%まで変化させ、鋼板に
加工硬化を加えた。表5,表6参照)した後、ハロゲン
タイプ電気スズめっき,エポキシフェノール系塗装等の
諸工程を経て加工して缶詰用ぶりきとし、更にこのぶり
きを使って製缶した。Next, the slab slab obtained by the above continuous casting was hot-rolled, pickled, cold-rolled, continuously annealed, and temper-rolled (where the rolling ratio was changed to 1 to 50%, the steel sheet (See Table 5 and Table 6), and then processed through various processes such as halogen type electrotin plating and epoxy phenolic coating to make tin plate for canning, and further manufacture using this tin plate. I made a can.
【0069】その缶に内容物として魚肉の味付液を充填
し、75℃恒温室での経時調査を一年間おこなった。な
お、この缶は図1に示したシングル,ダブル,トリプル
の各ネックイン加工を施したものを使用した。上記経時
調査で行った試験,検査項目は、耐錆性試験,介在物検
査,洩れ缶試験とした。The can was filled with a seasoning liquid for fish meat as a content, and a time course was measured in a constant temperature chamber at 75 ° C. for one year. In addition, this can used the thing which performed each neck-in process of the single, double, and triple shown in FIG. The tests and inspection items conducted in the above-mentioned time course examination were a rust resistance test, inclusion inspection, and a leak can test.
【0070】耐錆性試験は、無塗装の試験片を下記の条
件で乾燥状態と湿潤状態を30分毎に繰り返す試験槽中
に96時間保持し、発錆状況を観察した。 乾燥状態〔温度25℃,相対湿度50%〕 湿潤状態〔温度50℃,相対湿度98%〕 結果は、発錆が認められたものを×印、認められなかっ
たものを○印で表し、表5,表6に示した。In the rust resistance test, the uncoated test piece was kept for 96 hours in a test tank in which the dry state and the wet state were repeated every 30 minutes under the following conditions for 96 hours, and the rusting condition was observed. Dry state [Temperature 25 ° C, relative humidity 50%] Wet state [Temperature 50 ° C, relative humidity 98%] The results are shown in the table with a mark X when rust was observed, and with a mark O when it was not. 5, shown in Table 6.
【0071】介在物検査は、JIS光学顕微鏡400倍
の視野で200視野を観察し、5μm以上のAl2 O3
系介在物を観察した。結果は、介在物が発見されたもの
を×印、発見されなかったものを○印で表し、表5,表
6に示した。洩れ缶試験は、充填されている味付液の洩
れの有無を肉眼で観察し、洩れが発見されたものを×
印、発見されなかったものを○印で表し、表5,表6に
示した。The inclusions are inspected by observing 200 fields of view with a JIS optical microscope at a magnification of 400 times and observing Al 2 O 3 of 5 μm or more.
The system inclusions were observed. The results are shown in Tables 5 and 6 in which the inclusions were found in x and the inclusions were not found. In the leak can test, the filled seasoning liquid is visually inspected for leaks, and if leaks are found, x
The marks and those not found are indicated by ◯ and shown in Tables 5 and 6.
【0072】この試験結果では、本発明鋼を用いた各ネ
ックイン加工缶の場合、脱酸法がAl棒脱酸法またはA
l−Ca線脱酸法を問わず、洩れ缶は発生しなかった。
一方、Al棒脱酸法による従来法の鋼片を使ったものか
らは、発生率で1ppmの洩れ缶が発生した。また、鋼
中酸素30ppm以下のもの及Al2 O3 系介在物の粒
径が5μm以下のものには洩れ缶は発生しなかった。し
たがって、鋼の清浄度を改善することによって腐食缶の
発生を防止できるという効果のあることが判明した。According to the test results, in the case of each neck-in processed can using the steel of the present invention, the deoxidizing method is the Al bar deoxidizing method or the A deoxidizing method.
No leak cans were generated regardless of the l-Ca line deoxidation method.
On the other hand, a leak can having an occurrence rate of 1 ppm was generated from the one using the conventional steel billet by the Al rod deoxidizing method. No leak cans were generated in the steel containing oxygen of 30 ppm or less and the Al 2 O 3 -based inclusions having a particle diameter of 5 μm or less. Therefore, it has been found that the improvement of the cleanliness of steel has the effect of preventing the formation of a corrosion can.
【0073】また、電気スズめっき後、供試材を採取
し、ロックウエル硬さ(HR−30T)を測定した結
果、本発明により規制される範囲の成分組成の鋼板であ
れば、CAL法でも調質度T−1が得られるし、さらに
調質圧延の圧延率を高くして加工硬化を加えたもの(本
発明鋼No. 2,3,4,5,6,7)は、それぞれの圧
延率に応じてT−2〜T−6あるいはDR−8〜DR−
10のものが得られることが明らかにされた。After the electroplating with tin, the sample material was sampled and the Rockwell hardness (HR-30T) was measured. As a result, if the steel sheet had a composition within the range regulated by the present invention, the CAL method was used. The quality T-1 is obtained, and the workability is further increased by increasing the rolling ratio of temper rolling (steel No. 2, 3, 4, 5, 6, 7 of the present invention). T-2 to T-6 or DR-8 to DR- depending on the rate
It was revealed that 10 products were obtained.
【0074】ロックウエル硬さを(HR−30T)で5
0以下にした後、調質圧延の圧延率で調質度T−1〜T
−6につくりわけることができる。Rockwell hardness (HR-30T) of 5
After the temperature is set to 0 or less, the tempering rate of the temper rolling is T-1 to T.
Can be divided into -6.
【0075】[0075]
【発明の効果】以上説明したように、本発明によれば、
鋼中のAl成分量を0.03%以上に調整するとともに、鋼
中の全酸素量を30ppm以下、鋼中のAl2 O3 系介
在物の最大径を5μm以下とした連続鋳造鋼片を用い、
常法で熱間圧延,酸洗,冷間圧延後に連続焼鈍を施し、
その後に調質圧延することにより軟質材T−1が得ら
れ、さらに調質圧延の圧延率の変化によりT−1〜T−
6,DR−8〜DR−10に至る軟質,硬質,超硬質材
がつくりわけられ、且つ種々のネックイン加工を施した
缶においても洩れ缶の発生を防止でき、生産性の向上と
不良率の改善が図れるという効果が得られる。As described above, according to the present invention,
While adjusting the Al content in the steel to 0.03% or more, the total oxygen content in the steel is 30 ppm or less, and the maximum diameter of the Al 2 O 3 -based inclusions in the steel is 5 μm or less.
Hot rolling, pickling, cold rolling followed by continuous annealing in the usual manner,
After that, the soft rolling material T-1 is obtained by temper rolling, and T-1 to T- can be obtained by changing the rolling ratio of the temper rolling.
6, DR-8 to DR-10 soft, hard, and super hard materials are created, and even in cans that have been subjected to various neck-in processes, it is possible to prevent the occurrence of leaking cans, improve productivity, and improve the defect rate. It is possible to obtain the effect of improving the above.
【0076】なお、本発明の耐食性に優れた缶用鋼板は
Sn,Ni,Cu,Znめっきにも適用できるし、それ
らのめっき鋼板にコイル塗装あるいはフィルムラミネー
ト後にDRD缶,DTR缶,DWI缶に適用しても完全
な缶に仕上がることはいうまでもない。The steel sheet for cans having excellent corrosion resistance according to the present invention can be applied to Sn, Ni, Cu and Zn plating, and can be applied to DRD cans, DTR cans and DWI cans after coil coating or film lamination on these plated steel plates. It goes without saying that even if it is applied, it becomes a complete can.
【図1】各種缶デザインを例示した図で(a)はシング
ルネックイン缶、(b)はダブルネックイン缶、(c)
はトリプルネックイン缶、(d)はストレート缶を表し
たものである。FIG. 1 is a diagram illustrating various can designs, in which (a) is a single neck-in can, (b) is a double-neck-in can, and (c).
Is a triple neck-in can, and (d) is a straight can.
【図2】腐食試験に供したぶりき表面の非金属介在物を
電子顕微鏡で観察したスケッチ図である。FIG. 2 is a sketch diagram in which non-metallic inclusions on the tin plate surface subjected to a corrosion test are observed with an electron microscope.
【図3】缶用鋼板中の非金属介在物の個数と腐食缶発生
指数との関係を示すグラフである。FIG. 3 is a graph showing the relationship between the number of non-metallic inclusions in a can steel sheet and the corrosive can generation index.
【図4】腐食試験に供したぶりき表面のAl2 O3 系介
在物を電子顕微鏡で観察したスケッチ図である。FIG. 4 is a sketch diagram in which an Al 2 O 3 type inclusion on the tin plate surface subjected to a corrosion test is observed by an electron microscope.
【図5】腐食試験に供したぶりき表面のMnO,MnS
系介在物を電子顕微鏡で観察したスケッチ図である。FIG. 5: MnO and MnS on tin plate surface subjected to corrosion test
It is the sketch figure which observed the system inclusion with the electron microscope.
【図6】鋼中Al量と鋼中酸素量との関係を示すグラフ
である。FIG. 6 is a graph showing the relationship between the amount of Al in steel and the amount of oxygen in steel.
【図7】鋼中のC量と鋼のロックウエル硬さとの関係を
示すグラフである。FIG. 7 is a graph showing the relationship between the amount of C in steel and the Rockwell hardness of steel.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 龍 尚稔 千葉県千葉市中央区川崎町1番地 川崎製 鉄株式会社千葉製鉄所内 (72)発明者 古主 泰子 千葉県千葉市中央区川崎町1番地 川崎製 鉄株式会社千葉製鉄所内 (72)発明者 登坂 章男 千葉県千葉市中央区川崎町1番地 川崎製 鉄株式会社技術研究本部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minoru Ryusho Inventor 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Kawasaki Steel Co., Ltd. Chiba Works (72) Inventor Yasuko Furusho 1 Kawasaki-cho, Chuo-ku, Chiba-shi Kawasaki Steel Co., Ltd. Chiba Works (72) Inventor Akio Tosaka 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Kawasaki Steel Co., Ltd.
Claims (6)
Si:0.03%以下、Mn:0.1 〜0.60%、P:0.02%以
下、S:0.02%以下、N:0.02%以下、Al:0.03〜0.
20%、残部は不可避的不純物を除きFeよりなる炭素鋼
であって、鋼中の全酸素量を30ppm以下、鋼中のAl
2 O3 系介在物の最大径を5 μm以下としたことを特徴
とする耐食性に優れた缶用鋼板。1. The weight ratio of the components is C: 0.08% or less,
Si: 0.03% or less, Mn: 0.1 to 0.60%, P: 0.02% or less, S: 0.02% or less, N: 0.02% or less, Al: 0.03 to 0.
Carbon steel consisting of 20%, the balance being Fe excluding unavoidable impurities, the total oxygen content in the steel being 30 ppm or less, Al in the steel
A steel sheet for cans having excellent corrosion resistance, which has a maximum diameter of 2 O 3 -based inclusions of 5 μm or less.
低炭素鋼からなることを特徴とする耐食性に優れた缶用
鋼板。2. A steel sheet for cans having excellent corrosion resistance, which is made of an ultra-low carbon steel having a C content of 0.02% or less according to claim 1.
炭素鋼からなることを特徴とする耐食性に優れた缶用鋼
板。3. A steel plate for a can having excellent corrosion resistance, which is made of carbon steel having a C content of 0.09 to 0.2% in claim 1.
0001〜0.005 %を含有することを特徴とする請求項1な
いし請求項3のいずれかに記載の耐食性に優れた缶用鋼
板。4. Nb: 0.001 to 0.1% in the composition, B: 0.
The steel sheet for cans having excellent corrosion resistance according to any one of claims 1 to 3, which contains 0001 to 0.005%.
3 系としたことを特徴とする請求項1ないし請求項4の
いずれかに記載の耐食性に優れた缶用鋼板。5. The composition of inclusions in steel is CaO--Al 2 O.
The steel sheet for cans having excellent corrosion resistance according to any one of claims 1 to 4, wherein the steel sheet is made of 3 series.
ィッシュに移して旋回流により介在物を凝集浮上分離せ
しめ、かくして得られた高清浄度の鋼片を熱延,酸洗,
冷延したものを連続焼鈍し、その後調質圧延することを
特徴とする請求項1ないし請求項5のいずれかに記載の
耐食性に優れた缶用鋼板の製造方法。6. The molten steel is degassed, decarburized and deoxidized, and then transferred to a tundish to cause inclusions to flocculate and separate by a swirling flow. The thus obtained high cleanliness steel strip is hot rolled, pickled,
The method for producing a steel sheet for cans having excellent corrosion resistance according to any one of claims 1 to 5, wherein the cold rolled material is continuously annealed and then temper-rolled.
Priority Applications (1)
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JP27562093A JP3307737B2 (en) | 1993-11-04 | 1993-11-04 | Steel plate for cans with excellent corrosion resistance and its manufacturing method |
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Application Number | Priority Date | Filing Date | Title |
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JP27562093A JP3307737B2 (en) | 1993-11-04 | 1993-11-04 | Steel plate for cans with excellent corrosion resistance and its manufacturing method |
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Publication Number | Publication Date |
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JPH07126806A true JPH07126806A (en) | 1995-05-16 |
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ID=17557993
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7641169B2 (en) | 2003-05-29 | 2010-01-05 | Sumitomo Metal Industries, Ltd. | Substrate for a stamper |
KR101355596B1 (en) * | 2011-09-28 | 2014-01-28 | 현대제철 주식회사 | Refining method of boron-addes molten steel for thin slab |
CN108866451A (en) * | 2018-07-17 | 2018-11-23 | 张家港扬子江冷轧板有限公司 | Cold-rolled steel plate for 240 MPa-level yield strength structure and preparation method thereof |
CN111424204A (en) * | 2018-01-31 | 2020-07-17 | 日照钢铁控股集团有限公司 | Production process of calcium-treatment-free low-carbon silicon-containing killed clean steel |
-
1993
- 1993-11-04 JP JP27562093A patent/JP3307737B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7641169B2 (en) | 2003-05-29 | 2010-01-05 | Sumitomo Metal Industries, Ltd. | Substrate for a stamper |
KR101355596B1 (en) * | 2011-09-28 | 2014-01-28 | 현대제철 주식회사 | Refining method of boron-addes molten steel for thin slab |
CN111424204A (en) * | 2018-01-31 | 2020-07-17 | 日照钢铁控股集团有限公司 | Production process of calcium-treatment-free low-carbon silicon-containing killed clean steel |
CN111424204B (en) * | 2018-01-31 | 2021-03-19 | 日照钢铁控股集团有限公司 | Production process of calcium-treatment-free low-carbon silicon-containing killed clean steel |
CN108866451A (en) * | 2018-07-17 | 2018-11-23 | 张家港扬子江冷轧板有限公司 | Cold-rolled steel plate for 240 MPa-level yield strength structure and preparation method thereof |
Also Published As
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