JP4019083B2 - Aluminum alloy cold rolled sheet for bottle cans with excellent high temperature characteristics - Google Patents
Aluminum alloy cold rolled sheet for bottle cans with excellent high temperature characteristics Download PDFInfo
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本発明は、ボトル缶(飲料缶)の缶胴材として、0.2mm以下(缶胴中央部の肉厚が薄いところでは120 〜130 μm程度)の板厚に薄肉化されて高温で熱処理された際にも、強度低下が少なく高強度が確保でき、かつ、変形もし難い、などの高温特性に優れたボトル缶用アルミニウム合金冷延板(ボトル缶用素材板)に関するものである。なお、本発明で言うアルミニウム合金冷延板とは、熱間圧延−冷間圧延を通じて圧延された圧延板(冷間圧延板)である。以下、アルミニウム合金をAl合金とも言う。 The present invention is a can body material for a bottle can (beverage can), which is thinned to a plate thickness of 0.2 mm or less (about 120 to 130 μm where the thickness of the central portion of the can body is thin) and heat-treated at a high temperature. In addition, the present invention relates to an aluminum alloy cold-rolled plate for bottle cans (a material plate for bottle cans) having excellent high-temperature characteristics such as low strength reduction, ensuring high strength and being difficult to deform. In addition, the aluminum alloy cold-rolled sheet referred to in the present invention is a rolled sheet (cold-rolled sheet) rolled through hot rolling-cold rolling. Hereinafter, the aluminum alloy is also referred to as an Al alloy.
アルミニウム系飲料缶としては、缶胴体と缶蓋(缶エンド)とをシーミング加工することによって得られる2ピースアルミニウム缶が多用されている。前記缶胴体は、アルミニウム系冷間圧延板をDI加工(深絞り加工及びしごき加工)し、所定のサイズにトリミングを施した後、脱脂・洗浄処理を行い、さらに塗装および印刷を行って焼付け(ベーキング)を行い、缶胴縁部をネッキング加工及びフランジ加工することによって製造されている。 As an aluminum-based beverage can, a two-piece aluminum can obtained by seaming a can body and a can lid (can end) is frequently used. The can body is DI-processed (deep drawing and ironing) an aluminum cold-rolled plate, trimmed to a predetermined size, degreased and washed, and then painted and printed for baking ( The can body edge is necked and flanged.
前記缶胴体用の冷間圧延板としては、従来からAl−Mg−Mn系合金であるJIS3004合金、3104合金等の硬質板が広く用いられている。このJIS3004合金、3104合金は、しごき加工性に優れており、強度を高めるために高圧延率で冷間圧延を施した場合でも比較的良好な成形性を示すことから、DI缶胴材として好適であるとされている。 Conventionally, hard plates such as JIS3004 alloy and 3104 alloy, which are Al-Mg-Mn alloys, have been widely used as cold rolled plates for the can body. This JIS3004 alloy and 3104 alloy are excellent in ironing workability, and show relatively good formability even when subjected to cold rolling at a high rolling rate in order to increase strength. It is said that.
一方、ボトル缶は、アルミニウム合金板の両面に熱可塑性樹脂被膜層が形成され、潤滑剤が塗布されたものを打ち抜いてブランクを得、このブランクを絞り加工してカップ状に成形し、次いで、このカップ状の成形品に対し、再絞り加工とストレッチ加工又はしごき加工(DI加工)を行って、胴部が小径化され、薄肉化された有底円筒状の缶を成形する。そして、缶の底部側を複数回絞り加工することにより、肩部と未開口の口部を成形し、洗浄及びトリミング等の後に、缶胴部に印刷・塗装工程を実施し、口部を開口してカール部及びネジ部を形成し(ネジ・カール成形)、ネジ部の反対側の部分に対しネックイン加工とフランジ加工を施し、シーマーにより、別途成形した底蓋を巻き締めすることによりボトル缶が得られる(特許文献1参照)。 On the other hand, in the bottle can, a thermoplastic resin coating layer is formed on both surfaces of the aluminum alloy plate, a blank is obtained by punching out the one coated with a lubricant, the blank is drawn into a cup shape, The cup-shaped molded product is subjected to redrawing and stretching or ironing (DI processing) to form a bottomed cylindrical can with a barrel having a reduced diameter and a reduced thickness. Then, the bottom side of the can is drawn multiple times to form a shoulder and an unopened mouth, and after washing and trimming, a printing / painting process is performed on the can body, and the mouth is opened. Then, the curled part and the threaded part are formed (screw / curl molding), the neck part and the flange process are applied to the part on the opposite side of the threaded part, and the bottle is formed by tightening the separately formed bottom lid with a seamer. A can is obtained (see Patent Document 1).
このように、2ピース缶では、アルミニウム合金板に、下地処理(クロメート等)を行なった後、樹脂被覆(樹脂塗布又はフィルムラミネート)を行ない、続いて円形のブランクに打抜き、カップ成形した後、絞りしごき加工を施し、印刷・塗装、ネッキング、トリミング等の処理を実施している。 In this way, in the two-piece can, after performing the base treatment (chromate, etc.) on the aluminum alloy plate, the resin coating (resin coating or film lamination) is performed, and then punched into a circular blank and cup-shaped, Drawing and ironing is performed, and printing, painting, necking, trimming, etc. are performed.
また、ネジ付きの口部を有するボトル缶では、アルミニウム合金板に、下地処理(クロメート等)を行なった後、樹脂被覆(樹脂塗布又はフィルムラミネート)を行ない、続いて円形のブランクに打抜き、カップ成形した後、絞りしごき加工を施し、トリミング、印刷及び塗装を行ない、ネジ・カール成形後、ネックフランジ成形を実施している。 For bottle cans with threaded mouths, the aluminum alloy plate is grounded (chromate, etc.), then coated with resin (resin coating or film lamination), then punched into a circular blank, After molding, drawing and ironing is performed, trimming, printing and painting are performed, and after screw / curl molding, neck flange molding is performed.
ボトル缶の缶胴はDI加工直後には缶胴の水平方向断面が略真円状になっているのが普通である。しかし、印刷塗装時及びラミネートフィルムの密着性を向上させるための熱処理時に、缶胴は200℃以上の温度まで加熱される。 The can body of a bottle can usually has a substantially circular cross section in the horizontal direction immediately after DI processing. However, the can body is heated to a temperature of 200 ° C. or higher during printing and heat treatment for improving the adhesion of the laminate film.
この際、缶胴自体は元の約0.3〜0.4mm程度の板厚の冷延板から、0.2mm以下の肉厚にまで、薄肉化されている。したがって、このような200℃を超えるような高温における熱処理を受けると、缶胴は、DI加工時の加工歪及び残留応力が開放され、熱軟化が起きる。 At this time, the can body itself is thinned from a cold-rolled sheet having a thickness of about 0.3 to 0.4 mm to a thickness of 0.2 mm or less. Therefore, when subjected to heat treatment at such a high temperature exceeding 200 ° C., the can body is freed from processing strain and residual stress during DI processing, and thermal softening occurs.
この場合に、軟化しやすい材料では、軟化の度合いが顕著であり、缶の強度や硬度が著しく低下し、十分な缶強度を確保できなくなるという問題点がある。 In this case, a material that is easily softened has a problem that the degree of softening is significant, the strength and hardness of the can are significantly reduced, and sufficient can strength cannot be secured.
また、缶の円周方向について軟化の度合いが不均一になるため、缶胴の横断面が、成形された真円ではなく、楕円となって変形してしまい、缶胴の形状が不均一となるという問題点がある。 Also, since the degree of softening becomes uneven in the circumferential direction of the can, the cross section of the can body is deformed as an ellipse, not a formed perfect circle, and the shape of the can body is uneven. There is a problem of becoming.
近年では、缶軽量化の要求から、アルミニウム缶の板厚が0.2mm以下のレベルで、ますます薄くなってきており、上記熱軟化による、缶胴の強度や硬度の低下、缶胴の形状不均一化などの現象が顕著になってきている。 In recent years, due to the demand for lighter cans, the thickness of aluminum cans has become thinner and thinner at a level of 0.2 mm or less. Phenomena such as non-uniformity are becoming prominent.
更に、近年、缶の生産性向上の観点から、前記印刷塗装時及びラミネートフィルムの密着性を向上させるための熱処理が、例えば、290℃×20秒と、より高温化、短時間化された高速化が進展している。このような傾向も、上記熱軟化による、缶胴の強度や硬度の低下や、缶胴の形状不均一化をより助長する。 Furthermore, in recent years, from the viewpoint of improving the productivity of cans, the heat treatment for improving the adhesion of the print coating and the laminate film has been performed at a higher temperature and a shorter time, for example, 290 ° C. × 20 seconds. Is progressing. Such a tendency further promotes a decrease in strength and hardness of the can body and non-uniform shape of the can body due to the thermal softening.
これに対して、この熱軟化による缶胴の強度低下や変形を防止すべく、缶胴の板厚を増せば、缶重量の増加となり、また、板厚を増大させずにアルミニウム材料自体の強度を増加させると、前記しごき成形時に、破断が生じたりするという不都合がある。したがって、このような問題に対して、従来の胴缶材料や方法だけでは、対応できない。 On the other hand, if the plate thickness of the can body is increased in order to prevent the strength reduction and deformation of the can body due to this thermal softening, the weight of the can increases, and the strength of the aluminum material itself without increasing the plate thickness. When the value is increased, there is a disadvantage that breakage occurs during the ironing. Therefore, it is impossible to deal with such a problem only by the conventional can material and method.
上記熱軟化による缶胴の形状不均一化に対して、従来から、この塗装熱処理時の熱変形を防止し、真円度が高いDI缶を得ることができるDI缶用アルミニウム合金板が提案されてはいる(特許文献2)。具体的には、DI缶用アルミニウム合金板として、Mn:0.5乃至1.3質量%、Mg:0.5乃至1.3質量%、Cu:0.1乃至0.3質量%、Fe:0.2乃至0.6質量%、Si:0.1乃至0.5質量%を含有するアルミニウム合金組成によって、ベーキング温度T(℃)が230乃至270℃の条件で、20分間熱処理したときの、熱処理前後の引張り強さの変化ΔTSを小さくしようとするものである。 Conventionally, an aluminum alloy plate for DI cans has been proposed that can prevent the thermal deformation during the coating heat treatment and obtain a DI can with high roundness against the uneven shape of the can body due to the heat softening. (Patent Document 2). Specifically, as an aluminum alloy plate for a DI can, Mn: 0.5 to 1.3% by mass, Mg: 0.5 to 1.3% by mass, Cu: 0.1 to 0.3% by mass, Fe When heat-treated for 20 minutes at a baking temperature T (° C.) of 230 to 270 ° C. with an aluminum alloy composition containing 0.2 to 0.6 mass% and Si: 0.1 to 0.5 mass% The change in tensile strength ΔTS before and after heat treatment is to be reduced.
この他、缶への成形性向上のために、組織を制御することも、従来から多数提案されている。例えば、熱間圧延板のMn固溶量及び結晶粒径を所定の範囲に制御し、熱間圧延板の耳率を安定して−3〜−6%にし、これを、その後、中間焼鈍することなく冷間圧延することによって、得られる冷間圧延板の耳率を安定して0〜2%にすることが提案されている(特許文献3)。
ただ、前記Mn固溶量及び結晶粒径など、従来からの耳率安定化のためのアルミニウム合金板の組織の冶金的な因子を制御するだけでは、塗装熱処理時の熱変形を防止することができない。 However, only by controlling the metallurgical factors of the structure of the aluminum alloy plate for stabilizing the ear ratio such as the Mn solid solution amount and the crystal grain size, it is possible to prevent thermal deformation during the coating heat treatment. Can not.
また、前記特許文献2のように、Mn、Mg、Cu、Fe、Siなどのアルミニウム合金組成のみによっては、前記した熱軟化による缶胴の強度低下や変形を抑制することには大きな限界がある。 Further, as in Patent Document 2, depending on only the aluminum alloy composition such as Mn, Mg, Cu, Fe, Si, etc., there is a great limit to suppressing the strength reduction and deformation of the can body due to the thermal softening described above. .
即ち、前記特許文献2は、その規定している乃至想定している、230乃至270℃×20分間の熱処理に対しては有効かもしれない。しかしながら、これに対して、前記したように、290℃×20秒と、より高温化短時間化された高速化熱処理に対しては、特に熱処理温度がより高温となり、また、缶胴がより薄肉化されているために、熱軟化による缶胴の強度低下や変形を防止できない。 That is, Patent Document 2 may be effective for heat treatment at 230 to 270 ° C. × 20 minutes, as defined or assumed. However, as described above, especially for the high-speed heat treatment at 290 ° C. × 20 seconds, which is a higher temperature and shorter time, the heat treatment temperature is particularly high, and the can body is thinner. Therefore, it is impossible to prevent the strength reduction and deformation of the can body due to thermal softening.
本発明はかかる問題点に鑑みてなされたものであって、DI加工等の成形性の確保を前提に、より高温化短時間化された高速化熱処理に対しても、塗装熱処理時の熱変形を防止し、熱処理後の缶強度を確保するとともに、真円度が高いボトル缶を得ることができる、高温特性に優れたボトル缶用アルミニウム合金冷延板を提供することを目的とする。 The present invention has been made in view of such problems, and on the premise of ensuring moldability such as DI processing, thermal deformation at the time of coating heat treatment is also applied to high-speed heat treatment with higher temperature and shorter time. An object of the present invention is to provide an aluminum alloy cold-rolled sheet for a bottle can excellent in high-temperature characteristics, which can prevent the above-described problem, ensure the strength of the can after heat treatment, and obtain a bottle can with high roundness.
この目的を達成するために、本発明の高温特性に優れたボトル缶用アルミニウム合金冷延板の要旨は、 Mn:0.7〜1.5%(質量%、以下同じ)、Mg:0.8〜1.7%、Fe:0.1〜0.7%、Si:0.05〜0.5%、Cu:0.1〜0.6%を含有し、残部がAl及び不可避的不純物からなる組成を有し、かつ、結晶粒組織を、板厚方向中央部の上面観察による結晶粒の平均アスペクト比が3以上の圧延方向に伸長させた組織とし、Cu固溶量が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量として0.05〜0.3%、Mg固溶量が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量として0.75〜1.6%であることとする。 In order to achieve this object, the gist of the aluminum alloy cold-rolled sheet for bottle cans excellent in high temperature characteristics of the present invention is as follows: Mn: 0.7 to 1.5% (mass%, the same applies hereinafter), Mg: 0.00. 8 to 1.7%, Fe: 0.1 to 0.7%, Si: 0.05 to 0.5%, Cu: 0.1 to 0.6%, the balance being Al and inevitable impurities The crystal grain structure is a structure in which the average aspect ratio of the crystal grains is elongated in the rolling direction of 3 or more by observing the upper surface of the central portion in the plate thickness direction, and the Cu solid solution amount is hot phenol. The amount of Cu in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method by 0.05 to 0.3%, the Mg solid solution amount is the particles by the residual extraction method by hot phenol The amount of Mg in the solution separated from the precipitate having a size exceeding 0.2 μm is 0.75 to 0.75 And it is a .6%.
ボトル缶のDI缶胴については、主として製造コストの低減、及び軽量化の目的から、前記して通り、更なる薄肉化が求められている。この薄肉化を達成するためには、座屈強度の低下をきたさないように、材料であるアルミニウム合金冷延板の高強度化を図る必要がある。また、薄肉化を達成するためには、更に、DI成形時における耳率が低いことが強く求められる。DI成形時の耳率を低くすれば、DI成形時の歩留まりを高めることができ、さらには缶胴の耳切れに起因する缶胴破断を防止することができる。 As described above, the DI can body of the bottle can is required to be further thinned mainly for the purpose of reducing the manufacturing cost and reducing the weight. In order to achieve this reduction in thickness, it is necessary to increase the strength of the aluminum alloy cold-rolled sheet as a material so that the buckling strength does not decrease. Moreover, in order to achieve thinning, it is further strongly required that the ear rate during DI molding is low. If the ear rate at the time of DI molding is lowered, the yield at the time of DI molding can be increased, and furthermore, the can body can be prevented from being broken due to the cutting out of the can body.
このため、前記した通り、従来から、耳率を高度に安定化させるために、ボトル缶のDI缶胴材料であるアルミニウム合金冷延板の特に組織の冶金的な因子を制御することが公知である。代表的には、結晶粒径の微細化制御、Mg2 Siなどの化合物の個数や大きさの制御、添加元素のミクロ的偏析抑制、Mnなどの合金元素の固溶量制御、キューブ方位の制御、などである。 For this reason, as described above, conventionally, in order to highly stabilize the ear rate, it is known to control metallurgical factors of the structure of the aluminum alloy cold-rolled sheet, which is the DI can body material of the bottle can. is there. Typically, control of crystal grain refinement, control of the number and size of compounds such as Mg2Si, suppression of microsegregation of additive elements, control of solid solution amount of alloy elements such as Mn, control of cube orientation, Etc.
しかし、本発明の課題である、塗装熱処理時の熱変形を防止するための、材料であるアルミニウム合金冷延板の組織の冶金的な因子を制御する技術は未だ実質的に提案されていない。これは、塗装熱処理時の熱変形と相関する組織の冶金的な因子の知見が未だなされていないことによる。また、上記耳率安定化のための公知の組織の冶金的な因子を種々制御するだけでは、塗装熱処理時の熱変形を防止することができない。 However, a technique for controlling metallurgical factors of the structure of an aluminum alloy cold-rolled sheet, which is a subject of the present invention, to prevent thermal deformation during coating heat treatment has not been substantially proposed yet. This is because the knowledge of the metallurgical factor of the structure correlating with the thermal deformation during the coating heat treatment has not yet been made. Moreover, thermal deformation during the coating heat treatment cannot be prevented only by controlling various metallurgical factors of the known structure for stabilizing the ear rate.
これに対して、本発明では、数有る組織の冶金的な因子の内でも、結晶粒の形態と、更に、組織におけるCu固溶量とMg固溶量とが、熱処理後の缶強度や塗装熱処理時の熱変形と相関することを知見した。 On the other hand, in the present invention, among the metallurgical factors of a number of structures, the form of crystal grains, and further, the amount of Cu solid solution and the amount of Mg solid solution in the structure, can strength and coating after heat treatment It was found to correlate with thermal deformation during heat treatment.
また、これらの組織の冶金的な因子は、耳率の安定化を阻害せず、却って、耳率を安定化させる作用もあるため、熱処理後の缶強度の確保や塗装熱処理時の熱変形を抑制した上で、DI加工等の成形性を確保することができる。言い換えると、熱処理後の缶強度の確保や塗装熱処理時の熱変形を抑制した上で、基本的な要求特性であるDI加工等の成形性を確保した、アルミニウム合金冷延板とすることができる。 In addition, the metallurgical factors of these tissues do not hinder the stabilization of the ear rate, but also have the effect of stabilizing the ear rate, ensuring the strength of the can after heat treatment and thermal deformation during the heat treatment of the coating. In addition, moldability such as DI processing can be secured. In other words, the aluminum alloy cold-rolled sheet can ensure the formability such as DI processing, which is a basic required characteristic, while ensuring the strength of the can after heat treatment and suppressing thermal deformation at the time of coating heat treatment. .
アルミニウム合金冷延板の結晶粒を、等軸粒ではなく、平均アスペクト比が3以上の、圧延方向に伸長させた組織に制御することによって、より高温化短時間化された高速化熱処理に対しての、塗装熱処理時の熱変形が抑制され、熱処理後の缶強度も確保できる。
The crystal grains of the aluminum alloy cold-rolled sheet, rather than equiaxed grains, the average aspect ratio of 3 or higher, by controlling the elongation was achieved in the rolling direction tissue, the higher temperature of shorter time has been faster heat treatment On the other hand, thermal deformation during heat treatment for coating is suppressed, and can strength after heat treatment can be secured.
そして、本発明では、この結晶粒の形状制御に加えて、更に、組織におけるCu固溶量とMg固溶量とを併せて最適範囲に制御する。 In the present invention, in addition to the shape control of the crystal grains, the Cu solid solution amount and the Mg solid solution amount in the structure are further controlled within the optimum range.
Cu固溶量やMg固溶量は、高温熱処理時の耐軟化特性に大きく影響する。このため、Cu固溶量やMg固溶量を併せて確保することによって、高温熱処理時の耐軟化特性を向上させ、楕円変形を抑制することができる。また、Mg固溶量は、高温熱処理後の強度特性に大きく影響する。このため、Mg固溶量を確保することによって、高温熱処理後の強度をも確保することができる。 The amount of solid solution of Cu and the amount of solid solution of Mg greatly affect the softening resistance during high-temperature heat treatment. For this reason, by securing together the amount of Cu solid solution and the amount of Mg solid solution, the softening-proof characteristic at the time of high temperature heat processing can be improved, and elliptical deformation can be suppressed. Further, the amount of Mg solid solution greatly affects the strength characteristics after high-temperature heat treatment. For this reason, the intensity | strength after high temperature heat processing is securable by ensuring Mg solid solution amount.
なお、前記した従来技術のMnなど他の合金元素の固溶量制御は、冷間圧延板の耳率の低下など、DI加工等の成形性を向上させることには寄与する。しかし、本発明が課題とする、塗装熱処理時の熱変形抑制や、熱処理後の缶強度確保の点では、Cu固溶量とMg固溶量との制御効果に比して著しく小さい。したがって、Mnなど他の合金元素の固溶量を確保しても、塗装熱処理時の熱変形は抑制されず、熱処理後の缶強度も確保できない。
In addition, the solid solution amount control of other alloy elements such as Mn as described above contributes to improving the formability such as DI processing, such as a decrease in the ear rate of the cold rolled sheet. However, it is significantly smaller than the control effect of the Cu solid solution amount and the Mg solid solution amount in terms of suppressing thermal deformation during the coating heat treatment and securing the strength of the can after the heat treatment, which are problems of the present invention. Therefore, even if the solid solution amount of other alloy elements such as Mn is secured, thermal deformation during the coating heat treatment is not suppressed, and the strength of the can after the heat treatment cannot be secured.
(Al合金冷延板組成)
先ず、本発明のAl合金冷延板の好ましい化学成分組成(単位:質量%)について、各元素の限定理由を含めて、以下に説明する。
(Al alloy cold-rolled sheet composition)
First, the preferable chemical component composition (unit: mass%) of the Al alloy cold-rolled sheet of the present invention will be described below including the reasons for limiting each element.
本発明の高温特性に優れたボトル缶用アルミニウム合金冷延板の組成は、Mn:0.7〜1.5%、Mg:0.8〜1.7%、Fe:0.1〜0.7%、Si:0.05〜0.5%、Cu:0.1〜0.6%を含有し、残部がAl及び不可避的不純物からなる組成とする。 The composition of the aluminum alloy cold-rolled sheet for bottle cans excellent in high temperature characteristics of the present invention is as follows: Mn: 0.7 to 1.5%, Mg: 0.8 to 1.7%, Fe: 0.1 to 0.00. 7%, Si: 0.05 to 0.5%, Cu: 0.1 to 0.6%, with the balance being Al and inevitable impurities.
但し、本発明では、主要構成元素(Mn、Mg、Fe、Cu、Si)の成分バランスを、Mg、Cuの固溶量が確保できるように成分設計することが好ましい。これによって、鋳造時に、平均サイズが5μm以下で、微細で安定な晶出物が生成するとともに、最適なCu固溶量、あるいはMg固溶量の組織に制御することができる。 However, in the present invention, it is preferable that the component balance of the main constituent elements (Mn, Mg, Fe, Cu, Si) is designed so that the solid solution amount of Mg and Cu can be secured. Thus, during casting, an average size of 5 μm or less and a fine and stable crystallized product are generated, and the optimum Cu solid solution amount or Mg solid solution structure can be controlled.
Mn:0.7〜1.5%。
Mnは強度の向上に寄与し、さらには成形性の向上にも寄与する有効な元素である。特に本発明の缶胴材(冷間圧延板)では、DI成形時にしごき加工が行われるため、Mnは極めて重要となる。
Mn: 0.7 to 1.5%.
Mn is an effective element that contributes to improvement in strength and further contributes to improvement in formability. In particular, in the can body material (cold rolled plate) of the present invention, Mn is extremely important because ironing is performed during DI molding.
より詳細には、MnはAl−Fe−Mn−Si系金属間化合物(α相)などの種々のMn系金属間化合物を形成する。そして前記α相が適正に分布しているほど、しごき加工性を向上できる。すなわちアルミニウム板のしごき加工においては、通常エマルジョンタイプの潤滑剤が用いられているが、前記α相の量が少ないと、エマルジョンタイプの潤滑剤を使用しても潤滑性が不足し、ゴーリングと称される擦り疵や焼付きなどの外観不良が発生する虞がある。従ってα相を生成し、しごき加工時の表面疵を防止するためにもMnは不可欠な元素である。 More specifically, Mn forms various Mn-based intermetallic compounds such as an Al—Fe—Mn—Si-based intermetallic compound (α phase). And iron workability can be improved, so that the alpha phase is distributed appropriately. In other words, emulsion type lubricants are usually used in ironing of aluminum plates. However, if the amount of the α phase is small, lubricity is insufficient even when emulsion type lubricants are used. There is a risk of appearance defects such as scuffing and seizure. Accordingly, Mn is an indispensable element for generating an α phase and preventing surface flaws during ironing.
Mnの含有量が少な過ぎると上記効果が発揮されない。このため、Mnの含有量は0.7%以上、好ましくは0.8%以上、好ましくは0.85%以上、さらに好ましくは0.9%以上である。 If the Mn content is too small, the above effects cannot be exhibited. For this reason, the Mn content is 0.7% or more, preferably 0.8% or more, preferably 0.85% or more, and more preferably 0.9% or more.
一方、Mnが過剰になると、MnAl6 の初晶巨大金属化合物が晶出し、成形性が低下する。それゆえ、Mn含有量の上限は1.5%、好ましくは1.3%、さらに好ましくは1.1%、さらに好ましくは1.0%とする。 On the other hand, when Mn is excessive, the primary crystal giant metal compound of MnAl 6 is crystallized and the moldability is lowered. Therefore, the upper limit of the Mn content is 1.5%, preferably 1.3%, more preferably 1.1%, and still more preferably 1.0%.
(Mn固溶量)
アルミニウム合金冷延板のMn固溶量は、前記した通り、中間焼鈍無しの冷間圧延と組み合わせることによって、冷間圧延板の耳率の低下など、DI加工等の成形性を向上させることには寄与する。したがって、DI加工等の成形性を向上させるために、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMn量(固溶Mn量と粒子サイズが0.2μm以下の析出物中のMn量との合計量)として、0.12〜0.38%とすることが好ましい。Mn固溶量が0.12%未満では、DI加工等の成形性向上効果が無く、一方、Mn固溶量が0.38%を超えた場合、冷間圧延時の加工硬化が過剰となって、却ってDI加工等の成形性を低下させる可能性が高い。
(Mn solid solution amount)
As described above, the Mn solid solution amount of the aluminum alloy cold-rolled sheet is improved by combining with cold rolling without intermediate annealing to improve formability such as DI processing, such as a decrease in the ear rate of the cold-rolled sheet. Will contribute. Therefore, in order to improve moldability such as DI processing, the amount of Mn in the solution separated from precipitates having a particle size exceeding 0.2 μm by the residual extraction method with hot phenol (the amount of solid solution Mn and the particle size are The total amount with the amount of Mn in the precipitate of 0.2 μm or less is preferably 0.12 to 0.38%. If the Mn solid solution amount is less than 0.12%, there is no effect of improving the formability such as DI processing. On the other hand, if the Mn solid solution amount exceeds 0.38%, work hardening during cold rolling becomes excessive. On the other hand, there is a high possibility that the moldability such as DI processing is lowered.
Mg:0.8〜1.7%。
Mgは単独で固溶強化によって強度を向上できる点で有効である。更には、後述するCuと共に含有させることによって、本発明の缶胴材(冷間圧延板)を最終焼鈍(仕上焼鈍ともいう。例えば、温度:100〜150℃程度、時間:1〜2時間程度の焼鈍)し、その後に製缶してからベーキング(焼付印刷)する際に、軟化を抑制できる。即ち、Mg及びCuを両者含有すると、熱間圧延板の段階において、Cu固溶量を確保することができ、ベーキング(焼付印刷)を行う際にAl−Cu−Mgが析出するため、ベーキング時の軟化を抑制できる。
Mg: 0.8-1.7%.
Mg is effective in that the strength can be improved by solid solution strengthening alone. Furthermore, the can body material (cold rolled sheet) of the present invention is also referred to as final annealing (also called finish annealing, for example, temperature: about 100 to 150 ° C., time: about 1 to 2 hours, by containing with Cu described later. Softening can be suppressed when baking (baking printing) is performed after the can is made. That is, when both Mg and Cu are contained, the amount of Cu solid solution can be ensured at the stage of the hot-rolled sheet, and Al—Cu—Mg is precipitated during baking (baking printing). Can be softened.
Mgの含有量が少な過ぎると、Mg固溶量が確保できず、高温熱処理時の耐軟化特性の向上効果が発揮されない。このため、Mgの含有量は0.8%以上、好ましくは0.9%以上、さらに好ましくは1.0%以上とする。 If the Mg content is too small, the Mg solid solution amount cannot be secured, and the effect of improving the softening resistance during high-temperature heat treatment cannot be exhibited. For this reason, the Mg content is 0.8% or more, preferably 0.9% or more, and more preferably 1.0% or more.
一方、Mgが過剰になると加工硬化が生じやすくなるため、成形性が低下する。このため、Mg含有量の上限は1.7%、好ましくは1.6%、さらに好ましくは1.35%とする。 On the other hand, if Mg is excessive, work hardening is likely to occur, and formability is reduced. For this reason, the upper limit of the Mg content is 1.7%, preferably 1.6%, and more preferably 1.35%.
なお、MgはMnの析出量及び固溶量にも影響を与える。すなわちMgが多いほどAl−Fe−Mn−Si系金属間化合物(α相)の析出量が抑制されるため、Mn固溶量が多くなりやすい。このため、Mn固溶量との関係で、Mg含有量を決定することが好ましい。 Mg also affects the amount of precipitated Mn and the amount of solid solution. That is, since the precipitation amount of the Al—Fe—Mn—Si intermetallic compound (α phase) is suppressed as the amount of Mg increases, the Mn solid solution amount tends to increase. For this reason, it is preferable to determine the Mg content in relation to the Mn solid solution amount.
(Mg固溶量と0.2μm以下の微細析出中のMg量の和)
Mg固溶量と0.2μm以下の微細析出中のMg量の和は、Cu固溶量と0.2μm以下の微細析出中のCu量の和とともに、高温熱処理時の耐軟化特性に大きく影響する。
従来でも、前記特許文献3で、耳率ばらつきの安定化を目的として、Mn固溶量、およびCu固溶量を規定した特許があるが、本発明で解決しようとする課題である中間焼鈍工程で、缶加熱後の楕円変形を抑制するためには、従来の制御だけでは、不十分であり、Mgの固溶・析出状態も制御する必要がある。Mgの存在状態について、詳細に調査した結果、Mgは、従来言われているような固溶や微細析出物としてだけでなく、Al−Fe−Si系またはAl−Mn−Fe−Si系の粗大な析出物中にも、固溶していることがわかり、その量が多いと、固溶Mg、微細析出のMg量が少なくなり、楕円変形が生じやすいことがわかった。 またMg固溶量は、高温熱処理後の強度特性にも大きく影響する。したがって、本発明では、Cu固溶量とともに、Mg固溶量を確保して、高温熱処理時の耐軟化特性を向上させるとともに、高温熱処理後の強度をも確保する。
(Sum of Mg solid solution amount and Mg amount during fine precipitation of 0.2 μm or less)
The sum of the Mg solid solution amount and the Mg amount during fine precipitation of 0.2 μm or less, together with the sum of the Cu solid solution amount and Cu amount during the fine precipitation of 0.2 μm or less, greatly affects the softening resistance during high-temperature heat treatment. To do.
Conventionally, in Patent Document 3, there is a patent that defines the amount of Mn solid solution and the amount of Cu solid solution for the purpose of stabilizing the variation in the ear rate, but the intermediate annealing process is a problem to be solved by the present invention. In order to suppress the elliptical deformation after heating the can, the conventional control alone is not sufficient, and it is necessary to control the solid solution / precipitation state of Mg. As a result of investigating the state of Mg in detail, Mg is not only as a solid solution or fine precipitate as conventionally known, but also as coarse as Al—Fe—Si or Al—Mn—Fe—Si. It was also found that solid precipitates were dissolved, and when the amount was large, the solid solution Mg and the amount of finely precipitated Mg decreased, and it was found that elliptical deformation was likely to occur. The amount of Mg solid solution also greatly affects the strength characteristics after high-temperature heat treatment. Therefore, in the present invention, the Mg solid solution amount is ensured together with the Cu solid solution amount to improve the softening resistance during the high temperature heat treatment, and the strength after the high temperature heat treatment is also ensured.
このために、本発明では、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量(固溶Mg量と粒子サイズが0.2μm以下の析出物中のMg量との合計量)として、0.75〜1.6%とする。 Therefore, in the present invention, the amount of Mg in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method with hot phenol (the amount of solid solution Mg and the precipitation having a particle size of 0.2 μm or less). The total amount of Mg in the product) is set to 0.75 to 1.6%.
粒子サイズが0.2μmを超える粗大な析出物中のMg量は、高温熱処理時の耐軟化特性や高温熱処理後の強度特性を却って低下させる。したがって、Mg固溶量を確保することは、粒子サイズが0.2μmを超える粗大な析出物を規制することにも繋がる。 The amount of Mg in coarse precipitates having a particle size exceeding 0.2 μm reduces the softening resistance during high temperature heat treatment and the strength properties after high temperature heat treatment. Therefore, securing the Mg solid solution amount leads to regulation of coarse precipitates having a particle size exceeding 0.2 μm.
また、事実として固溶しているMgだけでなく、粒子サイズが0.2μm以下の析出物中のMg量も、固溶しているMgと同様に、高温熱処理時の耐軟化特性を向上させるとともに、高温熱処理後の強度をも確保する。このため、本発明では、固溶Mg量と粒子サイズが0.2μm以下の析出物中のMg量との合計量を固溶Mg量として規定する。そのために、固溶Mg量を、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量として規定する。 Moreover, not only the solid solution Mg but also the amount of Mg in the precipitate having a particle size of 0.2 μm or less improves the softening resistance during high-temperature heat treatment, similarly to the solid solution Mg. At the same time, the strength after high-temperature heat treatment is ensured. For this reason, in the present invention, the total amount of the solid solution Mg amount and the Mg amount in the precipitate having a particle size of 0.2 μm or less is defined as the solid solution Mg amount. Therefore, the amount of solid solution Mg is defined as the amount of Mg in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method using hot phenol.
このMg固溶量が0.75%未満では、高温熱処理時の耐軟化特性が不足し、缶の変形が抑制されず、また、高温熱処理後の強度も低下する。 If the Mg solid solution amount is less than 0.75%, the softening resistance at the time of high-temperature heat treatment is insufficient, the deformation of the can is not suppressed, and the strength after the high-temperature heat treatment is also reduced.
一方、このMg固溶量が1.6%を超えても、冷間圧延時の加工硬化が過剰となって、却ってDI加工等の成形性の方を低下させる。 On the other hand, even if the Mg solid solution amount exceeds 1.6%, work hardening during cold rolling becomes excessive, and the formability such as DI processing is reduced.
Fe:0.1〜0.7%。
Feは結晶粒を微細化させる作用があり、さらには上述のAl−Fe−Mn−Si系金属間化合物(α相)を生成するため、成形性の向上に寄与する。またFeは、Mnの晶出や析出を促進し、アルミニウム基地中のMn固溶量やMn系金属間化合物(前記α相など)の分散状態を制御する点でも有用である。一方、Mnの存在下でFeが過剰になると、巨大な初晶金属間化合物が発生しやすくなり、成形性を損なう虞がある。
Fe: 0.1 to 0.7%.
Fe has an effect of refining crystal grains, and further generates the above-described Al—Fe—Mn—Si intermetallic compound (α phase), which contributes to improvement of moldability. Fe is also useful in that it promotes Mn crystallization and precipitation, and controls the amount of Mn solid solution in the aluminum matrix and the dispersion state of Mn-based intermetallic compounds (such as the α phase). On the other hand, if Fe is excessive in the presence of Mn, a large primary intermetallic compound is likely to be generated, which may impair the moldability.
従って、Feの含有量は、Mnの含有量に応じて設定でき、FeとMnとの質量比(Fe/Mn)は、例えば、0.1〜0.7の範囲、好ましくは0.2〜0.6の範囲、さらに好ましくは0.3〜0.5の範囲である。 Accordingly, the Fe content can be set according to the Mn content, and the mass ratio of Fe to Mn (Fe / Mn) is, for example, in the range of 0.1 to 0.7, preferably 0.2 to It is in the range of 0.6, more preferably in the range of 0.3 to 0.5.
なお、Mnの含有量が上記範囲の場合、Feの下限含有量は0.1%以上、好ましくは0.2%以上、さらに好ましくは0.3%以上とする。また、Feの上限含有量は、0.7%以下、好ましくは0.6%以下、さらに好ましくは0.5%以下である。 When the Mn content is in the above range, the lower limit content of Fe is 0.1% or more, preferably 0.2% or more, and more preferably 0.3% or more. Further, the upper limit content of Fe is 0.7% or less, preferably 0.6% or less, and more preferably 0.5% or less.
Si:0.05〜0.5%。
Siは、Al−Fe−Mn−Si系金属間化合物(α相)を生成し、Mn系金属間化合物の分散状態を制御するために有用な元素である。α相が適正に分布している程、成形性を向上できる。
Si: 0.05 to 0.5%.
Si is an element useful for generating an Al—Fe—Mn—Si intermetallic compound (α phase) and controlling the dispersion state of the Mn intermetallic compound. As the α phase is appropriately distributed, the moldability can be improved.
このため、Siの含有量は0.05%以上、好ましくは0.1%以上、さらに好ましくは0.2%以上とする。一方、Siが過剰になると、時効硬化によって材料が硬くなり過ぎ、成形性が低下する。このため、Si含有量の上限は0.5%、好ましくは0.45%、さらに好ましくは0.4%とする。 Therefore, the Si content is 0.05% or more, preferably 0.1% or more, and more preferably 0.2% or more. On the other hand, when Si is excessive, the material becomes too hard due to age hardening, and the formability deteriorates. For this reason, the upper limit of the Si content is 0.5%, preferably 0.45%, and more preferably 0.4%.
Cu:0.1〜0.6%。
Cuは、冷間圧延板の製缶時にベーキング(焼付印刷)を行うときに、Al−Cu−Mgが析出するとともに、Mgと共に含有させて、固溶Mgと固溶Cuとの作用によって、軟化を抑制できる。このため、Cu含有の下限量は0.1%以上、好ましくは0.15%以上、さらに好ましくは0.2%以上とする。一方、Cuが過剰になると、時効硬化は容易に得られるものの、硬くなりすぎるために、成形性が低下し、さらには耐食性も劣化する。このため、Cu含有の上限量は0.6%、好ましくは0.5%、さらに好ましくは0.35%とする。
Cu: 0.1 to 0.6%.
Cu is softened by the action of solute Mg and solute Cu, while Al—Cu—Mg is precipitated when baking (baking printing) is performed at the time of making cold-rolled sheets. Can be suppressed. For this reason, the lower limit of Cu content is 0.1% or more, preferably 0.15% or more, and more preferably 0.2% or more. On the other hand, if Cu is excessive, age hardening can be easily obtained, but it becomes too hard, so that formability is lowered and corrosion resistance is also deteriorated. For this reason, the upper limit of Cu content is 0.6%, preferably 0.5%, and more preferably 0.35%.
Cuの他に、同効の強度向上元素としては、Cr、Znなどが挙げられる。この点、Cuに加えて、更に、Cr、Znの一種または二種を選択的に含有させることができる。 In addition to Cu, examples of the strength improving element having the same effect include Cr and Zn. In this respect, in addition to Cu, one or two of Cr and Zn can be selectively contained.
(Cu固溶量と0.2μm以下の微細析出中のCu量の和)
Cu固溶量と0.2μm以下の微細析出中のCu量の和は、Mg固溶量と0.2μm以下の微細析出中のMg量の和とともに、高温熱処理時の耐軟化特性に大きく影響する。
(Sum of Cu solid solution amount and Cu amount during fine precipitation of 0.2 μm or less)
The sum of the amount of Cu solid solution and the amount of Cu during fine precipitation of 0.2 μm or less, together with the sum of the amount of Mg solid solution and the amount of Mg during fine precipitation of 0.2 μm or less, greatly affects the softening resistance during high-temperature heat treatment. To do.
このために、本発明では、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量(固溶Cu量と粒子サイズが0.2μm以下の析出物中のCu量との合計量)として、0.05〜0.3%とする。 Therefore, in the present invention, the amount of Cu in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method with hot phenol (the amount of solid solution Cu and the precipitation having a particle size of 0.2 μm or less). The total amount of Cu in the product) is 0.05 to 0.3%.
粒子サイズが0.2μmを超える粗大な析出物中のCu量は、高温熱処理時の耐軟化特性や高温熱処理後の強度特性を却って低下させる。したがって、Cu固溶量を確保することは、粒子サイズが0.2μmを超える粗大な析出物を規制することにも繋がる。 The amount of Cu in coarse precipitates having a particle size exceeding 0.2 μm reduces the softening resistance during high temperature heat treatment and the strength properties after high temperature heat treatment. Therefore, securing the Cu solid solution amount leads to regulating coarse precipitates having a particle size exceeding 0.2 μm.
また、事実として固溶しているCuだけでなく、粒子サイズが0.2μm以下の析出物中のCu量も、固溶しているCuと同様に、高温熱処理時の耐軟化特性を向上させるとともに、高温熱処理後の強度をも確保する。このため、本発明では、固溶Cu量と粒子サイズが0.2μm以下の析出物中のCu量との合計量を固溶Cu量として規定する。そのために、固溶Cu量を、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量として規定する。 Moreover, not only the solid solution of Cu but also the amount of Cu in the precipitate having a particle size of 0.2 μm or less improves the softening resistance during high-temperature heat treatment, similarly to the solid solution of Cu. At the same time, the strength after high-temperature heat treatment is ensured. For this reason, in this invention, the total amount of solid solution Cu amount and the amount of Cu in the precipitate whose particle size is 0.2 micrometer or less is prescribed | regulated as solid solution Cu amount. Therefore, the amount of solid solution Cu is defined as the amount of Cu in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method using hot phenol.
このCu固溶量が0.05%未満では、高温熱処理時の耐軟化特性が不足し、缶の変形が抑制されず、また、高温熱処理後の強度も低下する。 If the Cu solid solution amount is less than 0.05%, the softening resistance during high-temperature heat treatment is insufficient, deformation of the can is not suppressed, and the strength after high-temperature heat treatment is also reduced.
一方、このCu固溶量が0.3%を超えても、冷間圧延時の加工硬化が過剰となって、却ってDI加工等の成形性の方を低下させる。また、耐食性も低下する。 On the other hand, even if this Cu solid solution amount exceeds 0.3%, work hardening at the time of cold rolling becomes excessive, and on the contrary, the formability such as DI processing is lowered. Moreover, corrosion resistance also falls.
Cr:0.001〜0.3%。
この際、Crの含有量は、強度向上効果の発揮のためには、0.001%以上、好ましくは0.002%以上とする。一方、Crが過剰になると、巨大晶出物が生成して成形性が低下する。このため、Cr含有量の上限は0.3%、好ましくは0.25%とする。
Cr: 0.001 to 0.3%.
At this time, the content of Cr is set to 0.001% or more, preferably 0.002% or more for exhibiting the effect of improving the strength. On the other hand, when Cr becomes excessive, a giant crystallized substance is generated and formability is lowered. For this reason, the upper limit of the Cr content is 0.3%, preferably 0.25%.
Zn:0.05〜1.0%。
また、Znを含有させると、Al−Mg−Zn系粒子が時効析出することによって強度を向上できる。この効果を発揮させるためには、Zn含有量は0.05%以上、好ましくは0.06%以上とする。一方、Znが過剰になると耐食性が低下する。このため、Zn含有量の上限は0.5%、好ましくは0.45%とする。
Zn: 0.05-1.0%.
Further, when Zn is contained, the strength can be improved by aging precipitation of Al—Mg—Zn-based particles. In order to exhibit this effect, the Zn content is 0.05% or more, preferably 0.06% or more. On the other hand, when Zn becomes excessive, corrosion resistance will fall. For this reason, the upper limit of Zn content is 0.5%, preferably 0.45%.
Ti:0.005〜0.2%。
Tiは結晶粒微細化元素である。この効果を発揮させたい時には選択的に含有させる。その際のTiの含有量は0.005%以上、好ましくは0.01%以上、さらに好ましくは0.015%以上とする。なお、Tiが過剰になると、巨大なAl−Ti系金属間化合物が晶出して成形性を阻害する。したがって、Ti含有量の上限は0.2%、好ましくは0.1%、さらに好ましくは0.05%とする。
Ti: 0.005 to 0.2%.
Ti is a grain refinement element. When it is desired to exert this effect, it is selectively contained. In this case, the Ti content is 0.005% or more, preferably 0.01% or more, and more preferably 0.015% or more. In addition, when Ti becomes excess, a huge Al-Ti type intermetallic compound will crystallize and will inhibit a moldability. Therefore, the upper limit of the Ti content is 0.2%, preferably 0.1%, more preferably 0.05%.
前記Tiは単独で含有させてもよいが、微量のBと共に含有してもよい。Bと併用すると、結晶粒の微細化効果がさらに向上する。このために選択的含有させる際のBの含有量は0.0001%以上、好ましくは0.0005%以上、さらに好ましくは0.0008%以上とする。一方、Bが過剰になると、Ti−B系の粗大粒子が生成して成形性を低下させる。したがって、B含有量の上限は0.05%、好ましくは0.01%、さらに好ましくは0.005%とする。 Ti may be contained alone, but may be contained together with a small amount of B. When used in combination with B, the effect of crystal grain refinement is further improved. For this reason, the B content when selectively contained is 0.0001% or more, preferably 0.0005% or more, and more preferably 0.0008% or more. On the other hand, when B is excessive, Ti-B-based coarse particles are generated and formability is lowered. Therefore, the upper limit of the B content is 0.05%, preferably 0.01%, and more preferably 0.005%.
以上記載した元素以外は不可避的不純物であり、上記板特性を阻害しないために、含有量は基本的に少ない方が良いが、上記板特性を阻害しない範囲で、JIS規格などで記載された、3000系アルミニウム合金の各元素の上限値程度までの含有は許容される。 Other than the elements described above are unavoidable impurities, and in order not to inhibit the plate properties, the content should be basically low, but as long as the plate properties are not inhibited, it was described in JIS standards, Inclusion of up to about the upper limit of each element of 3000 series aluminum alloy is allowed.
(Al合金冷延板組織)
次ぎに、本発明Al合金冷延板組織について、以下に説明する。
(Al alloy cold rolled sheet structure)
Next, the Al alloy cold-rolled sheet structure of the present invention will be described below.
(結晶粒の平均アスペクト比)
前記した通り、アルミニウム合金冷延板の結晶粒を、通常の等軸粒ではなく、平均アスペクト比が3以上の、圧延方向に伸長させたものにすることによって、より高温化短時間化された高速化熱処理に対しての、塗装熱処理時の熱変形が抑制され、熱処理後の缶強度も確保できる。
(Average aspect ratio of crystal grains)
As described above, the temperature of the aluminum alloy cold-rolled sheet was shortened by increasing the average aspect ratio to 3 or more in the rolling direction, instead of normal equiaxed grains. Thermal deformation at the time of coating heat treatment against high-speed heat treatment is suppressed, and can strength after heat treatment can be secured.
即ち、アルミニウム合金冷延板の結晶粒を圧延方向への伸長粒とすることによって、しごき加工性を付与して、DI加工等の成形性を確保した上で、本発明で規定した、上記成分組成と、後述する固溶、析出状態組織のもとで、熱処理後の缶強度を確保できる。これによって、塗装熱処理時の熱変形も抑制される。 That is, by making the crystal grains of the aluminum alloy cold-rolled sheet into elongated grains in the rolling direction, ironing workability is provided, and formability such as DI processing is secured, and then the above-mentioned components defined in the present invention The strength of the can after heat treatment can be secured under the composition and the solid solution and precipitation state structure described later. As a result, thermal deformation during the coating heat treatment is also suppressed.
結晶粒の平均アスペクト比が3未満では、通常の等軸粒と大差なくなり、上記効果が不足するため、塗装熱処理時の熱変形抑制や、熱処理後の缶強度確保が達成できない。この点で、結晶粒の圧延方向への伸長は大きいほど良く、より好ましくは、結晶粒の平均アスペクト比は3.1以上である。 When the average aspect ratio of the crystal grains is less than 3, the difference from the normal equiaxed grains is not so large and the above effect is insufficient, so that it is impossible to achieve thermal deformation suppression during coating heat treatment and securing of can strength after heat treatment. In this respect, the elongation of the crystal grains in the rolling direction is better, and more preferably, the average aspect ratio of the crystal grains is 3.1 or more.
結晶粒のアスペクト比は、中間焼鈍を施さない工程では、熱延板の結晶粒組織、冷間圧延率および冷間圧延温度によって決まる。この点で、結晶粒の平均アスペクト比の上限は、熱間圧延や冷間圧延など、伸長粒とするための製造工程の能力限界から決定されるが、そのレベルは6程度である。 The aspect ratio of the crystal grains is determined by the crystal grain structure of the hot-rolled sheet, the cold rolling rate, and the cold rolling temperature in the process without intermediate annealing. In this respect, the upper limit of the average aspect ratio of the crystal grains is determined from the capability limit of the manufacturing process for forming elongated grains such as hot rolling and cold rolling, but the level is about 6.
(平均アスペクト比測定方法)
結晶粒の平均アスペクト比は、板厚方向中央部の上面観察(偏光観察)によって測定される。調質処理後(ボトル缶成形前)の板の板厚方向中央部、圧延面上面を、機械研磨、電解研磨、およびバーカー液による陽極酸化処理後、偏光観察によって行う。
(Average aspect ratio measurement method)
The average aspect ratio of the crystal grains is measured by observing the upper surface (polarized light observation) at the center in the thickness direction. The central part in the plate thickness direction of the plate after the tempering treatment (before bottle can molding) and the upper surface of the rolled surface are subjected to polarization observation after mechanical polishing, electrolytic polishing, and anodizing treatment with Barker liquid.
上記板の板厚方向中央部を上面から、結晶粒組織を偏光観察したとき、結晶方位の違いによって白黒の違いがでる。この際の観察で、輪郭がはっきり観察できる、視野内の結晶粒を対象に、個々の結晶粒の圧延方向の最大長さと、板幅方向の最大長さを計測する。そして、この個々の結晶粒の(圧延方向の最大長さ)/(板幅方向の最大長さ)をアスペクト比として計算する。×100倍の光学顕微鏡の観察で、測定する結晶粒を100個として、それら結晶粒のアスペクト比の平均値によって、結晶粒の平均アスペクト比を求める。 When the crystal grain structure is polarized and observed from the upper surface of the plate thickness direction center portion of the above plate, a black and white difference is caused by a difference in crystal orientation. In this observation, the maximum length in the rolling direction and the maximum length in the plate width direction of each crystal grain are measured for crystal grains in the field of view where the outline can be clearly observed. Then, the (maximum length in the rolling direction) / (maximum length in the sheet width direction) of each individual crystal grain is calculated as the aspect ratio. The average aspect ratio of the crystal grains is obtained from the average value of the aspect ratios of the crystal grains with 100 crystal grains to be measured by observation with an optical microscope of × 100 magnification.
(製造方法)
本発明Al合金冷延板は、従来の均熱、熱延、冷延の製造工程を大きく変えることなく製造が可能である。但し、本発明規定の組織とし、かつ、ボトル缶成形のための基本的な材料特性(耳率、強度)や成形性、しごき加工性を阻害せずに確保するためには、上記個々の工程を最適条件範囲に限定するとともに、これらの工程を組み合わせる必要がある。
(Production method)
The Al alloy cold-rolled sheet of the present invention can be manufactured without greatly changing the conventional steps of soaking, hot rolling and cold rolling. However, in order to secure the structure defined in the present invention and not impair the basic material characteristics (ear ratio, strength), moldability, and ironing processability for bottle can molding, the above individual steps Must be limited to the optimum condition range, and these steps must be combined.
(均熱条件)
均熱温度は550〜650℃とする。均熱温度が低すぎると、均質化に時間がかかり過ぎて生産性が低下し、均熱温度が高すぎると、鋳塊表面に膨れが生じるため、前記範囲に均熱温度を設定する。好ましい均熱温度は、580℃以上(特に590℃以上)、615℃以下(特に610℃以下)である。
(Soaking conditions)
The soaking temperature is 550 to 650 ° C. If the soaking temperature is too low, it takes too much time to homogenize and the productivity is lowered. If the soaking temperature is too high, the ingot surface is swollen, so the soaking temperature is set in the above range. Preferable soaking temperatures are 580 ° C. or higher (particularly 590 ° C. or higher) and 615 ° C. or lower (particularly 610 ° C. or lower).
なお、均熱時間(均質化時間)は、鋳塊を均質化できれば短い程望ましく、例えば12時間以下、好ましくは6時間以下とするのが望ましいが、均熱温度を 550℃以上とする場合には均熱時間は6時間以上必要であり、均熱温度を580℃以上とする場合には均熱時間は5時間以上必要であり、均熱温度を590℃以上とする場合には均熱時間は4時間以上必要である。 The soaking time (homogenization time) is preferably as short as possible so that the ingot can be homogenized. For example, it is preferably 12 hours or less, preferably 6 hours or less, but when the soaking temperature is 550 ° C. or more. Soaking time needs 6 hours or more, soaking temperature is 580 ° C or more, soaking time is 5 hours or more, soaking temperature is 590 ° C or more, soaking time Requires more than 4 hours.
均熱処理は、複数の段階に分けて行っても良い。その場合、上記均熱処理の昇温速度、均熱処理の温度(均質化温度)、及び冷却速度の制御は、いずれの段階で行ってもよく、全ての段階で行ってもよいが、少なくとも第1回目の段階で行うのが望ましい。 The soaking process may be performed in a plurality of stages. In that case, the temperature increase rate of the soaking process, the temperature of the soaking process (homogenization temperature), and the cooling rate may be controlled in any stage, and may be performed in all stages. It is desirable to do this at the second stage.
第1回目の均熱処理の温度を上記範囲に設定する場合、第2回目以降の均熱処理の温度は、第1回目の均熱処理温度よりも低くする場合が多い。第2回目以降の均熱処理の温度は、第1回目の均熱処理温度に比べて、例えば、10〜100℃程度、好ましくは50〜100℃程度低くする。 When the temperature of the first soaking is set in the above range, the temperature of the soaking after the second is often lower than the soaking temperature of the first. The temperature of the soaking process after the second time is, for example, about 10 to 100 ° C., preferably about 50 to 100 ° C. lower than the soaking temperature of the first time.
(熱延開始条件)
均熱処理終了後の鋳塊の取り扱いは、一旦冷却し、再加熱してから熱間粗圧延してもよく、あるいは過度に冷却することなく、そのまま熱間粗圧延してもよい。過度に冷却することなく、そのまま熱間粗圧延する場合、Cu固溶量と0.2μm以下の微細析出中のCu量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量として0.05〜0.3%、Mg固溶量と0.2μm以下の微細析出中のMg量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量として0.75〜1.6%としやすい。また、均熱処理後の鋳塊の自己発熱を利用することができ、生産時間や熱エネルギーを節約できるだけでなく、合金元素の析出物の数密度を小さくでき、耳率を低減できる。
(Hot rolling start condition)
The ingot after the soaking process is handled may be cooled and reheated before hot rough rolling, or may be hot rough rolled as it is without being excessively cooled. In the case of hot rough rolling as it is without excessive cooling, the sum of the amount of Cu solid solution and the amount of Cu in fine precipitation of 0.2 μm or less is 0.2 μm in particle size by the residual extraction method using hot phenol. The amount of Cu in the separated solution and the amount of Cu in the separated solution is 0.05 to 0.3%, and the sum of the Mg solid solution amount and the Mg amount in the fine precipitation of 0.2 μm or less is determined by the residual extraction method using hot phenol. The Mg amount in the solution separated from the precipitate having a particle size exceeding 0.2 μm is easily set to 0.75 to 1.6%. In addition, the self-heating of the ingot after soaking can be used, and not only can the production time and heat energy be saved, but also the number density of precipitates of alloy elements can be reduced, and the ear rate can be reduced.
なお、鋳塊を一旦冷却し、再加熱する場合には、30℃/時間以上の速度で急速加熱するのが望ましい。この急速加熱によって、MgやCuが、それまでに生成した粗大な化合物への固溶、若しくは、粗大な析出物界面での析出が抑制でき、Cu固溶量と0.2μm以下の微細析出中のCu量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量として0.05〜0.3%、Mg固溶量と0.2μm以下の微細析出中のMg量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量として0.75〜1.6%としやすい。また、合金元素の析出物の数密度が高くなり過ぎるのを防止でき、耳率を低減できる。 In addition, when the ingot is once cooled and reheated, it is desirable to rapidly heat at a rate of 30 ° C./hour or more. Due to this rapid heating, Mg and Cu can be prevented from solid solution in the coarse compound produced so far, or precipitation at the coarse precipitate interface, while Cu solid solution amount and fine precipitation of 0.2 μm or less The amount of Cu in the solution was 0.05 to 0.3% as the amount of Cu in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method with hot phenol, and the amount of Mg solid solution and 0 The sum of the amount of Mg in the fine precipitate of 2 μm or less is 0.75 to 1.6% as the amount of Mg in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method using hot phenol. Easy to do. Moreover, it can prevent that the number density of the precipitate of an alloy element becomes high too much, and can reduce an ear rate.
(熱間粗圧延条件)
熱延を、粗圧延と仕上げ圧延とに分けて、かつ連続して実施するに際し、熱間粗圧延の終了温度が低くなり過ぎると、次工程の熱間仕上圧延で圧延温度が低くなってエッジ割れが生じやすくなる。また、熱間粗圧延の終了温度が低くなり過ぎると、仕上圧延後に再結晶するために必要となる自己熱が不足しやすくなるため、結晶粒径が小さくなり過ぎる。このため、熱間粗圧延の終了温度は420℃以上とすることが好ましい。更に好ましい終了温度は430℃以上(特に440℃以上)、470℃以下(特に460℃以下)である。
(Hot rough rolling conditions)
When hot rolling is divided into rough rolling and finish rolling and continuously carried out, if the end temperature of hot rough rolling becomes too low, the rolling temperature becomes lower in the next hot finishing rolling and the edge Cracks are likely to occur. In addition, if the end temperature of hot rough rolling is too low, the self-heating necessary for recrystallization after finish rolling tends to be insufficient, so that the crystal grain size becomes too small. For this reason, it is preferable that the completion | finish temperature of hot rough rolling shall be 420 degreeC or more. Further preferable end temperatures are 430 ° C. or higher (particularly 440 ° C. or higher) and 470 ° C. or lower (particularly 460 ° C. or lower).
この熱間粗圧延の終了温度を420〜480℃程度にしておくためには、熱間粗圧延の開始温度を、例えば、490〜550℃程度、好ましくは495〜540℃程度、さらに好ましくは500〜530℃程度にしておくのが望ましい。前記開始温度を550℃以下にしておけば、熱間圧延板の表面酸化を防止することもできる。更には、再結晶粒の粗大化を防止できるため、成形性をさらに高めることもできる。 In order to keep the end temperature of this hot rough rolling at about 420 to 480 ° C., the start temperature of hot rough rolling is, for example, about 490 to 550 ° C., preferably about 495 to 540 ° C., more preferably 500. It is desirable to keep it at about ˜530 ° C. If the starting temperature is set to 550 ° C. or lower, surface oxidation of the hot rolled sheet can be prevented. Furthermore, since the coarsening of recrystallized grains can be prevented, the moldability can be further improved.
熱間粗圧延が終了したアルミニウム合金板は、連続的など、速やかに熱間仕上圧延するのが望ましい。速やかに熱間仕上圧延することによって、熱間粗圧延で蓄積された歪みが回復してしまうのを防止でき、その後に得られる冷間圧延板の強度を高めることができる。熱間粗圧延が終了したアルミニウム合金板は、例えば、5分以内、好ましくは3分以内に熱間仕上圧延することが好ましい。 It is desirable that the aluminum alloy sheet that has been subjected to hot rough rolling is subjected to hot finish rolling quickly, such as continuously. By rapidly performing hot finish rolling, it is possible to prevent the distortion accumulated in the hot rough rolling from recovering, and it is possible to increase the strength of the cold rolled sheet obtained thereafter. The aluminum alloy sheet that has been subjected to the hot rough rolling is preferably hot finish rolled, for example, within 5 minutes, preferably within 3 minutes.
(熱間仕上圧延条件)
熱間仕上圧延の終了温度は310〜350℃とすることが好ましい。熱間仕上圧延工程は、合金冷延板を所定の寸法に仕上げる工程であり、圧延終了後の組織は自己発熱によって再結晶組織になるため、その終了温度は再結晶組織に影響を与える。熱間仕上圧延の終了温度を310℃以上とすることで、続く冷間圧延条件と併せて、最終板組織を、平均アスペクト比が3以上の圧延方向に伸長させた組織とし、かつ、本発明で規定のCu固溶量、Mg固溶量を確保することができる。熱間仕上圧延の終了温度が310℃未満では、続く冷間圧延の冷延率を大きくしても、上記本発明組織になりにくい。
(Hot finish rolling conditions)
The finishing temperature of hot finish rolling is preferably 310 to 350 ° C. The hot finish rolling step is a step of finishing the cold rolled alloy sheet to a predetermined dimension. Since the structure after rolling becomes a recrystallized structure due to self-heating, the end temperature affects the recrystallized structure. By setting the finish temperature of the hot finish rolling to 310 ° C. or higher, the final plate structure is made to be a structure in which the average aspect ratio is 3 or more in the rolling direction, together with the subsequent cold rolling conditions, and the present invention. Thus, it is possible to secure the prescribed Cu solid solution amount and Mg solid solution amount. When the finish temperature of hot finish rolling is less than 310 ° C., even if the cold rolling rate of the subsequent cold rolling is increased, the above-described structure of the present invention is hardly obtained.
一方、350℃を越えると、最終板組織を、平均アスペクト比が3以上の圧延方向に伸長させた組織とできず、かつ、所望のMg固溶量が確保できない。従って、熱間仕上圧延の終了温度の下限は310℃以上、好ましくは320℃以上とする。また、上限は350℃以下、好ましくは、340℃以下とする。 On the other hand, if the temperature exceeds 350 ° C., the final plate structure cannot be a structure that is elongated in the rolling direction with an average aspect ratio of 3 or more, and a desired Mg solid solution amount cannot be ensured. Therefore, the lower limit of the finish temperature of hot finish rolling is 310 ° C or higher, preferably 320 ° C or higher. The upper limit is 350 ° C. or lower, preferably 340 ° C. or lower.
(熱間仕上圧延機の種類)
熱間仕上圧延機としては、スタンド数が3以上のタンデム式熱間圧延機を使用する。スタンド数を3以上とすることによって、1スタンドあたりの圧延率を小さくでき、熱延板の表面性状を保ちつつ歪みを蓄積することができるため、冷間圧延板及びそのDI成形体の強度をさらに高めることができる。
(Hot finish rolling mill type)
As the hot finish rolling mill, a tandem hot rolling mill having three or more stands is used. By setting the number of stands to 3 or more, the rolling rate per stand can be reduced, and strain can be accumulated while maintaining the surface properties of the hot-rolled plate. Therefore, the strength of the cold-rolled plate and its DI molded body can be reduced. It can be further increased.
(熱間仕上圧延の総圧延率)
熱間仕上圧延の総圧延率は80%以上にするのが望ましい。総圧延率は80%以上とすることで、後述する冷間圧延と組み合わせて、最終板組織を、平均アスペクト比が3以上の圧延方向に伸長させた組織としやすい。また、冷間圧延板及びそのDI成形体の強度を高めることができる。
(Total rolling ratio of hot finish rolling)
The total rolling rate of hot finish rolling is preferably 80% or more. By making the total rolling rate 80% or more, it is easy to make the final plate structure elongated in the rolling direction with an average aspect ratio of 3 or more in combination with cold rolling described later. Moreover, the intensity | strength of a cold-rolled board and its DI molded object can be raised.
(熱間圧延板の板厚)
熱間 (仕上げ) 圧延終了後の合金板の板厚は、1.8〜3mm程度とするのが望ましい。板厚を1.8mm以上とすることによって、熱間圧延板の表面性状(焼付き、肌荒れなど)や板厚プロフィールの悪化を防止できる。一方、板厚が3mm以下とすることによって、冷間圧延板(通常、板厚:0.28〜0.35mm程度)を製造する際の圧延率が高くなりすぎるのを防止でき、DI成形後の耳率を抑制できる。
(Hot rolled sheet thickness)
Hot (Finish) The thickness of the alloy plate after rolling is preferably about 1.8 to 3 mm. By setting the plate thickness to 1.8 mm or more, it is possible to prevent the surface properties (seizure, rough skin, etc.) and the plate thickness profile of the hot rolled plate from deteriorating. On the other hand, by setting the plate thickness to 3 mm or less, it is possible to prevent the rolling rate from becoming too high when manufacturing a cold rolled plate (usually, plate thickness: about 0.28 to 0.35 mm). Can reduce the ear rate.
上述のようにして得られた熱間圧延板は、Cu固溶量及びMg固溶量が最適の範囲に制御されているため、平均耳率が所定の範囲に制御されている。そのため、中間焼鈍することなく冷間圧延して、冷間圧延板の平均耳率を0〜3.5%と小さくすることができる。また、後述する冷間圧延と組み合わせて、最終板組織を、平均アスペクト比が3以上の圧延方向に伸長させた組織とし、Cu固溶量と0.2μm以下の微細析出中のCu量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量として0.05〜0.3%、Mg固溶量と0.2μm以下の微細析出中のMg量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量として0.75〜1.6%としやすい。 In the hot-rolled sheet obtained as described above, the Cu solid solution amount and the Mg solid solution amount are controlled to the optimum ranges, and thus the average ear rate is controlled to a predetermined range. Therefore, it can cold-roll without intermediate annealing and can reduce the average ear rate of a cold-rolled sheet to 0 to 3.5%. Further, in combination with the cold rolling described later, the final plate structure is a structure in which the average aspect ratio is extended in the rolling direction of 3 or more, and the sum of the Cu solid solution amount and the Cu amount during fine precipitation of 0.2 μm or less. However, the amount of Cu in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method with hot phenol is 0.05 to 0.3%, the Mg solid solution amount and the fineness of 0.2 μm or less. The sum of the amount of Mg during precipitation tends to be 0.75 to 1.6% as the amount of Mg in the solution separated from precipitates having a particle size exceeding 0.2 μm by the residual extraction method using hot phenol.
(冷間圧延)
冷間圧延工程では、中間焼鈍することなく、複数のパス数による謂わば直通で圧延し、合計の圧延率を77〜90%にするのが望ましい。中間焼鈍することなく、合計の圧延率を77%以上とすることによって、最終板組織を、結晶粒の平均アスペクト比が3以上の圧延方向に伸長させた組織とし、Cu固溶量と0.2μm以下の微細析出中のCu量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のCu量として0.05〜0.3%、Mg固溶量と0.2μm以下の微細析出中のMg量の和が、熱フェノールによる残査抽出法により粒子サイズが0.2μmを超える析出物と分離された溶液中のMg量として0.75〜1.6%としやすい。また、缶の耐圧強度をより高めることができる。中間焼鈍を入れた場合、あるいは、合計の圧延率が低い場合、等軸粒になりやすく、結晶粒の平均アスペクト比が3以上の圧延方向に伸長させた組織になりにくい。
(Cold rolling)
In the cold rolling step, it is desirable to perform so-called direct through with a plurality of passes without intermediate annealing, so that the total rolling ratio is 77 to 90%. By making the total rolling ratio 77% or more without intermediate annealing, the final plate structure is made a structure in which the average aspect ratio of the crystal grains is elongated in the rolling direction of 3 or more, and the Cu solid solution amount and 0. The sum of the amount of Cu in fine precipitation of 2 μm or less is 0.05 to 0.3% as the amount of Cu in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method with hot phenol, The sum of the Mg solid solution amount and the Mg amount in the fine precipitation of 0.2 μm or less is 0. 5 as the Mg amount in the solution separated from the precipitate having a particle size exceeding 0.2 μm by the residual extraction method using hot phenol. It is easy to be 75 to 1.6%. In addition, the pressure resistance of the can can be further increased. When intermediate annealing is performed or when the total rolling ratio is low, it becomes easy to form equiaxed grains, and it is difficult to obtain a structure in which the average aspect ratio of crystal grains is elongated in the rolling direction of 3 or more.
一方、圧延率が90%を超えると、結晶粒の平均アスペクト比は大きくできるものの、DI成形時のプラス耳が大きくなり過ぎ、また強度が強くなり過ぎるために、DI成形時にカッピング割れや缶底割れが生じる可能性が高い。 On the other hand, if the rolling rate exceeds 90%, the average aspect ratio of the crystal grains can be increased, but the positive ears during DI molding become too large, and the strength becomes too strong. There is a high possibility of cracking.
冷間圧延後の板厚は、ボトル缶への成形上、0.28〜0.35mm程度とする。 The plate thickness after cold rolling is about 0.28 to 0.35 mm in terms of forming into a bottle can.
なお、冷間圧延工程では、圧延スタンドが2段以上直列に配置された、タンデム圧延機を使用することが望ましい。このようなタンデム圧延機を使用することにより、圧延スタンドが1段で、繰り返しパス(通板)を行なって所定板厚まで冷延するシングルの圧延機と比して、同じ合計冷延率でも、パス(通板)回数が少なくて済み、1回の通板における圧延率を高くすることができる。 In the cold rolling process, it is desirable to use a tandem rolling mill in which two or more rolling stands are arranged in series. By using such a tandem rolling mill, even with the same total cold rolling rate as compared with a single rolling mill that has a single rolling stand and repeatedly performs passes (passing plates) to cold roll to a predetermined plate thickness. The number of passes (passing plates) can be reduced, and the rolling rate in one pass can be increased.
したがって、最終板組織を、結晶粒の平均アスペクト比が3以上の圧延方向に伸長させた組織が得やすくなる。 Therefore, it becomes easy to obtain a structure obtained by extending the final plate structure in the rolling direction in which the average aspect ratio of crystal grains is 3 or more.
また、従来のように、シングルの圧延機を用いた冷間圧延後に、仕上げ焼鈍を施す場合に比して、より低温で、かつ連続的に回復を生じさせ、サブグレインを生成することができる。但し、このように、冷間圧延により回復を生じさせて十分にサブグレインを生成することができるものであれば、圧延機はタンデム圧延機に限定されるものではない。 Further, as in the conventional case, after cold rolling using a single rolling mill, it is possible to generate subgrains by causing recovery at a lower temperature and continuously compared to the case where finish annealing is performed. . However, the rolling mill is not limited to a tandem rolling mill as long as it can recover sufficiently by cold rolling and sufficiently generate subgrains.
但し、タンデム圧延機による冷延では、1回の通板における圧延率が高くなるために、1回の通板における発熱量が高くなる。この発熱量が高くなり過ぎた場合、加工時の歪み導入と発熱によって、CuやMgの析出物発生量、特に、粗大析出物界面での析出物が増加して、その結果、CuやMgの固溶量および微細析出物量が確保できない可能性がある。 However, in cold rolling with a tandem rolling mill, the rolling rate in one pass plate increases, so the amount of heat generated in one pass plate increases. If this calorific value becomes too high, the amount of precipitates generated in Cu and Mg, particularly the precipitates at the coarse precipitate interface, increases due to the introduction of strain and heat generation during processing. There is a possibility that the amount of solid solution and the amount of fine precipitates cannot be secured.
このため、タンデム圧延機による冷延では、冷間圧延工程における冷間圧延直後のアルミニウム合金板の温度が最も上昇する際に、アルミニウム合金板を強制的に冷却し、冷間圧延後のアルミニウム板の温度が200℃を超える温度に上昇しないようにすることが好ましい。 For this reason, in cold rolling with a tandem rolling mill, when the temperature of the aluminum alloy plate immediately after cold rolling in the cold rolling process rises most, the aluminum alloy plate is forcibly cooled, and the aluminum plate after cold rolling It is preferable to prevent the temperature of the glass from rising to a temperature exceeding 200 ° C.
このような冷間圧延時のアルミニウム合金板の強制的な冷却手段としては、通常使用される水を含まない圧延油を、水溶性油や水溶性潤滑剤などのエマルジョンタイプに変えて、このエマルジョン水溶液を用い、潤滑性能を低下させずに、冷却性能を強化させることが好ましい。 As a means for forcibly cooling the aluminum alloy sheet during such cold rolling, the usual rolling oil containing no water is changed to an emulsion type such as water-soluble oil or water-soluble lubricant, and this emulsion is used. It is preferable to use an aqueous solution to enhance the cooling performance without deteriorating the lubrication performance.
冷間圧延後は、必要に応じて、再結晶温度よりも低い温度で仕上焼鈍(最終焼鈍)を行ってもよい。仕上焼鈍を行うと加工組織が回復し、DI成形性や缶底成形性が向上する。仕上焼鈍の温度は、例えば、100〜150℃程度、特に115〜150℃程度にするのが望ましい。温度を100℃以上とすることによって、加工組織を充分に回復させることができる。一方、温度が150℃以下とすることによって、固溶元素の過剰な析出を防止でき、DI成形性やフランジ成形性をさらに高めることができる。 After cold rolling, if necessary, finish annealing (final annealing) may be performed at a temperature lower than the recrystallization temperature. When finish annealing is performed, the processed structure is recovered, and DI moldability and can bottom moldability are improved. The finish annealing temperature is preferably about 100 to 150 ° C., and more preferably about 115 to 150 ° C., for example. By setting the temperature to 100 ° C. or higher, the processed structure can be sufficiently recovered. On the other hand, by setting the temperature to 150 ° C. or less, excessive precipitation of solid solution elements can be prevented, and DI moldability and flange moldability can be further improved.
仕上焼鈍の時間は、4時間以下(特に1〜3時間程度)とするのが望ましい。長すぎる焼鈍を避けることによって、固溶元素の過剰な析出を防止でき、DI成形性をさらに高めることができる。 The finish annealing time is preferably 4 hours or less (particularly about 1 to 3 hours). By avoiding annealing too long, excessive precipitation of solid solution elements can be prevented, and DI moldability can be further enhanced.
但し、前記したタンデム圧延機による冷延では、より低温で、かつ連続的に回復を生じさせ、サブグレインを生成することができるために、仕上焼鈍が基本的には不要である。 However, in the cold rolling by the tandem rolling mill described above, finish annealing is basically unnecessary because it is possible to generate recovery continuously and generate subgrains at a lower temperature.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and both are included in the technical scope of the present invention.
アルミ地金のみを溶解原料として、下記表1に示すA〜Nの成分組成のAl合金の溶湯を溶解し、DC鋳造法にて板厚600mm、幅2100mmの鋳塊を製造した。なお、表1において「−」で示す元素含有量は検出限界以下であることを示す。 Using only the aluminum ingot as a melting raw material, the molten aluminum alloy having the composition of components A to N shown in Table 1 below was melted, and an ingot having a plate thickness of 600 mm and a width of 2100 mm was produced by a DC casting method. In Table 1, the element content indicated by “−” is below the detection limit.
この鋳塊には、表1に示す通り、発明例、比較例ともに、その他元素の総量として、不可避的な不純物元素、Zr、Bi,Sn、Ga,V,Co,Ni,Ca、Mo,Be、Pb,Wを、これらの元素の含有量の総和で0.01%以下含んでいた。 In this ingot, as shown in Table 1, inventive and comparative examples, the total amount of other elements is inevitable impurity elements, Zr, Bi, Sn, Ga, V, Co, Ni, Ca, Mo, Be. , Pb and W were contained in an amount of 0.01% or less in terms of the total content of these elements.
この鋳塊を表2に示す条件に従って、均熱処理を行なった。均熱処理は、1回目の均熱処理後に室温まで表2に示す冷却速度にて冷却した後、再加熱して2回目の均熱処理を行う、2回の均熱処理とした。
ここで、1回目均熱条件の昇温速度は、実質上、特性に影響を及ぼす“300℃から最高温度までの昇温速度を指す。
また、1回目均熱条件の冷却速度は、実質上、特性に影響を及ぼす“最高温度から300℃までの冷却速度を指す。
この均熱処理後に、熱間粗圧延として、スタンド数が1個のリバース熱間粗圧延機、熱間仕上圧延機として、スタンド数が4個のタンデム式熱間圧延機を使用して、熱間圧延を行なった。その際、熱間粗圧延終了後に熱間仕上圧延を開始する時間は3分以内とした。そして、共通して熱間仕上圧延後の板厚を2〜2.5mmとしたアルミニウム合金熱延板を製造した。
The ingot was subjected to soaking treatment according to the conditions shown in Table 2. The soaking process was two soaking processes in which after the first soaking process, after cooling to room temperature at the cooling rate shown in Table 2, reheating and performing the second soaking process.
Here, the rate of temperature increase under the first soaking condition substantially refers to the rate of temperature increase from “300 ° C. to the maximum temperature, which affects the characteristics.
The cooling rate under the first soaking condition substantially refers to the cooling rate from the highest temperature to 300 ° C., which affects the characteristics.
After this soaking, hot reverse rolling is performed using a reverse hot roughing mill with one stand, and a hot finish rolling mill with a tandem hot rolling mill with four stands. Rolled. At that time, the time for starting hot finish rolling after completion of hot rough rolling was set to be within 3 minutes. And the aluminum alloy hot-rolled sheet which made the board thickness after hot finish rolling 2-2.5 mm in common was manufactured.
得られた熱間圧延板を、中間焼鈍することなく、ロールスタンドが2段のタンデム圧延機により1回のみの通板で冷間圧延し、共通して、最終板厚0.3mmのボトル缶胴用板材(冷間圧延板)を製造した。この際、タンデム圧延機による冷延では、冷間圧延直後のアルミニウム板の温度が250℃を超える温度に上昇しないように、エマルジョン水溶液を用い、アルミニウム板を強制的に冷却した。この冷間圧延後の仕上焼鈍(最終焼鈍)は行なわなかった。 The obtained hot-rolled sheet is cold-rolled by a single pass through a two-stage tandem rolling mill without intermediate annealing, and in common a bottle can with a final sheet thickness of 0.3 mm A plate material for a trunk (cold rolled plate) was produced. At this time, in cold rolling with a tandem rolling mill, the aluminum plate was forcibly cooled using an aqueous emulsion solution so that the temperature of the aluminum plate immediately after cold rolling did not rise to a temperature exceeding 250 ° C. Finish annealing (final annealing) after this cold rolling was not performed.
なお、比較例10のみは、総冷延率は同じであるが、比較のために、ロールスタンドが1段のシングル圧延機で2回通板し、1回目と2回目とのパス間に、150℃×1時間の中間焼鈍を施した。 In addition, only the comparative example 10 has the same total cold rolling ratio, but for comparison, the roll stand is passed twice with a single rolling mill with one stage, and between the first and second passes, Intermediate annealing at 150 ° C. for 1 hour was performed.
冷延後のボトル缶胴用板材(コイル)から試験片を採取し、試験片の組織として、結晶粒の平均アスペクト比、およびCu固溶量、Mg固溶量を、各々前記した方法で調査した。これらの結果を表3に示す。 Samples are collected from the plate material (coil) for bottle cans after cold rolling, and the average aspect ratio of the crystal grains, the Cu solid solution amount, and the Mg solid solution amount are investigated as the structure of the test piece by the methods described above. did. These results are shown in Table 3.
また、試験片の高温特性として、室温での試験片表面の硬さと0.2%耐力、および、試験片を290℃×20秒熱処理した時の表面の硬さと0.2%耐力を各々測定し、この熱処理前後での試験片表面の硬さ変化(硬さ減少量)ΔHv(Hv)を求めた。更に、成形後の缶胴のベークハード後の楕円変形量を測定した。これらの結果も表3に示す。 Further, as the high temperature characteristics of the test piece, the hardness and 0.2% proof stress of the surface of the test piece at room temperature, and the hardness and 0.2% proof stress of the surface when the test piece is heat treated at 290 ° C. for 20 seconds, respectively. Then, the hardness change (hardness reduction amount) ΔHv (Hv) of the test piece surface before and after the heat treatment was obtained. Furthermore, the amount of elliptic deformation after baking of the can body after molding was measured. These results are also shown in Table 3.
(0.2%耐力測定)
0.2%耐力測定の引張試験はJIS Z 2201にしたがって行うとともに、試験片形状はJIS 5 号試験片で行い、試験片長手方向が圧延方向と一致するように作製した。また、クロスヘッド速度は5mm/分で、試験片が破断するまで一定の速度で行った。
(0.2% proof stress measurement)
A tensile test for 0.2% proof stress measurement was performed according to JIS Z 2201, and the shape of the test piece was a JIS No. 5 test piece so that the longitudinal direction of the test piece coincided with the rolling direction. The crosshead speed was 5 mm / min, and the test piece was run at a constant speed until the test piece broke.
(硬さ測定)
冷延板試料の硬さ測定は、マイクロビッカース硬度計にて、100gの荷重を加えて4箇所行い、硬さはそれらの平均値とした。
(Hardness measurement)
The hardness of the cold-rolled sheet sample was measured with a micro Vickers hardness tester by applying a load of 100 g at four locations, and the hardness was an average value thereof.
(楕円変形評価)
楕円変形の評価は、後述するように、上記ボトル缶胴用板材をDI成形したボトル缶胴を、洗浄後、缶の実体温度が300℃に、30秒で達する条件でベーキングした上で、楕円変形度を調査した。楕円変形度調査は、ボトル缶胴の口部の径を順に円周方向に調査し、その中での最大径から最小径を減算した量を楕円変形量(mm)として求め、これをN=10缶の平均値として評価した。なお、この楕円変形量は4mm以下を楕円変形性が合格と評価した。この楕円変形量が4mmを超えると、缶製造工程における、後工程の搬送工程及びネッキング工程で、転倒及びジャムなどの不良が発生し、缶の連続的で効率的な製造を困難にする。
(Ellipse deformation evaluation)
As will be described later, the elliptical deformation was evaluated by baking the bottle can body formed by DI molding of the above-mentioned plate material for the bottle can body after being washed and baked under the condition that the body temperature of the can reaches 300 ° C. in 30 seconds. The degree of deformation was investigated. In the ellipse deformation degree investigation, the diameter of the mouth portion of the bottle can body is sequentially investigated in the circumferential direction, and the amount obtained by subtracting the minimum diameter from the maximum diameter is obtained as the amount of ellipse deformation (mm). The average value of 10 cans was evaluated. In addition, this ellipse deformation amount evaluated that the ellipse deformation property was 4 mm or less. When this elliptical deformation exceeds 4 mm, in the can manufacturing process, defects such as overturning and jamming occur in the transport process and necking process in the subsequent process, making continuous and efficient manufacture of the can difficult.
更に、ボトル缶胴用板材が基本的に満たすべき成形性として、耳率とDI(しごき)成形性(成形時の割れ発生回数)を測定、評価した。これらの結果も表3に示す。 Furthermore, as a formability that the bottle can body plate material should basically satisfy, the ear rate and DI (ironing) formability (number of cracks generated during forming) were measured and evaluated. These results are also shown in Table 3.
(耳率)
耳率は、このボトル缶胴用板材からブランクを採取し、潤滑油[D.A.Stuart社製、ナルコ147]を塗布した上で、エリクセン試験機によって、40%深絞り試験、カップ状に成形して調査した。試験条件は、ブランクの直径=66.7mm、ポンチの直径=40mm、ダイス側肩部のRを2.0mm、ポンチの肩R=3.0mm、しわ押さえ圧=400kgfで行なった。
(Ear rate)
The ear rate was obtained by collecting a blank from the plate material for the bottle can body and lubricating oil [D. A. After applying Naruco 147] manufactured by Stuart, a 40% deep-drawing test was conducted by using an Erichsen tester, which was then formed into a cup shape and investigated. The test conditions were as follows: blank diameter = 66.7 mm, punch diameter = 40 mm, die side shoulder R = 2.0 mm, punch shoulder R = 3.0 mm, wrinkle holding pressure = 400 kgf.
このように得られたカップの開口周縁部の8方向(圧延方向を0°として、0°方向、45°方向、90°方向、135°方向、180°方向、225°方向、270°方向、及び315°方向)に生じる山谷の形状を測定し、平均耳率を算出した。 8 directions of the opening peripheral edge of the cup thus obtained (0 ° direction, 45 ° direction, 90 ° direction, 135 ° direction, 180 ° direction, 225 ° direction, 270 ° direction, assuming the rolling direction as 0 °, And 315 ° direction) were measured, and the average ear rate was calculated.
平均耳率の算出方法は、図1に基づいて説明する。図1は、ボトル缶胴用板材をDI成形することによって得られるカップの展開図である。この展開図では、圧延方向を0°として、0°、90°、180°、及び270°方向に生じる耳の高さ(T1,T2,T3,T4;マイナス耳と称する)を測定し、45°、135°、225°、及び315°方向に生じる耳の高さ(Y1,Y2,Y3,Y4;プラス耳と称する)を測定する。なお各高さY1〜Y4,T1〜T4は、カップの底部からの高さである。そして各測定値から、次式に基づいて平均耳率を算出する。
平均耳率(%)=[{(Y1+Y2+Y3+Y4)−(T1+T2+T3+T4)}/{1/2×(Y1+Y2+Y3+Y4+T1+T2+T3+T4)}]×100
A method of calculating the average ear rate will be described with reference to FIG. FIG. 1 is a development view of a cup obtained by DI molding a plate material for a bottle can body. In this development view, the height of the ears (T1, T2, T3, T4; referred to as minus ears) measured in the directions of 0 °, 90 °, 180 °, and 270 °, where the rolling direction is 0 °, is measured. Measure the height of the ears (Y1, Y2, Y3, Y4; referred to as plus ears) occurring in the directions of °, 135 °, 225 °, and 315 °. Each of the heights Y1 to Y4 and T1 to T4 is a height from the bottom of the cup. Then, the average ear rate is calculated from each measured value based on the following equation.
Average Ear Ratio (%) = [{(Y1 + Y2 + Y3 + Y4) − (T1 + T2 + T3 + T4)} / {1/2 × (Y1 + Y2 + Y3 + Y4 + T1 + T2 + T3 + T4)}] × 100
なお本発明の対象としている冷間圧延板では、平均耳率を0近くにした場合、4つのプラス耳(Y1〜Y4)並びに90°方向及び270°方向の2つのマイナス耳(図1のT2、T4)の発達は抑制されるものの、0°方向及び180°方向の2つのマイナス耳(図1のT1、T3)の発達は抑制されにくい。そして単に平均耳率の絶対値を小さくした場合には、例えば、平均耳率を−2〜2%(絶対値では2%以下)にした場合には、平均耳率を−2以上0%未満としても、マイナス耳(図1のT1、T3)の抑制が不十分なために、絞り成形のシワ押さえ圧が、この2つのマイナス耳(図1のT1、T3)に集中し、耳立ち、耳切れなどが発生して生産に不具合が生じるのに対して、平均耳率を0〜2%(プラス側)にした場合には、残りの2つのマイナス耳(図1のT1、T3)も十分に抑制できるために、耳切れに起因する缶胴破壊を防止できる。なお、本発明においては、+0%〜+3.5%を許容範囲とした。 In the cold-rolled sheet of the present invention, when the average ear rate is close to 0, four plus ears (Y1 to Y4) and two minus ears in the 90 ° direction and the 270 ° direction (T2 in FIG. 1). , T4) is suppressed, but the development of two minus ears (T1, T3 in FIG. 1) in the 0 ° direction and 180 ° direction is difficult to be suppressed. When the absolute value of the average ear rate is simply reduced, for example, when the average ear rate is -2 to 2% (2% or less in absolute value), the average ear rate is -2 to less than 0%. However, since the negative ears (T1, T3 in FIG. 1) are not sufficiently suppressed, the wrinkle pressing pressure of the drawing molding is concentrated on these two negative ears (T1, T3 in FIG. 1). When the average ear rate is 0 to 2% (plus side), the remaining two minus ears (T1 and T3 in FIG. 1) are also sufficient. Therefore, it is possible to prevent the can body from being broken due to the cutting of the ears. In the present invention, the allowable range is + 0% to + 3.5%.
(DI成形性)
前記ボトル缶胴用板材(板厚が0.3mm)から、直径156mmのブランクを打ち抜き、カップ径92mmのカップを成形し、再絞り加工、しごき加工、及びトリミングにより、製缶速度300缶/分の速さで、ボトル缶用DI缶胴(内径66mmφ、高さが170mm、側壁板厚103μm、側壁先端部板厚165μm、最終第3しごき率40%)を製造した。成形缶5万缶あたりの胴割れの発生個数を求め、DI成形性を評価した。全く存在しなかったものを◎(極めて良好)、1缶以下であったものを○(良好)、2乃至4缶であったものを△(概ね良好)、5缶を超えたものを×(不良)として評価した。
(DI moldability)
A blank with a diameter of 156 mm is punched from the plate material for the bottle can body (plate thickness is 0.3 mm), a cup with a cup diameter of 92 mm is formed, redrawing, ironing, and trimming, and a can-making speed of 300 cans / minute A DI can barrel (inner diameter 66 mmφ, height 170 mm, side wall plate thickness 103 μm, side wall tip plate thickness 165 μm, final third ironing rate 40%) was manufactured at a speed of The number of occurrences of body cracks per 50,000 cans was determined, and the DI moldability was evaluated. Those that did not exist at all ◎ (very good), those that were 1 can or less ○ (good), those that were 2 to 4 cans △ (generally good), those that exceeded 5 cans × ( Bad).
表3から明らかなように、発明例1〜6は、本発明成分組成を有し、かつ、結晶粒の平均アスペクト比が3以上、Cu固溶量が前記した測定方法で0.05〜0.3%、Mg固溶量が前記した測定方法で0.75〜1.6%である。 As is apparent from Table 3, Invention Examples 1 to 6 have the composition of the present invention, an average aspect ratio of crystal grains of 3 or more, and a Cu solid solution amount of 0.05 to 0 by the measurement method described above. .3%, Mg solid solution amount is 0.75 to 1.6% by the measuring method described above.
この結果、発明例1〜6は、表3から明らかなように、290℃×20秒熱処理後(ベークハード後)の、硬さ変化ΔHvが30Hv以下であり、かつ、0.2%耐力が210MPa以上であり、硬度低下や強度低下が少なく、高温特性に優れている。 As a result, as is apparent from Table 3, Invention Examples 1 to 6 have a hardness change ΔHv of 30 Hv or less after heat treatment (after baking hard) at 290 ° C. × 20 seconds and 0.2% proof stress. The pressure is 210 MPa or more, and there is little decrease in hardness or strength, and excellent high temperature characteristics.
更に、発明例1〜6は、耳率とDI成形性にも優れている。したがって、本発明における高温特性の改良が、ボトル缶胴用板材が基本的に満たすべき成形性を阻害していないことが分かる。 Further, Invention Examples 1 to 6 are excellent in the ear rate and DI moldability. Therefore, it turns out that the improvement of the high temperature characteristic in this invention has not inhibited the moldability which the board | plate material for bottle can bodies should satisfy | fill fundamentally.
これに対して、比較例7、9〜10は、本発明成分組成ではあるものの、均熱処理や熱間圧延の条件が前記好ましい条件から外れるために、結晶粒の平均アスペクト比、Cu固溶量、Mg固溶量のいずれかが外れる。この結果、上記発明例に比して、硬度低下や強度低下が大きく、高温特性が劣っている。 On the other hand, Comparative Examples 7 and 9 to 10 have the composition of the present invention, but the conditions of soaking and hot rolling deviate from the preferable conditions. , Either Mg solid solution amount is lost. As a result, the hardness and strength are greatly reduced and the high temperature characteristics are inferior to those of the above invention examples.
比較例7は2回目の均熱温度が低過ぎる。また、熱間仕上げ圧延終了温度が低過ぎる。比較例9は熱間仕上げ圧延終了温度が低過ぎる。比較例10はシングル冷間圧延機であり、しかも冷間圧延途中で中間焼鈍を施している。 In Comparative Example 7, the second soaking temperature is too low. Moreover, the hot finish rolling finish temperature is too low . The ratio Comparative Examples 9 hot finish rolling end temperature is too low. Comparative Example 10 is a single cold rolling mill, and intermediate annealing is performed during cold rolling.
比較例11〜20は、好ましい製造条件で製造されている。しかし、合金組成が本発明成分組成から外れる。この結果、上記発明例に比して、硬度低下や強度低下が大きく、高温特性が劣っている。また、成形性も低くなっている。 Comparative Examples 11 to 20 are manufactured under preferable manufacturing conditions. However, the alloy composition deviates from the composition of the present invention. As a result, the hardness and strength are greatly reduced and the high temperature characteristics are inferior to those of the above invention examples. Moreover, the moldability is also low.
以上の結果から、本発明の各要件の臨界的な意義が分かる。 From the above results, the critical significance of each requirement of the present invention can be understood.
以上説明したように、本発明は、DI加工等の成形性の確保を前提に、より高温化短時間化された高速化熱処理に対しても、塗装熱処理時の熱変形を防止し、熱処理後の缶強度を確保するとともに、真円度が高いボトル缶を得ることができる、高温特性に優れたボトル缶用アルミニウム合金冷延板を提供できる。したがって、ボトル缶のような、薄肉で熱処理されても、強度低下や変形が無いことが求められ、しかも成形性はそのまま維持する必要がある、厳しい要求特性用途に好適である。 As described above, the present invention prevents thermal deformation during coating heat treatment even after high-speed heat treatment with higher temperature and shorter time on the premise of ensuring moldability such as DI processing, and so on. It is possible to provide an aluminum alloy cold-rolled sheet for a bottle can excellent in high-temperature characteristics, which can secure a high strength of the can and obtain a bottle can having a high roundness. Therefore, even if it is heat-treated with a thin wall such as a bottle can, it is demanded that there is no strength reduction or deformation, and it is suitable for severe demand characteristic applications where the moldability needs to be maintained as it is.
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JP2005089370A JP4019083B2 (en) | 2005-03-25 | 2005-03-25 | Aluminum alloy cold rolled sheet for bottle cans with excellent high temperature characteristics |
EP10010379A EP2281911A1 (en) | 2005-03-25 | 2006-03-07 | Aluminium alloy sheet for bottle cans superior in high-temperature properties |
CA002602657A CA2602657A1 (en) | 2005-03-25 | 2006-03-07 | Aluminum alloy sheet for bottle cans superior in high-temperature properties |
US11/909,665 US20090053099A1 (en) | 2005-03-25 | 2006-03-07 | Aluminum alloy sheet with excellent high-temperature property for bottle can |
KR1020077021791A KR100953799B1 (en) | 2005-03-25 | 2006-03-07 | Aluminum alloy sheet with excellent high-temperature property for bottle can |
EP06715351A EP1870481A4 (en) | 2005-03-25 | 2006-03-07 | Aluminum alloy sheet with excellent high-temperature property for bottle can |
EP10010378A EP2281910A1 (en) | 2005-03-25 | 2006-03-07 | Aluminium alloy sheet for bottle cans superior in high-temperature properties |
PCT/JP2006/304381 WO2006103887A1 (en) | 2005-03-25 | 2006-03-07 | Aluminum alloy sheet with excellent high-temperature property for bottle can |
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CN104903481A (en) * | 2012-12-27 | 2015-09-09 | 株式会社神户制钢所 | Aluminum alloy sheet for DI can body |
KR20160084862A (en) | 2012-02-09 | 2016-07-14 | 가부시키가이샤 고베 세이코쇼 | Manufacturing method of aluminum alloy sheet for di can body |
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JP2015045076A (en) * | 2013-08-29 | 2015-03-12 | 三菱アルミニウム株式会社 | Aluminum alloy sheet for beverage can body excellent in surface property |
JP6227691B2 (en) * | 2016-03-08 | 2017-11-08 | 株式会社神戸製鋼所 | Manufacturing method of aluminum alloy plate for DI can body |
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CN104903481A (en) * | 2012-12-27 | 2015-09-09 | 株式会社神户制钢所 | Aluminum alloy sheet for DI can body |
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