JP2004345214A - RESIN-COATED Sn PLATED STEEL SHEET, CAN USING THIS STEEL SHEET AND METHOD FOR MANUFACTURING RESIN-COATED Sn PLATED STEEL SHEET - Google Patents
RESIN-COATED Sn PLATED STEEL SHEET, CAN USING THIS STEEL SHEET AND METHOD FOR MANUFACTURING RESIN-COATED Sn PLATED STEEL SHEET Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、樹脂被覆層の加工接着性に優れた樹脂被覆Ｓｎめっき鋼板、それを絞り加工等の厳しい成形加工を施してなる缶、およびこの樹脂被覆Ｓｎめっき鋼板の製造方法に関する。
【０００２】
【従来の技術】
近年、樹脂を被覆してなる鋼板を絞り加工、絞り加工後のさらなるストレッチ加工、絞り加工後のさらなるしごき加工、絞り加工後のさらなるストレッチ加工としごき加工を併用する加工などの厳しい加工を施してなる缶胴部と缶底部が一体で加工成形された缶に内容物を充填し、天板を巻締めたものが市販されている。これらの缶においては、これらの厳しい成形加工中および成形加工後に被覆樹脂が剥離もしくは破断することがないように、鋼板に対する樹脂の優れた接着性が要求される。そのため、これらの用途における樹脂被覆鋼板としては、有機樹脂との加工接着性に優れるクロメート皮膜を表面に形成させたティンフリースチールなどのクロメート処理鋼板に樹脂を被覆したものが用いられていた。
【０００３】
しかし、樹脂被覆クロメート処理鋼板を用いた缶においては、樹脂層に鋼板面に達する微細な孔や亀裂が生じた場合、クロメート処理鋼板が耐食性に乏しいために、特に酸性度の大きな内容物を充填した場合に鋼板の腐食が急速に進行して穿孔しやすい欠点を有している。そのため、酸性度の大きな内容物を充填した場合に優れた耐食性を示すＳｎめっき鋼板に樹脂を被覆してなる樹脂被覆Ｓｎめっき鋼板の適用が試みられたが、Ｓｎめっき層に対する樹脂の接着性、特に加工接着性に乏しく、上記のような厳しい加工用途に適用可能な樹脂被覆Ｓｎめっき鋼板が求められている。
【０００４】
本発明の発明者等は、厳しい加工用途に適用可能な樹脂被覆Ｓｎめっき鋼板として、樹脂被覆Ｓｎめっき鋼板を提案した（例えば特許文献１参照）。この公報に記載された樹脂被覆Ｓｎめっき鋼板は、ノーリフローＳｎめっき鋼板またはリフローＳｎめっき鋼板のＳｎめっき層上にシランカップリング剤塗布層を設けてなるＳｎめっき鋼板に有機樹脂皮膜を積層してなる樹脂被覆Ｓｎめっき鋼板である。この樹脂被覆Ｓｎめっき鋼板においては、缶に成形加工する前の有機樹脂皮膜の接着強度がＴピール強度で２ｋｇ／１０ｍｍ以上であることを特徴としている。しかし、この樹脂被覆Ｓｎめっき鋼板を成形加工して缶に成形加工した場合、特により厳しい、絞り加工後にさらにストレッチ加工としごき加工を併用して缶に成形加工した場合、問題なく成形加工可能な場合もあるが、成形加工途中で缶の上部で樹脂が剥離することがあり、Ｓｎめっき層に対する樹脂の優れた接着性が安定して得られないことが判明した。また、缶に成形加工する前の有機樹脂皮膜の接着強度では、成形加工時や成形加工後の接着性を必ずしも正確に反映していないことも判明した。
【０００５】
本発明においては、ノーリフローＳｎめっき鋼板またはリフローＳｎめっき鋼板のＳｎめっき層上にシランカップリング剤塗布層を設けてなるＳｎめっき鋼板に、コロナ放電処理を施した有機樹脂皮膜を積層することにより、成形加工時や成形加工後の安定した接着性を示す樹脂被覆Ｓｎめっき鋼板が得られることが判明した。また、ポリプロピレン系樹脂フィルムにコロナ放電処理を施すことが開示されている（例えば特許文献２参照）。これは有機樹脂にコロナ放電処理を施すことにより積層する基板との接着性が向上することは公知である。しかし、有機樹脂との加工接着性に乏しいＳｎめっき鋼板に有機樹脂を積層して、絞り加工後にさらにストレッチ加工としごき加工を併用して缶に成形加工する過酷な加工に耐える加工接着性を得るために、Ｓｎめっき層上にシランカップリング剤塗布層を設け、このシランカップリング剤塗布層にコロナ放電処理面が接するようにしてコロナ放電処理を施した有機樹脂を被覆することにより、耐食性に優れたＳｎめっき鋼板を基板とする樹脂被覆Ｓｎめっき鋼板からこのような過酷な加工による缶を安定して得られることが初めて可能となったのである。
【０００６】
本出願に関する先行技術文献情報として次のものがある。
【特許文献１】
特開２００２−２８５３５４号公報
【特許文献２】
特許３３５２５５３号公報
【０００７】
【発明が解決しようとする課題】
本発明は、厳しい成形加工を施した際の優れた加工接着性を有する樹脂被覆Ｓｎめっき鋼板、それを用いた缶、およびこの樹脂被覆Ｓｎめっき鋼板の製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明の樹脂被覆Ｓｎめっき鋼板は、Ｓｎめっき層上にシランカップリング剤塗布層を形成させてなるＳｎめっき鋼板の少なくとも片面に、コロナ放電処理を施した有機樹脂フィルムを被覆してなる樹脂被覆Ｓｎめっき鋼板（請求項１）であり、
Ｓｎめっき鋼板が、鋼板上にＳｎめっき層を形成させたままのＳｎめっき鋼板（ノーリフローＳｎめっき鋼板）、または鋼板とＳｎめっき層の間にＳｎ−Ｆｅ合金層を形成させてなるＳｎめっき鋼板（リフローＳｎめっき鋼板）であること、（請求項２）また
シランカップリング剤の塗布量が、Ｓｉ量で１〜５０ｍｇ／ｍ２ であること（請求項３）、さらにまた、
コロナ放電処理が電圧：２００Ｖ、電流：０．２〜８Ａ／２５ｃｍの条件で施したものであること（請求項４）、さらにまた
上記の請求項１〜４のいずれかの樹脂被覆Ｓｎめっき鋼板を、絞り比：１．６４の１段絞り加工で径：９６ｍｍ、高さ：４２ｍｍの絞りカップに成形した後の、カップ側壁部の樹脂フィルムの剥離強度が０．０５ｋｇ／１５ｍｍ以上であること（請求項５）を特徴とする。
【０００９】
また本発明の缶は、上記の請求項１〜５のいずれかの樹脂被覆Ｓｎめっき鋼板を絞り加工してなる缶（請求項６）、または
絞り加工後さらにストレッチ加工してなる缶（請求項７）、さらにまたは
絞り加工後さらにしごき加工してなる缶（請求項８）、さらにまたは
絞り加工後さらにストレッチ加工としごき加工を併用して加工してなる缶（請求項９）である。
【００１０】
また本発明の樹脂被覆Ｓｎめっき鋼板の製造方法は、鋼板の少なくとも片面にＳｎめっき層を形成させ、次いでＳｎめっき層上にシランカップリング剤を塗布し乾燥させた後、シランカップリング剤塗布層上にコロナ放電処理面が接するようにしてコロナ放電処理を施した有機樹脂フィルムを積層することを特徴とする、樹脂被覆Ｓｎめっき鋼板の製造方法、または
鋼板の少なくとも片面にＳｎめっき層を形成させ、次いでＳｎの溶融温度以上に加熱した後急冷することにより鋼板とＳｎめっき層の間にＳｎ−Ｆｅ合金層を形成させ、その後Ｓｎめっき層上にシランカップリング剤を塗布し乾燥させた後、シランカップリング剤塗布層上にコロナ放電処理面が接するようにしてコロナ放電処理を施した有機樹脂フィルムを積層することを特徴とする、樹脂被覆Ｓｎめっき鋼板の製造方法である。
【００１１】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の樹脂被覆Ｓｎめっき鋼板に用いる鋼板としては、通常のアルミキルド鋼の熱間圧延板を冷間圧延し、焼鈍した後調質圧延した冷延鋼板、または焼鈍後さらに冷間圧延を施して強度を増加させた冷延鋼板のいずれかが、用途に応じて選択的に用いられる。これらの冷延鋼板を電解脱脂し酸洗した後、鋼板上にＳｎめっき層を形成させてＳｎめっき鋼板とする。Ｓｎめっき鋼板としては、公知のフェロスタン浴やハロゲン浴を用いてＳｎをめっきしたままのＳｎめっき鋼板（ノーリフローＳｎめっき鋼板）、Ｓｎをめっきした後、Ｓｎの溶融温度以上に加熱した後急冷することにより、Ｓｎめっき層の間にＳｎ−Ｆｅ合金層を形成させたＳｎめっき鋼板（リフローＳｎめっき鋼板）がある。またこれらのＳｎめっき鋼板の他に、Ｎｉを電気めっきし、その上層にそのまま、またはＮｉめっき後加熱してＮｉを鋼中に拡散させてＮｉ−Ｆｅ合金層を形成させ、その後Ｓｎを電気めっきした後、Ｓｎの溶融温度以上に加熱した後急冷する、などの方法を用いて、島状のＳｎ層を形成させた島状Ｓｎめっき鋼板なども用いることができる。
【００１２】
無光沢のノーリフローＳｎめっき鋼板におけるＳｎめっき量は、耐食性および経済性の観点から０．１〜１０ｇ／ｍ２ の範囲にあることが好ましい。光沢を有するリフローＳｎめっき鋼板においてはＳｎめっき層と鋼板の間にＳｎ−Ｆｅ合金層が形成されるので、めっき鋼板の表面に金属Ｓｎを残存させる場合は全Ｓｎめっき量は１〜１０ｇ／ｍ２ の範囲にあることが必要である。めっき鋼板の表面に金属Ｓｎを残存させず、Ｓｎ−Ｆｅ合金層のみからなる層を表面層とする場合は、全Ｓｎめっき量は０．１〜１０ｇ／ｍ２ の範囲にあることが好ましい。
【００１３】
島状Ｓｎめっき鋼板の場合は、Ｓｎめっきを施す前に鋼板上に形成させるＮｉめっきの量が０．００５〜０．１ｇ／ｍ２ 、その上層に形成させるＳｎめっきの量が０．１〜１．５ｇ／ｍ２ の範囲にあることが好ましい。このようなめっき量でそれぞれのめっき層を形成させた後、またはＮｉを上記のめっき量でめっきした後拡散熱処理を施し、その後Ｓｎを上記のめっき量でめっきした後、Ｓｎの溶融温度以上に加熱することにより、表面にＳｎが島状に分散して存在する島状Ｓｎめっき鋼板が得られる。
【００１４】
上記のようにして得られるＳｎめっき鋼板の表面にシランカップリング剤を塗布し乾燥させる。シランカップリング剤としては、ビニル系、アクリル系、エポキシ系、アミノ系、メルカプト系、クロロピル系などの各種のものがあるが、本発明においてはアミノ系のシランカップリング剤を用いることが好ましい。アミノ系のシランカップリング剤としては、アミノプロピルトリメトキシシラン、アミノプロピルメチルジエトキシシラン、アミノプロピルトリエトキシシラン、フェニルアミノプロピルトリメトキシシランなどを用いることができる。これらのシランカップリング剤の５〜２００ｇ／Ｌの水溶液を上記のＳｎめっき鋼板に塗布し、乾燥させる。塗布方法としては公知の方法が適用でき、例えば、浸漬法、ロールコート法、浸漬後に絞りロールを用いて余剰分を絞る方法、スプレー法、電解処理法など、いずれも適用することができる。乾燥後の塗布膜量は、蛍光Ｘ線法で測定したＳｉ量で１〜５０ｍｇ／ｍ２ であることが好ましい。Ｓｉ量で１ｍｇ／ｍ２ 未満である場合はこのシランカップリング剤塗布層上に積層する樹脂皮膜の加工接着強度に乏しくなる。一方、Ｓｉ量で５０ｍｇ／ｍ２ を超えても樹脂皮膜の加工接着強度は不十分となり、また経済的でなくなる。このようにして本発明の樹脂被覆Ｓｎめっき鋼板に用いるＳｎめっき鋼板が得られる。
【００１５】
本発明の樹脂被覆Ｓｎめっき鋼板は、上記のようにして得られたＳｎめっき鋼板の片面または両面に、コロナ放電処理を施した有機樹脂フィルムをコロナ放電処理面がシランカップリング剤塗布層に接するようにして積層することにより得られる。有機樹脂フィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、エチレンテレフタレート・エチレンイソフタレート共重合体、ブチレンテレフタレート・ブチレンイソフタレート共重合体などのポリエステル樹脂、あるいはこれらのポリエステル樹脂の２種類以上をブレンドした樹脂、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体、およびそれらをマレイン酸変性したもの、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体などのポリオレフィン樹脂、６−ナイロン、６，６−ナイロン、６，１０−ナイロンなどのポリアミド樹脂、ポリカーボネート、ポリメチルペンテン、さらに上記のポリエステル樹脂とアイオノマーをブレンドしたものからなる単層の樹脂フィルム、さらにこれらの樹脂の２種類以上からなる複層の樹脂フィルムなどを用いることができる。樹脂フィルムの厚さとしては、フィルム積層作業のしやすさ、樹脂被覆Ｓｎめっき鋼板の成形加工した後の成形体（缶）における樹脂フィルムの接着強度、耐食性、および経済性の観点から１０〜１００μｍであることが好ましい。
【００１６】
これらの樹脂フィルムは、樹脂ペレットを加熱溶融し、それを押出機のＴダイから押し出して所望の厚さのフィルムに製膜したものを上記のＳｎめっき鋼板に熱接着法を用いて接着積層する。熱接着法は、樹脂が接着する温度範囲に加熱したＳｎめっき鋼板に樹脂フィルムを当接し、１対の加圧ロールで挟み付けて加圧して圧接する方法であり、樹脂フィルムに延伸加工を施さずに製膜した樹脂フィルムを用いることにより、Ｓｎの溶融温度よりかなり低い温度で熱接着することができる。１軸方向、または２軸方向に延伸加工して製膜した樹脂フィルムを積層する場合は、延伸加工後の熱固定をＳｎの溶融温度よりかなり低い温度で行わないと、樹脂の溶融温度より高温に加熱しないかぎりＳｎめっき鋼板に対する良好な加工接着強度が得られないので、溶融温度がＳｎの溶融温度よりも高い樹脂を用いる場合は、熱接着することが困難になることがある。
【００１７】
本発明においては、特に、絞り加工後さらにストレッチ加工としごき加工を併用して加工して缶に成形するような厳しい成形加工を施した場合でも安定した優れた樹脂膜の加工接着性を得るために、上記のようにして得られる樹脂フィルムのＳｎめっき鋼板に当接する面にコロナ放電処理を施したものを用いる。コロナ放電処理は電圧：２００Ｖ、電流：０．２〜８Ａ／２５ｃｍの条件で行う。電流が０．２Ａ／２５ｃｍ未満であるとコロナ放電処理の効果が発現しない。一方、電流が８Ａ／２５ｃｍを超えると放電電流が過剰となり、樹脂フィルムに皺や膨れが生じるようになり、好ましくない。より好ましい電流の範囲は１〜５Ａ／２５ｃｍである。このようにして樹脂フィルムのコロナ放電処理を施した側を、上記のＳｎめっき鋼板のシランカップリング剤を塗布した面に当接して上記のようにして熱接着することにより、厳しい成形加工を施した場合でも安定した優れた樹脂膜の加工接着性が得られるようになる。
【００１８】
樹脂膜のＳｎめっき鋼板に対する剥離強度すなわち接着強度は、従来は加工前の平板の状態でＴピール強度を測定して評価していた。しかし、平板の状態で測定したＴピール強度では、特に、絞り加工後さらにストレッチ加工としごき加工を併用して加工して缶に成形するような厳しい成形加工を施した場合の加工中および加工後の接着強度、すなわち加工接着強度を必ずしも正確に反映しないことが判明した。そこで本発明においては、樹脂被覆Ｓｎめっき鋼板に絞り加工を施してカップに成形加工し、カップ側壁から試片を切り出し、その試片の樹脂膜の剥離強度で加工接着強度（以下Ｓピール強度という）を評価する。
【００１９】
Ｓピール強度の測定方法を以下に示す。上記のようにして得られる本発明の樹脂被覆Ｓｎめっき鋼板から１５４ｍｍのブランクを打ち抜き、絞り比：１．６４で１段の絞り加工を施して、径：９６ｍｍ、高さ：４２ｍｍの絞りカップに成形する。このカップから、カップ高さ方向：３０ｍｍ、カップ周方向：１２０ｍｍの大きさで側壁部を切り出して平板状に曲げ戻した後、図１に示すＴ字状の形状の試片１を打ち抜く。次いで図２に示すようにカッターナイフを用いて試片１の一方の端部１ａの接着強度測定面と反対の側の樹脂膜にＳｎめっき鋼板面に達するように切れ目２を入れる。次いで図３および図４に示すようにして、スコア加工用ダイセットを用いて接着強度測定面と反対の側からスコア３を入れた後、スコア部を折り曲げてＳｎめっき鋼板を切断する。この時、接着強度測定面においては樹脂膜は切断されることなく、切断されたＳｎめっき鋼板の両側に繋がったまま残っている。次いで図５に示すように、試片ホルダー４の試片挿入部４ａに片端部１ａを挿入して試片１を試片ホルダー４に固定した後、試片ホルダー４の上部４ｂと試片１の他方の端部１ｂをテンシロン引張試験機のチャック部で挟んで引張って、樹脂膜をＳｎめっき鋼板から強制剥離して引張強度を測定し、Ｓピール強度として加工接着強度を評価する。
【００２０】
上記のようにして測定されるＳピール強度は０．０５ｋｇ／１５ｍｍ以上であることが好ましい。Ｓピール強度が０．０５ｋｇ／１５ｍｍ未満であると、特に、絞り加工後さらにストレッチ加工としごき加工を併用して加工して缶に成形するような厳しい成形加工を施した場合に安定した良好な加工接着強度が得られない。
【００２１】
本発明の樹脂被覆Ｓｎめっき鋼板を絞り缶に成形加工する場合は、片面または両面に樹脂を積層した樹脂被覆Ｓｎめっき鋼板から打ち抜いたブランクを絞りダイスを用いてカップ状に絞り加工する。径を狭めて側壁の高さを高める場合は、前段よりも小径の絞りダイスを用いて再絞り加工する。絞り加工は通常１段または２段の絞り加工で行われ、比較的缶径が大きく、側壁高さが低い缶に適用される。
【００２２】
本発明の樹脂被覆Ｓｎめっき鋼板を絞り加工し次いでストレッチ加工して缶に成形加工する場合は、片面または両面に樹脂を積層した樹脂被覆Ｓｎめっき鋼板から打ち抜いたブランクを絞りダイスを用いてカップ状に絞り加工する。次いで複数段の絞りダイスを用いて、順次縮径しつつ側壁高さを高めていくが、ストレッチ加工においては、カップが加工ポンチに押されて絞り加工ダイスおよびしわ抑え治具に出入りする際に側壁が曲げおよび曲げ戻し加工され、側壁部分が伸びて薄肉化しながら絞り加工される。比較的缶径が小さく、側壁高さが高い缶に適用される。
【００２３】
本発明の樹脂被覆Ｓｎめっき鋼板を絞り加工し次いでしごき加工して缶に成形加工する場合は、片面または両面に樹脂を積層した樹脂被覆Ｓｎめっき鋼板から打ち抜いたブランクを１段または複数段の絞りダイスを用いてカップ状に絞り加工する。次いで１段または複数段のしごきダイスを用いて、カップの側壁厚みより小さく設定したしごきダイスとパンチの間のクリアランス部分に側壁部を強制的に押し込んで薄肉化しながら側壁高さを高めていくしごき加工を施す。このため、比較的缶径が小さく、側壁高さが高く、かつ側壁厚みの小さい缶に適用される。片面のみに樹脂を積層した樹脂被覆Ｓｎめっき鋼板を、非樹脂被覆面が缶外面となるようにしてしごき加工すると、Ｓｎめっき層がしごきダイスに擦られて鏡面になり、美麗な表面光沢が得られる。
【００２４】
本発明の樹脂被覆Ｓｎめっき鋼板を絞り加工し次いでストレッチ加工としごき加工を併用して缶に成形加工する場合は、片面または両面に樹脂を積層した樹脂被覆Ｓｎめっき鋼板から打ち抜いたブランクを１段または複数段の絞りダイスを用いてカップ状に絞り加工する。次いで通常のストレッチ加工と同様にして複数段の絞りダイスを用いて、順次縮径しつつ側壁高さを高めていくが、しごき加工におけるしごきダイスのようにダイスとパンチの間のクリアランス部分をカップの側壁厚みより小さく設定しておくことにより、側壁が曲げおよび曲げ戻し加工されると同時にしごき加工され、側壁部分が伸びて薄肉化しながら絞りしごき加工される。この加工において、片面のみに樹脂を積層した樹脂被覆Ｓｎめっき鋼板を用いた場合も、美麗な表面光沢が得られる。
【００２５】
【実施例】
以下、実施例にて本発明をさらに詳細に説明する。
［Ｓｎめっき鋼板の作成］
表１に示す板厚およびテンパーの冷延鋼板をアルカリ水溶液中で電解脱脂し、水洗し、次いで硫酸酸洗し、水洗した後、公知のフェロスタン浴を用いて、表１に示す条件でＳｎめっき層を形成させるか、またはＳｎめっき層を形成させた後リフロー処理を施して鋼板とＳｎめっき層の間にＳｎ−Ｆｅ合金層を形成させた。次いで表１に示す処理浴を用い、表１に示すシランカップリング剤の５〜２００ｇ／Ｌ水溶液を、表１に示す塗布量となるように、浸漬法を用いて塗布し乾燥してＳｎめっき上にシランカップリング剤塗布層を形成させた。また比較材として、試料番号１０で示す、冷延鋼板に電解クロム酸処理を施してＣｒめっき層とＣｒ水和酸化物層の２層を形成させたティンフリースチールを作成した。
【００２６】
【表１】
【表２】
［樹脂被覆Ｓｎめっき鋼板の作成］
表１に示すＳｎめっき鋼板およびティンフリースチールの片面に、片側に表２に示す条件でコロナ放電処理を施した厚さ：２８μｍの無配向の透明のエチレンテレフタレート・エチレンイソフタレート共重合体（ＰＥＴＩで表示）の２層フィルム（上層がＰＥＴＩ１５（厚さ：１２μｍ）、下層がＰＥＴＩ５（厚さ：１６μｍ）、数字はエチレンイソフタレートのモル％を示し、ＰＥＴＩ５側が鋼板側と接する）、他の片面に同一のエチレンテレフタレート・エチレンイソフタレート共重合体にチタン系白色顔料を２０重量％含有させた白色の無配向の２層フィルム（上層がＰＥＴＩ１５（厚さ：５μｍ）、下層がＰＥＴＩ５（厚さ：１１μｍ））を熱接着法を用い、２２５℃で熱接着して積層し、試料番号１〜８で示す樹脂被覆Ｓｎめっき鋼板および試料番号１０で示す樹脂被覆ティンフリースチールを作成した。また比較材として、試料番号９で示すコロナ放電処理を施さない樹脂フィルムを積層した被覆Ｓｎめっき鋼板も作成した。
【００２９】
［Ｓピール強度測定用の試片の作成］
表１に示す樹脂被覆Ｓｎめっき鋼板および樹脂被覆ティンフリースチールから、透明樹脂フィルム被覆面がカップ内面側となるようにして、先に示したようにして絞り比：１．６４の１段絞り加工を施して絞りカップを作成し、透明樹脂フィルム被覆面が測定面となるようにして、先に示したようにしてＳピール強度測定用の試片を作成した。次いでテンシロンを用いて先に示したようにしてＳピール強度を測定した。結果を表３に示す。
【００３０】
【表３】
［絞り加工缶の成形］
表１に示す試料番号１〜２、６〜９の樹脂被覆Ｓｎめっき鋼板および試料番号１０の樹脂被覆ティンフリースチールを、直径：１１２ｍｍのブランクに打ち抜いた後、透明樹脂フィルム被覆面がカップ内面側となるようにして、絞り比：１．５０の絞り比で絞り加工し、次いで絞り比：２．１で再絞り加工し、缶径：５３ｍｍの絞り缶に成形加工した。次いで公知の方法で缶上部をトリミングし、ネックイン加工、フランジ加工を施した。このようにして１０００個の絞り缶を成形した後、樹脂フィルムの剥離の有無を肉眼観察し、剥離が認められた成形缶の発生率を％で評価した。結果を表４に示す。
【００３２】
［絞り加工後ストレッチ加工を施してなる缶の成形］
表１に示す試料番号１〜２、６〜９の樹脂被覆Ｓｎめっき鋼板および試料番号１０の樹脂被覆ティンフリースチールを、直径：１８７ｍｍのブランクに打ち抜いた後、透明樹脂フィルム被覆面がカップ内面側となるようにして、絞り比：１．７０の絞り比で絞り加工し、カップに成形した。次いで第一次再絞り比：１．２９、第二次再絞り比：１．２４、第三次再絞り比：１．２０、再絞りダイス肩の曲率半径：０．４ｍｍ、しわ抑え荷重：５８Ｎの条件で複数段のストレッチ加工を行い、缶径：６６ｍｍのストレッチ加工缶に成形加工した。次いで公知の方法で缶上部をトリミングし、ネックイン加工、フランジ加工を施した。このようにして１０００個のストレッチ加工缶を成形した後、樹脂フィルムの剥離の有無を肉眼観察し、剥離が認められた成形缶の発生率を％で評価した。結果を表４に示す。
【００３３】
［絞り加工後しごき加工を施してなる缶の成形］
表２に示す試料番号３〜５の樹脂被覆Ｓｎめっき鋼板および樹脂被覆ティンフリースチールを、直径：１４０ｍｍのブランクに打ち抜いた後、透明樹脂フィルム被覆面がカップ内面側となるようにして、絞り比：１．６３の絞り比で絞り加工し、次いで絞り比：１．３０の絞り比で再絞り加工して缶径：６６ｍｍのカップに成形した。次いで３段のしごき加工（総しごき率：６５％）を施し、缶径：６６ｍｍの缶に成形加工した。次いで公知の方法で缶上部をトリミングし、ネックイン加工、フランジ加工を施した。このようにして１０００個のストレッチ加工缶を成形した後、樹脂フィルムの剥離の有無を肉眼観察し、剥離が認められた成形缶の発生率を％で評価した。結果を表４に示す。
【００３４】
［絞り加工後ストレッチ加工としごき加工を併用して加工してなる缶の成形］
表１に示す試料番号１〜２、６〜９の樹脂被覆Ｓｎめっき鋼板およびおよび試料番号１０の樹脂被覆ティンフリースチールを、直径：１６０ｍｍのブランクに打ち抜いた後、透明樹脂フィルム被覆面がカップ内面側となるようにして、缶径：１００ｍｍのカップに絞り加工した。次いで再絞り加工により缶径：８０ｍｍの再絞りカップとした。さらにこの再絞りカップにストレッチ加工としごき加工を併用して缶径：６５ｍｍの缶とした。ストレッチ加工としごき加工を併用する加工は、缶の上端部となる再絞り加工部としごき加工部の間隔が２０ｍｍ、再絞りダイス肩の曲率半径が板厚の１．５倍、再絞りダイスとポンチのクリアランスが板厚の１．０倍、しごき加工部のクリアランスが板厚の０．５倍となる条件で実施した。次いで公知の方法で缶上部をトリミングし、ネックイン加工、フランジ加工を施した。このようにして３００個のストレッチ加工缶を成形した後、樹脂フィルムの剥離の有無を肉眼観察し、剥離が認められた成形缶の発生率を％で評価した。結果を表４に示す。
【００３５】
【表４】
表４に示すように、コロナ放電処理を施した樹脂フィルムを、シランカップリング塗布層を設けたＳｎめっき鋼板に積層してなる本発明の樹脂被覆Ｓｎめっき鋼板は、コロナ放電処理を施さない樹脂フィルムを、シランカップリング塗布層を設けたＳｎめっき鋼板に積層してなる樹脂被覆Ｓｎめっき鋼板に比べて樹脂フィルムのＳｎめっき鋼板に対する加工接着性に優れており、表３に示したＳピール強度、すなわち１段の絞り加工による加工後の接着性の結果と一致している。このように、本発明の樹脂被覆Ｓｎめっき鋼板は、複数段の絞り加工、絞り加工後のスチレッチ加工、絞り加工後のしごき加工、絞り加工後ストレッチ加工としごき加工を併用して加工する厳しい加工を施した場合に、樹脂被覆ティンフリースチールにおけるのと同様に、安定した優れた加工接着性を示す。
【００３７】
【発明の効果】
本発明の樹脂被覆Ｓｎめっき鋼板は、Ｓｎめっき層上にシランカップリング塗布層を設けてなるＳｎめっき鋼板に、コロナ放電処理を施した樹脂フィルムを熱接着して積層してなり、絞り加工、絞り加工後のさらなるストレッチ加工、絞り加工後のさらなるしごき加工、のいずれの加工を施しても樹脂フィルムが剥離することなく安定した優れた加工接着性を示す。さらに、より過酷な絞り加工後にさらにストレッチ加工としごき加工を併用する加工を施した場合においても、樹脂フィルムが剥離することがなく、Ｓｎめっき層上にシランカップリング塗布層を設けてなるＳｎめっき鋼板に、コロナ放電処理を施さない樹脂フィルムを熱接着して積層してなる樹脂被覆Ｓｎめっき鋼板に比べて安定した優れた加工接着性を示す。
【図面の簡単な説明】
【図１】Ｓピール強度測定用の試片の形状を示す平面図。
【図２】Ｓピール強度測定用の試片の樹脂面に切れ目を入れる箇所を示す平面図。
【図３】Ｓピール強度測定用の試片にスコアを入れる箇所を示す平面図。
【図４】スコアを入れた部分の形状を示す試片の一部の断面図
【図５】試片ホルダーの概略図
【符号の説明】
１ ： 試片
１ａ： 試片の一方の端部
１ｂ： 試片の他方の端部
２： 切れ目
３： スコア
４： 試片ホルダー
４ａ： 試片挿入部
４ｂ： 試片ホルダー上部[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin-coated Sn-plated steel sheet having excellent work adhesion of a resin-coated layer, a can formed by subjecting the resin-coated Sn-plated sheet to severe forming such as drawing, and a method for producing the resin-coated Sn-plated steel sheet.
[0002]
[Prior art]
In recent years, steel plates coated with resin have been subjected to severe processing such as drawing, further stretching after drawing, further ironing after drawing, and further stretching and drawing combined with drawing. A can in which the can body and the bottom of the can are integrally formed and processed is filled with the contents and a top plate is wound around the can, which is commercially available. In these cans, excellent adhesiveness of the resin to the steel sheet is required so that the coating resin does not peel or break during and after these severe forming processes. Therefore, as a resin-coated steel sheet for these applications, a steel sheet coated with a chromate-treated steel sheet such as tin-free steel having a surface formed with a chromate film having excellent workability with an organic resin has been used.
[0003]
However, in cans using resin-coated chromate-treated steel sheets, if fine holes or cracks that reach the steel sheet surface occur in the resin layer, the chromate-treated steel sheets have poor corrosion resistance and are filled with contents with particularly high acidity. In this case, the steel sheet has a disadvantage that corrosion of the steel sheet progresses rapidly and piercing is easily caused. Therefore, application of a resin-coated Sn-plated steel sheet obtained by coating a resin on a Sn-plated steel sheet exhibiting excellent corrosion resistance when filled with contents having a large acidity has been attempted. In particular, there is a demand for a resin-coated Sn-plated steel sheet which has poor workability and is applicable to such severe processing applications as described above.
[0004]
The inventors of the present invention have proposed a resin-coated Sn-plated steel sheet as a resin-coated Sn-plated steel sheet applicable to severe processing applications (for example, see Patent Document 1). The resin-coated Sn-plated steel sheet described in this publication is obtained by laminating an organic resin film on a Sn-plated steel sheet in which a silane coupling agent coating layer is provided on a Sn-plated layer of a no-reflow Sn-plated steel sheet or a reflow Sn-plated steel sheet. Resin-coated Sn-plated steel sheet. This resin-coated Sn-plated steel sheet is characterized in that the adhesive strength of the organic resin film before forming into a can is 2 kg / 10 mm or more in T peel strength. However, when the resin-coated Sn-plated steel sheet is formed into a can and formed into a can, in particular, when it is formed into a can by using a more severe stretching process and ironing after drawing, it can be formed without any problem. In some cases, it was found that the resin sometimes peeled off at the top of the can during the molding process, and that excellent adhesion of the resin to the Sn plating layer could not be stably obtained. It has also been found that the adhesive strength of the organic resin film before forming into a can does not always accurately reflect the adhesiveness at the time of forming or after forming.
[0005]
In the present invention, a corona discharge-treated organic resin film is laminated on a Sn-plated steel sheet having a silane coupling agent coating layer provided on a Sn-plated layer of a no-reflow Sn-plated steel sheet or a reflow Sn-plated steel sheet. It has been found that a resin-coated Sn-plated steel sheet exhibiting stable adhesiveness during and after forming can be obtained. Further, it is disclosed that a corona discharge treatment is applied to a polypropylene-based resin film (for example, see Patent Document 2). It is known that the adhesion to a substrate to be laminated is improved by performing a corona discharge treatment on an organic resin. However, the organic resin is laminated on a Sn-plated steel sheet with poor processing adhesion with the organic resin, and after the drawing, the processing adhesion that withstands the severe processing of forming into a can using a combination of stretching and ironing after drawing is obtained. Therefore, by providing a silane coupling agent coating layer on the Sn plating layer and coating the silane coupling agent coating layer with an organic resin that has been subjected to corona discharge treatment such that the corona discharge treatment surface is in contact with the silane coupling agent coating layer, the corrosion resistance is improved. For the first time, it was possible to stably obtain a can by such severe processing from a resin-coated Sn-plated steel sheet using an excellent Sn-plated steel sheet as a substrate.
[0006]
Prior art document information on the present application includes the following.
[Patent Document 1]
JP-A-2002-285354
[Patent Document 2]
Japanese Patent No. 3352553
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a resin-coated Sn-plated steel sheet having excellent work adhesion when subjected to severe molding, a can using the same, and a method for producing the resin-coated Sn-plated steel sheet.
[0008]
[Means for Solving the Problems]
The resin-coated Sn-plated steel sheet of the present invention is a resin coating obtained by coating at least one surface of an Sn-plated steel sheet having a silane coupling agent coating layer formed on a Sn plating layer with an organic resin film subjected to a corona discharge treatment. An Sn-plated steel sheet (Claim 1),
Sn-plated steel sheet, Sn-plated steel sheet with no Sn-plated layer formed on the steel sheet (No reflow Sn-plated steel sheet), or Sn-plated steel sheet formed by forming Sn-Fe alloy layer between steel sheet and Sn-plated layer (Reflow Sn plated steel sheet), (Claim 2)
The amount of the silane coupling agent applied is 1 to 50 mg / m in terms of Si amount. 2 (Claim 3)
The corona discharge treatment is performed under the conditions of a voltage of 200 V and a current of 0.2 to 8 A / 25 cm (Claim 4).
Cup side wall after forming the resin-coated Sn-plated steel sheet according to any one of
[0009]
Further, the can of the present invention is obtained by drawing the resin-coated Sn-plated steel sheet according to any one of
After drawing, the can is further stretched (Claim 7), or
After drawing, the can is further ironed (claim 8), or
The can (claim 9) is obtained by further performing stretching and ironing after drawing.
[0010]
Further, the method for producing a resin-coated Sn-plated steel sheet of the present invention comprises forming an Sn-plated layer on at least one side of the steel sheet, applying a silane coupling agent on the Sn-plated layer and drying, and then applying a silane coupling agent-coated layer. A method for producing a resin-coated Sn-plated steel sheet, characterized by laminating an organic resin film subjected to corona discharge treatment so that a corona discharge treatment surface is in contact therewith, or
A Sn plating layer is formed on at least one side of the steel sheet, and then heated to a temperature equal to or higher than the melting temperature of Sn and rapidly cooled to form a Sn—Fe alloy layer between the steel sheet and the Sn plating layer. After coating and drying a coupling agent, a resin-coated Sn plating is characterized in that an organic resin film subjected to a corona discharge treatment is laminated on the silane coupling agent application layer so that the corona discharge treatment surface is in contact with the resin film. This is a method for manufacturing a steel sheet.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
As the steel sheet used for the resin-coated Sn-plated steel sheet of the present invention, a normal aluminum-killed steel hot-rolled sheet is cold-rolled, and then subjected to temper-rolled cold-rolled steel sheet after annealing, or further cold-rolled after annealing. Any of the cold-rolled steel sheets having increased strength is selectively used depending on the application. After electrolytically degreased and pickled these cold-rolled steel sheets, an Sn-plated layer is formed on the steel sheets to obtain Sn-plated steel sheets. As the Sn-plated steel sheet, an Sn-plated steel sheet (Sn-plated no-reflow Sn-plated steel sheet) with Sn plated using a well-known ferrostan bath or halogen bath, after plating Sn, heating to the melting temperature of Sn or more and then quenching. Thus, there is an Sn-plated steel sheet (a reflow Sn-plated steel sheet) in which an Sn-Fe alloy layer is formed between Sn plating layers. In addition to these Sn-plated steel sheets, Ni is electroplated, and Ni is plated on the upper layer as it is, or after Ni plating, heated to diffuse Ni into the steel to form a Ni—Fe alloy layer, and then Sn is electroplated. Then, an island-shaped Sn-plated steel sheet having an island-shaped Sn layer formed thereon may be used by using a method of heating to a temperature not lower than the melting temperature of Sn and then rapidly cooling.
[0012]
The amount of Sn plating in the matte no-reflow Sn-plated steel sheet is 0.1 to 10 g / m from the viewpoint of corrosion resistance and economy. 2 Is preferably within the range. In a glossy reflow Sn-plated steel sheet, an Sn-Fe alloy layer is formed between the Sn plating layer and the steel sheet. Therefore, when metal Sn is left on the surface of the plated steel sheet, the total Sn plating amount is 1 to 10 g / m. 2 Must be within the range. In the case where the metal Sn is not left on the surface of the plated steel sheet and a layer composed of only the Sn—Fe alloy layer is used as the surface layer, the total Sn plating amount is 0.1 to 10 g / m. 2 Is preferably within the range.
[0013]
In the case of an island-shaped Sn-plated steel sheet, the amount of Ni plating to be formed on the steel sheet before Sn plating is 0.005 to 0.1 g / m. 2 And the amount of Sn plating to be formed on the upper layer is 0.1 to 1.5 g / m. 2 Is preferably within the range. After forming each plating layer with such a plating amount, or after plating Ni with the above-described plating amount and performing a diffusion heat treatment, and then plating Sn with the above-described plating amount, the temperature is equal to or higher than the melting temperature of Sn. By heating, an island-shaped Sn-plated steel sheet in which Sn is dispersed in an island form on the surface is obtained.
[0014]
A silane coupling agent is applied to the surface of the Sn-plated steel sheet obtained as described above and dried. Examples of the silane coupling agent include various types such as a vinyl type, an acrylic type, an epoxy type, an amino type, a mercapto type and a chloropyr type. In the present invention, it is preferable to use an amino type silane coupling agent. As an amino-based silane coupling agent, aminopropyltrimethoxysilane, aminopropylmethyldiethoxysilane, aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane, and the like can be used. A 5-200 g / L aqueous solution of these silane coupling agents is applied to the above-mentioned Sn-plated steel sheet and dried. As the coating method, a known method can be applied, and for example, any of a dipping method, a roll coating method, a method of squeezing a surplus using a squeezing roll after dipping, a spray method, an electrolytic treatment method, and the like can be applied. The amount of the coating film after drying was 1 to 50 mg / m as the amount of Si measured by a fluorescent X-ray method. 2 It is preferable that 1 mg / m in Si amount 2 If it is less than this, the processing adhesive strength of the resin film laminated on the silane coupling agent coating layer will be poor. On the other hand, the amount of Si is 50 mg / m 2 Even if it exceeds 2,000, the processing adhesive strength of the resin film becomes insufficient and it is not economical. Thus, the Sn-plated steel sheet used for the resin-coated Sn-plated steel sheet of the present invention is obtained.
[0015]
In the resin-coated Sn-plated steel sheet of the present invention, an organic resin film subjected to corona discharge treatment on one or both sides of the Sn-plated steel sheet obtained as described above is brought into contact with the silane coupling agent coated layer on the corona discharge treated surface. It is obtained by laminating as described above. As the organic resin film, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene terephthalate / ethylene isophthalate copolymer, butylene terephthalate / butylene isophthalate copolymer, or two or more of these polyester resins , Polyethylene, polypropylene, ethylene-propylene copolymers, and those obtained by modifying them with maleic acid, polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, 6-nylon, 6 Polyamide resins such as 6,6-nylon and 6,10-nylon, polycarbonate, polymethylpentene, and blends of the above polyester resins and ionomers Resin film layer, further can be used as the resin film multilayer of two or more kinds of these resins. The thickness of the resin film is 10 to 100 μm from the viewpoints of ease of film lamination work, adhesion strength of the resin film in a molded article (can) after molding of the resin-coated Sn-plated steel sheet, corrosion resistance, and economy. It is preferable that
[0016]
These resin films are obtained by heating and melting resin pellets, extruding the resin pellets from a T-die of an extruder, and forming a film having a desired thickness on the Sn-plated steel sheet by using a thermal bonding method. . The thermal bonding method is a method in which a resin film is brought into contact with a Sn-plated steel sheet heated to a temperature range in which the resin is bonded, sandwiched between a pair of pressure rolls, and pressed to press the resin film. By using a resin film formed without using a film, heat bonding can be performed at a temperature considerably lower than the melting temperature of Sn. In the case of laminating a resin film formed by stretching in a uniaxial direction or a biaxial direction, if the heat setting after the stretching process is not performed at a temperature considerably lower than the melting temperature of Sn, the temperature is higher than the melting temperature of the resin. Unless the resin is heated to a high temperature, good working adhesive strength to the Sn-plated steel sheet cannot be obtained. Therefore, when a resin having a melting temperature higher than the melting temperature of Sn is used, heat bonding may be difficult.
[0017]
In the present invention, in particular, in order to obtain a stable and excellent resin film processing adhesion even when subjected to severe forming processing such as forming into a can by processing in combination with stretching and ironing after drawing and further processing. Then, a resin film obtained by performing a corona discharge treatment on the surface of the resin film obtained as described above, which is in contact with the Sn-plated steel sheet, is used. The corona discharge treatment is performed under the conditions of a voltage: 200 V and a current: 0.2 to 8 A / 25 cm. If the current is less than 0.2 A / 25 cm, the effect of the corona discharge treatment will not be exhibited. On the other hand, when the current exceeds 8 A / 25 cm, the discharge current becomes excessive, and wrinkles and swelling occur in the resin film, which is not preferable. A more preferable current range is 1 to 5 A / 25 cm. The corona discharge-treated side of the resin film is brought into contact with the surface of the Sn-plated steel sheet to which the silane coupling agent has been applied, and is thermally bonded as described above, thereby performing severe forming processing. Even in this case, stable and excellent processing adhesion of the resin film can be obtained.
[0018]
Conventionally, the peel strength, that is, the adhesive strength of the resin film to the Sn-plated steel sheet has been evaluated by measuring the T-peel strength in a flat state before processing. However, the T-peel strength measured in the state of a flat plate is particularly during and after processing in the case where severe forming such as forming into a can is performed by using a combination of stretching and ironing after drawing. It was found that the adhesive strength, ie, the processed adhesive strength was not always accurately reflected. Therefore, in the present invention, the resin-coated Sn-plated steel sheet is drawn and formed into a cup, a test piece is cut out from the cup side wall, and the processing adhesive strength (hereinafter referred to as S-peel strength) is obtained from the peel strength of the resin film of the test piece. ) To evaluate.
[0019]
The method for measuring the S peel strength is described below. A 154 mm blank was punched out of the resin-coated Sn-plated steel sheet of the present invention obtained as described above, and subjected to one-step drawing at a drawing ratio of 1.64 to form a drawing cup having a diameter of 96 mm and a height of 42 mm. Mold. From this cup, a side wall portion is cut out in a size of 30 mm in a cup height direction and 120 mm in a cup circumferential direction and bent back to a flat plate shape, and then a T-shaped
[0020]
The S-peel strength measured as described above is preferably 0.05 kg / 15 mm or more. When the S-peel strength is less than 0.05 kg / 15 mm, it is stable and good especially when a severe forming process such as forming into a can by performing a combination of stretching and ironing after drawing is performed. Unable to obtain processing adhesive strength.
[0021]
When the resin-coated Sn-plated steel sheet of the present invention is formed into a drawn can, a blank punched from a resin-coated Sn-plated steel sheet having resin laminated on one or both sides is drawn into a cup shape using a drawing die. To increase the height of the side wall by reducing the diameter, redrawing is performed using a drawing die having a smaller diameter than the former stage. The drawing is usually performed by one or two steps of drawing, and is applied to a can having a relatively large can diameter and a low side wall height.
[0022]
When the resin-coated Sn-plated steel sheet of the present invention is drawn and then stretched to form a can, a blank punched from a resin-coated Sn-plated steel sheet having resin laminated on one or both sides is cup-shaped using a drawing die. And drawing. Next, using a plurality of stages of drawing dies, the height of the side wall is increased while sequentially reducing the diameter.In stretch processing, when the cup is pressed by a processing punch and enters and exits the drawing die and wrinkle suppressing jig The side wall is bent and unbent, and the side wall portion is stretched and drawn while being thinned. It is applied to cans with relatively small can diameter and high side wall height.
[0023]
When the resin-coated Sn-plated steel sheet of the present invention is drawn and then ironed to form a can, a blank punched from a resin-coated Sn-plated steel sheet having resin laminated on one or both sides is drawn in one or more stages. It is drawn into a cup shape using a die. Then, using one or more stages of ironing dies, the side wall is forcibly pushed into the clearance between the ironing die and the punch, which is set smaller than the side wall thickness of the cup, to increase the side wall height while reducing the thickness. Apply processing. Therefore, the present invention is applied to a can having a relatively small can diameter, a high side wall height, and a small side wall thickness. When ironing a resin-coated Sn-plated steel sheet with resin laminated on one side only so that the non-resin-coated surface becomes the outer surface of the can, the Sn-plated layer is rubbed by an ironing die and becomes a mirror surface, resulting in a beautiful surface gloss. Can be
[0024]
When the resin-coated Sn-plated steel sheet of the present invention is drawn and then formed into a can by using both stretching and ironing, a blank punched from a resin-coated Sn-plated steel sheet having resin laminated on one or both sides is formed in one step. Alternatively, drawing is performed in a cup shape using a plurality of stages of drawing dies. Next, the side wall height is increased while reducing the diameter sequentially using multiple stages of drawing dies in the same way as in normal stretching, but the clearance between the dies and the punch is cupped like the ironing dies in ironing. By setting the side wall thickness to be smaller than the side wall thickness, the side wall is bent and unbent, and at the same time is ironed, and the side wall portion is stretched and thinned to draw and iron. In this processing, even when a resin-coated Sn-plated steel sheet in which a resin is laminated on only one side is used, a beautiful surface gloss can be obtained.
[0025]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
[Preparation of Sn-plated steel sheet]
A cold-rolled steel sheet having a thickness and a temper shown in Table 1 is electrolytically degreased in an alkaline aqueous solution, washed with water, washed with sulfuric acid, washed with water, and then subjected to Sn plating using a known ferrostan bath under the conditions shown in Table 1. After forming the layer, or after forming the Sn plating layer, reflow treatment was performed to form an Sn—Fe alloy layer between the steel sheet and the Sn plating layer. Next, using a treatment bath shown in Table 1, a 5-200 g / L aqueous solution of the silane coupling agent shown in Table 1 was applied by an immersion method so as to have an application amount shown in Table 1, and dried to obtain Sn plating. A silane coupling agent coating layer was formed thereon. Further, as a comparative material, a tin-free steel in which two layers of a Cr plating layer and a Cr hydrated oxide layer were formed by subjecting a cold-rolled steel sheet to electrolytic chromic acid treatment, which is shown in Sample No. 10, was produced.
[0026]
[Table 1]
[Table 2]
[Preparation of resin-coated Sn-plated steel sheet]
One side of a Sn-plated steel sheet and tin-free steel shown in Table 1 was subjected to a corona discharge treatment on one side under the conditions shown in Table 2. Thickness: 28 μm non-oriented transparent ethylene terephthalate / ethylene isophthalate copolymer (PETI) 2 layer film (upper layer is PETI15 (thickness: 12 μm), lower layer is PETI5 (thickness: 16 μm), numbers indicate mol% of ethylene isophthalate, and PETI5 side is in contact with the steel sheet side), and one other side A white non-oriented two-layer film containing the same ethylene terephthalate / ethylene isophthalate copolymer containing 20% by weight of a titanium-based white pigment (the upper layer is PETI15 (thickness: 5 μm), and the lower layer is PETI5 (thickness: 11 μm)) by heat bonding at 225 ° C. using a heat bonding method, and laminated, and a resin-coated Sn-plated steel sheet indicated by
[0029]
[Preparation of specimen for S peel strength measurement]
From the resin-coated Sn-plated steel sheet and the resin-coated tin-free steel shown in Table 1, the transparent resin film-coated surface was on the cup inner surface side, and as described above, a one-step drawing process with a drawing ratio of 1.64 was performed. Was performed to prepare a drawing cup, and a sample for measuring the S-peel strength was prepared as described above, with the transparent resin film-coated surface serving as a measurement surface. The S-peel strength was then measured using Tensilon as described above. Table 3 shows the results.
[0030]
[Table 3]
[Formation of drawn cans]
After punching a resin-coated Sn-plated steel plate of Sample Nos. 1-2 and 6-9 and a resin-coated tin-free steel of Sample No. 10 shown in Table 1 into a blank having a diameter of 112 mm, the transparent resin film-coated surface was on the cup inner surface side. Then, drawing was performed at a drawing ratio of 1.50, then re-drawing was performed at a drawing ratio of 2.1, and formed into a drawn can having a can diameter of 53 mm. Next, the upper part of the can was trimmed by a known method, and neck-in processing and flange processing were performed. After forming 1,000 drawn cans in this way, the presence or absence of peeling of the resin film was visually observed, and the occurrence rate of molded cans in which peeling was recognized was evaluated in%. Table 4 shows the results.
[0032]
[Forming cans that are stretched after drawing]
After punching a resin-coated Sn-plated steel plate of Sample Nos. 1-2 and 6-9 and a resin-coated tin-free steel of Sample No. 10 shown in Table 1 into a blank having a diameter of 187 mm, the transparent resin film-coated surface was on the cup inner surface side. Then, drawing was performed at a drawing ratio of 1.70 and a cup was formed. Next, the primary redrawing ratio: 1.29, the secondary redrawing ratio: 1.24, the tertiary redrawing ratio: 1.20, the radius of curvature of the redrawing die shoulder: 0.4 mm, and the wrinkle suppressing load: Stretching was performed in a plurality of stages under the condition of 58N, and formed into a stretched can having a can diameter of 66 mm. Next, the upper part of the can was trimmed by a known method and subjected to neck-in processing and flange processing. After forming 1,000 stretched cans in this way, the presence or absence of peeling of the resin film was visually observed, and the occurrence rate of molded cans in which peeling was recognized was evaluated in%. Table 4 shows the results.
[0033]
[Forming of cans made by drawing and then ironing]
After punching a resin-coated Sn-plated steel plate and resin-coated tin-free steel of
[0034]
[Forming of cans that are processed by using both stretching and ironing after drawing]
After punching the resin-coated Sn-plated steel sheets of Sample Nos. 1-2 and 6-9 and the resin-coated tin-free steel of Sample No. 10 shown in Table 1 into a blank having a diameter of 160 mm, the transparent resin film-coated surface was the cup inner surface. And drawn into a cup with a can diameter of 100 mm. Next, a redraw cup having a can diameter of 80 mm was obtained by redrawing. Further, the redrawn cup was subjected to stretching and ironing in combination to obtain a can having a can diameter of 65 mm. Stretching and ironing are used together. The distance between the redrawing part, which is the upper end of the can, and the ironing part is 20 mm, the radius of curvature of the redrawing die shoulder is 1.5 times the plate thickness, and the redrawing die is used. The test was performed under the condition that the clearance of the punch was 1.0 times the plate thickness and the clearance of the ironed portion was 0.5 times the plate thickness. Next, the upper part of the can was trimmed by a known method and subjected to neck-in processing and flange processing. After forming 300 stretched cans in this way, the presence or absence of peeling of the resin film was visually observed, and the occurrence rate of molded cans in which peeling was observed was evaluated in%. Table 4 shows the results.
[0035]
[Table 4]
As shown in Table 4, the resin-coated Sn-plated steel sheet of the present invention obtained by laminating the resin film subjected to the corona discharge treatment on the Sn-plated steel sheet provided with the silane coupling coating layer is made of a resin not subjected to the corona discharge treatment. Compared to a resin-coated Sn-plated steel sheet obtained by laminating a film on a Sn-plated steel sheet provided with a silane coupling coating layer, the resin film has better work adhesion to the Sn-plated steel sheet, and the S-peel strength shown in Table 3 That is, the result is consistent with the result of the adhesiveness after processing by one-step drawing. As described above, the resin-coated Sn-plated steel sheet of the present invention is subjected to severe processing in which a plurality of stages of drawing, styret after drawing, ironing after drawing, stretching after drawing, and ironing are used in combination. Shows stable and excellent work adhesion as in resin-coated tin-free steel.
[0037]
【The invention's effect】
The resin-coated Sn-plated steel sheet of the present invention is obtained by laminating a resin film that has been subjected to corona discharge treatment to a Sn-plated steel sheet provided with a silane coupling coating layer on the Sn plating layer by heat bonding, drawing, The resin film shows stable and excellent work adhesion without peeling even when any of stretch processing after drawing and further ironing after drawing are performed. Furthermore, even in the case of performing a process using a combination of stretching and ironing after a more severe drawing process, the Sn film formed by providing the silane coupling coating layer on the Sn plating layer without peeling the resin film. It shows a stable and excellent work adhesion as compared with a resin-coated Sn-plated steel sheet obtained by thermally bonding a resin film not subjected to corona discharge treatment to a steel sheet.
[Brief description of the drawings]
FIG. 1 is a plan view showing the shape of a test piece for measuring S-peel strength.
FIG. 2 is a plan view showing a place where a cut is made in a resin surface of a test piece for S-peel strength measurement.
FIG. 3 is a plan view showing a place where a score is put on a test piece for measuring S peel strength.
FIG. 4 is a partial cross-sectional view of a test piece showing the shape of a scored portion.
FIG. 5 is a schematic view of a specimen holder.
[Explanation of symbols]
1: Specimen
1a: One end of specimen
1b: the other end of the specimen
2: Break
3: Score
4: Specimen holder
4a: specimen insertion part
4b: Upper part of specimen holder
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003144583A JP2004345214A (en) | 2003-05-22 | 2003-05-22 | RESIN-COATED Sn PLATED STEEL SHEET, CAN USING THIS STEEL SHEET AND METHOD FOR MANUFACTURING RESIN-COATED Sn PLATED STEEL SHEET |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003144583A JP2004345214A (en) | 2003-05-22 | 2003-05-22 | RESIN-COATED Sn PLATED STEEL SHEET, CAN USING THIS STEEL SHEET AND METHOD FOR MANUFACTURING RESIN-COATED Sn PLATED STEEL SHEET |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004345214A true JP2004345214A (en) | 2004-12-09 |
Family
ID=33532002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003144583A Pending JP2004345214A (en) | 2003-05-22 | 2003-05-22 | RESIN-COATED Sn PLATED STEEL SHEET, CAN USING THIS STEEL SHEET AND METHOD FOR MANUFACTURING RESIN-COATED Sn PLATED STEEL SHEET |
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| Country | Link |
|---|---|
| JP (1) | JP2004345214A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110740A1 (en) * | 2004-05-14 | 2005-11-24 | Toyo Kohan Co., Ltd. | Sn-PLATED STEEL SHEET COATED WITH RESIN, CAN USING THE SAME, AND METHOD FOR PRODUCING Sn-PLATED STEEL SHEET COATED WITH RESIN |
| JP2023505688A (en) * | 2019-12-11 | 2023-02-10 | ポスコホールディングス インコーポレーティッド | METAL-PLASTIC COMPOSITE MATERIAL AND PRODUCTION METHOD THEREOF |
-
2003
- 2003-05-22 JP JP2003144583A patent/JP2004345214A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110740A1 (en) * | 2004-05-14 | 2005-11-24 | Toyo Kohan Co., Ltd. | Sn-PLATED STEEL SHEET COATED WITH RESIN, CAN USING THE SAME, AND METHOD FOR PRODUCING Sn-PLATED STEEL SHEET COATED WITH RESIN |
| JP2023505688A (en) * | 2019-12-11 | 2023-02-10 | ポスコホールディングス インコーポレーティッド | METAL-PLASTIC COMPOSITE MATERIAL AND PRODUCTION METHOD THEREOF |
| JP7368627B2 (en) | 2019-12-11 | 2023-10-24 | ポスコホールディングス インコーポレーティッド | Metal-plastic composite material and its manufacturing method |
| US11993056B2 (en) | 2019-12-11 | 2024-05-28 | Posco | Metal-plastic composite material and method for manufacturing same |
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