JP4285924B2 - A can body comprising a resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a method for producing the same - Google Patents
A can body comprising a resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a method for producing the same Download PDFInfo
- Publication number
- JP4285924B2 JP4285924B2 JP2001085965A JP2001085965A JP4285924B2 JP 4285924 B2 JP4285924 B2 JP 4285924B2 JP 2001085965 A JP2001085965 A JP 2001085965A JP 2001085965 A JP2001085965 A JP 2001085965A JP 4285924 B2 JP4285924 B2 JP 4285924B2
- Authority
- JP
- Japan
- Prior art keywords
- coated
- steel sheet
- resin
- plated steel
- ironing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、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、有機樹脂層との接着強度に優れたＳｎめっき鋼板、Ｓｎめっき鋼板に樹脂皮膜を被覆してなる樹脂被覆Ｓｎめっき鋼板、それを用いた缶、およびＳｎめっき鋼板と樹脂被覆Ｓｎめっき鋼板の製造方法に関する。
【０００２】
【従来の技術】
従来より、鋼板上にＳｎを電気めっきしたＳｎめっき鋼板においては、Ｓｎめっき後に重クロム酸ナトリウムのようなクロム酸塩系の水溶液中で浸積処理、または電解処理を施し、めっき面上にクロム水和酸化物層を形成させたものが用いられている。しかし、これらの処理を施したＳｎめっき鋼板を用い、Ｓｎめっき層上に有機樹脂を塗装したり有機樹脂フィルムを積層した樹脂被覆Ｓｎめっき鋼板を成形加工すると、被覆した樹脂層のＳｎめっき鋼板に対する接着強度、特に加工後の接着強度に乏しく、食缶や飲料缶等の成形加工で用いられている絞り加工、絞り加工後のさらなるスチレッチ加工、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チレッチ加工としごき加工を併用した加工等の厳しい成形加工を施すと被覆樹脂層が剥離してしまう、という欠点を有していた。そのため、成形加工を施す樹脂被覆鋼板の樹脂を被覆する下地としては、加工後の樹脂被膜の接着強度に優れる、鋼板に電解クロム酸処理を施し、クロムめっき層とクロム水和酸化物層を形成させたティン・フリー・スチールが用いられていた。しかし、ティン・フリー・スチールにはＳｎにおけるような、防食効果がないために、被覆した樹脂被膜に欠陥がある場合は、下地の鋼板が腐食されるという欠点を有している。
【０００３】
【発明が解決しようとする課題】
本発明は上記の欠点を解消し、被覆下地の耐食性に優れ、厳しい加工を施しても被覆した有機樹脂層が剥離することのない、被覆樹脂層の優れた接着強度を有するＳｎめっき鋼板、Ｓｎめっき鋼板に樹脂皮膜を被覆してなる樹脂被覆Ｓｎめっき鋼板、それを用いた缶、およびＳｎめっき鋼板と樹脂被覆Ｓｎめっき鋼板の製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明によれば、鋼板の両面にＳｎ層と、その上層に乾燥後の皮膜量がＳｉ量として１〜５０ｍｇ／ｍ２のアミノ系シランカップリング剤塗布層を設け、更に無配向のポリエステル樹脂フィルムを被覆してなる樹脂被覆Ｓｎめっき鋼板を用いて、絞り加工、絞り加工後更にストレッチ加工、絞り加工後さらにしごき加工、絞り加工後さらにストレッチ加工としごき加工を併用する加工、のいずれかの加工により成形されることを特徴とする缶体が提供される。
本発明によればまた、鋼板の両面にＦｅ−Ｓｎ合金層と、その上層にＳｎ層と、さらにその上層に乾燥後の皮膜量がＳｉ量として１〜５０ｍｇ／ｍ２のアミノ系シランカップリング剤塗布層を設け、更に無配向のポリエステル樹脂フィルムを被覆してなる樹脂被覆Ｓｎめっき鋼板を用いて、絞り加工、絞り加工後更にストレッチ加工、絞り加工後さらにしごき加工、絞り加工後さらにストレッチ加工としごき加工を併用する加工、のいずれかの加工により成形されることを特徴とする缶体が提供される。
【０００５】
本発明の缶体においては、ポリエステル樹脂フィルムが、エチレンテレフタレート・イソフタレート共重合フィルムであることが好適である。
【０００６】
また、本発明によれば、鋼板の両面にＳｎめっき層を形成させ、次いでＳｎめっき層上に、乾燥後の皮膜量がＳｉ量として１〜５０ｍｇ／ｍ２となるようにアミノ系シランカップリング剤を塗布し乾燥した後、シランカップリング剤塗布層上に、無配向のポリエステル樹脂フィルムを積層又は押出機のＴダイからポリエステル樹脂を押出すことによりポリエステル樹脂フィルムを積層して成る樹脂被覆Ｓｎめっき鋼板を、絞り加工、絞り加工後更にストレッチ加工、絞り加工後更にしごき加工、絞り加工後さらにストレッチ加工としごき加工を併用する加工、のいずれかの加工により成形することを特徴とする缶体の製造方法が提供される。
本発明によれば更に、鋼板の両面にＳｎめっき層を形成させ、次いでＳｎの融点以上の温度に加熱し、次いで急冷した後、Ｓｎめっき層上に、乾燥後の皮膜量がＳｉ量として１〜５０ｍｇ／ｍ２となるようにアミノ系シランカップリング剤を塗布し乾燥した後、シランカップリング剤塗布層上に、無配向のポリエステル樹脂フィルムを積層又は押出機のＴダイからポリエステル樹脂を押出すことによりポリエステル樹脂フィルムを積層して成る樹脂被覆Ｓｎめっき鋼板を、絞り加工、絞り加工後更にストレッチ加工、絞り加工後更にしごき加工、絞り加工後さらにストレッチ加工としごき加工を併用する加工、のいずれかの加工により成形することを特徴とする缶体の製造方法が提供される。
【０００７】
本発明の缶体の製造方法においては、ポリエステル樹脂フィルムが、エチレンテレフタレート・イソフタレート共重合フィルムであることが好適である。
【０００８】
【発明の実施の形態】
本発明においては、鋼板表面にＳｎめっきを施し、次いでシランカップリング剤を塗布したＳｎめっき鋼板とすることにより、その上層に被覆した樹脂皮膜が厳しい成形加工を施しても剥離することのない、極めて優れた接着強度が得られることが判明した。
以下、本発明について説明する。
【０００９】
本発明のＳｎめっき鋼板のＳｎめっきを施す鋼板としては、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る。
本発明の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を電気めっきしたままのＳｎめっき鋼板（ノーリフローぶりき）、Ｓｎを電気めっきした後、Ｓｎの融点以上の温度に加熱し、Ｓｎを溶融させた後、水中に急冷（リフロー処理）して得られる通常の光沢表面を有するＳｎめっき鋼板（リフローぶりき）がある。また、これらのＳｎめっき鋼板の他に、Ｎｉ−Ｆｅ合金を電気めっきし、その上層にＳｎを電気めっきした後、Ｓｎの融点以上の温度に加熱し、次いで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。
【００１０】
無光沢のノーリフローの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。リフローぶりきにおいては、Ｓｎめっき層と鋼板の間にＦｅ−Ｓｎ合金層が形成されるので、めっき鋼板の表面に金属Ｓｎ層を残す場合は全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層を残さず、Ｆｅ−Ｓｎ合金層のみからなる層とする場合は、全Ｓｎめっき量は０.１〜１０ｇ／ｍ２の範囲にあることが好ましい。
【００１１】
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の量が０．００５〜０．１ｇ／ｍ２、その上層に形成させるＳｎめっきの量は０.１〜１．５ｇ／ｍ２の範囲とすることが好ましい。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、Ｓｎの融点以上の温度に加熱することにより、表面にＳｎが縞状に分散して存在する縞状Ｓｎめっき鋼板が得られる。
【００１２】
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、クロロプ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、浸漬後ロールによる絞り法、スプレーによる方法あるいは電解処理法が適用できる。乾燥後の皮膜量は蛍光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量が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設ける樹脂皮膜層の十分な接着強度が得られない。また ５０ｍｇ／ｍ２を越えても接着強度は低下するようになり、また経済的ではなくなる。以上のようにして本発明のＳｎめっき鋼板が得られる。
【００１３】
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、有機樹脂塗料を塗装するか、または有機樹脂フィルムを積層することによって得ることができる。
有機樹脂塗料としては、熱硬化性または熱可塑性の樹脂塗料、例えば、フェノール・エポキシ塗料、尿素・エポキシ塗料、アミノ・エポキシ塗料、エポキシ・エステル塗料などの変性エポキシ塗料、例えば、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル共重合体部分ケン化物、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体などの用いた−ビニル塗料、例えば、エポキシ変性−ビニル樹脂塗料、エポキシアミノ変性−ビニル樹脂塗料、エポキシフェノール変性−ビニル樹脂塗料などの変性ビニル樹脂塗料、アクリル樹脂系塗料、油性塗料、アルキド樹脂塗料、ポリエステル塗料、スチレン−ブタジエン系共重合体などの合成ゴム系塗料などを用いることができる。塗布量としては樹脂被覆Ｓｎめっき鋼板を成形加工した後の成形体における塗膜の接着強度、耐食性、および経済性の観点から１〜２００ｍｇ／dｍ２、好ましくは１０〜１００ｍｇ／dｍ２であることが好ましい。
【００１４】
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易さ、樹脂被覆Ｓｎめっき鋼板を成形加工した後の成形体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。
【００１５】
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ダイから直接上記のＳｎめっき鋼板上に押し出して積層してもよいし、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、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してもよい。
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対のロールで挟み付けて、加圧して圧接する方法である。熱接着法を用いて樹脂フィルムをＳｎめっき鋼板に熱接着する場合は、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の融点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、または縦横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の融点よりかなり低い温度で行わないと、樹脂の融点以上の温度より高温に加熱しないかぎりＳｎめっき鋼板との良好な接着強度が得られないので、融点がＳｎの融点よりも高い樹脂を用いる場合には、熱接着することが困難になる場合がある。
【００１６】
このようにして得られた樹脂被覆Ｓｎめっき鋼板の接着強度は、Ｔピール強度で２ｋｇ／１０ｍｍ以上であることが好ましい。２ｋｇ／１０ｍｍ未満の場合は絞り加工のような厳しい加工を施した場合に、樹脂層が剥離する場合がある。絞り加工後にさらにスチレッチ加工、またはしごき加工、もしくはストレッチ加工としごき加工を併用した加工を施すなど、より厳しい加工を施す場合は、接着強度はＴピール強度で４ｋｇ／１０ｍｍ以上であることが好ましい。
なお、ここでいうＴピール強度とは次のことを指す。すなわち、有機樹脂塗料を塗布した樹脂被覆Ｓｎめっき鋼板の場合は、樹脂被覆Ｓｎめっき鋼板を１０ｍｍ×１００ｍｍの大きさに切り出した２つの試片を、樹脂塗布面が向き合うようにしてその間に６，６ナイロンのフィルムを挟み、ホットプレスを用いてナイロンの融点以上に加熱しながら加圧して接着し、接着部分の一端をナイフなどを強制剥離し、２枚に分かれた部分を折り曲げてＴ字状にした引っ張り試片を、Ｔ字の横棒に相当する部分をテンシロンのチャックで挟み付け、１００ｍ／分の速度で引っ張った場合に接着が破壊する強度のことを言う。有機樹脂フィルムを積層した樹脂被覆Ｓｎめっき鋼板の場合は、樹脂被覆Ｓｎめっき鋼板を１０ｍｍ×１００ｍｍの大きさに切り出した２つの試片を、樹脂塗布面が向き合うようにしてその間に積層した樹脂と同一樹脂からなる非晶の無配向のフィルムを挟み、ホットプレスを用いて樹脂の融点以上に加熱しながら加圧して接着し、直ちに水中に急冷した試料を、有機樹脂塗料を塗布した樹脂被覆Ｓｎめっき鋼板の場合と同様にして引っ張り試片に作成し、同様にして求めた強度を言う。
【００１７】
上記の樹脂被覆Ｓｎめっき鋼板を絞り缶に成形する場合は、片面または両面に樹脂を被覆した樹脂被覆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、側壁高さの低い缶に適用される。
【００１８】
上記の樹脂被覆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する場合は、片面または両面に樹脂を被覆した樹脂被覆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行くが、ストレッチ加工においては。加工パンチに押されて、カップが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、側壁高さの高い缶に適用される。
【００１９】
上記の樹脂被覆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する場合は、片面または両面に樹脂を被覆した樹脂被覆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、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側壁を薄肉化しながら側壁高さを高めて行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、かつ側壁厚みの薄い缶に適用される。本発明の樹脂被覆Ｓｎめっき鋼板を絞りしごき加工を用いて缶に成形する場合、片面のみに樹脂を被覆した樹脂被覆Ｓｎめっき鋼板を用い、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。
【００２０】
上記の樹脂被覆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する場合は、片面または両面に樹脂を被覆した樹脂被覆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行くが、しごき加工におけるしごきダイスのように、ダイスとパンチのクリアランスをカップ側壁厚みよりも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、片面のみに樹脂を被覆した樹脂被覆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。
【００２１】
【実施例】
以下、実施例にて本発明をさらに詳細に説明する。
（実施例）
[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、表１に示す条件にて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Ｆｅ−Ｓｎ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溶液を、表１に示す付着量となるように浸漬法による方法で塗布し乾燥してめっき面上にシランカップリング塗布層を形成させた。
また、比較材として、鋼板にＳｎめっき層を形成させた後リフロー処理を施し、次いで重クロム酸ナトリウム溶液中で処理し、表１に示したクロム水和酸化物量有する通常のぶりき、および鋼板に電解クロム酸処理を施してクロムめっき層とクロム水和酸化物層の２層を形成させたティン・フリー・スチールを作成した。
【００２２】
【表１】
[樹脂被覆Ｓｎめっき鋼板の作成]
表１に示すＳｎめっき鋼板および比較材の片面に、エポキシ・フェノール系塗料を表２に示す塗布量で塗布し、２１０℃で１０分間焼き付け、樹脂被覆Ｓｎめっき鋼板および樹脂被覆ティン・フリー・スチールを得た。
また、表１に示すＳｎめっき鋼板および比較材の片面に、表２に示す無配向のポリエチレンテレフタレートフィルム（表中PETで表示）、または２種類の無配向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の２層フィルム（表中PETI15/PETI5で表示、数字はエチレンイソフタレートのモル％を示し、PETI15側がＳｎめっき鋼板または金属側と接する）を熱接着法を用い、２２５℃で熱接着して積層し、樹脂被覆Ｓｎめっき鋼板および樹脂被覆ティン・フリー・スチールを得た。
【００２４】
【表２】
上記のようにして得られた樹脂被覆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、幅１０ｍｍ×長さ１００ｍｍの大きさの試片を切り出し、その２つを１対として、樹脂被覆面同士を対向させ、有機樹脂塗料を塗布した試片の場合は、その間に６，６ナイロンのフィルムを挟み、ホットプレスを用いてナイロンの融点以上に加熱しながら加圧して接着し、接着強度試験用供試材とした。
有機樹脂フィルムを塗布した試片の場合は、その間に被覆した有機樹脂と同一樹脂からなる非晶の無配向フィルムを挟み、ホットプレスを用いて樹脂の融点以上に加熱しながら加圧して接着し、接着強度試験用供試材とした。次いで、これらの供試材の接着部分の一端をナイフなどを強制剥離し、２枚に分かれた部分を折り曲げてＴ字状にした引っ張り試片を、Ｔ字の横棒に相当する部分をテンシロンのチャックで挟み付け、１００ｍ／分の速度で引っ張った場合に接着が破壊する強度を測定し、試験片の幅１０ｍｍ当たりの接着強度（Ｔピール強度：（ｋｇ／１０ｍｍ））として、結果を表２に示す。
【００２６】
(絞り加工缶の成形)
実施例の試料番号１および２のＳｎめっき鋼板、および試料番号１１のＳｎめっき鋼板と試料番号１２のティン・フリー・スチールの両面に、実施例のエポキシ・フェノール系塗料を７０ｍｇ／dｍ２の塗布量で塗布し、２１０℃で１０分間焼き付け、樹脂被覆Ｓｎめっき鋼板および樹脂被覆ティン・フリー・スチールを得た。これらの樹脂被覆板を直径：１１２ｍｍのブランクに打ち抜いた後、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、缶底径：約５３ｍｍのカップに成形した。
この加工において、試料番号１および２のＳｎめっき鋼板を用いた樹脂被覆板、および試料番号１２のティン・フリー・スチールを用いた樹脂被覆板は、樹脂皮膜が剥離することなく成形可能であったが、試料番号１１のＳｎめっき鋼板を用いた樹脂被覆板は、再絞り加工する工程で樹脂皮膜が剥離した。
【００２７】
(絞り加工後ストレッチ加工してなる缶の成形)
実施例の試料番号８および９のＳｎめっき鋼板、および試料番号７、１０および１６のＳｎめっき鋼板と試料番号１７のティン・フリー・スチールの片面に、実施例の無配向のポリエチレンテレフタレートフィルム（厚さ：２８μｍ)、他の片面に同一のポリエチレンテレフタレートにチタン系白色顔料を２０重量％含有させた白色の無配向フィルム（厚さ：１６μｍ)を、熱接着法を用いて２２５℃で熱接着し、積層した。
これらの樹脂被覆板を直径：１８７ｍｍのブランクに打ち抜いた後、白色顔料含を有するフィルムを被覆した面が缶の外面となるようにして、絞り比：１．７０の絞り比で絞り缶とした。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チレッチ加工により、缶底径：６６ｍｍのストレッチ加工缶とした。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。
この加工において、試料番号８および９のＳｎめっき鋼板を用いた樹脂被覆板、および試料番号１７のティン・フリー・スチールを用いた樹脂被覆板は、フランジ加工に至るまで樹脂フィルムが剥離することなく成形可能であったが、試料番号７、１０及び１６のＳｎめっき鋼板を用いた樹脂被覆板は、再絞り缶をストレッチ加工する工程で樹脂皮膜が剥離した。
【００２８】
(絞り加工後しごき加工してなる缶の成形)
実施例の試料番号６のＳｎめっき鋼板、および試料番号１５のＳｎめっき鋼板の片面に、実施例の無配向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の２層フィルム（厚さ：(PETI15)12μｍ/(PETI5)16μｍ)、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フィルム（厚さ：(PETI15)5μｍ/(PETI5)11μｍ)を、熱接着法を用いて２２５℃で熱接着し、積層した（以後、それぞれ樹脂被覆板６ａおよび１５ａという）。
また、試料番号６のＳｎめっき鋼板、および試料番号１５のＳｎめっき鋼板に、白色フィルムを積層せず、片面のみ同一条件で厚さ２8μｍの２層フィルムを積層した樹脂被覆板（以後、それぞれ樹脂被覆板６ｂおよび１５ｂという）を作成した。
これらの樹脂被覆板を、直径：１４０ｍｍのブランクに打ち抜いた後、白色顔料含有する樹脂フィルムを被覆した面、または樹脂フィルムを被覆していない面が缶の外面となるようにして、絞り比：１．６３で絞り加工し、次いで絞り比：１．３０で再絞り加工し、缶底径：約６６ｍｍのカップに成形した後、３段のしごき加工（総しごき率：６５％）を施し、缶底径：６５ｍｍの缶とした。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。
この加工において、６ａおよび６ｂの樹脂被覆板は、フランジ加工に至るまで樹脂皮膜が剥離することなく成形可能であったが、１５ａおよび１５ｂの樹脂被覆板は、再絞り缶をしごき加工する工程で樹脂皮膜が剥離した。また、６ｂの樹脂被覆板による缶では美麗な鏡面光沢が得られた。
【００２９】
(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)
実施例の試料番号４のＳｎめっき鋼板、および試料番号１３のＳｎめっき鋼板と試料番号１４のティン・フリー・スチールの片面に、実施例の無配向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の２層フィルム（厚さ：(PETI15)12μｍ/(PETI5)16μｍ)、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フィルム（厚さ：(PETI15)5μｍ/(PETI5)11μｍ)を、熱接着法を用いて２２５℃で熱接着し、積層した（以後、それぞれ樹脂被覆板４ａ、１３ａおよび１４という）。
また、試料番号４のＳｎめっき鋼板、および試料番号１３のＳｎめっき鋼板に、白色フィルムを積層せず、片面のみ同一条件で厚さ２８μｍの２層フィルムを積層した樹脂被覆板（以後、それぞれ樹脂被覆板４ｂおよび１３ｂという）を作成した。
これらの樹脂被覆板を、直径：１６０ｍｍのブランクに打ち抜いた後、白色顔料を含有する樹脂フィルムを被覆した面、または樹脂フィルムを被覆していない面が缶の外面となるようにして、缶底径：１００ｍｍの絞り缶とした。次いで再絞り加工により、缶底径：８０ｍｍの再絞り缶とした。さらにこの再絞り缶をストレッチ加工と同時にしごき加工を行い、缶底径：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、再絞りダイス肩アールが板厚の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元板厚の５０％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。
この加工において、４ａ、４ｂ、および１４の樹脂被覆板は、フランジ加工に至るまで樹脂皮膜が剥離することなく成形可能であったが、１３ａおよび１３ｂの樹脂被覆板は、再絞り缶をストレッチ加工と同時にしごき加工する工程で樹脂皮膜が剥離した。また、４ｂの樹脂被覆板による缶では美麗な鏡面光沢が得られた。
【００３０】
以上に示すように、本発明のＳｎめっき鋼板に有機樹脂を被覆してなる樹脂被覆Ｓｎめっき鋼板は、従来のＳｎめっき鋼板よりも被覆樹脂層の接着強度が優れ、被覆樹脂層の接着強度に優れる樹脂被覆電解クロム酸処理鋼板と同程度の接着強度を有しており、絞り加工、絞り加工後さらにストレッチ加工、絞り加工後さらにしごき加工、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た加工を施して缶体に成形しても、樹脂皮膜が剥離しないことが判明した。
【００３１】
【発明の効果】
本発明は、鋼板表面にＳｎめっきを施し、次いでめっき上にシランカップリング剤塗布層を設けたＳｎめっき鋼板であり、このＳｎめっき鋼板に塗料を塗布し、焼き付けるか、樹脂フィルムを積層てなる樹脂被覆Ｓｎめっき鋼板とした場合、２ｋｇ／１０ｍｍ以上のＴピール強度の優れた接着強度が得られる。そのため、これらの樹脂被覆Ｓｎめっき鋼板に絞り加工、または絞り加工後ストレッチ加工、または絞り加工後しごき加工、または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た場合に樹脂フィルムが剥離することなく、缶体に成形することが可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a Sn-plated steel sheet having a silane coupling agent coating layer on a Sn-plated layer of a Sn-plated steel sheet, excellent in adhesive strength with an organic resin layer, and a resin obtained by coating a Sn-coated steel sheet with a resin film. The present invention relates to a coated Sn-plated steel sheet, a can using the same, and a method for producing a Sn-plated steel sheet and a resin-coated Sn-plated steel sheet.
[0002]
[Prior art]
Conventionally, in Sn-plated steel sheets in which Sn is electroplated on steel sheets, immersion plating or electrolytic treatment is performed in a chromate-based aqueous solution such as sodium dichromate after Sn plating. What formed the hydrated oxide layer is used. However, when a Sn-coated steel sheet subjected to these treatments is used to form a resin-coated Sn-plated steel sheet in which an organic resin is coated or an organic resin film is laminated on the Sn-plated layer, the coated resin layer is applied to the Sn-plated steel sheet. Adhesive strength, especially after processing, is poor, drawing processing used in food and beverage cans, further stretch processing after drawing, further ironing after drawing, further after drawing When severe molding processing such as processing using both steel processing and ironing is performed, the coating resin layer peels off. Therefore, the base of the resin-coated steel sheet to be molded is coated with a resin, which has excellent adhesive strength of the resin film after processing. The steel sheet is subjected to electrolytic chromic acid treatment to form a chromium plating layer and a chromium hydrated oxide layer. Tin-free steel was used. However, since tin-free steel does not have an anticorrosive effect as in Sn, if the coated resin film has a defect, the underlying steel sheet is corroded.
[0003]
[Problems to be solved by the invention]
The present invention eliminates the above-mentioned drawbacks, has excellent corrosion resistance of the coating base, and does not peel off the coated organic resin layer even when subjected to severe processing. An object is to provide a resin-coated Sn-plated steel sheet obtained by coating a plated steel sheet with a resin film, a can using the same, and a method for producing a Sn-plated steel sheet and a resin-coated Sn-plated steel sheet.
[0004]
[Means for Solving the Problems]
According to the invention, a steel plateBothSn layer on the surface, and the coating amount after drying on the upper layer is 1-50 mg / m as Si amount2An amino-based silane coupling agent coating layer ofNon-oriented polyester resin filmResin-coated Sn-plated steel sheetA can characterized by being formed by any of the following processes: drawing, further drawing after drawing, further ironing after drawing, and further drawing and drawing combined with ironing Body is provided.
According to the invention also a steel plateBothFe-Sn alloy layer on the surface, Sn layer on the upper layer, and the coating amount after drying on the upper layer is 1 to 50 mg / m as Si amount2An amino-based silane coupling agent coating layer ofNon-oriented polyester resin filmResin-coated Sn-plated steel sheetA can characterized by being formed by any of the following processes: drawing, further drawing after drawing, further ironing after drawing, and further drawing and drawing combined with ironing bodyIs providedThe
[0005]
In the can of the present invention, the polyester resin film is preferably an ethylene terephthalate / isophthalate copolymer film.
[0006]
Moreover, according to the present invention, a steel plateBothAn Sn plating layer is formed on the surface, and then the coating amount after drying is 1 to 50 mg / m as the Si amount on the Sn plating layer.2After applying and drying an amino silane coupling agent so as to be on the silane coupling agent coating layerA non-oriented polyester resin film is laminated or a polyester resin film is laminated by extruding a polyester resin from a T-die of an extruder. A resin-coated Sn-plated steel sheet is drawn, drawn and then stretched and drawn. A can body characterized in that it is formed by any one of post-ironing processing, drawing processing, stretching processing, and ironing processing in combination.A manufacturing method is provided.
According to the present invention, further, a steel plateBothAn Sn plating layer is formed on the surface, heated to a temperature equal to or higher than the melting point of Sn, and then rapidly cooled, and then the coating amount after drying is 1 to 50 mg / m as the Si amount on the Sn plating layer.2After applying and drying an amino silane coupling agent so as to become, on the silane coupling agent coating layer,Laminating non-oriented polyester resin film or extruding polyester resin from T-die of extruder and laminating polyester resin film to draw resin-coated Sn-plated steel sheet A can body characterized by being formed by any of the following processes: ironing, drawing, and further stretching and ironingA manufacturing method is provided.
[0007]
In the can manufacturing method of the present invention, the polyester resin film is preferably an ethylene terephthalate / isophthalate copolymer film.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, by applying Sn plating to the surface of the steel sheet and then applying the Sn-plated steel sheet coated with a silane coupling agent, the resin film coated on the upper layer does not peel off even if subjected to severe molding processing, It has been found that very good adhesive strength can be obtained.
The present invention will be described below.
[0009]
As a steel sheet to which Sn plating of the Sn-plated steel sheet of the present invention is applied, a cold rolled steel sheet obtained by cold rolling, annealing and tempering after rolling a normal aluminum killed steel, or further performing cold rolling after annealing. Cold-rolled steel sheets with increased strength are selectively used depending on the application. These cold-rolled steel sheets are electrolytically degreased and pickled, and then an Sn plating layer is formed on the steel sheets.
As the Sn-plated steel sheet of the present invention, using a known ferrostan bath or halogen bath, Sn-plated steel sheet that has been electroplated with Sn (no reflow tinting), and after Sn is electroplated, the temperature is equal to or higher than the melting point of Sn. There is a Sn-plated steel sheet (reflow tinplate) having a normal glossy surface obtained by heating to, melting Sn and then rapidly cooling in water (reflow treatment). In addition to these Sn-plated steel plates, Ni-Fe alloy is electroplated, Sn is electroplated on the upper layer, heated to a temperature equal to or higher than the melting point of Sn, and then rapidly cooled. An island-shaped Sn-plated steel sheet on which an island-shaped Sn layer is formed can also be used.
[0010]
The Sn plating amount in the matte no-reflow Sn-plated steel sheet is 0.1 to 10 g / m from the viewpoint of corrosion resistance and economy.2It is preferable that it exists in the range. In reflow tinting, an Fe—Sn alloy layer is formed between the Sn plating layer and the steel plate. Therefore, when the metal Sn layer is left on the surface of the plated steel plate, the total Sn plating amount is 1 to 10 g / m.2It is necessary to be in the range. In the case where the metal Sn layer is not left on the surface of the plated steel sheet and the layer is composed only of the Fe—Sn alloy layer, the total Sn plating amount is 0.1 to 10 g / m.2It is preferable that it exists in the range.
[0011]
In the case of an island-shaped Sn-plated steel plate, the amount of Ni formed on the steel plate before Sn plating is 0.005 to 0.1 g / m.2The amount of Sn plating formed on the upper layer is 0.1 to 1.5 g / m.2It is preferable to set it as the range. After each plating layer is formed with such a plating amount, by heating to a temperature equal to or higher than the melting point of Sn, a striped Sn-plated steel sheet in which Sn is dispersed and present on the surface is obtained.
[0012]
A silane coupling agent is applied to the surface of the Sn-plated steel sheet obtained as described above and dried.
There are various types of silane coupling agents such as vinyl, acrylic, epoxy, amino, mercapto, and chloropropyl. In the present invention, it is preferable to use an amino silane coupling agent. . As the amino silane coupling agent, aminopropyltrimethoxysilane, aminopropylmethyldiethoxysilane, aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane and the like can be used.
An aqueous solution of 5 to 200 g / l of these silane coupling agents is applied to the Sn-plated steel sheet and dried. As a coating method, a known method can be applied. For example, a dipping method, a roll coating method, a drawing method using a roll after dipping, a spray method, or an electrolytic treatment method can be applied. The coating amount after drying is 1 to 50 mg / m in terms of the Si amount measured by the fluorescent X-ray method.2It is preferable that Si amount is 1mg / m2When it is less than this, sufficient adhesive strength of the resin film layer provided on this silane coupling agent coating layer cannot be obtained. 50mg / m2Even if it exceeds the range, the adhesive strength will decrease, and it will not be economical. As described above, the Sn-plated steel sheet of the present invention is obtained.
[0013]
The resin-coated Sn-plated steel sheet of the present invention can be obtained by coating an organic resin paint or laminating an organic resin film on one or both sides of the Sn-plated steel sheet obtained as described above.
Organic resin coatings include thermosetting or thermoplastic resin coatings such as phenol / epoxy coatings, urea / epoxy coatings, amino / epoxy coatings, epoxy / ester coatings, and other modified epoxy coatings such as vinyl chloride-vinyl acetate. Copolymer, vinyl chloride-vinyl acetate copolymer partially saponified product, vinyl chloride-vinyl acetate-maleic anhydride copolymer, etc.-vinyl paint, for example, epoxy-modified-vinyl resin paint, epoxy-amino-modified-vinyl Use of resin paints, modified vinyl resin paints such as epoxyphenol-modified vinyl resin paints, acrylic resin paints, oil paints, alkyd resin paints, polyester paints, synthetic rubber paints such as styrene-butadiene copolymers, etc. it can. The coating amount is 1 to 200 mg / dm from the viewpoint of the adhesive strength, corrosion resistance, and economy of the coating film in the molded body after the resin-coated Sn-plated steel sheet is formed.2, Preferably 10-100 mg / dm2It is preferable that
[0014]
As the organic resin film, polyethylene terephthalate, polybrene terephthalate, polyethylene naphthalate, polyester resin such as ethylene terephthalate / ethylene isophthalate copolymer, butylene terephthalate / butylene isophthalate copolymer, or two or more of these polyester resins are used. Blended resin, polyethylene, polypropylene, ethylene / propylene copolymer, and those modified with maleic acid, polyolefin resin such as ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, 6-nylon, 6, 6-nylon, 6,10-nylon and other polyamide resins, polycarbonate, polymethylpentene, and a simple blend of the above polyester resin and ionomer. Resin film, 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 laminating work, resin film adhesive strength, corrosion resistance, and economic efficiency in the molded body after the resin-coated Sn-plated steel sheet is formed. Is preferred.
[0015]
These resin films may be laminated by heating and melting resin pellets and extruding them directly onto the Sn-plated steel sheet from the T-die of the extruder, or by heating and melting the resin pellets and What was extruded from the T-die and formed into a film having a desired thickness may be bonded to the above Sn-plated steel sheet 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 where the resin adheres, and is sandwiched between a pair of rolls and pressed and pressed. When heat-bonding a resin film to a Sn-plated steel sheet using the thermal bonding method, heat-bonding at a temperature considerably lower than the melting point of Sn by using a resin film formed without stretching the resin film Can do. In the case of laminating a resin film formed by stretching in one axial direction or two longitudinal and lateral directions, if the heat setting after stretching is not performed at a temperature considerably lower than the melting point of Sn, the temperature is higher than the melting point of the resin. Since good adhesive strength with the Sn-plated steel sheet cannot be obtained unless heated to a higher temperature, it may be difficult to perform thermal bonding when using a resin having a melting point higher than that of Sn.
[0016]
The adhesive strength of the resin-coated Sn-plated steel sheet thus obtained is preferably 2 kg / 10 mm or more in terms of T peel strength. In the case of less than 2 kg / 10 mm, the resin layer may be peeled off when severe processing such as drawing is performed. In the case where more severe processing is performed after the drawing processing, such as further steel processing, ironing processing, or processing using both ironing and stretch processing, the adhesive strength is preferably 4 kg / 10 mm or more in terms of T peel strength.
In addition, the T peel strength here refers to the following. That is, in the case of a resin-coated Sn-plated steel sheet coated with an organic resin paint, two test pieces obtained by cutting the resin-coated Sn-plated steel sheet into a size of 10 mm × 100 mm are placed between 6 Nylon film is sandwiched, heated and heated to a temperature higher than the melting point of nylon using a hot press, and then bonded, the knife is forcedly peeled off at one end, and the two parts are folded into a T-shape. The tensile test piece is a strength at which the bond breaks when the portion corresponding to the T-shaped horizontal bar is sandwiched between tensilon chucks and pulled at a speed of 100 m / min. In the case of a resin-coated Sn-plated steel sheet laminated with an organic resin film, two specimens obtained by cutting the resin-coated Sn-plated steel sheet into a size of 10 mm x 100 mm are laminated between the resin-coated surfaces facing each other. A non-oriented non-oriented film made of the same resin is sandwiched, and heated and pressurized to a temperature higher than the melting point of the resin using a hot press. It refers to the strength obtained in the same manner as that for a plated specimen in the same manner as for a plated steel sheet.
[0017]
When the above resin-coated Sn-plated steel sheet is formed into a drawn can, a blank punched from the resin-coated Sn-plated steel sheet coated with resin on one or both sides is drawn into a cup shape using a drawing die. When narrowing the diameter and increasing the height of the side wall, redrawing is performed using a drawing die having a smaller diameter than the preceding stage. The drawing process is usually performed by one or two drawing processes, and is applied to a can having a relatively large can diameter and a low side wall height.
[0018]
When the above resin-coated Sn-plated steel sheet is drawn and then stretched to form a can, a blank punched from the resin-coated Sn-plated steel sheet coated with resin on one or both sides is drawn into a cup shape using a drawing die. Process. Next, using a plurality of drawing dies, the side wall height is increased while sequentially reducing the diameter. When the cup is pushed by the machining punch, the side wall is bent and unbent when the cup enters and exits the drawing die and the wrinkle restraining jig, and the side wall portion is drawn and drawn while being thinned. Applicable to cans with relatively small can diameter and high side wall height.
[0019]
When the above resin-coated Sn-plated steel sheet is drawn and then ironed to form a can, a blank punched from a resin-coated Sn-plated steel sheet coated with resin on one or both sides is used with one or more stages of drawing dies. Used to draw into a cup shape. Next, using one or more stages of squeezing dies, the side walls are forcibly pushed into the clearance between the squeezing dies set to be smaller than the side wall thickness of the cup and the punch to increase the side wall height while thinning the side walls. Apply ironing. For this reason, it is applied to a can having a relatively small can diameter, a high side wall height, and a thin side wall thickness. When the resin-coated Sn-plated steel sheet of the present invention is formed into a can by drawing and ironing, the resin-coated Sn-plated steel sheet coated with resin on only one side is used, and the non-resin-coated surface is the outer surface of the can. Then, the Sn plating layer is rubbed by the ironing die to become a mirror surface, and a beautiful surface gloss is obtained.
[0020]
When the above resin-coated Sn-plated steel sheet is drawn and then formed into a can by using both stretch and ironing, a blank punched from the resin-coated Sn-plated steel sheet coated with resin on one or both sides is used with a drawing die. And draw it into a cup shape. Next, using the multi-stage drawing dies in the same way as normal stretch processing, the side wall height is increased while sequentially reducing the diameter. However, as with the ironing die in ironing processing, the clearance between the die and punch is set to the thickness of the cup side wall. By setting it to be smaller than that, the side wall is bent and unbent and simultaneously ironed, and the side wall portion is stretched and thinned while being thinned. In this processing, even when a resin-coated Sn-plated steel sheet coated with resin only on one side is used, a beautiful surface gloss can be obtained.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
(Example)
[Preparation of Sn-plated steel sheet]
The cold-rolled steel sheets having the thicknesses and tempers shown in Table 1 were electrolytically degreased in an alkaline aqueous solution, washed with water, then washed with sulfuric acid, washed with water, and then Sn in the conditions shown in Table 1 using a known ferrostan bath. A plating layer was formed or a Sn plating layer was formed and then a reflow treatment was performed to form an Fe—Sn alloy layer between the steel plate and the Sn plating layer. Next, using the treatment bath shown in Table 1, a 5-200 g / l solution of the silane coupling agent shown in Table 1 was applied by a dipping method so as to have the adhesion amount shown in Table 1, and then dried on the plating surface. A silane coupling coating layer was formed on the substrate.
Further, as a comparative material, a normal plating having an amount of chromium hydrated oxide shown in Table 1 and a steel plate which was subjected to a reflow treatment after forming a Sn plating layer on the steel plate and then treated in a sodium dichromate solution, and a steel plate A tin-free steel was prepared in which two layers of a chromium plating layer and a chromium hydrated oxide layer were formed by performing electrolytic chromic acid treatment.
[0022]
[Table 1]
[Preparation of resin-coated Sn-plated steel sheet]
An epoxy / phenolic paint is applied to one side of the Sn-plated steel sheet and the comparative material shown in Table 1 in the application amount shown in Table 2, and baked at 210 ° C. for 10 minutes, and then resin-coated Sn-plated steel sheet and resin-coated tin-free steel. Got.
In addition, the non-oriented polyethylene terephthalate film (shown as PET in the table) shown in Table 2 or two types of non-oriented ethylene terephthalate / ethylene isophthalate copolymers on one side of the Sn-plated steel sheet and the comparative material shown in Table 1 A two-layer film (indicated by PETI15 / PETI5 in the table, the number indicates the mol% of ethylene isophthalate, and the PETI15 side is in contact with the Sn-plated steel sheet or metal side) is heat bonded at 225 ° C and laminated. Thus, a resin-coated Sn-plated steel plate and a resin-coated tin-free steel were obtained.
[0024]
[Table 2]
From the resin-coated Sn-plated steel plate and resin-coated tin-free steel obtained as described above, specimens each having a width of 10 mm and a length of 100 mm were cut out, and the two were paired to form resin-coated surfaces. In the case of a test piece coated with an organic resin paint, a 6,6 nylon film is sandwiched between them, and heated and heated to a temperature higher than the melting point of nylon using a hot press to adhere and test. A test material was used.
In the case of a specimen coated with an organic resin film, an amorphous non-oriented film composed of the same resin as the coated organic resin is sandwiched between them, and heated and heated to a temperature higher than the melting point of the resin using a hot press. A test material for an adhesive strength test was used. Next, one end of the bonded portion of these test materials was forcibly peeled off with a knife or the like, a tensile test piece formed by bending a two-part portion into a T-shape, and a portion corresponding to a T-shaped horizontal bar as Tensilon The strength at which the adhesive breaks when measured at a speed of 100 m / min is measured, and the result is shown as the adhesive strength (T peel strength: (kg / 10 mm)) per 10 mm width of the test piece. It is shown in 2.
[0026]
(Molding can forming)
70 mg / dm of the epoxy-phenolic paint of the example on both surfaces of the Sn-plated steel plate of sample numbers 1 and 2 of the example, and the Sn-plated steel plate of sample number 11 and the tin-free steel of sample number 122And baked at 210 ° C. for 10 minutes to obtain a resin-coated Sn-plated steel sheet and a resin-coated tin-free steel. These resin-coated plates are punched into a blank having a diameter of 112 mm, then drawn with a drawing ratio of 1.50, then redrawed with a drawing ratio of 2.1, and a can bottom diameter of about 53 mm. Molded into a cup.
In this processing, the resin-coated plate using the Sn-plated steel plates of sample numbers 1 and 2 and the resin-coated plate using the tin-free steel of sample number 12 could be molded without peeling off the resin film. However, in the resin-coated plate using the Sn-plated steel plate of sample number 11, the resin film was peeled off during the redrawing process.
[0027]
(Molding of cans that are stretched after drawing)
A non-oriented polyethylene terephthalate film (thickness) was formed on one side of the Sn-plated steel sheets of Sample Nos. 8 and 9 and the Sn-plated steel sheets of Sample Nos. 7, 10 and 16 and the tin-free steel of Sample No. 17. And a white non-oriented film (thickness: 16 μm) containing 20% by weight of a titanium-based white pigment in the same polyethylene terephthalate on the other side and thermally bonded at 225 ° C. using a thermal bonding method. And laminated.
These resin-coated plates were punched into a blank having a diameter of 187 mm, and then the surface coated with the film containing the white pigment became the outer surface of the can so that a drawing can with a drawing ratio of 1.70 was obtained. . Next, primary redrawing ratio: 1.29, secondary redrawing ratio: 1.24, tertiary redrawing ratio: 1.20, radius of curvature of redrawing die shoulder: 0.4 mm, wrinkle restraining load: A stretch-processed can with a can bottom diameter of 66 mm was obtained by a plurality of steps of stitching under the condition of 58N. Next, the upper part of the can was trimmed by a known method, and neck-in processing and flange processing were performed.
In this processing, the resin-coated plate using the Sn-plated steel plates of sample numbers 8 and 9 and the resin-coated plate using the tin-free steel of sample number 17 are not peeled off until the flange processing. Although it was possible to mold, the resin-coated plates using the Sn-plated steel plates of Sample Nos. 7, 10 and 16 were peeled off in the process of stretching the redrawn can.
[0028]
(Forming cans made by ironing after drawing)
A two-layer film of unoriented ethylene terephthalate / ethylene isophthalate copolymer of the example (thickness: (PETI15) 12 μm) on one side of the Sn-plated steel plate of Sample No. 6 and the Sn-plated steel plate of Sample No. 15 / (PETI5) 16μm), white non-oriented film (thickness: (PETI15) 5μm / (PETI5) containing 20% by weight of titanium-based white pigment in the same ethylene terephthalate / ethylene isophthalate copolymer on one side) 11 μm) was thermally bonded at 225 ° C. using a thermal bonding method and laminated (hereinafter referred to as resin-coated plates 6a and 15a, respectively).
Also, a resin-coated plate in which a white film is not laminated on a Sn-plated steel plate of Sample No. 6 and an Sn-plated steel plate of Sample No. 15 and a two-layer film having a thickness of 28 μm is laminated on the same condition only on one side (hereinafter each referred to as a resin) Cover plates 6b and 15b) were prepared.
After punching these resin-coated plates into a blank having a diameter of 140 mm, the surface coated with the resin film containing the white pigment or the surface not coated with the resin film becomes the outer surface of the can, and the drawing ratio: After drawing at 1.63, then redrawing at a drawing ratio of 1.30, forming into a cup with a can bottom diameter of about 66 mm, and performing a three-stage ironing process (total ironing ratio: 65%), Can bottom diameter: 65 mm can. Next, the upper part of the can was trimmed by a known method, and neck-in processing and flange processing were performed.
In this processing, the resin-coated plates 6a and 6b could be molded without peeling off the resin film until the flange processing, but the resin-coated plates 15a and 15b were processed in the process of ironing the redrawn can. The resin film peeled off. In addition, a beautiful mirror gloss was obtained with the can of the resin-coated plate of 6b.
[0029]
(Molding of cans processed by drawing and drawing together with ironing)
2 of the non-oriented ethylene terephthalate / ethylene isophthalate copolymer of the example on one side of the Sn-plated steel plate of the sample number 4 of the example, the Sn-plated steel plate of the sample number 13 and the tin-free steel of the sample number 14 Layer film (thickness: (PETI15) 12μm / (PETI5) 16μm), white non-oriented film containing 20% by weight of titanium-based white pigment in the same ethylene terephthalate / ethylene isophthalate copolymer on the other side ( Thickness: (PETI15) 5 μm / (PETI5) 11 μm) was thermally bonded at 225 ° C. using a thermal bonding method and laminated (hereinafter referred to as resin-coated plates 4a, 13a and 14 respectively).
Also, a resin-coated plate in which a white film is not laminated on a Sn-plated steel plate of Sample No. 4 and an Sn-plated steel plate of Sample No. 13 and a two-layer film having a thickness of 28 μm is laminated on the same condition only on one side (hereinafter each referred to as a resin) Cover plates 4b and 13b) were prepared.
After punching these resin-coated plates into a blank having a diameter of 160 mm, the surface coated with the resin film containing the white pigment or the surface not coated with the resin film becomes the outer surface of the can. A diameter: 100 mm drawn can. Next, a redraw can with a can bottom diameter of 80 mm was made by redraw processing. Furthermore, this redrawn can was subjected to ironing at the same time as stretch processing to obtain a can having a can bottom diameter of 65 mm.
Stretching and ironing are used in combination with the redrawing part, which is the upper end of the can, the distance between the ironing part is 20 mm, the redrawing die shoulder radius is 1.5 times the plate thickness, and the redrawing die and punch The clearance was 1.0 times the plate thickness, and the ironing portion clearance was 50% of the original plate thickness. Next, the upper part of the can was trimmed by a known method, and neck-in processing and flange processing were performed.
In this processing, the resin-coated plates 4a, 4b, and 14 were able to be molded without peeling off the resin film until the flange processing, but the resin-coated plates 13a and 13b were subjected to stretch processing of the redrawn cans. At the same time, the resin film peeled off during the ironing process. In addition, a beautiful mirror gloss was obtained with the can of the resin-coated plate 4b.
[0030]
As described above, the resin-coated Sn-plated steel sheet obtained by coating the Sn-plated steel sheet of the present invention with an organic resin has better adhesive strength of the coated resin layer than the conventional Sn-plated steel sheet, and the adhesive strength of the coated resin layer is improved. It has the same adhesive strength as that of an excellent resin-coated electrolytic chromic acid-treated steel sheet, and after drawing, drawing and further stretching, drawing and further ironing, and drawing and drawing. It has been found that the resin film does not peel off even when molded into a can body.
[0031]
【The invention's effect】
The present invention is a Sn-plated steel plate in which Sn plating is applied to the surface of the steel plate, and then a silane coupling agent coating layer is provided on the plating. The Sn-plated steel plate is coated and baked or laminated with a resin film. When a resin-coated Sn-plated steel sheet is used, an excellent adhesive strength with a T peel strength of 2 kg / 10 mm or more is obtained. Therefore, when these resin-coated Sn-plated steel sheets are processed by drawing, stretching after drawing, or ironing after drawing, or by combining ironing with stretching after drawing, the resin film peels off. And can be formed into a can.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001085965A JP4285924B2 (en) | 2001-03-23 | 2001-03-23 | A can body comprising a resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001085965A JP4285924B2 (en) | 2001-03-23 | 2001-03-23 | A can body comprising a resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002285354A JP2002285354A (en) | 2002-10-03 |
| JP4285924B2 true JP4285924B2 (en) | 2009-06-24 |
Family
ID=18941404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001085965A Expired - Fee Related JP4285924B2 (en) | 2001-03-23 | 2001-03-23 | A can body comprising a resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4285924B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110739A1 (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 |
| TWI391530B (en) | 2007-04-04 | 2013-04-01 | Nippon Steel Corp | A plated steel sheet for use in a tank and a method for manufacturing the same |
| JP2009046754A (en) * | 2007-08-23 | 2009-03-05 | Toyo Seikan Kaisha Ltd | Surface treated tinned steel sheet for welded can, and welded can composed thereof |
| WO2009104773A1 (en) | 2008-02-18 | 2009-08-27 | 新日本製鐵株式会社 | Plated steel sheet for can and process for producing the plated steel sheet |
| JP5398024B2 (en) | 2008-12-19 | 2014-01-29 | 東洋鋼鈑株式会社 | Resin coated steel sheet |
| JP5557465B2 (en) * | 2009-04-24 | 2014-07-23 | 岩城フィルム化工株式会社 | Product and product manufacturing method |
| WO2011045833A1 (en) | 2009-10-14 | 2011-04-21 | 東洋鋼鈑株式会社 | Method for producing resin-coated metal plate |
| JP5419638B2 (en) | 2009-11-04 | 2014-02-19 | 東洋鋼鈑株式会社 | Manufacturing method of surface-treated steel sheet |
| JP2013033949A (en) * | 2011-06-30 | 2013-02-14 | Sumitomo Bakelite Co Ltd | Substrate, metal film, method for producing substrate, and method for producing metal film |
| KR102428824B1 (en) | 2019-12-11 | 2022-08-02 | 주식회사 포스코 | Metal-plastic composite material and method for manufacturing the same |
-
2001
- 2001-03-23 JP JP2001085965A patent/JP4285924B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002285354A (en) | 2002-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0146355B1 (en) | Process for production of covered deep-drawn can | |
| JPH07106394B2 (en) | Squeeze ironing can manufacturing method | |
| JPH0757390B2 (en) | Redrawing method | |
| JP4285924B2 (en) | A can body comprising a resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a method for producing the same | |
| JPH01258822A (en) | Redrawing method and drawing/redrawing can | |
| JP3117727B2 (en) | Thermoplastic resin-coated aluminum alloy sheet, method for manufacturing the same, and manufacturing apparatus | |
| JP3655592B2 (en) | Manufacturing method of Sn-plated steel sheet, Sn-plated steel sheet, resin-coated Sn-plated steel sheet obtained by coating a Sn-coated steel sheet with a resin film, and a can using the same | |
| JPH0571035B2 (en) | ||
| JP2001262371A (en) | Laminated seamless can | |
| WO2011045833A1 (en) | Method for producing resin-coated metal plate | |
| JP2711947B2 (en) | Method for producing resin-coated tin-plated steel sheet for thinned deep drawn cans with excellent processing corrosion resistance | |
| JP2504164B2 (en) | Method for manufacturing thinned deep-drawn can | |
| JP2004345214A (en) | RESIN-COATED Sn PLATED STEEL SHEET, CAN USING THIS STEEL SHEET AND METHOD FOR MANUFACTURING RESIN-COATED Sn PLATED STEEL SHEET | |
| JP2003277886A (en) | Resin-coated steel sheet for shear spun can, method of producing resin-coated steel sheet for shear spun can and shear spun can produced by using the same | |
| WO2005110739A1 (en) | Sn-PLATED STEEL SHEET COATED WITH RESIN, CAN USING THE SAME, AND METHOD FOR PRODUCING Sn-PLATED STEEL SHEET COATED WITH RESIN | |
| JP3140929B2 (en) | Resin-coated steel sheet for dry drawing and ironing can | |
| JP3282994B2 (en) | Surface treatment method of steel sheet, surface treated steel sheet, and thermoplastic resin coated steel sheet using the surface treated steel sheet | |
| JP2000006979A (en) | Polyester resin-coated aluminum seamless can and its manufacture | |
| WO2010070795A1 (en) | Surface-treated steel sheet on which particulate tin is deposited and resin-coated steel sheet | |
| JP3270684B2 (en) | Resin-coated aluminum alloy plate for drawing and ironing cans | |
| JP4278272B2 (en) | Film-coated two-piece can | |
| JPH11302898A (en) | Surface treatment of steel sheet, surface treated steel sheet and thermoplastic resin coated steel sheet using surface treated steel sheet | |
| JPH09287044A (en) | Resin coated aluminum alloy sheet for drawn and ironed can | |
| JP3781156B2 (en) | Resin film for metal plate lamination, resin film laminated metal plate, manufacturing method thereof, and container using resin film laminated metal plate | |
| JPH09276949A (en) | Resin coated aluminum alloy sheet for can of drawing/ ironing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050119 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060713 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060718 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060913 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20061017 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061218 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20070123 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070326 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20070326 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20070501 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20070525 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090324 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120403 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120403 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120403 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130403 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130403 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140403 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140403 Year of fee payment: 5 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |