JP3927329B2 - Thermoplastic resin laminated metal plate for containers with excellent impact resistance - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、金属容器用の熱可塑性樹脂積層金属板に関するものであり、特に、缶形状に成形後に落下等の衝撃を受けても熱可塑性樹脂皮膜に亀裂やピンホールの入りにくい絞り缶及び絞りしごき缶用の熱可塑性樹脂積層金属板に関するものである。
【０００２】
【従来の技術】
従来、金属缶の内面には腐食防止として一般的には塗装が施こされているが、有機溶剤を用いずに熱可塑性樹脂を表面に積層した金属板を容器用金属板として使用する開発が行なわれている。即ち、（１）二軸配向ポリエチレンテレフタレートフィルムを低融点ポリエステルの接着層を介してラミネートし、製缶材として用いる方法（特開昭５６−１０４５１号公報、特公平１−１９２５４６号公報等）、（２）非晶質又は低結晶性の芳香族ポリエステルフィルムを金属板にラミネートし、製缶材として用いる方法（特開平１−１９２５４５号公報、特開平２−５７３３９号公報等）、（３）低配向ポリエチレンテレフタレートフィルムを金属板にラミネートし、製缶材として用いる方法（特開昭６４−２２５３０号公報等）など多層構造あるいは複合構造のポリエステルフィルムを金属板にラミネートし、製缶材として用いる方法（特開平６−２９７６４４号公報、特開平６−３２０６５８号公報等）が提案されてきた。
【０００３】
また、熱可塑性樹脂皮膜の耐衝撃性が十分でないため内容物を充填後、輸送や落下の衝撃で熱可塑性樹脂皮膜に亀裂が生じ、金属が溶出したり腐食する問題がある。そのための対応策としてポリエステル樹脂皮膜の耐衝撃性を改善する方法として、固有粘度と加工後の缶壁皮膜の配向度を規定する方法（特開平７−１７８４８５号公報）が提案されている。しかしながら、特に絞りしごき缶の場合には加工前の熱可塑性樹脂皮膜は絞りしごき加工へ追随するために非晶質構造であることが望ましい。非晶質構造皮膜の場合、缶側壁部では絞りしごき加工されて配向結晶化するが、缶底部では配向結晶化しない。そのため、缶底部の耐衝撃性が不足しており、その改善が切望されていた。
【０００４】
【発明が解決しようとする課題】
本発明は、前記事情に鑑みてなされたものであり、耐衝撃性に優れた熱可塑性樹脂積層金属板を提供することを目的とするものである。
【０００５】
【課題を解決するための手段】
本発明は、以上の課題を解決するためになされたものであり、
（１）少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面に熱処理を行わない時の衝撃強度値が４．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜を有することを特徴とする耐衝撃性に優れた熱可塑性樹脂積層金属板。
（２）少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面に２２０℃で１０分間の熱処理後の衝撃強度値が４．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜を有することを特徴とする耐衝撃性に優れた熱可塑性樹脂積層金属板。
【０００６】
（３）少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面に２２０℃で１０分間の熱処理及び１２０℃で３０分のレトルト処理後の衝撃強度値が４．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜を有することを特徴とする耐衝撃性に優れた熱可塑性樹脂積層金属板。
（４）少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面に衝撃強度値が８．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜を有することを特徴とする耐衝撃性に優れた熱可塑性樹脂積層金属板。
【０００７】
（５）少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面に２２０℃で１０分間の熱処理後の衝撃強度値が８．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜を有することを特徴とする耐衝撃性に優れた熱可塑性樹脂積層金属板。
（６）少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面に２２０℃で１０分間の熱処理及び１２０℃で３０分のレトルト処理後の衝撃強度値が８．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜を有することを特徴とする耐衝撃性に優れた熱可塑性樹脂積層金属板。
【０００８】
（７）熱可塑性樹脂皮膜の表面粗度Ｒａが０．２０μｍ以下であることを特徴とする前記（１）〜（６）に記載の耐衝撃性に優れた熱可塑性樹脂積層金属板。
（８）熱可塑性樹脂がポリエステル組成物主体であることを特徴とする前記（１）〜（７）に記載の耐衝撃性に優れた熱可塑性樹脂積層金属板である。
【０００９】
以下に本発明を詳細に説明する。
本発明における熱可塑性樹脂積層金属板の少なくとも容器の内面となる表面粗度Ｒａが０．７μｍ以下の金属板表面上の樹脂皮膜が、そのままで、２２０℃で１０分間の熱処理後或いはさらにその後１２０℃で３０分のレトルト処理後の衝撃強度値が４．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜であることが重要である。
【００１０】
我々は、種々の検討の結果、特に、絞りしごき缶缶底部の耐衝撃性改善のためには、容器の内面となる金属板の表面粗度Ｒａが０．７μｍ以下で、かつ金属板表面上の樹脂皮膜は、２２０℃で１０分間の熱処理後或いはさらに、その後１２０℃で３０分のレトルト処理を行った後の熱可塑性樹脂皮膜が４．０ｇ・ｃｍ／厚μｍ以上の衝撃強度値を有していれば、缶体に成形され内容物を充填した後の輸送や落下の衝撃を受けた場合にも熱可塑性樹脂皮膜に亀裂が生じることが無く、金属が溶出したり腐食する問題が発生しないことを見出し本発明に至ったものである。
【００１１】
金属板に積層された熱可塑性樹脂皮膜の衝撃強度値が４．０ｇ・ｃｍ／厚μｍ未満では、缶体に成形され内容物を充填した後の輸送や落下の衝撃を受けた場合に、熱可塑性樹脂皮膜に亀裂が生じたり、金属が溶出したり腐食する問題が生じる。熱可塑性樹脂皮膜自体の衝撃強度値が高い場合でも、金属板の表面粗度Ｒａが０．７μｍ超では、缶体に成形され内容物を充填した後の輸送や落下の衝撃を受けた場合に、熱可塑性樹脂皮膜に亀裂が生じることがあり、金属が溶出したり腐食する場合があることもあわせて見出したものである。即ち、本発明者らは、鋼板の表面粗度と樹脂皮膜の衝撃強度値の限定の相互作用効果を知見し、これに基づいて本発明を完成させたものである。
【００１２】
表面粗度が高い場合には、皮膜と金属板との密着性が不十分となることは考えられるが、これとは別に衝撃によって金属板が変形するときに、微少領域で変形或いは衝撃の大きなところが生じることが皮膜に亀裂が生じる原因ではないかと推定される。
缶体が外面塗装あるいは印刷焼付け工程や、充填時にレトルト処理を経る場合には、熱可塑性樹脂皮膜は結晶化や加水分解を受けるため、衝撃強度値が変化する。このため、充填後を考慮する必要がある。従って、２２０℃で１０分間の熱処理後或いはさらに、その後１２０℃で３０分のレトルト処理後の衝撃強度値が４．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜であることが望ましい。
熱可塑性樹脂皮膜の衝撃強度値は、８．０ｇ・ｃｍ／厚μｍ以上である熱可塑性樹脂皮膜であることがより好ましい。
【００１３】
本発明での熱可塑性樹脂皮膜の衝撃強度値は、皮膜が金属板上に積層された状態で２２０℃で１０分間の熱処理後或いはさらにその後１２０℃で３０分のレトルト処理を行った後、金属板を塩酸で溶解し樹脂皮膜を単離して、東洋精機社製のインパクトテスターを用いて、衝撃頭を直径１インチの半球とすることによって求めることができる。
本発明の熱可塑性樹脂積層金属板の母材となる金属板には、鋼板、表面処理鋼板、アルミニウム板、アルミニウム合金板等が使用できる。特に限定するものではないが、鋼板としては、通常、板厚ｔ0 ：０．１２〜０．６０ｍｍの範囲にあり、硬度（ＨＲ３０Ｔ）４６〜７を有するものが望ましい。
【００１４】
この鋼板の表面に、Ｓｎ，Ｃｒ，Ｎｉ，Ａｌ，Ｚｎの１種または２種以上の金属めっきを行い、クロメート処理皮膜の上に、塗装を不要にするために密着性・加工性・耐食性に優れる樹脂皮膜が積層されることが望ましい。
具体例としては、付着量０．５〜５．０ｇ／ｍ2 の錫めっき後化成処理を施した錫めっき鋼板、付着量０．３〜２．０ｇ／ｍ2 のニッケルめっき後化成処理を施したニッケルめっき鋼板、Ｓｎ及びＮｉ付着量として各々０．５〜２．０ｇ／ｍ2 、０．０１〜０．５ｇ／ｍ2 をＮｉ、Ｓｎの順にめっき後化成処理を施したＳｎ／Ｎｉめっき鋼板、金属Ｃｒ付着量５０〜２００ｍｇ／ｍ2 、酸化Ｃｒ５〜３０ｍｇ／ｍ2 の通常ＴＦＳ（Ｔｉｎ Ｆｒｅｅ Ｓｔｅｅｌ）と呼ばれているクロム・クロメート処理鋼板などがある。
【００１５】
また、本発明に使用されるアルミニウム板としては、通常、板厚ｔ0 ：０．１８〜０．６０ｍｍの範囲にあり、合金組成としては、５０５２，５０８２，５１８２，５３５２，５３４９，５０１７系で調質はＨ１９が望ましい。このアルミニウム板にクロメート処理、ジルコメート処理あるいはリン酸−クロム酸系の化成処理を施した表面処理金属板も使用することができる。
本発明においては、熱可塑性樹脂皮膜の表面粗度Ｒａが０．２０μｍ以下であることが望ましい。表面粗度Ｒａが０．２０μｍ超では絞り加工及び／又はしごき加工における成形性が低下する傾向があるとともに、絞り加工及び／又はしごき加工に伴い、樹脂皮膜の耐衝撃性が低下することがあり、熱可塑性樹脂皮膜の表面粗度Ｒａが０．２０μｍ以下であることが望ましい。
【００１６】
本発明における樹脂皮膜としては、ポリエステル系樹脂、ナイロン系樹脂、ポリエチレン、ポリプロピレンなどのオレフィン系樹脂、エチレン酢酸ビニル共重合体、アイオノマーなどの変性オレフィン樹脂、ポリビニルアルコールおよびその共重合体、アクリル系樹脂単体およびその混合物等からなる樹脂の単層及び複層フィルムを挙げることができる。
【００１７】
特にその中でも、コスト、フレーバー性の点からポリエステル組成物主体であることが好ましい。ポリエステル組成物としては、特に限定されないが、代表的なものとして以下の例を挙げることができる。酸成分としては、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸のような芳香族二塩基酸、アジピン酸、セバチン酸、アゼライン酸、ドデカジオン酸のような脂肪族ジカルボン酸、ダイマー酸、シクロヘキサンジカルボン酸のような脂環族ジカルボン酸等が例示できる。又アルコール成分としては、エチレングリコール、ジエチレングリコール、ブタンジオール、ヘキサンジオールのような脂肪族ジオールを挙げることができる。これらを１種以上組み合わせて使用される。例えば好ましい例として、酸成分としてテレフタル酸７５モル％以上、アルコール成分としてエチレングリコール８５モル％以上よりなるポリエステル組成物を挙げることができる。
【００１８】
また、樹脂皮膜を表面層と接着層の２層構造とし、接着層中にポリオレフィン系樹脂あるいはスチレンブタジエンラバーなどのように衝撃吸収樹脂を分散させた構造とすることもできる。
また、本発明における樹脂皮膜厚みは特に限定されないが、２〜８０μｍ程度が適当であり、好ましくは８〜６０μｍ、更に好ましくは１２〜４０μｍの範囲である。表面層、接着層の厚さ比は特に限定されないが、表面層の厚さとしては１〜１０μｍであることが望ましい。
【００１９】
【実施例】
本発明の実施例及び比較例について説明する。
（実施例１）
片側の表面に付着量２．８ｇ／ｍ2 の錫めっき層を有し、他の片面にはＳｎ及びＮｉ付着量として各々１．０ｇ／ｍ2 、２．５ｇ／ｍ2 をＮｉ、Ｓｎの順にめっき後化成処理を施したＳｎ／Ｎｉめっき層を有する鋼板｛板厚０．２４ｍｍ、硬度（ＨＲ３０Ｔ）６１｝のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が３μｍで接着層が２７μｍ）を積層した。なお、ポリエステル系フィルムは表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはスチレンブタジエンラバーを衝撃吸収樹脂として平均粒子径０．２μｍとして９ｗｔ％分散させた。また表面層の融点２２８℃接着層の融点２１３℃とした。
【００２０】
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．４１μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板の樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は９．０ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験１を行った。缶底接地部耐衝撃性試験１での通電値は良好（０．０１ｍＡ）であった。
【００２１】
（１）缶底接地部耐衝撃性試験１
成形した缶体にコカ・コーラ（日本コカ・コーラ株式会社商品名）を低温で充填し、コーティングされたアルミ蓋を巻締め、２日間室温に保管した後０℃に１日貯蔵した後、０℃のままで缶底の接地部に重さ６００ｇの直角ブロックを高さ５０ｍｍから直角部が缶底の接地部に衝突するように落として衝撃的変形をあたえた後、開缶し缶胴の衝撃変形部を通電測定し、０．１ｍＡ未満を良好（〇）、０．１ｍＡ以上を不良（×）と評価した。通電測定は、１％ＮａＣｌ溶液を用い電極（陰極）と缶体との間に６．０ｖの電圧をかけ、流れる電流を測定した。
【００２２】
（実施例２）
板厚０．２６ｍｍ、５０１７系合金のアルミニウム板の片方の表面に厚み２５μｍ単層の融点１５０℃のエチレン共重合ポリプロピレンフィルムを積層した。
樹脂皮膜積層面側のアルミニウム板の表面粗度Ｒａは０．５１μｍであった。樹脂皮膜の表面粗度Ｒａは０．１８μｍであった。この樹脂積層鋼板の樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は５．０ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験１での通電値は良好（０．０７ｍＡ）であった。
【００２３】
（実施例３）
片側の表面に付着量２．８ｇ／ｍ2 の錫めっきを、他の片面には付着量１．０ｇ／ｍ2 の錫めっき後に化成処理を施した鋼板｛板厚０．２４ｍｍ、硬度（ＨＲ３０Ｔ）６１｝の付着量１．０ｇ／ｍ2 側の表面に厚み３０μｍの単層のポリアミドフィルム（ナイロン６融点２２０℃）を積層した。付着量１．０ｇ／ｍ2 側の鋼板の表面粗度Ｒａは０．６２μｍであった。樹脂皮膜の表面粗度Ｒａは０．１０μｍであった。この樹脂積層鋼板の樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は７．４ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、３回絞り成形より深絞り缶を作成した。缶底接地部耐衝撃性試験１での通電値は良好（０．０２ｍＡ）であった。
【００２４】
（実施例４）
実施例３と同じ鋼板の付着量１．０ｇ／ｍ2 側の表面に厚み３５μｍの２層構造のポリエステル系フィルム（表面層が３μｍで接着層が３２μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはポリアミド樹脂を衝撃吸収樹脂として平均粒子径０．２μｍとして１５ｗｔ％分散させた。また表面層の融点２３０℃接着層の融点２２０℃とした。
付着量１．０ｇ／ｍ2 側の鋼板の表面粗度Ｒａは０．３０μｍであった。樹脂皮膜の表面粗度Ｒａは０．２３μｍであった。
樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は９．０ｇ・ｃｍ／厚μｍであった。樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験１を行った。缶底接地部耐衝撃性試験１での通電値は良好（０．０６ｍＡ）であった。
【００２５】
（比較例１）
実施例１と同じ鋼板のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が２μｍで接着層が２８μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルである。また表面層の融点２３０℃接着層の融点２１５℃とした。
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．４５μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板の樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は３．７ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験１を行った。缶底接地部耐衝撃性試験１での通電値は不良（０．４ｍＡ）であった。
【００２６】
（比較例２）
実施例１と同じ鋼板のＳｎ／Ｎｉにめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が２μｍで接着層が２８μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはポリアミド樹脂を衝撃吸収樹脂として平均粒子径０．２μｍとして１５ｗｔ％分散させた。また表面層の融点２３０℃接着層の融点２２０℃とした。
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．９１μｍであった。樹脂皮膜の表面粗度Ｒａは０．１５μｍであった。この樹脂積層鋼板の樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．５ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験１を行った。缶底接地部耐衝撃性試験１での通電値は不良（０．２ｍＡ）であった。
【００２７】
（実施例５）
片側の表面に付着量２．８ｇ／ｍ2 の錫めっき層を有し、他の片面にはＳｎ及びＮｉ付着量として各々１．０ｇ／ｍ2 、０．２５ｇ／ｍ2 をＮｉ、Ｓｎの順にめっき後化成処理を施したＳｎ／Ｎｉめっき層を有する鋼板｛板厚０．２４ｍｍ、硬度（ＨＲ３０Ｔ）６１｝のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が３μｍで接着層が２７μｍ）を積層した。なお、ポリエステル系フィルムは表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはスチレンブタジエンラバーを衝撃吸収樹脂として平均粒子径０．２μｍとして９ｗｔ％分散させた。また表面層の融点２２８℃接着層の融点２１３℃とした。
【００２８】
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．４１μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理を行った後樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．７ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験２を行った。缶底接地部耐衝撃性試験２での通電値は良好（０．０１ｍＡ）であった。
【００２９】
（２）缶底接地部耐衝撃性試験２
成形加工後、缶体外面に印刷を施しその後２１０℃で５分間の焼付けを施した缶体にコカ・コーラ（日本コカ・コーラ株式会社商品名）を低温で充填し、コーティングされたアルミ蓋を巻締め、２日間室温に保管した後０℃に１日貯蔵した後、０℃のままで缶底の接地部に重さ６００ｇの直角ブロックを高さ５０ｍｍから直角部が缶底の接地部に衝突するように落として衝撃的変形をあたえた後、開缶し缶胴の衝撃変形部を通電測定し、０．１ｍＡ未満を良好（〇）、０．１ｍＡ以上を不良（×）と評価した。通電測定は、１％ＮａＣｌ溶液を用い電極（陰極）と缶体との間に６．０ｖの電圧をかけ、流れる電流を測定した。
【００３０】
（実施例６）
板厚０．２６ｍｍ、５０１７系合金のアルミニウム板の片方の表面に厚み２５μｍの単層の融点２２５℃のテレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルフィルムを積層した。
樹脂皮膜積層面側のアルミニウム板の表面粗度Ｒａは０．５１μｍであった。樹脂皮膜の表面粗度Ｒａは０．１８μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理を行った後樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は４．５ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験２での通電値は良好（０．０８ｍＡ）であった。
【００３１】
（実施例７）
片側の表面に付着量２．８ｇ／ｍ2 の錫めっきを、他の片面には付着量１．０ｇ／ｍ2 の錫めっき後に化成処理を施した鋼板｛板厚０．２４ｍｍ、硬度（ＨＲ３０Ｔ）６１｝の付着量１．０ｇ／ｍ2 側の表面に厚み３０μｍの単層のポリアミドフィルム（ナイロン６融点２２０℃）を積層した。
付着量１．０ｇ／ｍ2 側の鋼板の表面粗度Ｒａは０．６２μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理を行った後樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は７．２ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、３回絞り成形より深絞り缶を作成した。缶底接地部耐衝撃性試験２での通電値は良好（０．０３ｍＡ）であった。
【００３２】
（実施例８）
実施例７と同じ鋼板の付着量１．０ｇ／ｍ2 側の表面に厚み３５μｍの２層構造のポリエステル系フィルム（表面層が３μｍで接着層が３２μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはポリアミド樹脂を衝撃吸収樹脂として平均粒子径０．２μｍとして１５ｗｔ％分散させた。また表面層の融点２３０℃接着層の融点２２０℃とした。
付着量１．０ｇ／ｍ2 側の鋼板の表面粗度Ｒａは０．３０μｍであった。樹脂皮膜の表面粗度Ｒａは０．２３μｍであった。
この樹脂積層鋼板を２２０℃で１０分間の熱処理を行った後樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．６ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験２を行った。缶底接地部耐衝撃性試験２での通電値は良好（０．０６ｍＡ）であった。
【００３３】
（比較例３）
実施例５と同じ鋼板のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が２μｍで接着層が２８μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルである。また表面層の融点２３０℃接着層の融点２１５℃とした。
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．４５μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理を行った後樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は３．６ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験２を行った。缶底接地部耐衝撃性試験２での通電値は不良（０．５ｍＡ）であった。
【００３４】
（比較例４）
実施例５と同じ鋼板のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が２μｍで接着層が２８μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはポリアミド樹脂を衝撃吸収樹脂として平均粒子径０．２μｍとして１５ｗｔ％分散させた。また表面層の融点２３０℃接着層の融点２２０℃とした。
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．９１μｍであった。樹脂皮膜の表面粗度Ｒａは０．１０μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理を行った後樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．５ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験２を行った。缶底接地部耐衝撃性試験２での通電値は不良（０．４ｍＡ）であった。
【００３５】
（実施例９）
片側の表面に付着量２．８ｇ／ｍ2 の錫めっき層を有し、他の片面にはＳｎ及びＮｉ付着量として各々１．０ｇ／ｍ2 、０．２５ｇ／ｍ2 をＮｉ、Ｓｎの順にめっき後化成処理を施したＳｎ／Ｎｉめっき層を有する鋼板｛板厚０．２４ｍｍ、硬度（ＨＲ３０Ｔ）６１｝のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が３μｍで接着層が２７μｍ）を積層した。なお、ポリエステル系フィルムは表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはスチレンブタジエンラバーを衝撃吸収樹脂として平均粒子径０．２μｍとして９ｗｔ％分散させた。また表面層の融点２２８℃接着層の融点２１３℃とした。
【００３６】
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．４１μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理後１２０℃で３０分のレトルト処理を行った後、樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．２ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験３を行った。缶底接地部耐衝撃性試験３での通電値は良好（０．０１ｍＡ）であった。
【００３７】
（３）缶底接地部耐衝撃性試験３
成形加工後、缶体外面に印刷を施しその後２１０℃で５分間の焼付けを施した缶体にウーロン茶を充填し、コーティングされたアルミ蓋を巻締め、１２０℃で３０分のレトルト処理を行い２日間室温に保管した後２０℃に１日貯蔵した後、２０℃のままで缶底の接地部に重さ６００ｇの直角ブロックを高さ５０ｍｍから直角部が缶底の接地部に衝突するように落として衝撃的変形をあたえた後、開缶し缶胴の衝撃変形部を通電測定し、０．１ｍＡ未満を良好（〇）、０．１ｍＡ以上を不良（×）と評価した。通電測定は、１％ＮａＣｌ溶液を用い電極（陰極）と缶体との間に６．０ｖの電圧をかけ、流れる電流を測定した。
【００３８】
（実施例１０）
板厚０．２６ｍｍ、５０１７系合金のアルミニウム板の片方の表面に厚み２５μｍの単層の融点２２５℃のテレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルフィルムを積層した。
樹脂皮膜積層面側のアルミニウム板の表面粗度Ｒａは０．５１μｍであった。樹脂皮膜の表面粗度Ｒａは０．１８μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理後１２０℃で３０分のレトルト処理を行った後、樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は４．１ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験３での通電値は良好（０．０９ｍＡ）であった。
【００３９】
（実施例１１）
片側の表面に付着量２．８ｇ／ｍ2 の錫めっきを、他の片面には付着量１．０ｇ／ｍ2 の錫めっき後に化成処理を施した鋼板｛板厚０．２４ｍｍ、硬度（ＨＲ３０Ｔ）６１｝の付着量１．０ｇ／ｍ2 側の表面に厚み３０μｍの単層のポリアミドフィルム（ナイロン６融点２２０℃）を積層した。
付着量１．０ｇ／ｍ2 側の鋼板の表面粗度Ｒａは０．６２μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理後１２０℃で３０分のレトルト処理を行った後、樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は７．０ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、３回絞り成形より深絞り缶を作成した。缶底接地部耐衝撃性試験３での通電値は良好（０．０４ｍＡ）であった。
【００４０】
（実施例１２）
実施例１１と同じ鋼板の付着量１．０ｇ／ｍ2 側の表面に厚み３５μｍの２層構造のポリエステル系フィルム（表面層が３μｍで接着層が３２μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはポリアミド樹脂を衝撃吸収樹脂として平均粒子径０．２μｍとして１５ｗｔ％分散させた。また表面層の融点２３０℃接着層の融点２２０℃とした。付着量１．０ｇ／ｍ2 側の鋼板の表面粗度Ｒａは０．３０μｍであった。樹脂皮膜の表面粗度Ｒａは０．２３μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理後１２０℃で３０分のレトルト処理を行った後、樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．３ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験３を行った。缶底接地部耐衝撃性試験３での通電値は良好（０．０７ｍＡ）であった。
【００４１】
（比較例５）
実施例９と同じ鋼板のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が２μｍで接着層が２８μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルである。また表面層の融点２３０℃接着層の融点２１５℃とした。
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．４５μｍであった。樹脂皮膜の表面粗度Ｒａは０．０５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理後１２０℃で３０分のレトルト処理を行った後、樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は３．５ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験３を行った。缶底接地部耐衝撃性試験３での通電値は不良（０．６ｍＡ）であった。
【００４２】
（比較例６）
実施例９と同じ鋼板のＳｎ／Ｎｉめっき層面に、厚み３０μｍの２層構造のポリエステル系フィルム（表面層が２μｍで接着層が２８μｍ）を積層した。なお、表面層及び接着層とも、テレフタル酸、イソフタル酸とエチレングリコールからなるポリエステルであり、接着層にはポリアミド樹脂を衝撃吸収樹脂として平均粒子径０．２μｍとして１５ｗｔ％分散させた。また表面層の融点２３０℃接着層の融点２２０℃とした。
Ｓｎ／Ｎｉめっき層側の鋼板の表面粗度Ｒａは０．９１μｍであった。樹脂皮膜の表面粗度Ｒａは０．１５μｍであった。この樹脂積層鋼板を２２０℃で１０分間の熱処理後１２０℃で３０分のレトルト処理を行った後、樹脂皮膜を単離して測定した樹脂皮膜の衝撃強度値は８．２ｇ・ｃｍ／厚μｍであった。
樹脂皮膜を缶内面となるようにして、２回絞り３回しごき成形より絞りしごき缶を作成した。缶底接地部耐衝撃性試験３を行った。缶底接地部耐衝撃性試験３での通電値は不良（０．４ｍＡ）であった。
【００４３】
【発明の効果】
以上述べたように、本発明による鋼板の表面粗度と樹脂皮膜の衝撃強度値の限定の相互作用効果により、缶形状に成形後に落下等の衝撃を受けても熱可塑性樹脂皮膜に亀裂やピンホールの入りにくい絞り缶及び絞りしごき缶用の耐衝撃性に優れた熱可塑性樹脂積層金属板にある。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a thermoplastic resin laminated metal plate for a metal container, and more particularly, a drawn can and a drawn plate in which a thermoplastic resin film is not easily cracked or pinholed even when subjected to an impact such as dropping after being formed into a can shape. The present invention relates to a thermoplastic resin laminated metal plate for ironing cans.
[0002]
[Prior art]
Conventionally, the inner surface of metal cans is generally painted to prevent corrosion, but there is a development that uses a metal plate laminated with thermoplastic resin on the surface without using an organic solvent as a metal plate for containers. It is done. (1) A method of laminating a biaxially oriented polyethylene terephthalate film through a low-melting polyester adhesive layer and using it as a can-making material (JP 56-10451, JP-B 1-192546, etc.), (2) A method of laminating an amorphous or low crystallinity aromatic polyester film on a metal plate and using it as a can-making material (JP-A-1-192545, JP-A-2-57339, etc.), (3) A method of laminating a low-orientation polyethylene terephthalate film on a metal plate and using it as a can-making material (Japanese Patent Laid-Open No. 64-22530) etc. Methods (JP-A-6-297644, JP-A-6-320658, etc.) have been proposed.
[0003]
Further, since the impact resistance of the thermoplastic resin film is not sufficient, there is a problem that after the contents are filled, the thermoplastic resin film is cracked by the impact of transportation or dropping, and the metal is eluted or corroded. As a countermeasure for that, as a method for improving the impact resistance of the polyester resin film, a method for defining the intrinsic viscosity and the degree of orientation of the can wall film after processing (JP-A-7-178485) has been proposed. However, particularly in the case of a drawn and ironed can, the thermoplastic resin film before processing desirably has an amorphous structure in order to follow the drawn and ironed processing. In the case of an amorphous structure film, the squeezing and squeezing process is performed on the side wall of the can, and orientation crystallization occurs, but the orientation crystallization does not occur on the bottom of the can. For this reason, the impact resistance of the bottom of the can is insufficient, and the improvement has been eagerly desired.
[0004]
[Problems to be solved by the invention]
This invention is made | formed in view of the said situation, and aims at providing the thermoplastic resin laminated metal plate excellent in impact resistance.
[0005]
[Means for Solving the Problems]
The present invention has been made to solve the above problems,
(1) At least a thermoplastic resin film having an impact strength value of 4.0 g · cm / thickness μm or more when heat treatment is not performed on the surface of a metal plate having a surface roughness Ra of 0.7 μm or less which is an inner surface of the container A thermoplastic resin laminated metal plate having excellent impact resistance.
(2) A thermoplastic resin having an impact strength value of at least 4.0 g · cm / thickness μm after heat treatment at 220 ° C. for 10 minutes on a metal plate surface having a surface roughness Ra of 0.7 μm or less, which is at least the inner surface of the container A thermoplastic resin laminated metal plate excellent in impact resistance, characterized by having a film.
[0006]
(3) The impact strength value after a heat treatment at 220 ° C. for 10 minutes and a retort treatment at 120 ° C. for 30 minutes on the surface of a metal plate having a surface roughness Ra of 0.7 μm or less, which is at least the inner surface of the container, is 4.0 g · cm. / A thermoplastic resin laminated metal plate having excellent impact resistance, characterized by having a thermoplastic resin film having a thickness of at least μm.
(4) At least a thermoplastic resin film having an impact strength value of 8.0 g · cm / thickness μm or more is provided on the surface of a metal plate having a surface roughness Ra of 0.7 μm or less, which is an inner surface of the container. Thermoplastic resin laminated metal plate with excellent impact properties.
[0007]
(5) A thermoplastic resin having an impact strength value of not less than 8.0 g · cm / thickness μm after heat treatment at 220 ° C. for 10 minutes on a metal plate surface having a surface roughness Ra of 0.7 μm or less, which is at least the inner surface of the container. A thermoplastic resin laminated metal plate excellent in impact resistance, characterized by having a film.
(6) The impact strength value after a heat treatment at 220 ° C. for 10 minutes and a retort treatment at 120 ° C. for 30 minutes on the surface of a metal plate having a surface roughness Ra of 0.7 μm or less that is at least the inner surface of the container is 8.0 g · cm. / A thermoplastic resin laminated metal plate having excellent impact resistance, characterized by having a thermoplastic resin film having a thickness of at least μm.
[0008]
(7) The thermoplastic resin laminated metal plate having excellent impact resistance according to the above (1) to (6), wherein the surface roughness Ra of the thermoplastic resin film is 0.20 μm or less.
(8) The thermoplastic resin laminated metal plate having excellent impact resistance according to the above (1) to (7), wherein the thermoplastic resin is mainly a polyester composition.
[0009]
The present invention is described in detail below.
The resin film on the surface of the metal plate having a surface roughness Ra of 0.7 μm or less, which is at least the inner surface of the container, of the thermoplastic resin laminated metal plate in the present invention is left as it is after heat treatment at 220 ° C. for 10 minutes or further 120 It is important that the thermoplastic resin film has an impact strength value of 4.0 g · cm / thickness μm or more after retorting for 30 minutes at a temperature.
[0010]
As a result of various studies, in particular, in order to improve the impact resistance of the bottom of the squeezed iron can, the surface roughness Ra of the metal plate serving as the inner surface of the container is 0.7 μm or less and on the surface of the metal plate. The thermoplastic resin film after the heat treatment at 220 ° C. for 10 minutes or after the retort treatment at 120 ° C. for 30 minutes has an impact strength value of 4.0 g · cm / thickness μm or more. If this is the case, the thermoplastic resin film will not crack even if it is transported after being molded into a can and filled with contents, or if it is subjected to a drop impact. It has been found that this is not the case and has led to the present invention.
[0011]
When the impact strength value of the thermoplastic resin film laminated on the metal plate is less than 4.0 g · cm / thickness μm, heat is generated when the container is molded and filled with contents and subjected to impact of transportation or dropping. There are problems that cracks occur in the plastic resin film, and that metal is eluted and corroded. Even when the impact strength value of the thermoplastic resin film itself is high, if the surface roughness Ra of the metal plate is more than 0.7 μm, it may be subjected to transportation or dropping impact after being molded into a can and filled with contents. It has also been found that cracks may occur in the thermoplastic resin film, and metal may be eluted or corroded. That is, the present inventors have discovered the interaction effect of limiting the surface roughness of the steel sheet and the impact strength value of the resin film, and have completed the present invention based on this.
[0012]
If the surface roughness is high, the adhesion between the film and the metal plate may be insufficient, but apart from this, when the metal plate is deformed by impact, the deformation or impact is large in a very small area. However, it is presumed that the occurrence of cracks may cause cracks in the film.
When the can body is subjected to an outer surface coating or printing baking process or a retort process at the time of filling, the thermoplastic resin film undergoes crystallization and hydrolysis, so that the impact strength value changes. For this reason, it is necessary to consider after filling. Therefore, it is desirable that the thermoplastic resin film has an impact strength value of 4.0 g · cm / thickness μm or more after heat treatment at 220 ° C. for 10 minutes or after retorting at 120 ° C. for 30 minutes.
The impact strength value of the thermoplastic resin film is more preferably 8.0 g · cm / thickness μm or more.
[0013]
The impact strength value of the thermoplastic resin film in the present invention is determined after the heat treatment at 220 ° C. for 10 minutes or after the retort treatment at 120 ° C. for 30 minutes with the film laminated on the metal plate. It can be determined by dissolving the plate with hydrochloric acid and isolating the resin film, and using an impact tester manufactured by Toyo Seiki Co., Ltd., and making the impact head a hemisphere with a diameter of 1 inch.
A steel plate, a surface-treated steel plate, an aluminum plate, an aluminum alloy plate, or the like can be used as the metal plate serving as a base material of the thermoplastic resin laminated metal plate of the present invention. Although not particularly limited, as a steel plate, a plate thickness t is usually used. 0 : A range of 0.12 to 0.60 mm and a hardness (HR30T) of 46 to 7 are desirable.
[0014]
The surface of this steel sheet is plated with one or more of Sn, Cr, Ni, Al, Zn, and the adhesion, workability, and corrosion resistance are eliminated on the chromate-treated film to eliminate the need for coating. It is desirable that an excellent resin film is laminated.
As a specific example, the adhesion amount is 0.5 to 5.0 g / m. 2 Tin-plated steel sheet with post-tin plating treatment, 0.3 to 2.0 g / m 2 Nickel-plated steel sheet subjected to chemical conversion treatment after nickel plating, and the amount of Sn and Ni deposited is 0.5 to 2.0 g / m, respectively. 2 0.01-0.5 g / m 2 Sn / Ni-plated steel sheet that is subjected to post-plating chemical conversion treatment in the order of Ni and Sn, metal Cr adhesion amount 50 to 200 mg / m 2 , Cr oxide 5 to 30 mg / m 2 There is a chromium-chromate-treated steel sheet, which is usually called TFS (Tin Free Steel).
[0015]
In addition, the aluminum plate used in the present invention is usually a plate thickness t. 0 : The range is 0.18 to 0.60 mm, and the alloy composition is 5052, 5082, 5182, 5352, 5349, 5017, and the tempering is preferably H19. A surface-treated metal plate obtained by subjecting this aluminum plate to chromate treatment, zircomate treatment or phosphoric acid-chromic acid chemical conversion treatment can also be used.
In the present invention, the surface roughness Ra of the thermoplastic resin film is desirably 0.20 μm or less. If the surface roughness Ra exceeds 0.20 μm, the moldability in drawing and / or ironing tends to be reduced, and the impact resistance of the resin film may be reduced due to drawing and / or ironing. The surface roughness Ra of the thermoplastic resin film is preferably 0.20 μm or less.
[0016]
Examples of the resin film in the present invention include polyester resins, nylon resins, olefin resins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, modified olefin resins such as ionomers, polyvinyl alcohol and copolymers thereof, and acrylic resins. Examples thereof include a single layer and a multilayer film of a resin composed of a simple substance and a mixture thereof.
[0017]
Among them, the polyester composition is preferred mainly from the viewpoint of cost and flavor. Although it does not specifically limit as a polyester composition, The following examples can be given as a typical thing. Acid components include aromatic dibasic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecadioic acid, dimer acid and cyclohexanedicarboxylic acid. Examples thereof include alicyclic dicarboxylic acids. Examples of the alcohol component include aliphatic diols such as ethylene glycol, diethylene glycol, butanediol, and hexanediol. These are used in combination of one or more. For example, as a preferable example, a polyester composition comprising 75 mol% or more of terephthalic acid as an acid component and 85 mol% or more of ethylene glycol as an alcohol component can be mentioned.
[0018]
Further, the resin film may have a two-layer structure of a surface layer and an adhesive layer, and a structure in which an impact absorbing resin such as a polyolefin resin or styrene butadiene rubber is dispersed in the adhesive layer may be used.
Moreover, the resin film thickness in this invention is although it does not specifically limit, About 2-80 micrometers is suitable, Preferably it is 8-60 micrometers, More preferably, it is the range of 12-40 micrometers. The thickness ratio between the surface layer and the adhesive layer is not particularly limited, but the thickness of the surface layer is preferably 1 to 10 μm.
[0019]
【Example】
Examples of the present invention and comparative examples will be described.
Example 1
2.8 g / m on the surface of one side 2 The other one side has a Sn and Ni adhesion amount of 1.0 g / m each. 2 2.5 g / m 2 A steel sheet having a Sn / Ni plating layer that has been subjected to a chemical conversion treatment after plating in the order of Ni and Sn, and a two-layer polyester having a thickness of 30 μm on the Sn / Ni plating layer surface of 0.24 mm thickness and hardness (HR30T) 61} A system film (the surface layer was 3 μm and the adhesive layer was 27 μm) was laminated. The polyester film is a polyester composed of terephthalic acid, isophthalic acid and ethylene glycol for both the surface layer and the adhesive layer, and styrene butadiene rubber is dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and dispersed by 9 wt%. It was. The melting point of the surface layer was 228 ° C., and the melting point of the adhesive layer was 213 ° C.
[0020]
The surface roughness Ra of the steel sheet on the Sn / Ni plating layer side was 0.41 μm. The surface roughness Ra of the resin film was 0.05 μm. The impact strength value of the resin film measured by isolating the resin film of the resin-laminated steel sheet was 9.0 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 1 was performed. The energization value in can bottom grounding portion impact resistance test 1 was good (0.01 mA).
[0021]
(1) Can bottom grounding part impact resistance test 1
Coca-Cola (Nippon Coca-Cola Co., Ltd. trade name) is filled into the molded can body at a low temperature, the coated aluminum lid is wrapped, stored at room temperature for 2 days, and stored at 0 ° C. for 1 day. At 600 ° C, a right-angle block weighing 600g was dropped from the height of 50mm so that the right-angled part collided with the grounding part of the can bottom. The impact deformation part was measured by energization, and less than 0.1 mA was evaluated as good (◯), and 0.1 mA or more was evaluated as defective (x). In the current measurement, a 1% NaCl solution was used, a voltage of 6.0 V was applied between the electrode (cathode) and the can, and the flowing current was measured.
[0022]
(Example 2)
An ethylene copolymer polypropylene film having a melting point of 150 ° C. having a thickness of 25 μm was laminated on one surface of an aluminum plate having a thickness of 0.26 mm and a 5017 series alloy.
The surface roughness Ra of the aluminum plate on the resin film lamination surface side was 0.51 μm. The surface roughness Ra of the resin film was 0.18 μm. The impact strength value of the resin film measured by isolating the resin film of the resin-laminated steel sheet was 5.0 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. The energization value in can bottom grounding portion impact resistance test 1 was good (0.07 mA).
[0023]
(Example 3)
2.8 g / m on the surface of one side 2 Tin plating on the other side of 1.0g / m 2 Steel plate {plate thickness 0.24 mm, hardness (HR30T) 61} deposited amount 1.0 g / m 2 A single-layer polyamide film (nylon 6 melting point 220 ° C.) having a thickness of 30 μm was laminated on the surface on the side. Adhesion amount 1.0g / m 2 The surface roughness Ra of the steel plate on the side was 0.62 μm. The surface roughness Ra of the resin film was 0.10 μm. The impact strength value of the resin film measured by isolating the resin film of this resin laminated steel sheet was 7.4 g · cm / thickness μm.
A deep-drawn can was created by three-time drawing with the resin film on the inner surface of the can. The energization value in can bottom grounding portion impact resistance test 1 was good (0.02 mA).
[0024]
Example 4
The same steel sheet adhesion amount as Example 3 1.0 g / m 2 A polyester film having a two-layer structure with a thickness of 35 μm (a surface layer of 3 μm and an adhesive layer of 32 μm) was laminated on the surface on the side. Both the surface layer and the adhesive layer were polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol, and a polyamide resin was dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and 15 wt%. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 220 ° C.
Adhesion amount 1.0g / m 2 The surface roughness Ra of the steel plate on the side was 0.30 μm. The surface roughness Ra of the resin film was 0.23 μm.
The impact strength value of the resin film measured by isolating the resin film was 9.0 g · cm / thickness μm. A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 1 was performed. The energization value in can bottom grounding portion impact resistance test 1 was good (0.06 mA).
[0025]
(Comparative Example 1)
On the Sn / Ni plating layer surface of the same steel plate as in Example 1, a 30 μm thick two-layer polyester film (the surface layer was 2 μm and the adhesive layer was 28 μm) was laminated. The surface layer and the adhesive layer are both polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 215 ° C.
The surface roughness Ra of the steel plate on the Sn / Ni plating layer side was 0.45 μm. The surface roughness Ra of the resin film was 0.05 μm. The impact strength value of the resin film measured by isolating the resin film of the resin-laminated steel sheet was 3.7 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 1 was performed. The energization value in can bottom grounding portion impact resistance test 1 was poor (0.4 mA).
[0026]
(Comparative Example 2)
A polyester film having a two-layer structure with a thickness of 30 μm (a surface layer of 2 μm and an adhesive layer of 28 μm) was laminated on the plated layer surface of Sn / Ni of the same steel plate as in Example 1. The surface layer and the adhesive layer are both polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol. In the adhesive layer, a polyamide resin was dispersed as an impact absorbing resin at an average particle diameter of 0.2 μm and dispersed by 15 wt%. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 220 ° C.
The surface roughness Ra of the steel plate on the Sn / Ni plating layer side was 0.91 μm. The surface roughness Ra of the resin film was 0.15 μm. The impact strength value of the resin film measured by isolating the resin film of this resin-laminated steel sheet was 8.5 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 1 was performed. The energization value in can bottom grounding portion impact resistance test 1 was poor (0.2 mA).
[0027]
(Example 5)
2.8 g / m on the surface of one side 2 The other one side has a Sn and Ni adhesion amount of 1.0 g / m each. 2 0.25 g / m 2 A steel sheet having a Sn / Ni plating layer that has been subjected to a chemical conversion treatment after plating in the order of Ni and Sn, and a two-layer polyester having a thickness of 30 μm on the Sn / Ni plating layer surface of 0.24 mm thickness and hardness (HR30T) 61} A system film (the surface layer was 3 μm and the adhesive layer was 27 μm) was laminated. The polyester film is a polyester composed of terephthalic acid, isophthalic acid and ethylene glycol for both the surface layer and the adhesive layer, and styrene butadiene rubber is dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and dispersed by 9 wt%. It was. The melting point of the surface layer was 228 ° C., and the melting point of the adhesive layer was 213 ° C.
[0028]
The surface roughness Ra of the steel sheet on the Sn / Ni plating layer side was 0.41 μm. The surface roughness Ra of the resin film was 0.05 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes, and the impact strength value of the resin film measured by isolating the resin film was 8.7 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 2 was performed. The energization value in the can bottom contact portion impact resistance test 2 was good (0.01 mA).
[0029]
(2) Can bottom grounding part impact resistance test 2
After the molding process, the outer surface of the can is printed, and then the can body that has been baked at 210 ° C for 5 minutes is filled with Coca-Cola (Nippon Coca-Cola Co., Ltd.) at a low temperature, and the coated aluminum lid is applied. Clamping, storage at room temperature for 2 days, storage at 0 ° C for 1 day, and then keep the 0 ° C at the grounding part of the can bottom with a right-angle block weighing 600g from the height of 50mm to the grounding part of the can bottom After impacting and dropping so as to collide, the can was opened and the impact deformation part of the can body was energized, and less than 0.1 mA was evaluated as good (◯) and 0.1 mA or more was evaluated as poor (x). . In the current measurement, a 1% NaCl solution was used, a voltage of 6.0 V was applied between the electrode (cathode) and the can, and the flowing current was measured.
[0030]
(Example 6)
A polyester film made of terephthalic acid, isophthalic acid and ethylene glycol having a melting point of 225 ° C. and a single layer having a thickness of 25 μm was laminated on one surface of an aluminum plate having a thickness of 0.26 mm and a 5017 series alloy.
The surface roughness Ra of the aluminum plate on the resin film lamination surface side was 0.51 μm. The surface roughness Ra of the resin film was 0.18 μm. The resin laminated steel sheet was heat treated at 220 ° C. for 10 minutes, and the impact strength value of the resin film measured by isolating the resin film was 4.5 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. The energization value in the can bottom contact portion impact resistance test 2 was good (0.08 mA).
[0031]
(Example 7)
2.8 g / m on the surface of one side 2 Tin plating on the other side of 1.0g / m 2 Steel plate {plate thickness 0.24 mm, hardness (HR30T) 61} deposited amount 1.0 g / m 2 A single-layer polyamide film (nylon 6 melting point 220 ° C.) having a thickness of 30 μm was laminated on the surface on the side.
Adhesion amount 1.0g / m 2 The surface roughness Ra of the steel plate on the side was 0.62 μm. The surface roughness Ra of the resin film was 0.05 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes, and the impact strength value of the resin film measured by isolating the resin film was 7.2 g · cm / thickness μm.
A deep-drawn can was created by three-time drawing with the resin film on the inner surface of the can. The energization value in the can bottom contact portion impact resistance test 2 was good (0.03 mA).
[0032]
(Example 8)
The same steel sheet adhesion amount as Example 7 1.0g / m 2 A polyester film having a two-layer structure with a thickness of 35 μm (a surface layer of 3 μm and an adhesive layer of 32 μm) was laminated on the surface on the side. Both the surface layer and the adhesive layer were polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol, and a polyamide resin was dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and 15 wt%. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 220 ° C.
Adhesion amount 1.0g / m 2 The surface roughness Ra of the steel plate on the side was 0.30 μm. The surface roughness Ra of the resin film was 0.23 μm.
The impact strength value of the resin film was 8.6 g · cm / thickness μm measured by isolating the resin film after heat-treating the resin-laminated steel sheet at 220 ° C. for 10 minutes.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 2 was performed. The energization value in the can bottom contact portion impact resistance test 2 was good (0.06 mA).
[0033]
(Comparative Example 3)
On the Sn / Ni plating layer surface of the same steel plate as in Example 5, a polyester film having a two-layer structure with a thickness of 30 μm (the surface layer was 2 μm and the adhesive layer was 28 μm) was laminated. The surface layer and the adhesive layer are both polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 215 ° C.
The surface roughness Ra of the steel plate on the Sn / Ni plating layer side was 0.45 μm. The surface roughness Ra of the resin film was 0.05 μm. The resin laminated steel sheet was heat treated at 220 ° C. for 10 minutes, and the impact strength value of the resin film measured by isolating the resin film was 3.6 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 2 was performed. The energization value in the can bottom contact portion impact resistance test 2 was poor (0.5 mA).
[0034]
(Comparative Example 4)
On the Sn / Ni plating layer surface of the same steel plate as in Example 5, a polyester film having a two-layer structure with a thickness of 30 μm (the surface layer was 2 μm and the adhesive layer was 28 μm) was laminated. Both the surface layer and the adhesive layer were polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol, and a polyamide resin was dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and 15 wt%. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 220 ° C.
The surface roughness Ra of the steel plate on the Sn / Ni plating layer side was 0.91 μm. The surface roughness Ra of the resin film was 0.10 μm. The resin laminated steel sheet was heat treated at 220 ° C. for 10 minutes, and the impact strength value of the resin film measured by isolating the resin film was 8.5 g · cm / thickness μm.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 2 was performed. The energization value in the can bottom contact portion impact resistance test 2 was poor (0.4 mA).
[0035]
Example 9
2.8 g / m on the surface of one side 2 The other one side has a Sn and Ni adhesion amount of 1.0 g / m each. 2 0.25 g / m 2 A steel sheet having a Sn / Ni plating layer that has been subjected to a chemical conversion treatment after plating in the order of Ni and Sn, and a two-layer polyester having a thickness of 30 μm on the Sn / Ni plating layer surface of 0.24 mm thickness and hardness (HR30T) 61} A system film (the surface layer was 3 μm and the adhesive layer was 27 μm) was laminated. The polyester film is a polyester composed of terephthalic acid, isophthalic acid and ethylene glycol for both the surface layer and the adhesive layer, and styrene butadiene rubber is dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and dispersed by 9 wt%. It was. The melting point of the surface layer was 228 ° C., and the melting point of the adhesive layer was 213 ° C.
[0036]
The surface roughness Ra of the steel sheet on the Sn / Ni plating layer side was 0.41 μm. The surface roughness Ra of the resin film was 0.05 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes and then subjected to a retort treatment at 120 ° C. for 30 minutes, and the impact strength value of the resin film measured by isolating the resin film was 8.2 g · cm / thickness μm. there were.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 3 was performed. The energization value in the can bottom contact portion impact resistance test 3 was good (0.01 mA).
[0037]
(3) Can bottom grounding part impact resistance test 3
After the forming process, the outer surface of the can body is printed, and then the can body that has been baked at 210 ° C for 5 minutes is filled with oolong tea, the coated aluminum lid is wound, and the retort treatment is performed at 120 ° C for 30 minutes. After storing at room temperature for 1 day and storing at 20 ° C for 1 day, keep the 20 ° C at a grounding part of the bottom of the can with a 600g weight right angle block from 50mm in height so that the right angle part collides with the grounding part of the can bottom. After dropping and giving impact deformation, the can was opened, and the impact deformation portion of the can body was measured by energization, and less than 0.1 mA was evaluated as good (◯), and 0.1 mA or more was evaluated as defective (×). In the current measurement, a 1% NaCl solution was used, a voltage of 6.0 V was applied between the electrode (cathode) and the can, and the flowing current was measured.
[0038]
(Example 10)
A polyester film made of terephthalic acid, isophthalic acid and ethylene glycol having a melting point of 225 ° C. and a single layer having a thickness of 25 μm was laminated on one surface of an aluminum plate having a thickness of 0.26 mm and a 5017 series alloy.
The surface roughness Ra of the aluminum plate on the resin film lamination surface side was 0.51 μm. The surface roughness Ra of the resin film was 0.18 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes and then subjected to a retort treatment at 120 ° C. for 30 minutes. The impact strength value of the resin film measured by isolating the resin film was 4.1 g · cm / thickness μm. there were.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. The energization value in the can bottom grounding portion impact resistance test 3 was good (0.09 mA).
[0039]
(Example 11)
2.8 g / m on the surface of one side 2 Tin plating on the other side of 1.0g / m 2 Steel plate {plate thickness 0.24 mm, hardness (HR30T) 61} deposited amount 1.0 g / m 2 A single-layer polyamide film (nylon 6 melting point 220 ° C.) having a thickness of 30 μm was laminated on the surface on the side.
Adhesion amount 1.0g / m 2 The surface roughness Ra of the steel plate on the side was 0.62 μm. The surface roughness Ra of the resin film was 0.05 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes and then subjected to a retort treatment at 120 ° C. for 30 minutes, and the impact strength value of the resin film measured by isolating the resin film was 7.0 g · cm / thickness μm. there were.
A deep-drawn can was created by three-time drawing with the resin film on the inner surface of the can. The energization value in the can bottom contact portion impact resistance test 3 was good (0.04 mA).
[0040]
(Example 12)
The same steel sheet adhesion amount as Example 11 1.0g / m 2 A polyester film having a two-layer structure with a thickness of 35 μm (a surface layer of 3 μm and an adhesive layer of 32 μm) was laminated on the surface on the side. Both the surface layer and the adhesive layer were polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol, and a polyamide resin was dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and 15 wt%. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 220 ° C. Adhesion amount 1.0g / m 2 The surface roughness Ra of the steel plate on the side was 0.30 μm. The surface roughness Ra of the resin film was 0.23 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes and then subjected to a retort treatment at 120 ° C. for 30 minutes, and the impact strength value of the resin film measured by isolating the resin film was 8.3 g · cm / thickness μm. there were.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 3 was performed. The energization value in can bottom grounding portion impact resistance test 3 was good (0.07 mA).
[0041]
(Comparative Example 5)
On the Sn / Ni plating layer surface of the same steel plate as in Example 9, a 30 μm thick two-layer polyester film (2 μm surface layer and 28 μm adhesive layer) was laminated. The surface layer and the adhesive layer are both polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 215 ° C.
The surface roughness Ra of the steel plate on the Sn / Ni plating layer side was 0.45 μm. The surface roughness Ra of the resin film was 0.05 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes and then subjected to a retort treatment at 120 ° C. for 30 minutes, and the impact strength value of the resin film measured by isolating the resin film was 3.5 g · cm / thickness μm. there were.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 3 was performed. The energization value in the can bottom contact portion impact resistance test 3 was poor (0.6 mA).
[0042]
(Comparative Example 6)
On the Sn / Ni plating layer surface of the same steel plate as in Example 9, a 30 μm thick two-layer polyester film (2 μm surface layer and 28 μm adhesive layer) was laminated. Both the surface layer and the adhesive layer were polyesters composed of terephthalic acid, isophthalic acid and ethylene glycol, and a polyamide resin was dispersed in the adhesive layer as an impact-absorbing resin with an average particle diameter of 0.2 μm and 15 wt%. The melting point of the surface layer was 230 ° C., and the melting point of the adhesive layer was 220 ° C.
The surface roughness Ra of the steel plate on the Sn / Ni plating layer side was 0.91 μm. The surface roughness Ra of the resin film was 0.15 μm. The resin laminated steel sheet was heat-treated at 220 ° C. for 10 minutes and then subjected to a retort treatment at 120 ° C. for 30 minutes, and the impact strength value of the resin film measured by isolating the resin film was 8.2 g · cm / thickness μm. there were.
A squeezed and ironed can was prepared by two times of squeezing and three times of squeeze molding so that the resin film was on the inner surface of the can. Can bottom grounding portion impact resistance test 3 was performed. The energization value in the can bottom grounding portion impact resistance test 3 was poor (0.4 mA).
[0043]
【The invention's effect】
As described above, due to the interactive effect of limiting the surface roughness of the steel sheet and the impact strength value of the resin film according to the present invention, the thermoplastic resin film can be cracked or pinned even when subjected to an impact such as dropping after being formed into a can shape. It is a thermoplastic resin laminated metal plate excellent in impact resistance for use in squeezed cans and squeezed and squeezed cans that are difficult to enter holes.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37442998A JP3927329B2 (en) | 1998-12-28 | 1998-12-28 | Thermoplastic resin laminated metal plate for containers with excellent impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37442998A JP3927329B2 (en) | 1998-12-28 | 1998-12-28 | Thermoplastic resin laminated metal plate for containers with excellent impact resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000190423A JP2000190423A (en) | 2000-07-11 |
| JP3927329B2 true JP3927329B2 (en) | 2007-06-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP37442998A Expired - Fee Related JP3927329B2 (en) | 1998-12-28 | 1998-12-28 | Thermoplastic resin laminated metal plate for containers with excellent impact resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB0106046D0 (en) * | 2001-03-12 | 2001-05-02 | Glaxo Group Ltd | Canister |
| AU2003281685A1 (en) * | 2002-07-30 | 2004-02-16 | Toyo Kohan Co., Ltd. | Surface-roughened resin film, metal sheet coated with surface-roughened resin film, process for producing metal sheet coated with surface-roughened resin film, and metal can having surface coated with surface-roughened resin film and process for producing the same |
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