JP4065693B2 - Resin-coated metal plate and method for producing the same - Google Patents

Abstract

A resin-coated metal sheet which comprises a metal sheet, a thin chemical conversion coating film formed on the surface of the metal sheet, a thin film of a silane coupling agent formed on the surface of the coating film, and a coating film of a thermoplastic resin formed on the surface of the thin film. The resin-coated metal sheet is excellent in adhesiveness (adhesive property or adhesion strength), and is free from the occurrence of delamination at the interface of an aluminum sheet and a thermoplastic resin coating film and the damage or cracks of the thermoplastic resin coating film and is less prone to delamination for a long period of time, even when it is subjected to deep drawing or ironing, and further, can be produced with good efficiency.

Description

【００６４】
（結果）
表１から、次のことが明らかとなる。
（１）陽極酸化被膜としてリン酸アルマイト処理被膜であって、厚さが０．０５〜２μｍの被膜を形成したものは、絞り加工性、かしめ加工性に優れ、各工程で界面に層間剥離が認められず、経時変化（劣化）も認められない（試験例２、試験例４、試験例５参照）。
（２）これに対して、リン酸アルマイト処理被膜を形成しても厚さが０．１μｍ未満の被膜を形成したもの（試験例１参照）は、かしめ加工工程で界面に層間剥離が認められ、著しい経時変化が認められる。しかしながら、それなりの絞り加工は可能である。
（３）また、おなじ陽極酸化被膜であってもリン酸クロメート処理被膜を形成したものは、絞り加工は問題ないものの、かしめ加工性に劣り、著しい経時変化（劣化）が認められる（試験例６参照）。
（４）さらに、おなじ陽極酸化被膜であってもシュウ酸アルマイト処理被膜を形成したものは、かしめ加工性、経時変化ともに著しく劣る（試験例７参照）。
（５）リン酸アルマイト処理被膜を形成しても、これにシランカップリング剤を塗布しなかったものは、かしめ加工性に劣り、著しい経時変化（劣化）が認められる（試験例３参照）。
【００６５】
（試験例８〜１２）
厚さが０．３ｍのアルミニウム板（ＪＩＳ Ａ１０５０ Ｈ２２）の両面に、２０％リン酸溶液により陽極酸化処理を施し、厚さが０．６μｍのリン酸アルマイト処理被膜を形成した。この被膜の上に、表２に示した官能基を有するシランカップリング剤を２０ｍｇ／ｍ^２塗布し、この塗布面を２８０℃に加熱した。加熱した塗布面に、別途製造した厚さが１５μｍのポリアミド６（融点２２３℃）のフィルムを重ね、一対の加圧ロールによって加圧して積層し、樹脂被覆金属板を得た。得られた樹脂被覆金属板につき、上記項目の評価試験を行った。評価試験結果を、表２に示す。
【００６６】
【表２】

【００６７】
（結果）
表２から、次のことが明らかとなる。
（１）シランカップリング剤を塗布したものは、絞り加工性、かしめ加工性に優れ、各工程で界面に層間剥離が認められず、経時変化（劣化）も認められない（試験例８〜１２参照）。
【００６８】
（試験例１３〜１５）
厚さが０．３ｍｍのアルミニウム板（ＪＩＳ Ａ１０５０ Ｈ２２）の両面に、２０％リン酸溶液により陽極酸化処理を施し、厚さが０．５μｍのリン酸アルマイト処理被膜を形成した。この被膜の上に、ウレイド基をもつシランカップリング剤を２０ｍｇ／ｍ^２塗布し、この塗布面を２５０℃に加熱した。加熱した塗布面に、表３に示した樹脂で別途製造した厚さが１５μｍのフィルムを重ね、一対の加圧ロールによって加圧して積層し、樹脂被覆金属板を得た。この得られた樹脂被覆金属板につき、上記項目の評価試験を行った。評価試験結果を、表３に示す。
【００６９】
【表３】

【００７０】
（結果）
表３から、次のことが明らかとなる。
（１）アルミニウム板の被覆膜がポリエステル系樹脂、ポリアミド系樹脂の場合は、絞り加工性、かしめ加工性に優れ、各工程で界面に層間剥離が認められず、経時変化（劣化）も認められない（試験例１３、試験例１４参照）。
（２）これに対して、被覆膜がポリプロピレンの場合には、絞り加工の工程で界面に層間剥離が認められ、絞り加工性に劣る（試験例１５参照）。
【００７１】
（試験例１６〜１９）
陽極酸化処理法を下記の方法とした以外は、試験例１３の方法に従って樹脂被覆金属板を得た。この得られた樹脂被覆金属板につき、上記項目の評価試験を行った。評価試験結果を、表５に示す。
（陽極酸化処理方法）
陽極酸処理条件は表４に示す電解質番号１〜４の方法に従って行った。
なお、電解質番号４で使用される有機酸は、ジカルボン酸（マレイン酸、マロン酸）、芳香族スルホン酸（スルホサリチル酸、スルホフタール酸）、カルボン酸スルホネート（スルホマレイン酸）、スルホン酸アミン（スルファミン酸）等から選ばれる。
また、その処理条件は、リン酸濃度：０．１〜５００ｇ／ｌ、硫酸・シュウ酸・クロム酸・上記有機酸のいずれかの濃度：０．１〜５００ｇ／ｌ、電圧：１〜１００ｖＡＣ、１〜１００ｖＤＣの単独又は重畳、時間：１〜６０分、薄膜厚：５０Å〜５０μｍ、リン酸アニオン含有率：１〜５０００ｐｐｍの範囲内とした。
【００７２】
【表４】

【００７３】
さらに、その他の条件として下記に示す条件を用いた。
・その他の条件番号１：リン酸アルマイト形成後、シランカップリング添加浴中にて交流電解若しくは直流電解（基材がマイナス極）した後、フィルムラミネートする。
・その他の条件番号２：リン酸アルマイト形成後、エポキシエマルジョン浴中にて交流電解若しくは直流電解（基材がマイナス極）した後、フィルムラミネートする。
・その他の条件番号３：リン酸アルマイト形成後、シランカップリング剤とエポキシエマルジョン混合浴中にて交流電解若しくは直流電解（基材がマイナス極）した後、フィルムラミネートする。
・その他の条件番号４：上記のその他の条件番号１〜３までの電解処理後、シランカップリング処理又はエポキシエマルジョンコートをした後に、フィルムラミネートする。
【００７４】
【表５】

【００７５】
［実験例２］
次に、別の評価に基づく試験例を示す。以下に示す試験例２０〜３３で用いた評価方法を示す。
【００７６】
（ａ）ビッカース硬度：調製した樹脂被覆金属板のアルミニウム薄板の樹脂被覆面について、ＪＩＳＺ２２４４「ビッカース硬さ試験一試験方法」に準拠してビッカース硬度を測定した。なお、硬度測定の際の荷重は、０．９８０７Ｎとした。
【００７７】
（ｂ）加工性：調製した樹脂被覆金属板を用い、ランス順送り絞り機によって７段の絞り加工を行ない、樹脂被覆層を容器外側面として１０ｍｍφ×２０ｍｍ高さの円筒容器（しごき率２０％）を作成し、層間の剥離状態を目視観察した。層間剥離が全く認められなかったものを「○」、層間剥離が認められたものを「×」と表示した。
【００７８】
（ｃ）凹み性：上記１０ｍφ×２０ｍｍ高さの円筒容器に、コンデンサー用素子を充填して封口用ゴムを入れてかしめ加工した試料容器を作成した。この試料容器１００個を２００ｍｍ×２００ｍｍ×２００ｍｍの紙製容器に入れて、１０ｃｍ／秒の振動速度で縦の振動を１時間加えた。１時間後に試料容器を取り出し、天面部の外観を観察した。この時に、試料容器の底部、側壁部に凹みが認められたものを「×」、凹みが認められなかったものを「○」と表示した。
【００７９】
（ｄ）総合評価：上記（ａ）〜（ｃ）の総ての評価項目において合格品質のものを「○」、一評価項目でも不合格のものを「×」と判定した。
【００８０】
［試験例２０］
厚さが０．３ｍｍのアルミニウム（ＪＩＳ Ａ １１００）板の表面を、５０℃とした１０％水酸化ナトリウム水溶液で３０秒間エッチングした後、１０％硝酸水溶液で中和処理を行ない、１０秒間水洗した。ついで、このアルミニウム板の片面に、リン酸クロメート化成処理薄膜（Ｃｒ＝２０ｍｇ／ｍ^２）を形成した。この化成処理薄膜の上に、カップリング剤としてのγ−アミノプロピルトリエトキシシランを５０ｍｇ／ｍ^２塗布して乾燥した後に、アルミニウム板を２１０℃の温度に加熱し、カップリング剤を塗布した面に、厚さが１５μｍのポリアミド６フィルムを圧着し、ポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表６に示した。
【００８１】
［試験例２１］
試験例２０に記載の例において、化成処理薄膜をシュウ酸アルマイト化成処理によって形成した厚さが１０００Åの薄膜に代え、カップリング剤をγ−グリシドキシプロピルトリエトキシシランに代え、アルミニウム板の温度を２５０℃にそれぞれ代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表６に示した。
【００８２】
［試験例２２］
試験例２１に記載の例において、化成処理薄膜をリン酸アルマイト化成処理によって形成した薄膜に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表６に示した。
【００８３】
［試験例２３］
試験例２１に記載の例において、化成処理薄膜をリン酸クロメート処理によって形成した薄膜に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表６に示した。
【００８４】
［試験例２４］
試験例２３に記載の例において、カップリング剤をγ−アミノプロピルトリエトキシシランに代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表６に示した。
【００８５】
［試験例２５］
試験例２０に記載の例において、カップリング剤を塗布しなかったほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表７に示した。
【００８６】
［試験例２６］
試験例２０に記載の例において、カップリング剤をγ−メタクリロキシプロピルトリメトキシシランに代え、アルミニウム板の温度を３８０℃にそれぞれ代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表７に示した。
【００８７】
［試験例２７］
試験例２３に記載の例において、アルミニウム板の温度を３８０℃に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表７に示した。
【００８８】
［試験例２８］
試験例２４に記載の例において、アルミニウム板の温度を２００℃に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表７に示した。
【００８９】
【表６】

【００９０】
【表７】

【００９１】
（結果）
表６および表７より、次のことが明らかとなる。
（１）アルミニウム薄板の表面に化成処理薄膜を設け、この上にシラン系カップリング剤の層を設け、アルミニウム薄板の温度を２００〜３５０℃の範囲に加熱して樹脂フィルムを被覆・圧着し、アルミニウム薄板の樹脂被覆面の硬度がビカース硬度で２５〜６０の範囲にある樹脂被覆金属板は、アルミニウム薄板と被覆フィルムとの密着性に優れてプレス加工する際に被覆フィルムが剥離せず、容器同士が接触しあっても、壁面に凹みが生じ難い（試験例２０〜２４参照）。
（２）これに対して、アルミニウム薄板の表面に化成処理薄膜を設けてもシラン系カップリング剤の層を設けず、樹脂フィルムを被覆・圧着したものは、プレス加工時に被覆フィルムが剥離する（試験例２５参照）。
（３）また、アルミニウム薄板の表面に化成処理薄膜を設け、この上にシラン系カップリング剤の層を設けても、アルミニウム薄板の温度を３５０℃よりも高くして被覆・圧着したものは、樹脂被覆金属板の表面硬度がビカース硬度で２５より小さくなり、容器同士が接触しあうと壁面に凹みが生じ易い（試験例２６〜２７参照）。
（４）さらに、アルミニウム薄板の表面に化成処理薄膜、およびシラン系カップリング剤の層を設け、この上にアルミニウム薄板の温度を２００℃で被覆・圧着しても、樹脂被覆金属板の樹脂被覆面の硬度がビッカース硬度で６０を超えるものは、プレス加工の際に基体のアルミニウム薄板が破損してしまう（試験例２８参照）。
【００９２】
［試験例２９］
試験例２０に記載の例において、カップリング剤の塗布量を１００ｍｇ／ｍ^２に代え、アルミニウム板の温度を２９０℃に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表８に示した。
【００９３】
［試験例３０］
試験例２３に記載の例において、カップリング剤の塗布量を５００ｍｇ／ｍ^２に代え、アルミニウム板の温度を２９０℃に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表８に示した。
【００９４】
［試験例３１］
試験例３０に記載の例において、カップリング剤の塗布量を１０００ｍｇ／ｍ^２に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表８に示した。
【００９５】
［試験例３２］
試験例２９に記載の例において、カップリング剤の塗布量を０．００５ｍｇ／ｍ^２に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表８に示した。
【００９６】
［試験例３３］
試験例３１に記載の例において、カップリング剤の塗布量を１３００ｍｇ／ｍ^２に代えたほかは、同例におけると同様の手順でポリアミド樹脂被覆金属板を得た。得られたポリアミド樹脂被覆金属板につき、上記評価方法で評価した結果を、表８に示した。
【００９７】
【表８】

【００９８】
（結果）
表８より、次のことが明らかとなる。
（１）アルミニウム薄板の表面に薄膜を設け、この上にシラン系カップリング剤の層を設け、この際のシラン系カップリング剤の塗布量を０．０１〜１０００ｍｇ／ｍ２の範囲としたものは、プレス加工性に優れ、容器同士が接触しあっても、壁面に凹みが生じ難い（試験例２９〜３１参照）。
（２）これに対して、シラン系カップリング剤の塗布量が０．００５ｍｇ／ｍ^２と少ない場合は、アルミニウム薄板と被覆フィルムとの密着性に劣り、プレス加工時に被覆フィルムが剥離した（試験例３２参照）。
（３）また、シラン系カップリング剤の塗布量を１３００ｍｇ／ｍ^２と多くした場合は、カップリング剤液の安定性が悪く、アルミニウム薄板の表面に均一に塗布することができなかった（試験例３３参照）。
【００９９】
［実験例３］
次に、別の評価に基づく試験例を示す。以下に示す試験例３４〜５２で用いた評価方法を示す。なお、シランカップリング剤水溶液の評価方法は、次の（１）及び（２）記載の方法によったものである。また、樹脂積層板の評価方法は、次の（３）乃至（６）記載の方法によったものである。
【０１００】
（１）接触角の測定：気温２３℃、湿度５０％の条件下で、準備した金属板の表面にシランカップリング剤水溶液を必要量滴下し、接触角計（協和界面科学社製、商品名：ＣＡ−Ａ）を用いてその接触角を測定する。
【０１０１】
（２）ぬれ性の評価：準備した金属板をＡ４サイズに切断し、この表面にシランカップリング剤水溶液をバーコーターを用いて１０ｇ／ｍ^２塗布し、塗膜の状態を目視観察する。観察結果は、はじきがなく均一な塗膜が形成されたものを○、はじいて塗膜が斑点状になったものを×と判定した。
【０１０２】
（３）Ｓｉ元素量の測定：樹脂積層板を調製する工程において、シランカップリング剤水溶液を金属板の表面に塗布して乾燥させて塗膜を形成した後、ＥＳＣＡ法（Ｘ線源：ＭｇＫα、出力：１５ｋｖ×３３ｍＡ、真空度：５×１０−８Ｔｏｒｒ）によって、上記塗膜の表面のＳｉ元素量（原子％）を測定する。
【０１０３】
（４）加工性の評価：樹脂積層板を、ランス順送り絞り機によって７段絞り加工して、熱可塑性樹脂薄膜を積層した面が容器外側面となるように、直径１０ｍｍで高さ２０ｍｍの円筒容器を調製し、金属板から熱可塑性樹脂薄膜が剥離しているか否かを目視観察する。観察結果は、剥離が全く認められないものを○、剥離が認められたものを×と判定した。
【０１０４】
（５）加工後密着性の評価：上記の加工性の評価用に調製した円筒容器を、２７０℃の熱風乾燥炉内に入れて１分間放置し、その後、この円筒容器を熱風乾燥炉からとり出し、容器外側面に積層された熱可塑性樹脂薄膜が剥離しているか否かを目視観察する。観察結果は、剥離が全く認められないものを○、剥離が認められたものを×と判定した。
【０１０５】
（６）総合評価：上記加工性・加工後密着性の双方が○と判定されたものを総合評価でも○と判定し、これら双方が×と判定されたもの、および、いずれか一方が×と判定されたものを総合評価では×と判定した。
【０１０６】
［試験例３４〜４５］
＜シランカップリング剤水溶液の調製＞ 水１００ｇに、シランカップリング剤と非イオン系界面活性剤（有効成分：ポリオキシエチレンアルキルエーテル、曇点：４２．１℃）とを、それぞれ表９に示した量配合して、４種類のシランカップリング剤水溶液を調製した。
【０１０７】
【表９】

【０１０８】
＜金属板の準備＞
厚さ０．３ｍｍのステンレス板（ＳＵＳ４３０−２Ｂ）、厚さ０．３ｍｍのリン酸クロメート酸処理を施したアルミニウム板（合金番号：Ａ１１００ＰＨ２４、クロム水和酸化物内のクロム量：２０ｍｇ／ｍ^２）、及び、厚さ０．３ｍｍの電解クロム酸処理鋼板（下層の金属クロム量：１００ｍｇ／ｍ^２、上層のクロム水和酸化物内のクロム量日１８ｍｇ／ｍ^２）の３種類の金属板を準備した。
【０１０９】
＜シランカップリング剤水溶液の評価＞
表９に示した４種類のシランカップリング剤水溶液を、上記３種類の金属板の表面にそれぞれ滴下し、前記した（１）の測定を行った。さらに、表９に示した４種類のシランカップリング剤水溶液を、上記３種類の金属板の表面にそれぞれ塗布し、前記した（２）の評価試験を行った。これらの結果を表１０に示す。
【０１１０】
【表１０】

【０１１１】
表９および表１０から、次のことが明らかとなる。
（イ）上記３種類の金属板の表面に４種類のシランカップリング剤水溶液を滴下して接触角を測定した結果、いずれの金属板においても，シランカップリング剤水溶液Ｉないしシランカップリング剤水溶液ＩＩＩの接触角は５５°以下であった（試験例３４〜３６、試験例３８〜４０、試験例４２〜４４参照）。これに対し、シランカップリング剤水溶液ＩＶの接触角は５５°より大きかった（試験例３７、４１、４５参照）。これは、シランカップリング剤水溶液ＩＶ中の非イオン系界面活性剤の量が不足しているためである。
【０１１２】
（ロ）また、上記３種類の金属板の表面に４種類のシランカップリング剤水溶液を塗布してぬれ性を評価した結果、シランカップリング剤水溶液Ｉないしシランカップリング剤水溶液ＩＩＩを塗布した金属板の表面にはいずれも均一な塗膜が形成され、ぬれ性が良好だった（試験例３４〜３６、試験例３８〜４０、試験例４２〜４４参照）。これに対し、シランカップリング剤水溶液ＩＶを塗布した金属板の表面にはいずれも均一な塗膜が形成されず（塗膜が斑点状になり、ぬれ性が劣っていた（試験例３７、４１、４５参照）。これは、シランカップリング剤水溶液ＩＶの接触角が５５°より大きいためである。
【０１１３】
［試験例４６］
アルミニウム板（試験例３８で準備したものと同種）を長尺帯状として連続的に移送し、このアルミニウム板の表面に、水１００ｇにシランカップリング剤（γ−アミノプロピルトリエトキシシラン）０．１ｇと非イオン系界面活性剤（試験例３４で使用したものと同種）０．４ｇとを配合して、上記アルミニウム板の表面に塗布した際の接触角を５０°に調整したシランカップリング剤水溶液１０ｇ／ｍ^２を塗布し、昇温速度５℃／ｓで乾燥させて塗膜を形成し、次いで、この塗膜を２５０℃で加熱し、この塗膜の表面に、融点が２２０℃で厚さが２０μｍのポリアミド６薄膜を積層して、樹脂積層板を調製した。この樹脂積層板を調製する工程において、前記（３）の測定を行い、得られた樹脂積層板について、前記（４）ないし（６）の評価試験を行った。これらの結果を表１１に示す。
【０１１４】
［試験例４７〜５２］
試験例４６に記載の例において、シランカップリング剤の種類および配合量、シランカップリング剤水溶液塗布後の乾燥の際の昇温速度（塗膜の加熱温度、熱可塑性樹脂薄膜の種類を、それぞれ表１１に記載したものに変更したほかは、同例におけると同種の手法で樹脂積層板を調製した。これらの樹脂積層板を調製する工程において、同例におけると同様に測定を行い、得られた樹脂積層板について、同例におけると同様に評価試験を行った。これらの結果を表１１に示す。
【０１１５】
【表１１】

【０１１６】
表１０及び表１１から、次のことが明らかとなる。
（ハ）シランカップリング剤の配合量、シランカップリング剤水溶液の接触角、シランカップリング剤水溶液塗布後の乾燥の際の昇温速度、塗膜の加熱温度のいずれの条件をも特定の範囲内として調製した樹脂積層板は、塗膜の表面のＳｉ元素量が５〜１５原子％の範囲内となり、かつ、加工性および加工後密着性に優れていた（試験例４６〜４８参照）。
（ニ）シランカップリング剤の配合量が０．０１重量部以下であるシランカップリング剤水溶液を用いて調製した樹脂積層板は、塗膜の表面のＳｉ元素量が５原子％より低くなり、かつ、加工後密着性に劣っていた（試験例４９参照）。
（ホ）シランカップリング剤水溶液塗布後の乾燥の際の昇温速度を５０℃／ｓより大きくして調製した樹脂積層板は、塗膜の表面のＳｉ元素量が５原子％より低くなり、かつ、加工後密着性に劣っていた（試験例５０参照）。
（ヘ）塗膜の加熱温度を熱可塑性樹脂の融点（２２０℃）より低くして調製した樹脂積層板は、ポリアミド６薄膜が加工時に剥離するなど加工性に劣っていた。なお、この場合、加工後密着性の評価は不可能であるため実施していない（試験例５１参照）。
（ト）塗膜の加熱温度を３５０℃より高くして調製した樹脂積層板は、加工時にポリエチレンテレフタレート薄膜に亀裂が発生するなど加工性に劣り、また、加工後密着性にも劣っていた。（試験例５２参照）。
【産業上の利用可能性】
【０１１７】
本発明は、以上詳細に説明したとおりであり、次のような特別に有利な効果を奏し、その産業上の利用価値は極めて大である。
【０１１８】
（１）本発明に係る樹脂被覆金属板が、陽極酸化被膜として厚さが０．０５〜２μｍのリン酸アルマイト処理被膜を形成している場合、アルミニウム板表面と被覆膜の界面の密着性（接着性または接着強度）に優れ、絞り加工やしごき加工を行なっても熱可塑性樹脂製被覆膜の破損、クラックなどが発生せず、経時的に劣化し難く層間剥離も生じ難い。
（２）本発明に係る樹脂被覆金属板が、リン酸アルマイト処理被膜と樹脂被膜の間にシランカップリング剤を介在させている場合、アルミニウム板表面と被覆膜の界面の密着性（接着性または接着強度）に優れ、絞り加工やしごき加工を行なっても熱可塑性樹脂製被覆膜の破損、クラックなどが発生せず、経時的に劣化し難く層間剥離も生じ難い。
【０１１９】
（３）本発明に係る製造方法によれば、特開平１−６６０３０号公報、特開平２−１６０４３号公報に記載の方法のように、絞り加工やしごき加工を行なった後に、熱可塑性樹脂製被覆膜を加熱して再溶融させる必要がなく、アルミニウム板表面と被覆膜の界面の密着性（接着性または接着強度）に優れた樹脂被覆金属板を、効率良く製造することができる。
（４）本発明に係る樹脂被覆金属板の製造方法によれば、絞り加工などのプレス加工性に優れ、加工時に被覆フィルムが剥離し難い、樹脂被覆金属板が得られる。
【０１２０】
（５）本発明に係る樹脂被覆金属板の製造方法によれば、基体のアルミニウム薄板の片面が樹脂フィルムによって被覆されているので、容易に美麗な識別用の印刷表示を施すことができる。
（６）本発明に係る樹脂被覆金属板の製造方法によれば、アルミニウム薄板の樹脂被覆面の硬度をビカース硬度で２５〜６０の範囲とするので、プレス加工性に優れ、しかも加工して得られる容器同士が接触しあっても、壁面に凹みが生じ難い。
【０１２１】
（７）本発明に係るアルミニウム電解コンデンサー用外装容器は、従来のように熱収縮性チューブで被覆する工程が不要で、製造工程が簡単である。
（８）本発明の樹脂被覆金属板が、金属板の表面に特定のシランカップリング剤水溶液を塗布して特定の昇温速度で乾燥させて塗膜を形成し、この塗膜を特定の温度で加熱して熱可塑性樹脂薄膜を積層して調製される場合、この樹脂被覆金属板をしごき加工法によって加工した際に、熱可塑性樹脂薄膜に亀裂が発生し難く、かつ、熱可塑性樹脂薄膜が金属板から容易に剥離することがない。
【０１２２】
（９）本発明に係る樹脂被覆金属板が、金属板の表面に特定のシランカップリング剤水溶液を塗布して特定の昇温速度で乾燥させて塗膜を形成し、この塗膜を特定の温度で加熱して熱可塑陸樹脂薄膜を積層して調製される場合、この樹脂被覆金属板に、各種加工法による加工後に加熱処理を施しても、熱可塑性樹脂薄膜が金属板から容易に剥離することがない。
（１０）本発明に係る樹脂被覆金属板が、金属板の表面に形成された塗膜を、熱可塑性樹脂薄膜の融点から３５０℃の温度範囲で加熱して熱可塑性樹脂薄膜を積層して調製される場合、金属板の強度が低下することがなく、かつ、熱可塑性樹脂薄膜が劣化することがない。
【０１２３】
（１１）本発明に係る樹脂被覆金属板が、金属板の表面に形成された塗膜を、熱可塑性樹脂薄膜の融点から３５０℃の温度範囲で加熱して熱可塑性樹脂薄膜を積層して調製される場合、従来の高温の加熱処理の際に生じていた経済的不利益が解消される。
（１２）本発明に係る樹脂被覆金属板の製造方法によれば、上記各効果を奏する樹脂被覆金属板を製造することができる。
（１３）本発明に係るコンデンサー外装用容器は、上記樹脂被覆金属板が絞り加工法またはしごき加工法によって調製されてなるので、製品化された後に加熱処理が施された場合でも、このコンデンサー外装用容器を構成する熱可塑性樹脂薄膜が金属板から剥離することがなく、商品価値が高い。【Technical field】
[0001]
The present invention relates to a resin-coated metal plate, a method for producing the same, and a capacitor exterior container using the resin-coated metal plate.
[Background]
[0002]
Conventionally, a resin-coated metal plate coated with a thermoplastic resin coating on the surface of a metal plate such as an aluminum plate is excellent in corrosion resistance, electrical insulation and design, and is used in various fields. ing. For example, an aluminum electrolytic capacitor contains a capacitor element impregnated with an electrolyte in a cylindrical container made by drawing an aluminum plate, seals the opening of the container with rubber, and further provides electrical insulation and content display on the outer peripheral surface. For the purpose, it is covered with a heat shrinkable tube such as vinyl chloride resin or olefin resin.
[0003]
In recent years, electronic components have been reduced in size, aluminum electrolytic capacitors have been similarly reduced in size, and development of chip type electrolytic capacitors in which lead wires for surface mounting are eliminated has been promoted. In such an aluminum electrolytic capacitor, since the outer container becomes small, it is very difficult to cover it with a heat-shrinkable tube, and the capacitor element housed in the outer container comes into contact with the inner surface of the outer container and insulation is not achieved. It was.
[0004]
For the purpose of eliminating the above disadvantages, the surface of a metal plate such as an aluminum plate is a resin-coated plate coated with an insulating resin, and this resin-coated plate is made into an outer container or cap by drawing, ironing, etc., and using a heat-shrinkable tube Techniques have been proposed in which the covering step is omitted and insulation is achieved at the same time (see, for example, JP-A-1-175222, JP-A-3-79974, etc.).
[0005]
The technology for coating the surface of an aluminum plate with an insulating resin to form a resin-coated plate includes a method of applying an epoxy resin, a vinyl chloride resin or a polyester resin on the surface of the aluminum plate, and a resin on the surface of the aluminum plate. There is a method of laminating films.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0006]
However, the resin-coated metal plate formed with a coating film by these conventionally known methods has a drawback that the interface between the aluminum plate and the coating film is peeled off in a secondary processing step such as drawing or ironing. there were.
[0007]
Therefore, the present invention is excellent in adhesion (adhesiveness or adhesive strength), and even when drawing or ironing is performed, delamination and thermoplastic resin coating are formed at the interface between the aluminum plate and the thermoplastic resin coating film. It is an object of the present invention to provide a resin-coated metal plate that does not cause breakage of the covering film, cracks, or the like, does not easily cause delamination over time, and can be efficiently manufactured.
[Means for Solving the Problems]
[0008]
In order to solve the above problems, the present invention forms a chemical conversion treatment thin film on the surface of a metal plate, forms a thin film of a silane coupling agent on the surface of the chemical conversion treatment thin film, and is made of a thermoplastic resin on the surface of the thin film. The above-mentioned problem has been solved by forming a coating film.
【The invention's effect】
[0009]
Since the chemical conversion treatment thin film is provided, the corrosion resistance of the metal plate can be improved, and the adhesion between the metal plate and the thermoplastic resin coating film can be improved.
[0010]
Furthermore, since a thin film of the silane coupling agent is interposed, the organic functional group of the silane coupling agent reacts with the thermoplastic resin and bonds firmly, and the interface between the metal plate or the chemical conversion treatment thin film and the thermoplastic resin coating film Are firmly bonded via a silane coupling agent. Therefore, delamination between the metal plate and the thermoplastic resin coating film, damage to the thermoplastic resin coating film, and the like can be prevented.
BEST MODE FOR CARRYING OUT THE INVENTION
[0011]
Hereinafter, the present invention will be described in detail.
In the resin-coated metal plate according to the present invention, a chemical conversion treatment thin film is formed on the surface of the metal plate, and a thin film of a silane coupling agent (hereinafter referred to as “silane coupling agent thin film”) is formed on the surface of the chemical conversion treatment thin film. And a coating film made of a thermoplastic resin (hereinafter referred to as “coating film made of a thermoplastic resin”) is formed on the surface of the thin film.
[0012]
The said metal plate means the board which consists of various metals, such as iron, various stainless steel, copper, a copper alloy, aluminum, an aluminum alloy, a tin alloy, a steel plate, nickel, and zinc. Among these, an aluminum plate is more preferable.
[0013]
The aluminum which comprises the said aluminum plate means pure Al and Al alloy. Specifically, pure Al, JIS 1000 series alloys such as JIS A 1050, A 1100, A 1200, Al-Mn series JIS 3000 series alloys such as JIS A 3003, A 3004, Al-Mg series JIS 5000 series alloys, etc. However, aluminum is not limited to those exemplified.
[0014]
The thickness of the aluminum plate is preferably 0.1 mm to 0.5 mm, preferably 0.2 to 0.5 mm.
[0015]
The said chemical conversion treatment thin film improves the corrosion resistance and adhesiveness of a metal plate. As a chemical conversion treatment thin film on an aluminum thin plate, (a) a phosphoric acid chromate chemical conversion treatment thin film obtained by a phosphoric acid chromate chemical conversion treatment, (b) a thin film composed of an organic thermoplastic resin coating film and chromium, (c Examples thereof include a chemical conversion treatment thin film containing zirconium by chemical conversion treatment, a chemical conversion treatment thin film containing titanium by chemical conversion treatment, and an anodization thin film obtained by (e) anodization treatment.
[0016]
The thickness of the chemical conversion treatment thin film is not particularly limited, but is preferably 1 to 3000 mm (0.1 to 300 nm). When the thickness of the chemical conversion treatment thin film is less than 50 mm (5 nm), when the resin-coated metal plate is drawn, the coating resin may be peeled off. When the thickness exceeds 3000 mm (300 nm), the thin film is formed. May be difficult.
[0017]
Moreover, when the chemical conversion treatment thin film is an anodized thin film, the range of 500 to 20000 cm (0.05 to 2 μm) is preferable, and the range of 1000 to 20000 cm (0.1 to 2 μm) is more preferable. In the case of other thin films, the range of 50 to 3000 mm (5 to 300 nm) is preferable. If the thickness of the anodic oxide coating is less than 0.05 μm, the adhesion may not be improved. On the other hand, if it exceeds 2 μm, a long-time oxidation treatment may be required and productivity may be inferior. The thickness of the anodic oxide coating can be adjusted to a thickness within the above range by adjusting the processing conditions, particularly the energizing conditions and energizing time.
[0018]
The anodized thin film may be an alumite-treated thin film treated with an electrolyte containing at least phosphoric acid. For example, a phosphoric acid alumite-treated thin film using phosphoric acid as an electrolytic solution, and phosphoric acid and sulfuric acid are used as an electrolytic solution. Examples include an anodized thin film, an anodized thin film using phosphoric acid and oxalic acid as an electrolytic solution, and an anodized thin film using phosphoric acid and chromic acid as an electrolytic solution. Among these, it is preferable to use an alumite phosphate treatment.
[0019]
In addition to the above, after forming phosphoric acid alumite, a method of film laminating after electrolytic treatment in a silane coupling addition bath, after forming phosphoric acid alumite, a method of film laminating after electrolytic treatment in an epoxy emulsion bath, After the formation of phosphoric acid alumite, a method of film lamination after electrolytic treatment in a silane coupling agent and epoxy emulsion mixed bath, a method of film lamination after each of the above electrolytic treatments, silane coupling treatment or epoxy emulsion coating Can be adopted.
[0020]
When an anodized film is formed on the surface of the aluminum plate, the adhesion (adhesiveness or adhesive strength) between the aluminum plate and the thermoplastic resin-coated resin film interface can be improved.
[0021]
By the way, as a process of a metal surface, the method of giving a single layer plating, a multilayer plating, or alloy plating, an immersion chromic acid process, and a phosphoric acid chromic acid process other than forming a chemical conversion treatment thin film is mention | raise | lifted. In addition, by applying electrolytic chromic acid treatment, the surface of the metal plate is a single-layer film made of chromium hydrated oxide, or a two-layer film made of a metal chromium layer (lower layer) and a chromium hydrated oxide layer (upper layer). In the case of forming a single layer film, the amount of chromium is 3 to 30 mg / m. ² When forming a two-layer film, the lower layer chromium amount is 2 to 200 mg / m. ² , Upper layer chromium amount 5-30mg / m ² It is preferable to set the degree.
[0022]
Said silane coupling agent thin film is formed by apply | coating a silane coupling agent on the said metal plate or a chemical conversion treatment thin film, and drying. This thin film functions to improve the adhesive force between the metal plate and the thermoplastic resin coating film.
[0023]
The silane coupling agent refers to an organosilicon compound having two or more different reactive groups in the molecule. One of the two reactive groups is a reactive group that chemically bonds to an inorganic material such as glass or metal, and the other is a reactive group that chemically bonds to an organic material such as various synthetic resins. Although the reactive group couple | bonded with the metal plate which is an inorganic material, or a chemical conversion treatment thin film is not specifically limited, For example, a methoxy group, an ethoxy group, a silanol group etc. are mention | raise | lifted. On the other hand, examples of the reactive group chemically bonded to the organic material include an epoxy group, an amino group, a vinyl group, a methacryl group, and a mercapto group. Typical silane coupling agents include γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane and the like.
[0024]
The aluminum plate and the silane coupling agent are bonded firmly by forming an Al-O-Si bond, and the thermoplastic resin and the silane coupling agent have a thermoplastic resin in which the organic functional group of the silane coupling agent is a thermoplastic resin. Reacts and binds tightly. For this reason, the interface between the aluminum plate and the thermoplastic resin coating film is firmly bonded via the silane coupling agent.
[0025]
Examples of the silane coupling agent that can be used include vinyltrimethoxysilane, chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, ureidoaminopropylethoxysilane, etc. Can be given.
[0026]
The layer of the silane coupling agent thin film is 0.01 to 1000 mg / m of the silane coupling agent on the metal plate or the chemical conversion treatment thin film. ² Preferably formed by coating, 0.5 to 500 mg / m ² More preferably, it is formed by coating. Application amount of silane coupling agent is 0.01 mg / m ² If it is less than 1, the adhesion (adhesiveness) of the interface may not be sufficient, and 1000 mg / m ² If it exceeds 1, the adhesive strength reaches saturation, the increase in adhesive strength is not proportional to the coating amount, and the silane coupling agent tends to aggregate, making it difficult to apply uniformly.
[0027]
To apply a silane coupling agent on a metal plate or anodized film, in order to increase the wettability of the surface, dilute the silane coupling agent with alcohol or water to dissolve or disperse it uniformly, and surface tension It is preferable to apply uniformly with lowering. Further, as a method for reducing the surface tension, a method of adding an organic compound such as an organic solvent or a surfactant can be mentioned.
[0028]
When the silane coupling agent is applied as an aqueous solution to the surface of the metal plate or the chemical conversion thin film, the concentration of the silane coupling agent aqueous solution is not particularly limited, but the silane coupling agent is 0 with respect to 100 parts by weight of water. It is preferable to make it contain in the ratio of 0.01-1 weight part. If the amount of the silane coupling agent is less than 0.01 parts by weight, the above adhesion function may not be sufficiently achieved. On the other hand, when the amount exceeds 10 parts by weight, the silane coupling agent tends to aggregate, and similarly, the adhesion function may not be sufficiently achieved.
[0029]
Moreover, it is preferable to adjust silane coupling agent aqueous solution so that the contact angle at the time of apply | coating to the surface of a metal plate or a chemical conversion treatment thin film may be 55 degrees or less. The size of the contact angle is determined by the surface tension between the metal plate and the silane coupling agent aqueous solution, and this surface tension is easily determined by the type and amount of the organic solvent and surfactant added to the silane coupling agent aqueous solution. Can be adjusted. Examples of the organic solvent include ethanol and isopropanol. Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. These organic solvents and surfactants are appropriately selected from those that do not impair the stability of the aqueous silane coupling agent solution, and are added in appropriate addition amounts.
[0030]
If the contact angle is larger than 55 °, the surface tension between the metal plate and the aqueous solution of the silane coupling agent is increased, and a uniform coating film is hardly formed on the surface of the metal plate, so that the above-described adhesion function can be sufficiently achieved. There may be no cases.
[0031]
In addition to the organic solvent and surfactant, the silane coupling agent aqueous solution may be added with a thickening agent, an antiseptic, or the like having a contact angle of 55 ° or less. The method for measuring the contact angle is based on a so-called droplet method in which the contact angle of the droplet of the silane coupling agent aqueous solution attached to the surface of the metal plate is measured with various measuring instruments.
[0032]
As a method for applying the silane coupling agent aqueous solution to the surface of the metal plate, a commonly used method, for example, dipping method, spray method, roll coating method, gravure roll method, reverse roll method, air knife method, kiss roll Methods, spray coating methods, bar coating methods, dipping methods, gravure roll methods, reverse roll methods, air knife coating methods and the like can be employed.
[0033]
Various organic and inorganic additives such as viscosity modifiers, antifoaming agents, colorants such as pigments and dyes, stabilizers, and solvents for adjusting solubility can be added to the silane coupling agent. .
[0034]
After coating, it is preferable to dry the solvent by volatilizing and scattering the solvent. When drying, it is preferable to raise the temperature at a temperature increase rate of 50 ° C./s or less. When the temperature is increased at a temperature increase rate exceeding 50 ° C./s, the applied aqueous silane coupling agent solution is likely to be modified, and the adhesion function of the coating film formed by the aqueous silane coupling agent solution may be deteriorated. In addition, it is especially preferable that the temperature increase is performed at a temperature increase rate of 5 to 50 ° C./s in a range from room temperature to 150 ° C.
[0035]
The coating film formed by applying and drying the silane coupling agent aqueous solution has a Si element amount of 5 to 15 atomic% when the surface is measured by X-ray photoelectron spectroscopy (hereinafter referred to as “ESCA method”). Preferably there is. If the amount of Si element is less than 5 atomic%, the adhesion function of the silane coupling agent aqueous solution cannot be obtained sufficiently, which is not preferable. Moreover, even if the amount of Si element exceeds 15 atomic%, the adhesion function of the silane coupling agent aqueous solution is not further improved.
[0036]
The ESCA method is a solid surface analysis method using electron spectroscopy, and the surface of a solid sample such as a metal, ceramic, inorganic compound, or polymer material is irradiated with soft X-rays under high vacuum. In this method, photoelectrons emitted from the surface of the solid sample are detected by an electrostatic energy analyzer, and the element type, oxidation state, bonding state, and the like on the surface of the solid sample are analyzed. As the measurement conditions of this ESCA method, normal measurement conditions can be used without limitation. For example, MgKα, AlKα, etc. can be adopted as the X-ray source, the output is 15 kv × 33 mA, and the degree of vacuum is 5 × 10. It can be set to -8 Torr.
[0037]
A coating film made of a thermoplastic resin is formed on the silane coupling agent layer. This coating film made of thermoplastic resin improves the electrical insulation and chemical resistance of the resin-coated metal plate, and is used as a printing surface for identification display.
[0038]
An example of the thermoplastic resin coating film is a film made of a thermoplastic resin. Examples of the thermoplastic resin include polyester resins and polyamide resins. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexadimethylene terephthalate, polyester resins such as these copolyesters, each polyester resin, and polyolefins such as polyethylene and polypropylene. Examples thereof include resins, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, copolymers of ethylene and acrylic acid derivatives, and mixtures of these polyester resins.
[0039]
Polyamide resin, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 46, these copolyamides, mixed polyamide, produced by polycondensation reaction of metaxylylenediamine and adipic acid Examples thereof include aromatic polyamides such as polymetaxylylene adipamide containing 90 mol% or more of structural units, amorphous polyamides, polyamide elastomers, impact polyamides, and mixtures of these polyamide resins.
[0040]
Among these, from the viewpoint of heat resistance, in particular, heat resistance in the solder reflow process, a polyamide resin or a polyester resin having a melting point of 180 ° C. or more should be suitably used when manufacturing a container for a capacitor exterior from a resin laminate. Can do.
[0041]
The method for forming the coating film made of the above-mentioned thermoplastic land resin is not particularly limited. Extrusion method using a coat hanger die, T-die, I-die, inflation die, etc., calendar molding method, etc. It can be produced by a conventionally known method. This coating film made of thermoplastic land resin may be unstretched or biaxially stretched.
[0042]
Further, the thermoplastic resin coating film may be laminated on the silane coupling agent thin film using the above-mentioned film, and the thermoplastic resin may be coated with a die such as a T die or an I die. You may laminate | stack on a silane coupling agent thin film, extruding in the shape of a thin film with the equipped extruder.
[0043]
Various resin additives can be blended with the thermoplastic resin as necessary before film formation. Resin additives include dyes, pigments and other colorants, lubricants, antiblocking agents, thermal stabilizers, antistatic agents, light stabilizers, rust inhibitors, UV absorbers, impact modifiers, antioxidants, and electrification Examples include inhibitors. These resin additives can be blended within a range that does not adversely affect the thermoplastic resin coating film. Furthermore, surface treatments such as corona treatment and flame treatment can be applied for the purpose of improving adhesion.
[0044]
The thickness of the thermoplastic resin coating film is preferably 5 to 200 μm, preferably 5 to 100 μm, and more preferably 10 to 50 μm. If the thickness of the coating film is less than 5 μm, pinholes are likely to occur, and it may be difficult to improve the corrosion resistance, electrical insulation, etc. of the aluminum plate. It may be extremely difficult to laminate the metal plate. On the other hand, if it exceeds 200 μm, it will be too thick and not only will cracks easily occur during drawing or ironing, but it is also not economically preferable.
[0045]
Examples of a method for forming, ie, laminating a thermoplastic resin coating film on the silane coupling agent thin film include a continuous method and a batch method.
[0046]
With the said continuous method, first, the said silane coupling agent is apply | coated on the said metal plate or a chemical conversion treatment thin film. Subsequently, it heats to the temperature of 250-350 degreeC, and the liquid component which has disperse | distributed the silane coupling agent is scattered. Immediately, the thermoplastic resin is laminated while being extruded into a thin film by an extruder equipped with a die such as a T die or an I die, or a thermoplastic resin coating film already formed is below the melting point of the thermoplastic resin. Pressure lamination with a heated nip roll or the like. And after laminating | stacking, it is the method of cooling by air cooling or water cooling immediately.
[0047]
In this case, if the temperature at the time of lamination is lower than 250 ° C., the adhesion between the aluminum plate and the thermoplastic resin coating film may not be sufficient, and if it is higher than 350 ° C., the thermal deterioration of the coating film proceeds. In some cases, the coating film is damaged or cracks are easily generated during drawing or ironing.
[0048]
On the other hand, in the batch method, a metal plate on which a silane coupling agent thin film is formed is heated to a melting point to 350 ° C., preferably 200 to 350 ° C. Next, a thermoplastic resin is attached to a die such as a T die or an I die. Lamination is performed while extruding into a thin film with an equipped extruder, or a thermoplastic resin coating film that has already been formed is pressure-laminated by a nip roll or the like that has been heated below the melting point of the thermoplastic resin. And after laminating | stacking, it is the method of cooling by air cooling or water cooling immediately.
[0049]
In this case, when the melting point of the thermoplastic resin is lower, the thermoplastic land thermoplastic resin coating film is not sufficiently adhered, and when the resin coated metal plate is processed, the thermoplastic resin coating film is In some cases, the resin-coated metal sheet may peel off, and the thermoplastic resin coating film of the resin-coated metal plate may become too hard, resulting in poor formability. On the other hand, when the temperature is higher than 350 ° C., the metal of the resin-coated metal plate becomes too soft and the strength thereof is remarkably lowered, and a dent or the like may be easily generated, and the thermoplastic resin coating film may be deteriorated. is there. In addition, said melting | fusing point means the peak temperature of the crystal melting temperature when it heats up at 10 degree-C / min with a differential scanning calorimeter (DSC).
[0050]
The resin-coated metal plate according to the present invention preferably has a Vickers hardness in the range of 25 to 60 as measured from the outer surface of the thermoplastic resin coating film constituting the resin-coated metal plate. If the Vickers hardness of the resin-coated surface of the aluminum thin plate is less than 25, the resin-coated metal plate may become too soft and the moldability may deteriorate. On the other hand, if the Vickers hardness exceeds 60, in this case also the resin-coated metal The board may become too hard. The “Vickers hardness” refers to the hardness measured in accordance with JISZ 2244 “one test method for Vickers hardness test”.
[0051]
Next, several specific examples of the method for producing the resin-coated metal plate according to the present invention will be shown.
As a first example, an anodic oxide coating having a thickness of 0.05 to 2 μm is formed on the surface of an aluminum plate, and a silane coupling agent is applied to the anodic oxide coating at 0.5 to 500 mg / m. ² Furthermore, a coating film made of a thermoplastic resin having a thickness of 5 to 200 μm is melt-coated at a temperature range of 250 to 350 ° C. on the thin film of the silane coupling agent to form a resin-coated metal plate. The manufacturing method is mentioned.
[0052]
As a second example, a chemical conversion treatment thin film is formed on one surface of an aluminum plate having a thickness of 0.1 mm to 0.5 mm, and then a silane coupling agent is added to the thin film at a concentration of 0.01 to 1000 mg / m. ² A thin film is formed by coating, and an aluminum plate on which the chemical conversion treatment thin film and the thin film of the silane coupling agent are laminated is heated in a temperature range of 200 to 350 ° C., and the thickness is measured from above the thin film of the silane coupling agent. Is a method of producing a resin-coated metal plate having a Vickers hardness of 25 to 60 on the surface of the coating film made of a thermoplastic resin.
[0053]
Furthermore, as a third example, the contact angle when the silane coupling agent was blended at a ratio of 0.01 to 10 parts by weight with respect to 100 parts by weight of water and applied to the surface of the metal plate was 55 ° or less. A silane coupling agent aqueous solution is applied to the surface of the metal plate and dried at a heating rate of 50 ° C./s or less to form a coating film, and this coating film is heated in the temperature range from the melting point of the thermoplastic resin to 350 ° C. A method of manufacturing a resin-coated metal plate by laminating a coating film made of a thermoplastic resin on the surface of the coating film is mentioned.
[0054]
When the resin-coated metal plate according to the present invention is processed by the ironing method, cracks are hardly generated in the thermoplastic resin coating film, and the thermoplastic resin coating film can be easily peeled off from the metal plate. Therefore, this resin-coated metal plate can be suitably used as a material for containers manufactured through a plurality of secondary processes such as a bending process, a drawing process, and an ironing process. In addition, since this resin-coated metal plate is not easily peeled off from the metal plate even if heated after processing by various processing methods, the container manufactured using this resin-coated metal plate Can withstand heating.
[0055]
In addition, the resin-coated metal plate is excellent in pell workability such as drawing, and can be suitably used for producing an aluminum electrolytic capacitor exterior container. In addition, when the Vickers hardness of the resin-coated surface is in the range of 25 to 60, even if the containers are in contact with each other or the product containers are in contact with each other at the time of pressing, the top surface portion or the side surface portion of the container In addition, it is difficult to cause dents and the like, pressure resistance is improved, and a beautiful printed display for identification can be provided on the top surface of the container.
[0056]
Furthermore, the resin-coated metal plate can be suitably used as a material for a container for a capacitor exterior, in addition to a wall material for a building, a partition plate material, a design material, and various can manufacturing materials. In addition, since it is necessary to go through a solder reflow process when manufacturing this capacitor exterior container, it is necessary to use a resin-coated metal plate on which a coating film made of a thermoplastic thermoplastic resin excellent in heat resistance is laminated. It is also preferable to process so that the thermoplastic thermoplastic resin coating film is on the outside. Examples of the capacitor exterior container include an electrolytic capacitor exterior container and an electrolytic capacitor cap.
【Example】
[0057]
Hereinafter, although this invention is demonstrated further in detail based on a test example, this invention is not limited to the following description examples, unless the meaning is exceeded. The resin-coated metal plate obtained in the test examples described below was evaluated by the following method.
[0058]
(1) Drawing workability: The resin-coated metal plate obtained in the test example is sent to a lance forward-feed drawing machine, and a 10 mmφ × 20 mm cylindrical container (the ironing rate is 20%) with the thermoplastic resin coating film as the outer surface of the container ) Were visually observed, and the interface between the aluminum plate surface and the coating film was visually observed, and the one where no delamination was observed at the interface was regarded as a non-defective product and displayed as a non-defective product rate (%) or “◯”.
[0059]
(2) Caulking workability: 100 cylindrical containers of 10 mmφ × 20 mm are manufactured, and while rotating at 100 rpm, a disk-shaped caulking sesame with a thickness of 3 mm (side is semicircular with R = 1.5 mm) It was pressed and caulked so that the diameter became 7.5 mm (diameter change rate = 25%), the interface between the aluminum plate surface and the coating film was visually observed, and no delamination was observed at the interface Is displayed as a non-defective product rate (%) or “◯”.
[0060]
(3) Change over time: After 100 containers having been subjected to the caulking process evaluation test of (2) above were allowed to stand at room temperature for 10 days, the interface between the aluminum plate surface and the coating film was again visually observed, and the interface No delamination was observed as non-defective products and displayed as non-defective product rate (%).
[0061]
[Experimental Example 1]
(Test Examples 1 to 5)
<Manufacture of resin-coated metal plate>
Both surfaces of a 0.3 mm thick aluminum plate (JIS A 1050 H22) were anodized with a 20% phosphoric acid solution to form a phosphate alumite-treated film having the thickness shown in Table 1. Next, 50 mg / m of the silane coupling agent shown in Table 1 was applied to the anodized film. ² The coated surface was heated to 280 ° C. A separately manufactured film of polyamide 6 (melting point: 223 ° C.) having a thickness of 15 μm was stacked on the heated coated surface, and pressed by a pair of pressure rolls to obtain a resin-coated metal plate. The obtained resin-coated metal plate was subjected to the above-described evaluation test. The evaluation test results are shown in Table 1.
[0062]
(Test Examples 6 to 7)
In the example described in Test Example 1, instead of anodizing with a 20% phosphoric acid solution, phosphoric acid chromate treatment (chromium amount: 10 mg / m ² Test Example 6) or oxalic acid alumite treatment (Test Example 7) was performed to form respective coatings. The obtained resin-coated metal plate was subjected to the above-described evaluation test. The evaluation test results are shown in Table 1.
[0063]
[Table 1]

[0064]
(result)
From Table 1, the following becomes clear.
(1) Phosphoric acid alumite-treated coating as an anodic oxide coating with a thickness of 0.05-2 μm is excellent in drawing process and caulking process, and delamination at the interface in each step No change over time (deterioration) is observed (see Test Example 2, Test Example 4, Test Example 5).
(2) On the other hand, even when a phosphate alumite-treated film was formed, a film with a thickness of less than 0.1 μm (see Test Example 1) showed delamination at the interface in the caulking process. A significant change with time is observed. However, a reasonable drawing process is possible.
(3) Even in the same anodized film, a film formed with a phosphoric acid chromate treatment film is inferior in caulking workability but has a remarkable change with time (deterioration) although there is no problem with drawing (Test Example 6). reference).
(4) Further, even if the same anodized film is formed, an oxalic acid alumite-treated film is remarkably inferior in both caulking processability and change with time (see Test Example 7).
(5) Even if a phosphoric acid alumite-treated film is formed, a film in which a silane coupling agent is not applied is inferior in caulking processability, and a remarkable change with time (deterioration) is observed (see Test Example 3).
[0065]
(Test Examples 8-12)
Both surfaces of a 0.3 m thick aluminum plate (JIS A1050 H22) were anodized with a 20% phosphoric acid solution to form a phosphoric acid alumite-treated film having a thickness of 0.6 μm. On this coating, a silane coupling agent having a functional group shown in Table 2 was added at 20 mg / m. ² The coated surface was heated to 280 ° C. A separately manufactured film of polyamide 6 (melting point: 223 ° C.) having a thickness of 15 μm was stacked on the heated coated surface, and pressed by a pair of pressure rolls to obtain a resin-coated metal plate. The obtained resin-coated metal plate was subjected to the above-described evaluation test. The evaluation test results are shown in Table 2.
[0066]
[Table 2]

[0067]
(result)
From Table 2, the following becomes clear.
(1) The silane coupling agent applied is excellent in drawing workability and caulking workability, no delamination is observed at the interface in each step, and no change over time (deterioration) is observed (Test Examples 8 to 12). reference).
[0068]
(Test Examples 13 to 15)
Both surfaces of a 0.3 mm thick aluminum plate (JIS A1050 H22) were anodized with a 20% phosphoric acid solution to form a phosphoric acid alumite-treated film having a thickness of 0.5 μm. On this coating, a silane coupling agent having a ureido group is 20 mg / m 2. ² The coated surface was heated to 250 ° C. A film having a thickness of 15 μm separately produced from the resin shown in Table 3 was superimposed on the heated coated surface, and was laminated by pressing with a pair of pressure rolls to obtain a resin-coated metal plate. The obtained resin-coated metal plate was subjected to the above-described evaluation test. The evaluation test results are shown in Table 3.
[0069]
[Table 3]

[0070]
(result)
From Table 3, the following becomes clear.
(1) When the coating film of the aluminum plate is a polyester-based resin or a polyamide-based resin, it is excellent in drawing workability and caulking workability. (See Test Example 13 and Test Example 14).
(2) On the other hand, when the coating film is polypropylene, delamination is observed at the interface in the drawing process, and the drawing processability is poor (see Test Example 15).
[0071]
(Test Examples 16 to 19)
A resin-coated metal plate was obtained according to the method of Test Example 13 except that the anodizing method was changed to the following method. The obtained resin-coated metal plate was subjected to the above-described evaluation test. The evaluation test results are shown in Table 5.
(Anodizing method)
The anodic acid treatment conditions were performed according to the methods of electrolyte numbers 1 to 4 shown in Table 4.
The organic acid used in electrolyte number 4 is dicarboxylic acid (maleic acid, malonic acid), aromatic sulfonic acid (sulfosalicylic acid, sulfophthalic acid), carboxylic acid sulfonate (sulfomaleic acid), sulfonic acid amine (sulfamic acid). ) Etc.
The treatment conditions were as follows: phosphoric acid concentration: 0.1-500 g / l, sulfuric acid / oxalic acid / chromic acid / any of the above organic acids: 0.1-500 g / l, voltage: 1-100 vAC, 1 to 100 vDC alone or superimposed, time: 1 to 60 minutes, thin film thickness: 50 to 50 μm, phosphate anion content: 1 to 5000 ppm.
[0072]
[Table 4]

[0073]
Furthermore, the following conditions were used as other conditions.
Other condition number 1: After the formation of phosphoric acid alumite, AC electrolysis or DC electrolysis (base material is negative) in a silane coupling addition bath, and then film lamination.
-Other condition number 2: After the formation of phosphoric acid alumite, AC electrolysis or DC electrolysis (base material is negative) in an epoxy emulsion bath, followed by film lamination.
Other condition number 3: After the formation of phosphoric acid alumite, AC electrolysis or DC electrolysis (base material is negative electrode) in a silane coupling agent and epoxy emulsion mixed bath, and then film lamination.
Other condition number 4: After electrolytic treatment up to the above other condition numbers 1 to 3, silane coupling treatment or epoxy emulsion coating is performed, and then film lamination is performed.
[0074]
[Table 5]

[0075]
[Experiment 2]
Next, a test example based on another evaluation is shown. The evaluation methods used in Test Examples 20 to 33 shown below are shown.
[0076]
(A) Vickers hardness: Vickers hardness was measured on the resin-coated surface of the aluminum thin plate of the prepared resin-coated metal plate in accordance with JISZ2244 “One Test Method for Vickers Hardness Test”. The load at the time of hardness measurement was 0.9807N.
[0077]
(B) Workability: Using the prepared resin-coated metal plate, seven stages of drawing were performed with a lance forward-feed drawing machine, and a 10 mmφ × 20 mm-high cylindrical container with a resin coating layer as the outer surface of the container (steeling rate 20%) And the state of delamination between layers was visually observed. The case where no delamination was observed was indicated as “◯”, and the case where delamination was observed was indicated as “x”.
[0078]
(C) Concaveness: A sample container was prepared by filling the cylindrical container having a height of 10 mφ × 20 mm with a capacitor element and caulking with a sealing rubber. 100 sample containers were placed in a 200 mm × 200 mm × 200 mm paper container, and longitudinal vibration was applied for 1 hour at a vibration speed of 10 cm / second. One hour later, the sample container was taken out, and the appearance of the top surface portion was observed. At this time, the case where the dent was recognized in the bottom part and the side wall part of the sample container was indicated as “×”, and the case where the dent was not recognized was indicated as “◯”.
[0079]
(D) Comprehensive evaluation: In all the evaluation items (a) to (c), those with acceptable quality were judged as “◯”, and those with even one evaluation item were judged as “x”.
[0080]
[Test Example 20]
The surface of an aluminum (JIS A 1100) plate having a thickness of 0.3 mm was etched with a 10% aqueous sodium hydroxide solution at 50 ° C. for 30 seconds, neutralized with a 10% aqueous nitric acid solution, and washed with water for 10 seconds. . Next, a phosphoric acid chromate conversion treatment thin film (Cr = 20 mg / m 2) is formed on one surface of the aluminum plate. ² ) Was formed. On this chemical conversion thin film, γ-aminopropyltriethoxysilane as a coupling agent was added at 50 mg / m 2. ² After coating and drying, the aluminum plate was heated to a temperature of 210 ° C., and a polyamide 6 film having a thickness of 15 μm was pressure-bonded to the surface to which the coupling agent was applied, to obtain a polyamide resin-coated metal plate. Table 6 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0081]
[Test Example 21]
In the example described in Test Example 20, the conversion treatment thin film was replaced by a thin film having a thickness of 1000 mm formed by an oxalic acid alumite conversion treatment, the coupling agent was replaced by γ-glycidoxypropyltriethoxysilane, and the temperature of the aluminum plate A polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that was changed to 250 ° C. Table 6 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0082]
[Test Example 22]
In the example described in Test Example 21, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the chemical conversion treatment thin film was replaced with a thin film formed by phosphoric acid alumite chemical conversion treatment. Table 6 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0083]
[Test Example 23]
In the example described in Test Example 21, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the chemical conversion treatment thin film was replaced with a thin film formed by phosphoric acid chromate treatment. Table 6 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0084]
[Test Example 24]
In the example described in Test Example 23, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the coupling agent was replaced with γ-aminopropyltriethoxysilane. Table 6 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0085]
[Test Example 25]
In the example described in Test Example 20, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the coupling agent was not applied. Table 7 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0086]
[Test Example 26]
In the example described in Test Example 20, the polyamide resin-coated metal was processed in the same procedure as in the same example except that the coupling agent was replaced with γ-methacryloxypropyltrimethoxysilane and the temperature of the aluminum plate was changed to 380 ° C. I got a plate. Table 7 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0087]
[Test Example 27]
In the example described in Test Example 23, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the temperature of the aluminum plate was changed to 380 ° C. Table 7 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0088]
[Test Example 28]
In the example described in Test Example 24, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the temperature of the aluminum plate was changed to 200 ° C. Table 7 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0089]
[Table 6]

[0090]
[Table 7]

[0091]
(result)
From Tables 6 and 7, the following becomes clear.
(1) A chemical conversion treatment thin film is provided on the surface of an aluminum thin plate, a layer of a silane coupling agent is provided thereon, the temperature of the aluminum thin plate is heated to a range of 200 to 350 ° C., and a resin film is coated and pressed. The resin-coated metal plate having a resin-coated surface hardness of 25 to 60 in terms of Vickers hardness is excellent in the adhesion between the aluminum thin plate and the coated film, and the coated film does not peel off when pressed. Even if they are in contact with each other, dents are hardly generated on the wall surface (see Test Examples 20 to 24).
(2) On the other hand, even if a chemical conversion treatment thin film is provided on the surface of an aluminum thin plate, the coating film is peeled off at the time of press processing in which a silane coupling agent layer is not provided and a resin film is coated and pressure-bonded ( See Test Example 25).
(3) Moreover, even if a chemical conversion treatment thin film is provided on the surface of an aluminum thin plate and a layer of a silane coupling agent is provided thereon, the aluminum thin plate is coated and pressure-bonded at a temperature higher than 350 ° C. When the surface hardness of the resin-coated metal plate is less than 25 in terms of Vickers hardness, when the containers come into contact with each other, the wall surface is likely to be dented (see Test Examples 26 to 27).
(4) Furthermore, even if a chemical conversion treatment thin film and a silane coupling agent layer are provided on the surface of the aluminum thin plate, and the temperature of the aluminum thin plate is coated and pressure-bonded at 200 ° C., the resin coating of the resin-coated metal plate When the surface hardness exceeds 60 in terms of Vickers hardness, the aluminum thin plate of the substrate is damaged during press working (see Test Example 28).
[0092]
[Test Example 29]
In the example described in Test Example 20, the application amount of the coupling agent was 100 mg / m. ² Instead, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the temperature of the aluminum plate was changed to 290 ° C. Table 8 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0093]
[Test Example 30]
In the example described in Test Example 23, the coating amount of the coupling agent was 500 mg / m. ² Instead, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that the temperature of the aluminum plate was changed to 290 ° C. Table 8 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0094]
[Test Example 31]
In the example described in Test Example 30, the coating amount of the coupling agent was 1000 mg / m. ² A polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that. Table 8 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0095]
[Test Example 32]
In the example described in Test Example 29, the amount of coupling agent applied was 0.005 mg / m. ² A polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that. Table 8 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0096]
[Test Example 33]
In the example described in Test Example 31, the application amount of the coupling agent was 1300 mg / m. ² A polyamide resin-coated metal plate was obtained in the same procedure as in the same example except that. Table 8 shows the results of evaluating the obtained polyamide resin-coated metal plate by the above evaluation method.
[0097]
[Table 8]

[0098]
(result)
From Table 8, the following becomes clear.
(1) A thin film is provided on the surface of an aluminum thin plate, a silane coupling agent layer is provided thereon, and the coating amount of the silane coupling agent is 0.01 to 1000 mg / m 2. Moreover, it is excellent in press workability, and even if the containers are in contact with each other, it is difficult for dents to occur on the wall surface (see Test Examples 29 to 31).
(2) On the other hand, the coating amount of the silane coupling agent is 0.005 mg / m. ² When the amount is too small, the adhesion between the aluminum thin plate and the coating film is inferior, and the coating film peeled off during press working (see Test Example 32).
(3) The coating amount of the silane coupling agent is 1300 mg / m ² When the amount was too large, the stability of the coupling agent solution was poor, and it was not possible to uniformly coat the surface of the aluminum thin plate (see Test Example 33).
[0099]
[Experiment 3]
Next, a test example based on another evaluation is shown. The evaluation methods used in Test Examples 34 to 52 shown below are shown. In addition, the evaluation method of silane coupling agent aqueous solution is based on the method of following (1) and (2) description. Moreover, the evaluation method of a resin laminated board is based on the method of following (3) thru | or (6) description.
[0100]
(1) Contact angle measurement: A necessary amount of a silane coupling agent aqueous solution is dropped on the surface of a prepared metal plate under conditions of an air temperature of 23 ° C. and a humidity of 50%, and a contact angle meter (trade name, manufactured by Kyowa Interface Science Co., Ltd.) : The contact angle is measured using CA-A).
[0101]
(2) Evaluation of wettability: The prepared metal plate was cut into A4 size, and a silane coupling agent aqueous solution was applied to this surface at a rate of 10 g / m using a bar coater. ² Apply and visually observe the state of the coating. The observation results were judged as ○ when the uniform coating film was formed without repelling, and x when the coating film was spotted and repelled.
[0102]
(3) Measurement of the amount of Si element: In the step of preparing the resin laminate, an aqueous silane coupling agent solution was applied to the surface of the metal plate and dried to form a coating film, and then the ESCA method (X-ray source: MgKα) , Output: 15 kv × 33 mA, degree of vacuum: 5 × 10 −8 Torr), the amount of Si element (atomic%) on the surface of the coating film is measured.
[0103]
(4) Evaluation of workability: A cylinder having a diameter of 10 mm and a height of 20 mm so that the resin laminated plate is subjected to seven-stage drawing with a lance progressive feed drawing machine and the surface on which the thermoplastic resin thin film is laminated becomes the outer surface of the container. A container is prepared and visually observed whether the thermoplastic resin thin film has peeled from the metal plate. The observation results were determined to be ○ when no separation was observed and × when separation was observed.
[0104]
(5) Evaluation of adhesion after processing: The cylindrical container prepared for the above-described evaluation of workability is placed in a hot air drying furnace at 270 ° C. for 1 minute, and then the cylindrical container is removed from the hot air drying furnace. And visually observe whether or not the thermoplastic resin thin film laminated on the outer surface of the container is peeled off. The observation results were determined to be ○ when no separation was observed and × when separation was observed.
[0105]
(6) Comprehensive evaluation: A case where both of the above workability and post-working adhesion were determined to be “good” was determined to be “good” in the comprehensive evaluation, and both were determined to be “poor” and What was determined was determined as x in the overall evaluation.
[0106]
[Test Examples 34 to 45]
<Preparation of Aqueous Silane Coupling Agent> Table 9 shows silane coupling agent and nonionic surfactant (active ingredient: polyoxyethylene alkyl ether, cloud point: 42.1 ° C.) in 100 g of water. Four types of silane coupling agent aqueous solutions were prepared by blending the same amounts.
[0107]
[Table 9]

[0108]
<Preparation of metal plate>
Stainless steel plate (SUS430-2B) having a thickness of 0.3 mm, aluminum plate having a thickness of 0.3 mm treated with phosphoric acid chromate (alloy number: A1100PH24, chromium content in chromium hydrated oxide: 20 mg / m) ² ) And 0.3 mm-thick electrolytic chromic acid-treated steel sheet (lower layer metal chromium content: 100 mg / m) ² The amount of chromium in the upper layer of chromium hydrated oxide is 18 mg / m / day. ² 3 types of metal plates were prepared.
[0109]
<Evaluation of aqueous solution of silane coupling agent>
Four types of silane coupling agent aqueous solutions shown in Table 9 were dropped on the surfaces of the three types of metal plates, respectively, and the above-described measurement (1) was performed. Furthermore, the four types of silane coupling agent aqueous solutions shown in Table 9 were applied to the surfaces of the three types of metal plates, respectively, and the evaluation test (2) described above was performed. These results are shown in Table 10.
[0110]
[Table 10]

[0111]
From Tables 9 and 10, the following becomes clear.
(A) As a result of dropping four types of silane coupling agent aqueous solutions onto the surfaces of the above three types of metal plates and measuring contact angles, the silane coupling agent aqueous solution I or the silane coupling agent aqueous solution was measured in any metal plate. The contact angle of III was 55 ° or less (see Test Examples 34 to 36, Test Examples 38 to 40, Test Examples 42 to 44). On the other hand, the contact angle of the silane coupling agent aqueous solution IV was larger than 55 ° (see Test Examples 37, 41, and 45). This is because the amount of the nonionic surfactant in the silane coupling agent aqueous solution IV is insufficient.
[0112]
(B) In addition, as a result of applying wettability by applying four types of silane coupling agent aqueous solutions to the surfaces of the above three types of metal plates, metal coated with silane coupling agent aqueous solution I or silane coupling agent aqueous solution III A uniform coating film was formed on the surface of each plate, and the wettability was good (see Test Examples 34 to 36, Test Examples 38 to 40, Test Examples 42 to 44). On the other hand, no uniform coating film was formed on the surface of the metal plate coated with the silane coupling agent aqueous solution IV (the coating film was spotted and the wettability was poor (Test Examples 37 and 41). 45, because the contact angle of the aqueous silane coupling agent IV is greater than 55 °.
[0113]
[Test Example 46]
An aluminum plate (the same kind as that prepared in Test Example 38) was continuously transferred as a long band, and 100 g of water and 0.1 g of a silane coupling agent (γ-aminopropyltriethoxysilane) were added to the surface of the aluminum plate. And a nonionic surfactant (same type as used in Test Example 34) 0.4 g, and a silane coupling agent aqueous solution with a contact angle adjusted to 50 ° when applied to the surface of the aluminum plate 10 g / m ² Is applied and dried at a heating rate of 5 ° C./s to form a coating film. The coating film is then heated at 250 ° C., and the melting point is 220 ° C. and the thickness is 20 μm. A polyamide 6 thin film was laminated to prepare a resin laminate. In the step of preparing the resin laminate, the measurement (3) was performed, and the evaluation tests (4) to (6) were performed on the obtained resin laminate. These results are shown in Table 11.
[0114]
[Test Examples 47 to 52]
In the example described in Test Example 46, the type and blending amount of the silane coupling agent, the heating rate during drying after application of the aqueous silane coupling agent solution (the heating temperature of the coating film, the type of the thermoplastic resin thin film, Resin laminates were prepared in the same manner as in the same example except that they were changed to those described in Table 11. In the process of preparing these resin laminates, measurements were obtained in the same manner as in the example. The resin laminate was evaluated in the same manner as in the same example, and the results are shown in Table 11.
[0115]
[Table 11]

[0116]
From Tables 10 and 11, the following becomes clear.
(C) The specific range of the blending amount of the silane coupling agent, the contact angle of the aqueous solution of the silane coupling agent, the heating rate during drying after application of the aqueous solution of the silane coupling agent, and the heating temperature of the coating film The resin laminate prepared as the inside had a Si element amount on the surface of the coating film in the range of 5 to 15 atomic%, and was excellent in workability and adhesion after processing (see Test Examples 46 to 48).
(D) The resin laminate prepared using a silane coupling agent aqueous solution having a silane coupling agent content of 0.01 parts by weight or less has a Si element amount on the surface of the coating film lower than 5 atomic%, And it was inferior to the adhesiveness after a process (refer Test Example 49).
(E) The resin laminate prepared by increasing the heating rate at the time of drying after application of the aqueous solution of the silane coupling agent to more than 50 ° C./s has a Si element amount on the surface of the coating film lower than 5 atomic%, And it was inferior to the adhesiveness after a process (refer Test Example 50).
(F) The resin laminate prepared by lowering the heating temperature of the coating film below the melting point (220 ° C.) of the thermoplastic resin was inferior in workability such as peeling of the polyamide 6 thin film during processing. In this case, the post-processing adhesion is not evaluated because it cannot be evaluated (see Test Example 51).
(G) The resin laminate prepared by heating the coating film at a temperature higher than 350 ° C. was inferior in workability such as cracking in the polyethylene terephthalate thin film during processing, and inferior in adhesion after processing. (See Test Example 52).
[Industrial applicability]
[0117]
The present invention is as described above in detail, and has the following particularly advantageous effects, and its industrial utility value is extremely large.
[0118]
(1) When the resin-coated metal plate according to the present invention forms a phosphate alumite-treated film having a thickness of 0.05 to 2 μm as an anodized film, the adhesion between the aluminum plate surface and the coating film interface It is excellent in (adhesiveness or adhesive strength), and even when drawing or ironing is performed, the coating film made of thermoplastic resin is not damaged, cracked, etc., hardly deteriorates with time, and delamination hardly occurs.
(2) When the resin-coated metal plate according to the present invention has a silane coupling agent interposed between the phosphate alumite-treated film and the resin film, the adhesion (adhesiveness) between the aluminum plate surface and the coating film Also, it is excellent in adhesive strength), and even if drawing or ironing is performed, the coating film made of thermoplastic resin is not damaged, cracks, etc., hardly deteriorates with time, and delamination hardly occurs.
[0119]
(3) According to the production method of the present invention, after performing drawing and ironing as in the methods described in JP-A-1-66030 and JP-A-2-16043, it is made of a thermoplastic resin. There is no need to heat and remelt the coating film, and a resin-coated metal plate having excellent adhesion (adhesiveness or adhesive strength) at the interface between the aluminum plate surface and the coating film can be efficiently produced.
(4) According to the method for producing a resin-coated metal plate according to the present invention, a resin-coated metal plate is obtained that is excellent in press workability such as drawing and is difficult to peel off during coating.
[0120]
(5) According to the method for producing a resin-coated metal plate according to the present invention, since one surface of the aluminum thin plate of the base is coated with the resin film, it is possible to easily perform a beautiful printed display for identification.
(6) According to the method for producing a resin-coated metal plate according to the present invention, since the hardness of the resin-coated surface of the aluminum thin plate is in the range of 25 to 60 in terms of Vickers hardness, it is excellent in press workability and obtained by processing. Even if the containers to be in contact with each other, the wall surface is unlikely to be dented.
[0121]
(7) The outer container for an aluminum electrolytic capacitor according to the present invention does not require a process of coating with a heat-shrinkable tube as in the prior art, and the manufacturing process is simple.
(8) The resin-coated metal plate of the present invention is coated with a specific aqueous silane coupling agent solution on the surface of the metal plate and dried at a specific temperature increase rate to form a coating film. When the resin-coated metal sheet is prepared by laminating, it is difficult for cracks to occur in the thermoplastic resin thin film and the thermoplastic resin thin film is It does not peel easily from the metal plate.
[0122]
(9) The resin-coated metal plate according to the present invention forms a coating film by applying a specific silane coupling agent aqueous solution to the surface of the metal plate and drying it at a specific temperature increase rate. When it is prepared by laminating a thermoplastic land resin thin film by heating at a temperature, even if this resin-coated metal plate is subjected to heat treatment after processing by various processing methods, the thermoplastic resin thin film is easily peeled off from the metal plate There is nothing to do.
(10) The resin-coated metal plate according to the present invention is prepared by laminating a thermoplastic resin thin film by heating a coating film formed on the surface of the metal plate in a temperature range from the melting point of the thermoplastic resin thin film to 350 ° C. In this case, the strength of the metal plate does not decrease, and the thermoplastic resin thin film does not deteriorate.
[0123]
(11) A resin-coated metal plate according to the present invention is prepared by laminating a thermoplastic resin thin film by heating a coating film formed on the surface of the metal plate in a temperature range from the melting point of the thermoplastic resin thin film to 350 ° C. In this case, the economic disadvantage that has occurred during the conventional high-temperature heat treatment is eliminated.
(12) According to the method for producing a resin-coated metal plate according to the present invention, a resin-coated metal plate having the above effects can be produced.
(13) Since the above-mentioned resin-coated metal plate is prepared by a drawing method or an ironing method, the capacitor-exterior container according to the present invention can be used even when it is heat-treated after being commercialized. The thermoplastic resin thin film constituting the container is not peeled off from the metal plate, and the commercial value is high.

Claims (5)

A chemical conversion treatment thin film is formed on the surface of an aluminum plate having a thickness of 0.1 mm to 0.5 mm, and 0.01 to 10 parts by weight of a silane coupling agent is added to 100 parts by weight of water on the surface of the chemical conversion treatment thin film. A surfactant is blended at a ratio and a silane coupling agent aqueous solution having a contact angle of 55 ° or less when coated on the surface of the metal plate is applied, and the range from room temperature to 150 ° C. is 5 to By drying at a heating rate of 50 ° C./s, a thin film of a silane coupling agent having a thickness of 0.01 to 1000 mg / m ² is formed, and heat formed of a film having a thickness of 5 to 200 μm is formed on the surface of the thin film. The Vickers hardness after forming the thermoplastic resin coating film and the thermoplastic resin coating film is in the range of 25-60, and the thermoplastic resin coating film is 350 from its melting point. In the temperature range of ℃ Heated resin coated metal sheet in which it is laminated on the silane coupling agent surface of the thin film. 2. The resin-coated metal plate according to claim 1, wherein an amount of Si element when the surface of the silane coupling agent is measured by X-ray photoelectron spectroscopy is 5 to 15 atomic%. A container for capacitor exterior, wherein the resin-coated metal plate according to claim 1 or 2 is prepared by a drawing method or an ironing method. The capacitor exterior container according to claim 3, wherein the coating film made of the thermoplastic resin is arranged outside. A chemical conversion treatment thin film is formed on one surface of an aluminum plate having a thickness of 0.1 mm to 0.5 mm, and then 0.01 to 10 parts by weight of a silane coupling agent is added to 100 parts by weight of water on the thin film. A silane coupling agent aqueous solution having a contact angle of 55 ° or less when applied to the surface of the metal plate is applied to the surface of the metal plate, and from a room temperature to 150 ° C. The range is dried at a temperature rising rate of 5 to 50 ° C./s to form a thin film of a silane coupling agent of 0.01 to 1000 mg / m ² , and the chemical conversion treatment thin film and the thin film of the silane coupling agent An aluminum plate laminated with heat is heated in a temperature range of 200 to 350 ° C., and a thermoplastic resin film having a thickness of 5 to 200 μm is coated and pressed from above the thin film of the silane coupling agent. The method for producing a resin-coated metal sheet is in the range of Vickers hardness of the manufacturing of the coating film surface between 25 and 60.