JP4098567B2 - Method for producing film with plating film - Google Patents

Description

【００５３】
また、下記化２に示すような繰り返し単位を５０モル％以上含むポリマーからなり、湿式あるいは乾式製膜したフィルム、あるいは該フィルムを二軸延伸および／または熱処理せしめたフィルムも好ましく使用される。
【００５４】
【化２】

【００５５】
フレキシブル回路用の場合、基材であるプラスチックフィルムの厚さは６〜１２５μｍ程度のものが多用され、とくに１２〜５０μｍの厚さのものが好適に用いられる。
【００５６】
【実施例】
以下、本発明の実施例の一例を示すが、本発明はこれに限定されるものではない。なお、実施例中の各特性値は、次の方法に従って測定した。
【００５７】
（１）プラスチックフィルムの表面張力
ＪＩＳ Ｋ６７６６−１９７７（ポリエチレン及びポリプロピレンの濡れ試験方法）に準じ、表面張力５６ｄｙｎｅ／ｃｍ以下はホルムアミド／エチレングリコールモノエチルエーテル混合溶液を、標準液として表面張力を求めた。また、表面張力５７〜７３ｄｙｎｅ／ｃｍの範囲は、水（７２．８ｄｙｎｅ／ｃｍ）／エチレングリコール（４７．７ｄｙｎｅ／ｃｍ）の混合液を標準液として、表面張力を求めた。
【００５８】
（２）接触角
協和界面科学（株）製ＦＡＣＥ接触角計を用い、液滴法によって求めた。
【００５９】
（３）スパッタ膜の膜厚
触針式表面粗さ計を用いて、評価した。尚、試料はスパッタ膜形成前に溶剤で除去可能なインクを一部分に塗布しておいてスパッタ膜を形成し、ついで成膜後にインク塗布部分を除去して測定した。
【００６０】
（４）めっき膜の膜厚
めっき被膜の一部分をエッチング液により除去し、キーエンス（株）製のレーザ顕微鏡を用いて、その段差を測定して求めた。
【００６１】
（５）導電率
株式会社コス製の導電率メーターＣＥＨ−１２を用いて測定した。測定方式は、交流２電極方式で、測定範囲は０〜１９９ｍＳ／ｃｍセンサーである。
【００６２】
（６）液膜隙間
図６に示すような装置を使用して液膜隙間の大きさを測定した。図６に示す測定装置においては、液膜厚さ測定用架台４１に取り付けられたスライドガイド４２に沿って、ケーブル４３付きの変位計４４が移動され、検出信号をアンプユニット４５で増幅、出力させた。尚、測定センサ（変位計）は、キーエンス（株）製のレーザ変位計により、液膜の厚さを同定した。センサヘッドには、”ＬＫ−０１０”超小型・高精度ＣＣＤレーザ変位センサ、アンプユニットには、”ＬＫ−３１００”を用いて測定した。なお、センサスペックは、分解能０．１μｍ、スポット径２０μｍ、基準距離１０ｍｍとして測定した。
【００６３】
（７）搬送張力
搬送陰極ロールの両側にロードセルの方式のセンサーを取付け測定した。センサーは、ミネベア（株）製の”Ｃ２Ｇ１−２５Ｋ”型を用いた。測定範囲は０〜２５０Ｎの測定が可能なスペックである。ロール重さとフィルム搬送の抱き角から厳密に張力値を換算して校正したものの値を張力値とした。
【００６４】
実施例１
銅付きフィルムをフレキシブル回路基板に応用した例を示す。
（１）導電面つきフィルムの製作
減圧装置の中で、ロール状に巻き取ったフィルムを巻き出しながら処理し、その後フィルムを巻取ロール状にする装置で、プラズマ処理、ニッケル−クロム層成膜、銅層成膜を行った。
【００６５】
厚さ２５μｍ、幅５２０ｍｍ、長さ１２５００ｍのポリイミドフィルム”カプトン”１（米国デュポン社の登録商標）のロール状体を用意した。
【００６６】
上記フィルムの片面に、２ｍ／分の速度でアルゴンガスのグロー放電プラズマ処理を実施した。処理は高電圧を印加した棒状の電極に対して２ｃｍの距離でフィルムを搬送し、かつ接地電極となっている電極対をもつ内部電極方式のプラズマ装置を使用した。アルゴンガス圧力は２．５Ｐａ、１次出力電圧２ｋＶ、高周波電源周波数１１０ｋＨｚの条件でフィルムを２ｍ／分で処理を行い、グロー放電プラズマ層を形成した。なお、処理されたフィルムの表面張力は、７０ｄｙｎｅ／ｃｍ以上で、接触角は４３度であった。
【００６７】
次いで、アルゴンガス圧２．６×１０^-2Ｐａにて、クロム２０％、ニッケル８０％のターゲットを用いて３０ｎｍのニッケルクロム層をＤＣマグネトロンスパッタ法を適用して形成した。その後、純度９９．９９％の銅をターゲットを用いて１００ｎｍの銅層をＤＣマグネトロンスパッタ法を適用して形成した。
【００６８】
上記フィルムは、スパッタ膜形成のための条件出しやリード部分を除いて、１２０００ｍのスパッタ膜つきフィルムを製造した。
【００６９】
（２）めっき被膜の形成
上記（１）で得られたロール状のスパッタ膜つきフィルム１２０００ｍを、３０００ｍのロール状体に４分割して、５２０ｍｍ×３０００ｍのロール状体の導電膜つきフィルムを４本準備し、そのうち１本を次に示すめっき装置に通してめっき被膜を形成した。
【００７０】
めっき装置として、図１および図３に示す装置を用いて、陽極に銅を用いて、銅のめっき被膜を８μｍ形成した。図４において、一点鎖線内のユニットを１６ユニットとするめっき回路およびめっき装置を構成した。
【００７１】
陰極ロールは、直径２１０ｍｍ、長さ８００ｍｍ、肉厚１０ｍｍのＳＵＳ３１６の円管を用いてこれに給電するものとした。陰極ロール１ａから液中ロール１０１ａを介して陰極ロール１ｂまで、フィルムをパスさせたときのフィルムパス長は４ｍの装置を用いた。なおパス長は陰極ロールの頂点から頂点までをいう。従って、めっき部の全パス長は６４ｍである。
【００７２】
フィルムの前処理条件、めっき条件、防錆処理条件は、表１に示す条件で行った。なお、銅めっきは、陰極ロールと液中ロールのパスの繰り返し数が進むつれて徐々に電流密度が上昇するように設定した。第１から第１６ユニットの整流器毎の電流設定条件は、表２に示す通りである。
【００７３】
表２の電流条件と銅の還元電位０．３３７Ｖにより、各電流値に対して、（１）式を用いて液膜隙間ｄと導電率σの関係をグラフ化すると、図５のようになり、各グラフの上側になるように導電率を制御すればよいことになる。なお、銅の還元電位はＣｕイオンの活量、あるいは濃度により変化するが、銅の標準単位電極電位であるＣｕ²⁺／Ｃｕの値は０．３３７Ｖであり、銅イオンの濃度から、この値より小さい値になるのでこれを還元電位とした。また、フィルム導電面と陰極ロールの接触面積は抱き角が１２０度としたので、５２０ｍｍ幅×約２２０ｍｍで計算した。
【００７４】
液膜隙間ｄは、図６に示すようにレーザ変位計で隙間の大きさを測定し、隙間ｄが３００μｍ以下になるようにフィルム搬送張力の設定をした。フィルム張力設定は、図３に示すＳ字ラップの速度制御部３０９によって適度に張力をカットし、その後、順次ロールの回転速度にドローをかける方式で張力を設定した。張力は陰極ロール３２５（張力検出ロール）部でロードセルによって自動で圧力検出を行い、張力が１６０Ｎ／ｍになるように速度調整部３２１の駆動モータの速度でフィードバック制御した。そこで、もっとも張力の張りが悪い陰極ロール１ａ部の液膜隙間を図６を検出装置として測定したところ、１２５μｍであった。
【００７５】
搬送速度は１ｍ／分、陰極ロール１ａ〜１ｑまでの陰極ロールのモータ駆動設定に段階的にドロー比率設定を行い順次速度を上げ、張力を徐々に上げる方式とした。
【００７６】
一つ一つのユニット毎に導電率を変化させるように制御してもよいが、装置が高価になるために、すべてのユニットに対して、銅析出限界とならないように、液膜の導電率を１０ｍＳ／ｃｍになるように調整した。図１におけるタンク１１の硫酸濃度を調整して、１００ｍｌ／分となるようにポンプの設定を行い、受皿１０中の液濃度をコントロールした。
【００７７】
その結果、陰極ロール表面には銅の析出がなく、搬送状態も非常に安定していて、良好な巻姿のロール状フィルムを得た。
【００７８】
その後、検査で、めっき銅表面を観察したところ、めっき表面の異常な突起や凹みが少なく表面品位の優れた銅付きフィルムを得た。異常な突起や凹みの個数は、表３に示す結果となった。
【００７９】
（３）回路パターンの形成
感光性液体レジストをコーティングし、６０μｍピッチ、すなわち、銅導体線幅３０μｍ、導体線間３０μｍの回路パターン１０２４本のマスクを使い紫外線露光と現像を行い、塩化第二鉄エッチング液で回路パターンを形成した。その回路パターン５０枚を１５０倍の実態顕微鏡で観察し、欠け（１０μｍ以上の欠けは不合格で、それが１０２４本中に１本以上あればその回路パターンを不合格とする。）および断線によるパターンの良否を判定した結果を表４に示す。これにより１００％収率の回路パターンが得られた。
【００８０】
【表１】

【００８１】
【表２】

【００８２】
【表３】

【００８３】
【表４】

【００８４】
実施例２
銅付きフィルムをフレキシブル回路基板に応用した例を示す。
（１）導電面つきフィルムの製作
実施例１と全く同様の導電面つきフィルムを作成した。
【００８５】
（２）めっき被膜の形成
上記（１）で得られたロール状のスパッタ膜つきフィルム１２０００ｍを、３０００ｍのロール状体に４分割して、５２０ｍｍ×３０００ｍのロール状体の導電膜つきフィルムを４本準備し、そのうち１本を次に示すめっき装置に通してめっき被膜を形成した。
【００８６】
めっき装置として、図２および図３に示す装置を用いて、陽極に銅を用いて、銅のめっき被膜を８μｍ形成した。図４において、一点鎖線内のユニットを１６ユニットとするめっき回路およびめっき装置を構成した。
【００８７】
陰極ロールは、直径２１０ｍｍ、長さ８００ｍｍ、肉厚１０ｍｍのＳＵＳ３１６の円管を用いてこれに給電するものとした。陰極ロール１ａから液中ロール１０１ａを介して陰極ロール１ｂまで、フィルムをパスさせたときのフィルムパス長は４ｍの装置を用いた。なおパス長は陰極ロールの頂点から頂点までをいう。従って、めっき部の全パス長は６４ｍである。
【００８８】
フィルムの前処理条件、めっき条件、防錆処理条件は、表１に示す条件で行った。なお、銅めっきは、陰極ロールと液中ロールのパスの繰り返し数が進むつれて徐々に電流密度が上昇するように設定した。第１から第１６ユニットの整流器毎の電流設定条件は、表２に示す通りである。
【００８９】
表２の電流条件と銅の還元電位０．３３７Ｖにより、各電流値に対して、（１）式を用いて液膜隙間ｄと導電率σの関係をグラフ化すると、図５のようになり、各グラフの上側になるように導電率を制御すればよいことになる。なお、銅の還元電位はＣｕイオンの活量、あるいは濃度により変化するが、銅の標準単位電極電位であるＣｕ²⁺／Ｃｕの値は０．３３７Ｖであり、銅イオンの濃度から、この値より小さい値になるのでこれを還元電位とした。また、フィルム導電面と陰極ロールの接触面積は抱き角が１２０度としたので、５２０ｍｍ幅×約２２０ｍｍで計算した。
【００９０】
液膜隙間ｄは、図６に示すようにレーザ変位計で隙間の大きさを測定し、隙間ｄが３００μｍ以下になるようにフィルム搬送張力の設定をした。フィルム張力設定は、図３に示すＳ字ラップの速度制御部３０９によって適度に張力をカットし、その後、順次ロールの回転速度にドローをかける方式で張力を設定した。張力は陰極ロール（張力検出ロール）３２５部でロードセルによって自動で圧力検出を行い、張力が１６０Ｎ／ｍになるように速度調整部３２１の駆動モータの速度でフィードバック制御した。そこで、もっとも張力の張りが悪い陰極ロール１ａ部の液膜隙間を図６を検出装置として測定したところ、８０μｍであった。各陰極ロール上の液膜隙間を測定したところ、表３の通りであった。
【００９１】
搬送速度は１ｍ／分、陰極ロール１ａ〜１ｑまでの陰極ロールのモータ駆動設定に段階的にドロー比率設定を行い順次速度を上げ、張力を徐々に上げる方式とした。
【００９２】
一つ一つのユニット毎に導電率を変化させるように制御してもよいが、装置が高価になるために、すべてのユニットに対して、銅析出限界とならないように、液膜の導電率を２ｍＳ／ｃｍになるように調整した。すなわち、図２におけるドクターブレードを洗い流す液体２５として硫酸を用い、その導電率を２ｍＳ／ｃｍとし、３分毎に２秒間のシャワー供給で、２分毎に２００ｍｌの液体を供給した。また、スポンジ体に液体を供給する液体２７として硫酸を用い、その導電率を２ｍＳ／ｃｍとし、３分毎に２秒間のシャワー供給で、２分毎に２００ｍｌの液体を供給した。なお、ドクターブレードへの硫酸シャワー供給の１分後に供給するシーケンスとした。また、陰極ロールに供給する液体３０として硫酸を用い、その導電率を２ｍＳ／ｃｍとし、３分毎に２秒間のシャワー供給で、２分毎に２００ｍｌの液体を供給した。なお、スポンジ体への硫酸シャワー供給の１分後に供給するシーケンスとした。こうして、液膜の液濃度をコントロールした。
【００９３】
一部、液膜隙間と導電率の関係から、（１）式を満たさなくなり陰極ロールのフィルムからの離れ際に陰極ロール上の銅を確認したが、ブレードおよび、スポンジにより除去ができ、回転してその後、フィルムに接するときには清浄な陰極ロールであることを確認した。
【００９４】
その結果、陰極ロール表面には銅の析出が抑制でき、搬送状態も非常に安定していて、良好な巻姿のロール状フィルムを得た。
【００９５】
なお、このブレードは、イーエルジャパン（株）製のプラスチックブレードＥ５００を使用した。また、弾性体としてのスポンジは、ＰＶＡのスポンジを使用して、押し圧力が５０Ｎ／ｍになるように均一に押しつけた。
【００９６】
その後、検査で、めっき銅表面を観察したところ、めっき表面の異常な突起や凹みが少なく表面品位の優れた銅付きフィルムを得た。異常な突起や凹みの個数は、表３に示す結果となった。
【００９７】
（３）回路パターンの形成
感光性液体レジストをコーティングし、６０μｍピッチ、すなわち、銅導体線幅３０μｍ、導体線間３０μｍの回路パターン１０２４本のマスクを使い紫外線露光と現像を行い、塩化第二鉄エッチング液で回路パターンを形成した。その回路パターン５０枚を１５０倍の実態顕微鏡で観察し、欠け（１０μｍ以上の欠けは不合格で、それが１０２４本中に１本以上あればその回路パターンを不合格とする、）および断線によるパターンの良否を判定した結果を表４に示す。これにより１００％収率の回路パターンが得られた。
【００９８】
比較例１
銅付きフィルムをフレキシブル回路基板に応用した例を示す。
（１）導電面つきフィルムの製作
実施例１と全く同様の導電面つきフィルムを作成した。
【００９９】
（２）めっき被膜の形成
上記（１）で得られたロール状のスパッタ膜つきフィルム１２０００ｍを、３０００ｍのロール状体に４分割して、５２０ｍｍ×３０００ｍのロール状体の導電膜つきフィルムを４本準備し、そのうち１本を次に示すめっき装置に通してめっき被膜を形成した。
【０１００】
めっき装置として、図２および図３に示す装置を用いて、陽極に銅を用いて、銅のめっき被膜を８μｍ形成した。図４において、一点鎖線内のユニットを１６ユニットとするめっき回路およびめっき装置を構成した。
【０１０１】
陰極ロールは、直径２１０ｍｍ、長さ８００ｍｍ、肉厚１０ｍｍのＳＵＳ３１６の円管を用いてこれに給電するものとした。陰極ロール１ａから液中ロール１０１ａを介して陰極ロール１ｂまで、フィルムをパスさせたときのフィルムパス長は４ｍの装置を用いた。なおパス長は陰極ロールの頂点から頂点までをいう。従って、めっき部の全パス長は６４ｍである。
【０１０２】
フィルムの前処理条件、めっき条件、防錆処理条件は、表１に示す条件で行った。なお、銅めっきは、陰極ロールと液中ロールのパスの繰り返し数が進むつれて徐々に電流密度が上昇するように設定した。第１から第１６ユニットの整流器毎の電流設定条件は、表２に示す通りである。
【０１０３】
液膜隙間ｄは、図６に示すようにレーザ変位計で隙間の大きさを測定し、隙間ｄが３００μｍ以下になるようにフィルム搬送張力の設定をした。フィルム張力設定は、図３に示すＳ字ラップの速度制御部３０９によって適度に張力をカットし、その後、順次ロールの回転速度にドローをかける方式で張力を設定した。張力は陰極ロール３２５（張力検出ロール）でロードセルによって自動で圧力検出を行い、張力が１６０Ｎ／ｍになるように速度調整部３２１の駆動モータの速度でフィードバック制御した。そこで、もっとも張力の張りが悪い陰極ロール１ａ部の液膜隙間を図６を検出装置として測定したところ、１２５μｍであった。各陰極ロール上の液膜隙間を測定したところ、表３の通りであった。
【０１０４】
搬送速度は１ｍ／分、陰極ロール１ａ〜１ｑまでの陰極ロールのモータ駆動設定に段階的にドロー比率設定を行い順次速度を上げ、張力を徐々に上げる方式とした。
【０１０５】
図１におけるタンク１１にイオン交換水を入れて、１００ｍｌ／分となるようにポンプの設定を行い、受皿１０中に供給した。この時、受皿１０中の導電率は０．０２ｍＳ／ｃｍであった。
【０１０６】
その結果、陰極ロール表面には、搬送前半部の陰極ロールはうっすらと銅系色になり、第６番目の陰極ロールから第１４番目の陰極ロールには、銅の析出が発生し、陰極ロールが銅系色になった。初めは、搬送状況は安定して搬送できていたが、銅の析出したロールになってから徐々に搬送が不安になり、陰極ロール上でフィルムがグリップされ、張りと撓みが発生し、液中の撹拌エアーのあおりを受けてフィルムが蛇行し始め、陰極ロール上でシワが発生し、また、銅付きフィルムの剛性が大きいために折れシワの発生もあった。
【０１０７】
その後、検査で、めっき銅表面を観察したところ、フィルムの折れシワで製品にならず、一部シワのない場所でも、フィルム搬送方向に点々と長径１００μｍ、高さ６０μｍ大の以上突起がたくさん発生していた。異常な突起や凹みの個数は、表３に示す結果となった。
【０１０８】
（３）回路パターンの形成
感光性液体レジストとコーティングし、６０μｍピッチ、すなわち、銅導体線幅３０μｍ、導体線間３０μｍの回路パターン１０２４本のマスクを使い紫外線露光と現像を行い、塩化第二鉄エッチング液で回路パターンを形成した。その回路パターン５０枚を１５０倍の実態顕微鏡で観察し、欠け（１０μｍ以上の欠けは不合格で、それが１０２４本中に１本以上あればその回路パターンを不合格とする。）および断線によるパターンの良否を判定した結果を表４に示す。収率６％でほとんど正常な回路パターンは得られなかった。
【０１０９】
比較例２
銅付きフィルムをフレキシブル回路基板に応用した例を示す。
（１）導電面つきフィルムの製作
実施例１と全く同様の導電面つきフィルムを作成した。
【０１１０】
（２）めっき被膜の形成
上記（１）で得られたロール状のスパッタ膜つきフィルム１２０００ｍを、３０００ｍのロール状体に４分割して、５２０ｍｍ×３０００ｍのロール状体の導電膜つきフィルムを４本準備し、そのうち１本を次に示すめっき装置に通してめっき被膜を形成した。
【０１１１】
めっき装置として、図２および図３に示す装置を用いて、陽極に銅を用いて、銅のめっき被膜を８μｍ形成した。図４において、一点鎖線のユニットを第１ユニットとして、二点鎖線のユニットを１４ユニット構成し、一点鎖線内の対称形のユニットを最後の第１６ユニットとしてめっき回路およびめっき装置を構成した。
【０１１２】
陰極ロールは、直径２１０ｍｍ、長さ８００ｍｍ、肉厚１０ｍｍのＳＵＳ３１６の円管を用いてこれに給電するものとした。陰極ロール１ａから液中ロール１０１ａを介して陰極ロール１ｂまで、フィルムをパスさせたときのフィルムパス長は４ｍの装置を用いた。なおパス長は陰極ロールの頂点から頂点までをいう。従って、めっき部の全パス長は６４ｍである。
【０１１３】
フィルムの前処理条件、めっき条件、防錆処理条件は、表１に示す条件で行った。なお、銅めっきは、陰極ロールと液中ロールのパスの繰り返し数が進むつれて徐々に電流密度が上昇するように設定した。第１から第１６ユニットの整流器毎の電流設定条件は、表２に示す通りである。
【０１１４】
液膜隙間ｄは、図６に示すようにレーザ変位計で隙間の大きさを測定し、隙間ｄが５０μｍ以下になるようにフィルム搬送張力の設定をした。フィルム張力設定は、図３に示すＳ字ラップの速度制御部３０９によって適度に張力をカットし、その後、順次ロールの回転速度にドローをかける方式で張力を設定した。張力は陰極ロール３２５（張力検出ロール）でロードセルによって自動で圧力検出を行い、張力が３２０Ｎ／ｍになるように速度調整部３２１の駆動モータの速度でフィードバック制御した。
【０１１５】
搬送速度は１ｍ／分、陰極ロール１ａ〜１ｑまでの陰極ロールのモータ駆動設定に段階的にドロー比率設定を行い順次速度を上げ、張力を徐々に上げる方式とした。また、図１におけるタンク１１からの液体供給無しで搬送させた。
【０１１６】
その結果、陰極ロール表面には、搬送前半部の陰極ロールはうっすらと銅系色になり、第６番目の陰極ロールから第１４番目の陰極ロールには、銅の析出が発生し、陰極ロールが銅系色になった。初めは、少し搬送できていたが、張力がだんだんと張ってくると、フィルムは、非常に大きな引張状態になり、しばらくすると折れシワが発生し、その後、破断した。
【０１１７】
以上表３に示した特性から明らかなように、本発明の製造方法で作成したフレキシブル回路基板は、ファインピッチにも対応した非常に優れた外観品位をもつ銅付きフィルムを得ることができたと言える。
【０１１８】
【発明の効果】
本発明によれば、表面品位の優れためっき被膜を形成できる。特にフレキシブル回路基板用の銅付きフィルムにおいて、非常に優れた品質の製品を提供できる。銅表面に突起や凹み欠点が非常に少ないために、回路ピッチとしてのファインピッチ化に有効であり、特に６０μｍ以下のピッチに対応できる。
【０１１９】
また、本発明よれば、生産工程のめっき工程においてトラブルを防止し、特に陰極ロール部に発生するめっき被膜の異常析出を抑制できる。また、異常析出が一部発生したとしても陰極ロールについたドクターブレードや弾性体で除去可能な構成になっている。
【０１２０】
特にめっき被膜として銅が有効であり、フレキシブル回路基板に採用されるめっき型２層品の製造時に特に有効である。
【図面の簡単な説明】
【図１】本発明における一実施態様に係るめっき装置の陰極ロール部の拡大概略縦断面図である。
【図２】本発明における別の実施態様に係るめっき装置の陰極ロール部の拡大概略縦断面図である。
【図３】本発明におけるめっき装置の全体の一例を示す概略縦断面図である。
【図４】図３の装置の一部を拡大した図で、給電方法の一例を示す概略構成図である。
【図５】実施例における各整流器の投入電流値に対して、隙間と導電率の関係を表すグラフである。
【図６】実施例における液膜隙間の測定装置の概略斜視図である。
【符号の説明】
１ 陰極ロール
１ａ、１ｂ、１ｃ 陰極ロール
２ 陽極
３、３ａ、３ｂ 直流電源
４ フィルム
５ フィルムの導電面
６ めっき槽
７ めっき液
８ 液膜隙間
９ 受皿中の液体
１０ 受皿
１１ 電解液のタンク
１２ 電解液
１３ 配管
１４ ポンプ
１５ バルブ（電磁バルブ）
１６ 配管
１７ 受皿中の液体を排出する配管
２１ ブレード
２２ 弾性体
２３ 弾性体固定治具
２４ ブレード部へ液体を供給する配管
２５ ブレード部へ供給される液体
２６ ブレード固定治具
２７ 弾性体部へ液体を供給する配管
２８ 弾性体部へ供給される液体
２９ 陰極ロールへ液体を供給する配管
３０ 陰極ロールへ供給される液体
３１ 受皿
３２ 受皿中の液体
３３ 受皿中の液体を排出する配管
４１ 液膜厚さ測定用架台
４２ スライドガイド
４３ ケーブル
４４ 変位計
４５ アンプユニット
１０１ａ、１０１ｂ 液中のフィルム搬送ロール
１０２ａ、１０２ｂ、１０２ｃ、１０２ｄ、１０２ｅ 陽極の金属
１０６ａ、１０６ｂ、１０６ｃ 遮蔽板
３０１ 巻出部
３０２ 前処理部
３０３ 電気めっき部
３０４ 後処理部
３０５ 巻取部
３０６ めっき前のロール状フィルム
３０７ アキュムレータ
３０８ バランスロール部
３０９ 速度制御部
３１０ 酸、脱脂処理部
３１１ 酸、脱脂処理液
３１２ 水洗部
３１３ 水洗液
３１４ 水洗部
３１５ 水洗液
３１６ 防錆処理部
３１７ 防錆液
３１８ 水洗部
３１９ 水洗液
３２０ 乾燥工程部
３２１ 速度調整部
３２２ バランスロール部
３２３ アキュムレータ
３２４ めっき被膜付きロール状フィルム
３２５ 張力検出ロール
３３０ａ、３３０ｂ、３３０ｃ、３３０ｄ エアー撹拌用ノズル
３３１ａ、３３１ｂ、３３１ｃ、３３１ｄ 撹拌用エアー[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a film with a plating film by forming a plating film on the film while conveying the film, and particularly relates to a method for producing a film with a plating film suitable for a resin film. Among them, the present invention is suitable for the production of a flexible circuit board in which a plating film is formed on a film, and after depositing a metal on the film, a metal deposition film / metal plating film laminated film for forming a plating film, Suitable for the production of electroless plating / electroplating film laminated film, etc., which forms an electroplating film after electroless plating is applied to the film. These make electronic devices and parts smaller, lighter and less expensive. The adhesive-less two-layer flexible printed wiring board can be configured, and a flexible printed wiring board suitable for use in TAB, COF, PGA, etc. in semiconductor packaging can be provided.
[0002]
[Prior art]
As described in JP-A-7-22473, JP-A-2000-192793, etc., a method for continuously forming a plating film while conveying a film is as follows. There is known a method in which a plating bath in which an anode is introduced is disposed before or after the contact with the substrate and a plating film is formed in the plating bath. If a plating film is continuously formed on a film by such a method, it is possible to easily form a plating film having a desired thickness on the film by repeatedly passing a unit in which a cathode and an anode are arranged. It is.
[0003]
2. Description of the Related Art In recent years, attention has been paid to a wiring board in which a polyimide film or a polyester film and a copper foil are combined as a flexible circuit board that has come to be used in electronic devices, electronic components, semiconductor packages, and the like. This substrate has a so-called “three-layer type” in which a copper foil is bonded to a film through an adhesive, and a so-called “two-layer type” in which a metal film is formed by plating or the like without using an adhesive on the film. There is a flexible circuit board called "". Of these, the latter two-layer type is attracting more attention as the wiring pitch of the circuit advances.
[0004]
The current situation regarding these flexible circuit boards is as follows. The three-layer printed circuit board has a disadvantage that the electrical properties deteriorate due to the impurity ions contained in the epoxy resin or acrylic resin because the epoxy resin or acrylic resin is used as the adhesive. Since the heat-resistant temperature is at most 100 ° C to 150 ° C, even if polyimide is used as the base film material, its high heat resistance (300 ° C or higher) cannot be fully utilized. In bonding and the like, the specification of the heating temperature is forced down. In the three-layer type printed circuit board, since the general film thickness of the copper foil is 18 μm or 35 μm, the copper is too thick for patterning at a pitch of 80 μm (copper wiring 40 μm, gap 40 μm) or less. The etching rate is remarkably lowered, and the circuit width on the surface side of the copper foil and the circuit width on the adhesive surface side are remarkably different, or the whole is remarkably thinned by etching, and the target circuit pattern cannot be obtained.
[0005]
In recent years, in order to solve the problems in the three-layer type as described above, various vapor deposition methods such as a vacuum vapor deposition method, a sputtering method, or various ion plating methods without using an adhesive on the film, metal The so-called “two-layer” obtained by first depositing various metals on the film by the so-called CVD method for vaporizing and containing chemicals containing copper, or after plating various metals by the electroless plating method, followed by electrolytic copper plating A "type" substrate has been proposed. In this two-layer substrate, the copper film thickness can be freely changed by electrolytic copper plating. For example, if the copper film thickness is 8 μm, a circuit pattern with a pitch of 60 μm can be easily created. The heat resistance temperature of the film can be reflected as it is.
[0006]
From the above situation, the demand for films with plating films is increasing. However, when plating is performed on a film-like body in this way, it cannot be transported with such a large tension due to the rigidity of the film, and transport with the apparatus according to the above method is performed under a certain degree of tension. If the film needs to be transported and there is no slip between the plating film and the cathode roll, the film will be gripped, and the film will be wrinkled due to unbalanced transport tension in the film width direction, deteriorating the transport state. In addition, there is a problem that the film is broken, that is, a wrinkle is generated. In order to solve such problems, a certain amount of liquid lubrication is required. Conventionally, as can be seen from the apparatus configuration, the film is accompanied by a plating solution from a plating bath, and a liquid film is formed on the cathode roll. By forming, a certain amount of slip was generated between the film and the cathode roll, and the instability of the grip in the film width direction was suppressed, and the deterioration of the conveyance state was suppressed. However, as shown in Japanese Patent Application Laid-Open No. 2000-192793, etc., if the transport film is a metal stay such as a copper foil, the transport tension of the film can be increased and the surface resistance value is small. However, as shown in Japanese Patent Application Laid-Open No. 7-22473, when trying to transport a polyimide film having a thickness of 50 μm, the relationship between the Young's modulus and strength of the film is related. Therefore, there is a problem that the film may be broken or an internal stress is generated in the plating film to be coated. Therefore, a large tension cannot be applied, and a method of forming a plating film while balancing under a relatively low film tension has been adopted. In other words, by interposing a liquid film containing a certain amount of plating solution between the cathode roll and the conductive surface of the film, an appropriate slip is generated between the cathode roll and the film and the conveyance is stabilized. It was.
[0007]
However, even in such a method, when a current is passed from the cathode roll to form a plating film, the plating film metal component often precipitates on the cathode roll, and the deposited plating film metal is held in the film. In some cases, abnormal projections (convex defects) may occur due to electrolytic concentration using this as a nucleus in the plating bath. In addition, the deposited plating film metal may dent the film, or scratch the conductive surface or the plating film surface, and this dent or scratched part may become a concave defect by making the film thickness thinner than the final plating film thickness. There was often. Furthermore, the shape of the deposited plating film metal is transferred to the film conductive surface, resulting in a problem of deteriorating the surface quality. Such abnormal protrusions (convex type) and dent-like defects may cause defects such as disconnection in the etching process when making circuit wiring and bonding processes such as IC chips in the circuit mounting process, and the circuit can be guaranteed. Invite the problem of disappearing.
[0008]
No method has yet been found to suppress the plating film metal deposition on the cathode roll causing such problems, and currently, after operating the apparatus for a while, the production is stopped and the plating film metal deposited is removed from the cathode roll surface. I was scraped off and then restarted. Such removal of the plating film metal significantly reduces productivity.
[0009]
[Problems to be solved by the invention]
As a result of intensive studies to solve the above problems, the present inventors have been able to produce a film with a very excellent plating film having a surface quality free from abnormal protrusions (convex shapes) and dent defects. Reached.
[0010]
In recent years, ICs and high density / high integration of electric / electronic devices have rapidly advanced, and accordingly, the pattern width of flexible printed circuit boards has been increased from 150-200 μm pitch to 80-150 μm pitch. Currently, 30 to 80 μm pitch is required, but the method of the present invention has been developed as a very effective method to cope with such fine pitch.
[0011]
That is, the subject of this invention is obtaining the film with a plating film with few abnormal protrusions and a dent defect even if it is a flexible film substrate containing resin. Another object of the present invention is to obtain a two-layer printed wiring board that can obtain an ultrafine circuit pattern of 80 μm or less in a high yield. Another object of the present invention is to obtain a two-layer printed wiring board that is excellent in reliability when a circuit is formed.
[0012]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the method for producing a film with a plating film according to the present invention brings a film conductive surface into contact with a cathode roll through a liquid film while conveying a film having a conductive surface, and before or / And a method for producing a film with a plating film by forming a plating film on the film conductive surface in a plating bath disposed later, the gap d between the cathode roll and the film conductive surface, and the conductivity of the liquid present in the gap d It consists of a method characterized in that the rate σ and the value of the current passed through the cathode roll for plating are controlled within the range of the following relational expression.
E ₀ > [(I / A) × d] / σ
Where A: area of the conductive surface of the film in contact with the cathode roll, I: current value to be applied to plating, E ₀ : Reduction potential of plating film metal, d: size of gap, σ: conductivity.
[0013]
In this method for producing a film with a plating film, the conductivity of the liquid present in the gap can be controlled by, for example, the concentration of an electrolytic solution mainly composed of sulfuric acid. The conductivity of the liquid present in the gap is preferably 1 mS / cm or more and 100 mS / cm or less.
[0014]
The size of the gap d can be controlled by the film transport tension. The conveyance tension of the film is preferably 10 N / m or more and 320 N / m or less. The size of the gap d is preferably 2 μm or more and 500 μm or less.
[0015]
Moreover, in order to scrape the plating film component deposited on the cathode roll, a cathode roll structure including a blade and / or an elastic body can be employed. That is, in the method for producing a film with a plating film according to the present invention, the film conductive surface is brought into contact with the cathode roll through the liquid film while the film having the conductive surface is conveyed, and the plating disposed before or / and after that is disposed. A method for producing a film with a plating film, which forms a plating film on a film conductive surface in a bath, comprising scraping off a plating film component deposited on a cathode roll with a blade and / or an elastic body. Further, the liquid can be continuously or intermittently supplied to the cathode roll and / or the blade and / or the elastic body.
[0016]
As a plating film, it can typically form with copper. Moreover, as a film, what consists of a polyimide resin or a polyester resin can be used, for example. The present invention also provides a method for producing a circuit board for forming a circuit pattern on a film produced by such a method for producing a film with a plating film.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail together with preferred embodiments with reference to the drawings.
In the present invention, while conveying a film having a conductive surface, the film conductive surface is brought into contact with a cathode roll through a liquid film, and a plating film is formed on the film conductive surface in a plating bath disposed before or after that. In this case, the gap d between the cathode roll and the film conductive surface, the conductivity σ of the liquid existing in the gap d, and the current value flowing through the cathode roll are controlled within the range of the following relational expression. It is a manufacturing method of a film with a plating film.
E ₀ > [(I / A) × d] / σ
Where A: area of the conductive surface of the film in contact with the cathode roll, I: current value to be applied to plating, E ₀ : Reduction potential of plating film metal, d: size of gap, σ: conductivity.
[0018]
The method according to the present invention will be described with reference to the drawings showing an example of an apparatus expressing the features.
FIG. 3 is a schematic longitudinal sectional view showing an example of the entire plating apparatus for carrying out the method of the present invention. FIGS. 1 and 2 show examples of features of the method according to the present invention.
[0019]
FIG. 3 is an overall schematic longitudinal sectional view of a continuous electroplating apparatus for unwinding, plating and winding a long film from a roll state. The main steps are to remove the unrolled portion 301 for unwinding the roll-shaped film, the pretreatment portion 302 for subjecting the conductive surface of the film to acid treatment, degreasing treatment, water washing, etc., the electroplating portion 303, the plating solution, or washing away, It consists of a rust preventive treatment, a wash-out treatment, a post-treatment portion 304 for performing drying, and a winding portion 305 for winding on a roll film. In addition, when the electroconductive surface which is an electroplating to-be-processed part is clean, a pre-processing may be abbreviate | omitted and a post-processing process may be abbreviate | omitted as needed.
[0020]
In FIG. 3, the film unwound from the roll film 306 is adjusted in tension through the accumulator 307 and the balance roll unit 308, and then the speed is controlled to be substantially constant by the speed control unit 309. Then, after passing through the degreasing part 310 and the water washing part 312, the plating bath 6 is put into a plating bath containing the plating solution 7. A part of the plating bath shown in FIG. 3 is enlarged and shown in FIG. 4. After the film conductive surface is brought into contact with the cathode roll 1a, the inside of the plating bath is brought into contact with the cathode roll 1b through the submerged roll 101a. Let Cases 102a and 102b filled with copper balls are used as anodes, cathodes are used as cathode rolls 101a and 102b, and power is supplied from a DC power source 3a to form a plating film on the film. In the plating bath, shielding plates 106a to 106c are provided for the respective anodes. Hereinafter, cathode roll 1b and cathode roll 1c are used as cathodes, 102c and 102d are used as anodes, and power is supplied from DC power supply 3b to form a plating film on the film. Thereafter, the plating film is formed by repeating this process.
[0021]
One unit is a unit indicated by an alternate long and short dash line, and this is repeated. Current conditions are 0.2 to 10 A / dm for the film. ² A plating film is formed on the film so that the current density is as follows. Then, by repeating this, a plating film is sequentially formed, and a plating film having a thickness of 1 to 30 μm is formed on the conductive surface of the film in total.
[0022]
In order to maintain the uniformity of plating, fresh air 331a to 331d is introduced from the air inlets (air stirring nozzles) 330a to 330d, and the liquid in the plating tank 6 is sufficiently stirred. This is effective to aim at the plating film portion, and is performed in order to increase the concentration of plating film metal ions in the vicinity of the extreme surface of the formed plating film. Although not shown, the plating solution removes dirt through the filter and is constantly circulating.
[0023]
Next, as shown in FIG. 3, through a roll 325 capable of detecting film tension, a water washing part 314 for removing the plating solution and a rust prevention treatment part 316 containing a rust prevention treatment liquid 317 for protecting the plating film are provided. After that, the tension was adjusted via the water washing part 318 for removing excess rust prevention treatment liquid, the drying process part 320 having a drying furnace for removing moisture, the speed adjusting part 321, the balance roll part 322, and the like. Thereafter, a roll film 324 is formed through an accumulator 323. Thus, a film with a plating film is obtained.
[0024]
FIG. 1 is an enlarged view of an example of a cathode roll portion showing the features of the present invention. The film 4 rotates to the right while the conductive surface 5 is in contact with the cathode roll 1 side, and is conveyed to the plating tank. Here, the term “contact” includes contact with a liquid film interposed. Although not shown, the cathode roll 1 is connected to a motor and has a rotational driving force. A liquid film 8 is interposed between the film conductive surface 5 and the cathode roll 1. The liquid film thickness is d. Further, an electrolyte solution 9 having a controlled concentration and a receiving tray 10 for receiving the electrolyte solution 9 are received at the lower part of the cathode roll 1. The cathode roll 1 always rotates while being bathed in the electrolyte solution 9, so Supplying. The liquid 9 in the tray 10 is stored in a bathtub 11 with a concentration-controlled electrolyte 12, and is pumped by a pump 14 via a pipe 13, and is sent by a pipe 16 via a valve (electromagnetic valve) 15. Have been supplied. The supply of this liquid is strictly controlled by the operation of the valve 15 or the operation of the pump 14. Further, the liquid 9 in the tray 10 is always discharged from the discharge port 17 because the concentration of the electrolytic solution changes when the plating solution is brought in. In such a state, the case 2 filled and filled with copper balls is used as an anode, and the current is supplied from the cathode roll 1 to the copper anode 2 by the rectifier 3 by the current IA, and 0.2 to 10 A / dm is applied to the film. ² A plating film is formed on the film so that the current density is as follows. The current density here is a value obtained by dividing the current supplied from the DC power source by the area of the portion of the unit film portion immersed in the plating bath in the unit portion indicated by the one-dot chain line in FIG.
[0025]
FIG. 2 shows an enlarged view of another example of the cathode roll portion showing the features of the present invention. The general process is the same as that of FIG. 1, but the substructure of the cathode roll 1 is different. That is, it has a doctor blade 21 that removes deposits on the cathode roll 1, a support 26 that supports the doctor blade 21, and a liquid supply unit 24 that supplies the liquid 25 to the doctor blade 21. Further, an elastic body 22 that further removes deposits attached to the cathode roll 1, a support body 23 that supports the elastic body 22, and a liquid supply unit 27 that supplies a liquid 28 to the elastic body 22 are provided. Furthermore, the liquid supply part 29 which supplies the liquid 30 to the cathode roll 1 is provided. Although not shown, the supply of the liquids 25, 28, and 30 is strictly controlled by pumps and valves individually. Further, the trays 31 receive the liquids 25, 28, and 30 so as not to enter the plating tank 6, and the tray 31 is provided with a discharge port 33 for discharging the received liquid 32.
[0026]
In FIG. 1, the liquid film gap d between the cathode roll 1 and the film conductive surface 5, the conductivity σ of the liquid existing in the gap d, and the current value I flowing through the cathode are expressed by the following relational expression.
E ₀ > [(I / A) × d] / σ (1)
If controlled within the range, it is possible to suppress the deposition of the plating film metal on the cathode roll 1. Here, A is the area of the film conductive surface in contact with the cathode roll, E ₀ Is the reduction potential of the plated metal, and σ is the conductivity of the liquid film present in the gap.
[0027]
Actually, depending on the current condition and the reduction potential of the metal, the relationship between the liquid film gap d (horizontal axis) and the conductivity σ (vertical axis) is plotted against the current value using the equation (1). It would be better to have the conductivity in the range above the line.
[0028]
This is completely unthinkable that the cathode roll and the film conductive surface are in direct contact and exchange electrons as before. In other words, too much pursuit of how to complete the contact between the film and the roll has been done in the past, but the transport tension has been increased more than necessary. It led to enlargement.
[0029]
In actual contact, there is a mode in which the direct cathode roll and the film conductive surface are in direct contact with each other, but this is very rare, there is a mode in which a part of the contact area is in direct contact, and instantaneously, In many cases, the mode of the liquid film contact through the liquid film is dominant over the entire contact area. Even in a moment, when the entire surface is in a liquid film contact mode, when a potential difference exceeding the reduction potential of the plating film metal occurs between the cathode roll and the film conductive surface, the plating film metal is deposited on the cathode roll at once. Become.
[0030]
Therefore, by adjusting the electrical conductivity σ of the liquid in the gap between the film and the cathode roll so as to satisfy the above conditions, it is made conductive by ions existing in the liquid film, and even if the liquid film exists, the cathode of the plated film metal Precipitation into can be suppressed. If the liquid film is interposed, slippage between the film and the cathode roll occurs, the transport state is improved, the shift of the transport position does not occur, and good tension propagation from unwinding to winding is possible. Therefore, it is not necessary to increase the tension more than necessary, film breakage does not occur, and it is possible to form a plating film on a high-quality film with little internal distortion.
[0031]
In order to adjust the conductivity of the liquid film, it is preferable to use an electrolytic solution contained in the plating solution, but it is particularly preferable to use an electrolytic solution mainly composed of sulfuric acid from the viewpoint of hardly generating a metal salt. It is particularly preferably used when the plating film is copper. The conductivity of the electrolytic solution may be adjusted by monitoring the conductivity in the adjustment tank 11 and diluting high-concentration sulfuric acid with ion exchange water or the like. The adjusted electrolyte is monitored with a highly accurate conductivity meter. If the conductivity is low, high-concentration sulfuric acid is supplied to the adjustment tank and feedback control is performed by supplying ion-exchanged water to the adjustment tank. Is preferred.
[0032]
As shown in FIG. 1, the electrolyte solution supplied to the liquid film between the cathode roll unit 1 and the film conductive surface 5 is stored in the lower part with the electrolyte solution adjusted in the tray 10 in the cathode roll 1. It is possible to supply the electrolytic solution to the liquid film portion 8 by the rotation of the cathode roll 1, and the conductivity of the liquid film 8 can be adjusted.
[0033]
Further, as shown in FIG. 2, by supplying the liquid 25 from the liquid supply unit 24 to the blade 21, by supplying the liquid 28 from the liquid supply unit 27 to the elastic body 22, or the cathode roll 1. On the other hand, by supplying the liquid 30 directly from the liquid supply unit 29, the liquid is supplied to the liquid film 8, and the conductivity of the liquid film 8 is managed by managing the conductivity of these liquids in advance. You can also
[0034]
In addition, the electrical conductivity of the liquid present in the gap should basically satisfy the formula (1). However, as a practical management, the electrical conductivity should be 1 mS / cm or more and 100 mS / cm or less. preferable. If it is less than 1 mS / cm, the limit on the input current becomes too small. Therefore, it is not preferable from an industrial and productivity viewpoint to make the input current too low. In particular, in the case where the plating film is a copper film and the plating apparatus has a size as described in Example 1 described later, even if the gap is reduced to 40 μm, the deposition limit on the cathode roll is reached by applying a current of 200 A. It tends to cause problems such as copper precipitation. The current density in the formation of the plating film at this time is plated at an area of about 3.2 m × 0.52 m with respect to one rectifier, so that it is 1.2 A / dm at most. ² It becomes the design which can raise current density only to. On the other hand, if the electrical conductivity exceeds 100 mS, elution of the formed plated film metal tends to occur, which is not preferable.
[0035]
The size of the gap d can be controlled by the film transport tension. Theoretically, there is the following formula (2) of the foil, but the gap d can be controlled in a manner approximately inversely proportional to the 2/3 power of the tension T.
d = A × r × (B μv / T) ^2/3 (2)
Here, A and B are constants, r is the diameter of the roll, μ is the viscosity of the liquid film, v is the film transport speed, and T is the film transport tension.
[0036]
According to this equation, the size of the gap d is inversely proportional to the 2/3 power with respect to the tension T. For example, when the gap is to be halved, the conveyance tension is set to 2 ^(3/2) Approx. 2.83 times is sufficient. By controlling the gap d in this way, it can be controlled within the range of the expression (1).
[0037]
The substantial film transport tension is preferably 10 N / m or more and 320 N / m or less. When the tension was actually less than 10 N / m, the film began to meander and the control of the conveyance path was not successful. On the other hand, when it exceeds 320 / m, the plating film metal on which the film is formed has an internal distortion, which causes problems such as curling of the product.
[0038]
The size of the gap d is preferably 2 μm or more and 500 μm or less. If it is less than 2 μm, the surface roughness of the cathode roll surface is also present, which increases the chance that the conductive surface of the film and the cathode roll are in direct contact with each other. It becomes.
[0039]
In the conveyance tension control, it is preferable to perform a feedback control in which the conveyance tension is detected using the tension detection roll 325 and the speed is adjusted by the speed adjustment unit 321 so that the tension value becomes constant. In the speed control in FIG. 3, the cathode roll is a drive roll, the basic speed is set by the speed control unit 309, and the draw ratio can be set between the cathode roll 1 a and 1 b. Thus, the drawing ratio is set to gradually increase, and the final speed is controlled by the speed control unit 321. With such a configuration, the maximum transport tension of the film on the cathode roll on the plating tank is highest at 325 parts of the tension detection roll, and it is more preferable to control based on this value.
[0040]
Further, since the size of the gap becomes larger as the transport tension is smaller, the liquid film gap d is measured on the first cathode roll 1a having the lowest transport tension so that this value falls within the target value. You may perform control which raises / lowers tension | tensile_strength.
[0041]
Further, when a plating film component is deposited on the cathode roll for plating, a blade 21 for scraping the plating film on the cathode roll is attached to the deposition side in the rotation direction of the cathode roll, and the cutting edge of the blade 21 is directed in the rotation direction of the cathode roll 1. It is good to install. By doing so, even if the plating film component is deposited on the cathode roll 1, it is possible to remove the plating film deposited by scraping with the blade 21.
[0042]
The blade 21 is supported by a support 26, and the support 26 can adjust the pressing force in the direction perpendicular to the film transport direction. In this case, it is preferable that the pressing force in the direction perpendicular to the film transport direction is substantially uniform.
[0043]
As the material of the blade, since it contacts with the cathode roll for plating, there is a possibility that a battery reaction (oxidation-reduction phenomenon) may occur due to the presence of an electrolytic solution in a metal reaction or a direct contact portion between metals. Since the battery phenomenon is not preferable, resin or ceramic is preferably used. Plastic doctor blades such as plastic doctor blade “E500” from ELL Japan Co., Ltd. and plastic blades from Eco Blade Co., Ltd., UHMW polyethylene-type blades, and fluororesin series from TS Doctor Blade of Tokyo Seisakusho Co., Ltd. Or the like can be used. As the ceramic blade, SIC New Ceramic Blade manufactured by Tokyo Seisakusho Co., Ltd. is preferably used.
[0044]
As another method, an elastic body 22 for wiping off the film deposited on the cathode roll may be attached to the deposition side in the rotational direction of the cathode roll 1. By doing so, even if the plating film is deposited on the cathode roll 1, it is possible to remove the plating film deposited by wiping with the elastic body 22.
[0045]
The elastic body 22 is supported by a support body 23. The support body 23 can adjust a pressing force in a direction perpendicular to the film transport direction. In this case, it is preferable that the pressing force in the direction perpendicular to the film transport direction is substantially uniform.
[0046]
As the elastic body, a sponge-like body, a nonwoven fabric, foamed foam, or the like is preferably used, and polyurethane, PVA (polyvinyl alcohol), PVC (polyvinyl chloride), polyethylene, butyl-based, or neoprene-based rubber-based material should be used. Can do. Among these, use of PVA (polyvinyl alcohol) or PVC (polyvinyl chloride) is preferable because it is resistant to an electrolytic solution mainly composed of sulfuric acid and a plating solution.
[0047]
Furthermore, by using the blade and the elastic body together, the plating film deposited on the cathode roll can be efficiently removed. This is because, for example, it is possible to wipe off the deposits of the plating film that have passed through the area where the doctor hits the cathode roll with an elastic body.
[0048]
Furthermore, the liquid may be supplied continuously or intermittently to the cathode roll, blade, or elastic body on which the plating film is deposited. This has the effect of washing away the deposited plating film, and the deposited plating film can be removed more efficiently. Further, these liquids are preferable because the conductivity of the liquid film in the above formula (1) can be kept constant. For example, as illustrated in FIG. 2, the liquid 21 is supplied from the liquid supply unit 24 to the blade 21, the liquid 28 is supplied from the liquid supply unit 27 to the elastic body 22, and the liquid is supplied from the liquid supply unit 29 to the cathode roll 1. 30 will be supplied.
[0049]
As a film material of such a film with a plating film, a polyimide resin or a polyester resin is preferably used. When forming a film with copper for use in electronic circuit materials or the like, a general-purpose polyester resin is preferably used, and a polyimide resin is preferably used in terms of solder heat resistance in mounting circuit ICs or the like.
[0050]
Specific examples of the material of the base plastic film used in the present invention include polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-α, β-bis (2-chlorophenoxyethane-4,4′-dicarboxyl. Polyester), polyetheretherketone, aromatic polyamide, polyarylate, polyimide, polyamideimide, polyetherimide, polyparazic acid, polyoxadiazole, and halogen group or methyl group-substituted products thereof. These copolymers and those containing other organic polymers may also be used. Known additives such as lubricants and plasticizers may be added to these plastics.
[0051]
Among the plastics, an unstretched film obtained by melt-extruding a polymer containing 85 mol% or more of a repeating unit as shown in Chemical Formula 1 below is particularly preferably a film in which mechanical properties are improved by stretching and orientation in a biaxial direction. used.
[0052]
[Chemical 1]

[0053]
Further, a film made of a polymer containing 50 mol% or more of repeating units as shown in the following Chemical Formula 2 and wet or dry film formation, or a film obtained by biaxial stretching and / or heat treatment of the film is also preferably used.
[0054]
[Chemical 2]

[0055]
In the case of a flexible circuit, the thickness of the plastic film as a base material is frequently about 6 to 125 μm, and particularly preferably a thickness of 12 to 50 μm.
[0056]
【Example】
Hereinafter, although an example of the Example of this invention is shown, this invention is not limited to this. In addition, each characteristic value in an Example was measured in accordance with the following method.
[0057]
(1) Surface tension of plastic film
In accordance with JIS K6766-1977 (wetting test method for polyethylene and polypropylene), the surface tension of 56 dyne / cm or less was determined using a formamide / ethylene glycol monoethyl ether mixed solution as a standard solution. In the range of surface tension of 57 to 73 dyne / cm, the surface tension was determined using a mixed solution of water (72.8 dyne / cm) / ethylene glycol (47.7 dyne / cm) as a standard solution.
[0058]
(2) Contact angle
Using a FACE contact angle meter manufactured by Kyowa Interface Science Co., Ltd., the droplet method was used.
[0059]
(3) Film thickness of sputtered film
Evaluation was performed using a stylus type surface roughness meter. The sample was measured by coating a part of ink removable with a solvent before forming the sputtered film to form a sputtered film, and then removing the ink-applied part after the film formation.
[0060]
(4) Plating film thickness
A part of the plating film was removed with an etching solution, and the difference in level was measured using a laser microscope manufactured by Keyence Corporation.
[0061]
(5) Conductivity
Measurement was performed using a conductivity meter CEH-12 manufactured by Kos Co., Ltd. The measurement method is an AC two-electrode method, and the measurement range is a 0 to 199 mS / cm sensor.
[0062]
(6) Liquid film gap
The size of the liquid film gap was measured using an apparatus as shown in FIG. In the measuring apparatus shown in FIG. 6, a displacement meter 44 with a cable 43 is moved along a slide guide 42 attached to a liquid film thickness measurement base 41, and a detection signal is amplified and output by an amplifier unit 45. It was. The measurement sensor (displacement meter) identified the thickness of the liquid film with a laser displacement meter manufactured by Keyence Corporation. The measurement was performed using “LK-010” ultra-small and high-precision CCD laser displacement sensor for the sensor head and “LK-3100” for the amplifier unit. The sensor specifications were measured with a resolution of 0.1 μm, a spot diameter of 20 μm, and a reference distance of 10 mm.
[0063]
(7) Transport tension
A load cell type sensor was attached to both sides of the transport cathode roll and measured. As the sensor, a “C2G1-25K” type manufactured by Minebea Co., Ltd. was used. The measurement range is a specification capable of measuring 0 to 250N. The value obtained by calibrating by strictly converting the tension value from the roll weight and the holding angle of the film conveyance was taken as the tension value.
[0064]
Example 1
The example which applied the film with copper to the flexible circuit board is shown.
(1) Production of film with conductive surface
In the decompression device, the film wound up in a roll shape was processed while being unwound, and thereafter the plasma treatment, nickel-chromium layer film formation, and copper layer film formation were performed in an apparatus for forming the film into a take-up roll shape.
[0065]
A roll of polyimide film “Kapton” 1 (registered trademark of DuPont, USA) having a thickness of 25 μm, a width of 520 mm, and a length of 12,500 m was prepared.
[0066]
One side of the film was subjected to argon gas glow discharge plasma treatment at a rate of 2 m / min. For the treatment, an internal electrode type plasma apparatus having an electrode pair that transported the film at a distance of 2 cm to a rod-shaped electrode to which a high voltage was applied and had a ground electrode was used. The film was processed at 2 m / min under the conditions of an argon gas pressure of 2.5 Pa, a primary output voltage of 2 kV, and a high frequency power supply frequency of 110 kHz to form a glow discharge plasma layer. The treated film had a surface tension of 70 dyne / cm or more and a contact angle of 43 degrees.
[0067]
Then, argon gas pressure 2.6 × 10 ^-2 A 30 nm nickel chrome layer was formed by applying a DC magnetron sputtering method using a 20% chromium and 80% nickel target at Pa. Thereafter, a copper layer with a purity of 99.99% was formed by applying a DC magnetron sputtering method using a target with a copper layer of 100 nm.
[0068]
As the above film, a film with a sputtered film of 12000 m was produced except for the conditions for forming the sputtered film and the lead portion.
[0069]
(2) Formation of plating film
The roll-like sputtered film 12000 m obtained in the above (1) is divided into four 3000 m rolls, and four 520 mm × 3000 m rolls with a conductive film are prepared, one of which Was passed through a plating apparatus shown below to form a plating film.
[0070]
Using the apparatus shown in FIGS. 1 and 3 as the plating apparatus, copper was used for the anode, and a copper plating film was formed to 8 μm. In FIG. 4, a plating circuit and a plating apparatus having 16 units in the chain line are configured.
[0071]
As the cathode roll, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used to feed power. An apparatus having a film path length of 4 m was used when the film was passed from the cathode roll 1a through the submerged roll 101a to the cathode roll 1b. The path length is from the top to the top of the cathode roll. Therefore, the total path length of the plating part is 64 m.
[0072]
The film pretreatment conditions, plating conditions, and rust prevention treatment conditions were as shown in Table 1. The copper plating was set so that the current density gradually increased as the number of repetitions of the cathode roll and submerged roll passes increased. The current setting conditions for each rectifier of the first to sixteenth units are as shown in Table 2.
[0073]
When the current conditions in Table 2 and the reduction potential of copper of 0.337 V are used, the relationship between the liquid film gap d and the conductivity σ using the equation (1) is plotted for each current value as shown in FIG. Therefore, the conductivity should be controlled so as to be on the upper side of each graph. Note that the reduction potential of copper varies depending on the activity or concentration of Cu ions, but Cu is the standard unit electrode potential of copper. ²⁺ The value of / Cu is 0.337 V, which is smaller than this value due to the concentration of copper ions. The contact area between the film conductive surface and the cathode roll was calculated as 520 mm width × about 220 mm because the holding angle was 120 degrees.
[0074]
As shown in FIG. 6, the liquid film gap d was measured with a laser displacement meter, and the film transport tension was set so that the gap d was 300 μm or less. The film tension was set by a method in which the tension was appropriately cut by the S-wrap speed control unit 309 shown in FIG. 3 and then the roll rotation speed was sequentially drawn. The tension was automatically detected by the load cell at the cathode roll 325 (tension detection roll) section, and feedback control was performed at the speed of the drive motor of the speed adjustment section 321 so that the tension was 160 N / m. Therefore, when the liquid film gap of the cathode roll 1a portion having the worst tension was measured using FIG. 6 as a detection device, it was 125 μm.
[0075]
The conveyance speed was 1 m / min, and the draw ratio was set stepwise for the cathode roll motor drive settings of the cathode rolls 1a to 1q to increase the speed sequentially and gradually increase the tension.
[0076]
It may be controlled to change the conductivity for each unit, but since the equipment becomes expensive, the conductivity of the liquid film is set so that the copper deposition limit is not reached for all units. It adjusted so that it might become 10 mS / cm. The sulfuric acid concentration in the tank 11 in FIG. 1 was adjusted, the pump was set so as to be 100 ml / min, and the liquid concentration in the tray 10 was controlled.
[0077]
As a result, there was no copper deposition on the surface of the cathode roll, the conveyance state was very stable, and a roll film having a good winding shape was obtained.
[0078]
Then, when the plated copper surface was observed by inspection, a film with copper excellent in surface quality with few abnormal protrusions and dents on the plated surface was obtained. Table 3 shows the number of abnormal protrusions and depressions.
[0079]
(3) Formation of circuit pattern
Coating with photosensitive liquid resist, UV exposure and development using 1024 masks of circuit pattern with 60μm pitch, that is, copper conductor line width 30μm and conductor line 30μm, and form circuit pattern with ferric chloride etchant did. The 50 circuit patterns are observed with a 150-fold actual microscope, and chipping (chips of 10 μm or more are rejected, and if there are one or more of 1024 circuits, the circuit pattern is rejected) and disconnection. Table 4 shows the result of determining the quality of the pattern. As a result, a circuit pattern with a yield of 100% was obtained.
[0080]
[Table 1]

[0081]
[Table 2]

[0082]
[Table 3]

[0083]
[Table 4]

[0084]
Example 2
The example which applied the film with copper to the flexible circuit board is shown.
(1) Production of film with conductive surface
A film with a conductive surface exactly the same as in Example 1 was prepared.
[0085]
(2) Formation of plating film
The roll-like sputtered film 12000 m obtained in the above (1) is divided into four 3000 m rolls, and four 520 mm × 3000 m rolls with a conductive film are prepared, one of which Was passed through a plating apparatus shown below to form a plating film.
[0086]
As an apparatus for plating, an apparatus shown in FIGS. 2 and 3 was used, and copper was used for the anode to form a copper plating film having a thickness of 8 μm. In FIG. 4, a plating circuit and a plating apparatus having 16 units in the chain line are configured.
[0087]
As the cathode roll, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used to feed power. An apparatus having a film path length of 4 m was used when the film was passed from the cathode roll 1a through the submerged roll 101a to the cathode roll 1b. The path length is from the top to the top of the cathode roll. Therefore, the total path length of the plating part is 64 m.
[0088]
The film pretreatment conditions, plating conditions, and rust prevention treatment conditions were as shown in Table 1. The copper plating was set so that the current density gradually increased as the number of repetitions of the cathode roll and submerged roll passes increased. The current setting conditions for each rectifier of the first to sixteenth units are as shown in Table 2.
[0089]
When the current conditions in Table 2 and the reduction potential of copper of 0.337 V are used, the relationship between the liquid film gap d and the conductivity σ using the equation (1) is plotted for each current value as shown in FIG. Therefore, the conductivity should be controlled so as to be on the upper side of each graph. Note that the reduction potential of copper varies depending on the activity or concentration of Cu ions, but Cu is the standard unit electrode potential of copper. ²⁺ The value of / Cu is 0.337 V, which is smaller than this value due to the concentration of copper ions. The contact area between the film conductive surface and the cathode roll was calculated as 520 mm width × about 220 mm because the holding angle was 120 degrees.
[0090]
As shown in FIG. 6, the liquid film gap d was measured with a laser displacement meter, and the film transport tension was set so that the gap d was 300 μm or less. The film tension was set by a method in which the tension was appropriately cut by the S-wrap speed control unit 309 shown in FIG. 3 and then the roll rotation speed was sequentially drawn. The tension was automatically detected by a load cell at 325 parts of a cathode roll (tension detection roll), and feedback control was performed at the speed of the drive motor of the speed adjusting unit 321 so that the tension was 160 N / m. Therefore, when the liquid film gap of the cathode roll 1a portion having the worst tension was measured using FIG. 6 as a detection device, it was 80 μm. When the liquid film gap on each cathode roll was measured, it was as shown in Table 3.
[0091]
The conveyance speed was 1 m / min, and the draw ratio was set stepwise for the cathode roll motor drive settings of the cathode rolls 1a to 1q to increase the speed sequentially and gradually increase the tension.
[0092]
It may be controlled to change the conductivity for each unit, but since the equipment becomes expensive, the conductivity of the liquid film is set so that the copper deposition limit is not reached for all units. It adjusted so that it might become 2 mS / cm. That is, sulfuric acid was used as the liquid 25 to wash away the doctor blade in FIG. 2, its conductivity was set to 2 mS / cm, and 200 ml of liquid was supplied every 2 minutes by shower supply every 3 minutes for 2 seconds. Further, sulfuric acid was used as the liquid 27 for supplying the liquid to the sponge body, the conductivity was set to 2 mS / cm, and 200 ml of liquid was supplied every 2 minutes by shower supply every 3 minutes for 2 seconds. In addition, it was set as the sequence supplied 1 minute after the sulfuric acid shower supply to a doctor blade. In addition, sulfuric acid was used as the liquid 30 to be supplied to the cathode roll, its conductivity was set to 2 mS / cm, and 200 ml of liquid was supplied every 2 minutes by shower supply for 2 seconds every 3 minutes. In addition, it was set as the sequence supplied 1 minute after the sulfuric acid shower supply to a sponge body. Thus, the liquid concentration of the liquid film was controlled.
[0093]
Partly because of the relationship between the liquid film gap and the conductivity, the formula (1) was not satisfied and the copper on the cathode roll was confirmed when leaving the cathode roll film, but it could be removed with a blade and sponge and rotated. After that, it was confirmed that the cathode roll was clean when it contacted the film.
[0094]
As a result, it was possible to suppress copper deposition on the surface of the cathode roll, the transport state was very stable, and a roll film having a good winding shape was obtained.
[0095]
In addition, the plastic blade E500 by EL Japan Co., Ltd. was used for this blade. The sponge as an elastic body was uniformly pressed using a PVA sponge so that the pressing force was 50 N / m.
[0096]
Then, when the plated copper surface was observed by inspection, a film with copper excellent in surface quality with few abnormal protrusions and dents on the plated surface was obtained. Table 3 shows the number of abnormal protrusions and depressions.
[0097]
(3) Formation of circuit pattern
Coating with photosensitive liquid resist, UV exposure and development using 1024 masks of circuit pattern with 60μm pitch, that is, copper conductor line width 30μm and conductor line 30μm, and form circuit pattern with ferric chloride etchant did. 50 circuit patterns are observed with a 150-fold actual microscope, chipping (chips of 10 μm or more are rejected, and if there are one or more of 1024 circuits, the circuit pattern is rejected) and disconnection Table 4 shows the result of determining the quality of the pattern. As a result, a circuit pattern with a yield of 100% was obtained.
[0098]
Comparative Example 1
The example which applied the film with copper to the flexible circuit board is shown.
(1) Production of film with conductive surface
A film with a conductive surface exactly the same as in Example 1 was prepared.
[0099]
(2) Formation of plating film
The roll-like sputtered film 12000 m obtained in the above (1) is divided into four 3000 m rolls, and four 520 mm × 3000 m rolls with a conductive film are prepared, one of which Was passed through a plating apparatus shown below to form a plating film.
[0100]
As an apparatus for plating, an apparatus shown in FIGS. 2 and 3 was used, and copper was used for the anode to form a copper plating film having a thickness of 8 μm. In FIG. 4, a plating circuit and a plating apparatus having 16 units in the chain line are configured.
[0101]
As the cathode roll, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used to feed power. An apparatus having a film path length of 4 m was used when the film was passed from the cathode roll 1a through the submerged roll 101a to the cathode roll 1b. The path length is from the top to the top of the cathode roll. Therefore, the total path length of the plating part is 64 m.
[0102]
The film pretreatment conditions, plating conditions, and rust prevention treatment conditions were as shown in Table 1. The copper plating was set so that the current density gradually increased as the number of repetitions of the cathode roll and submerged roll passes increased. The current setting conditions for each rectifier of the first to sixteenth units are as shown in Table 2.
[0103]
As shown in FIG. 6, the liquid film gap d was measured with a laser displacement meter, and the film transport tension was set so that the gap d was 300 μm or less. The film tension was set by a method in which the tension was appropriately cut by the S-wrap speed control unit 309 shown in FIG. 3 and then the roll rotation speed was sequentially drawn. The tension was automatically detected by a load cell with a cathode roll 325 (tension detection roll), and feedback control was performed at the speed of the drive motor of the speed adjustment unit 321 so that the tension was 160 N / m. Therefore, when the liquid film gap of the cathode roll 1a portion having the worst tension was measured using FIG. 6 as a detection device, it was 125 μm. When the liquid film gap on each cathode roll was measured, it was as shown in Table 3.
[0104]
The conveyance speed was 1 m / min, and the draw ratio was set stepwise for the cathode roll motor drive settings of the cathode rolls 1a to 1q to increase the speed sequentially and gradually increase the tension.
[0105]
The ion exchange water was put into the tank 11 in FIG. 1, the pump was set so as to be 100 ml / min, and supplied into the tray 10. At this time, the electrical conductivity in the saucer 10 was 0.02 mS / cm.
[0106]
As a result, on the surface of the cathode roll, the cathode roll in the first half of the transport was slightly copper-based, and copper deposition occurred from the sixth cathode roll to the fourteenth cathode roll. It became a copper color. Initially, the transport condition was stable, but after the copper was deposited, the transport gradually became uneasy, and the film was gripped on the cathode roll, causing tension and bending. The film began to meander in response to the stirring air, and wrinkles were generated on the cathode roll. Also, since the rigidity of the film with copper was large, the film was wrinkled.
[0107]
Later, when the surface of the plated copper was observed during inspection, the product was not wrinkled on the film, and many protrusions with a major axis of 100 μm and a height of 60 μm were generated even in places where there were no wrinkles. Was. Table 3 shows the number of abnormal protrusions and depressions.
[0108]
(3) Formation of circuit pattern
Coating with photosensitive liquid resist, UV exposure and development using 1024 masks of circuit pattern of 60μm pitch, that is, copper conductor line width 30μm, conductor line 30μm, and form circuit pattern with ferric chloride etchant did. The 50 circuit patterns are observed with a 150-fold actual microscope, and chipping (chips of 10 μm or more are rejected, and if there are one or more of 1024 circuits, the circuit pattern is rejected) and disconnection. Table 4 shows the result of determining the quality of the pattern. An almost normal circuit pattern was not obtained with a yield of 6%.
[0109]
Comparative Example 2
The example which applied the film with copper to the flexible circuit board is shown.
(1) Production of film with conductive surface
A film with a conductive surface exactly the same as in Example 1 was prepared.
[0110]
(2) Formation of plating film
The roll-like sputtered film 12000 m obtained in the above (1) is divided into four 3000 m rolls, and four 520 mm × 3000 m rolls with a conductive film are prepared, one of which Was passed through a plating apparatus shown below to form a plating film.
[0111]
As an apparatus for plating, an apparatus shown in FIGS. 2 and 3 was used, and copper was used for the anode to form a copper plating film having a thickness of 8 μm. In FIG. 4, the plating circuit and the plating apparatus are configured with the unit of the alternate long and short dash line as the first unit, the unit of the alternate long and two short dashes line as 14 units, and the symmetrical unit within the alternate long and short dash line as the last 16th unit.
[0112]
As the cathode roll, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used to feed power. An apparatus having a film path length of 4 m was used when the film was passed from the cathode roll 1a through the submerged roll 101a to the cathode roll 1b. The path length is from the top to the top of the cathode roll. Therefore, the total path length of the plating part is 64 m.
[0113]
The film pretreatment conditions, plating conditions, and rust prevention treatment conditions were as shown in Table 1. The copper plating was set so that the current density gradually increased as the number of repetitions of the cathode roll and submerged roll passes increased. The current setting conditions for each rectifier of the first to sixteenth units are as shown in Table 2.
[0114]
As shown in FIG. 6, the liquid film gap d was measured with a laser displacement meter, and the film transport tension was set so that the gap d was 50 μm or less. The film tension was set by a method in which the tension was appropriately cut by the S-wrap speed control unit 309 shown in FIG. 3 and then the roll rotation speed was sequentially drawn. The tension was automatically detected by a load cell with a cathode roll 325 (tension detection roll), and feedback control was performed at the speed of the drive motor of the speed adjustment unit 321 so that the tension was 320 N / m.
[0115]
The conveyance speed was 1 m / min, and the draw ratio was set stepwise for the cathode roll motor drive settings of the cathode rolls 1a to 1q to increase the speed sequentially and gradually increase the tension. Moreover, it was conveyed without the liquid supply from the tank 11 in FIG.
[0116]
As a result, on the surface of the cathode roll, the cathode roll in the first half of the transport was slightly copper-based, and copper deposition occurred from the sixth cathode roll to the fourteenth cathode roll. It became a copper color. At first, the film could be transported a little, but when the tension gradually increased, the film was in a very large tensile state, and after a while, the film was broken and wrinkled, and then broke.
[0117]
As is apparent from the characteristics shown in Table 3 above, it can be said that the flexible circuit board produced by the production method of the present invention was able to obtain a film with copper having a very excellent appearance quality corresponding to fine pitch. .
[0118]
【The invention's effect】
According to the present invention, a plating film having excellent surface quality can be formed. In particular, in a film with copper for a flexible circuit board, it is possible to provide an excellent quality product. Since there are very few protrusions and dent defects on the copper surface, it is effective for making the fine pitch as the circuit pitch, and can cope with a pitch of 60 μm or less.
[0119]
Moreover, according to this invention, a trouble can be prevented in the plating process of a production process, and especially the abnormal deposition of the plating film which generate | occur | produces in a cathode roll part can be suppressed. Further, even if a part of abnormal precipitation occurs, it can be removed with a doctor blade or an elastic body attached to the cathode roll.
[0120]
In particular, copper is effective as a plating film, and is particularly effective during the production of a plating-type two-layer product used for a flexible circuit board.
[Brief description of the drawings]
FIG. 1 is an enlarged schematic longitudinal sectional view of a cathode roll portion of a plating apparatus according to an embodiment of the present invention.
FIG. 2 is an enlarged schematic longitudinal sectional view of a cathode roll portion of a plating apparatus according to another embodiment of the present invention.
FIG. 3 is a schematic longitudinal sectional view showing an example of the entire plating apparatus according to the present invention.
4 is an enlarged view of a part of the apparatus of FIG. 3, and is a schematic configuration diagram showing an example of a power feeding method.
FIG. 5 is a graph showing the relationship between the gap and the conductivity with respect to the input current value of each rectifier in the example.
FIG. 6 is a schematic perspective view of a liquid film gap measuring apparatus according to an embodiment.
[Explanation of symbols]
1 Cathode roll
1a, 1b, 1c Cathode roll
2 Anode
3, 3a, 3b DC power supply
4 films
5 Conductive surface of film
6 Plating tank
7 Plating solution
8 Liquid film gap
9 Liquid in the pan
10 saucer
11 Electrolyte tank
12 Electrolyte
13 Piping
14 Pump
15 Valve (Electromagnetic valve)
16 Piping
17 Piping for discharging the liquid in the pan
21 blade
22 Elastic body
23 Elastic body fixing jig
24 Piping for supplying liquid to the blade
25 Liquid supplied to the blade
26 Blade fixing jig
27 Piping for supplying liquid to the elastic body
28 Liquid supplied to elastic body
29 Piping for supplying liquid to the cathode roll
30 Liquid supplied to cathode roll
31 saucer
32 Liquid in saucer
33 Piping for discharging the liquid in the pan
41 Liquid film thickness measurement stand
42 Slide guide
43 Cable
44 Displacement meter
45 Amplifier unit
101a, 101b Film transport roll in liquid
102a, 102b, 102c, 102d, 102e Anode metal
106a, 106b, 106c Shield plate
301 Unwinding part
302 Pre-processing unit
303 Electroplating part
304 Post-processing section
305 Winding part
306 Roll film before plating
307 Accumulator
308 Balance roll
309 Speed control unit
310 Acid, degreasing section
311 Acid, degreasing solution
312 washing section
313 Washing liquid
314 Flushing Club
315 Washing liquid
316 Anti-rust treatment part
317 Antirust liquid
318 Flushing Club
319 Washing liquid
320 Drying process section
321 Speed adjustment unit
322 Balance roll section
323 Accumulator
324 Roll film with plating film
325 Tension detection roll
330a, 330b, 330c, 330d Air stirring nozzle
331a, 331b, 331c, 331d Air for stirring

Claims (11)

With a plating film, the film conductive surface is brought into contact with the cathode roll through a liquid film while a film having a conductive surface is conveyed, and a plating film is formed on the film conductive surface in a plating bath disposed before or after the film. A method for producing a film, wherein a gap d between a cathode roll and a film conductive surface, a conductivity σ of a liquid existing in the gap d, and a current value passed through the cathode roll for plating are within a range of the following relational expression: The manufacturing method of the film with a plating film characterized by controlling within.
E ₀ > [(I / A) × d] / σ
Here, A: area of the conductive surface of the film in contact with the cathode roll, I: current value to be applied to plating, E ₀ : reduction potential of the plated metal, d: size of gap, σ: conductivity. 2. The method for producing a film with a plating film according to claim 1, wherein the electrical conductivity of the liquid present in the gap is controlled by the concentration of an electrolytic solution mainly composed of sulfuric acid. The method for producing a film with a plating film according to claim 1 or 2, wherein the electrical conductivity of the liquid present in the gap is 1 mS / cm or more and 100 mS / cm or less. The method for producing a film with a plating film according to any one of claims 1 to 3, wherein the size of the gap d is controlled by the film transport tension. The method for producing a film with a plating film according to any one of claims 1 to 4, wherein the conveyance tension of the film is 10 N / m or more and 320 N / m or less. The method for producing a film with a plating film according to claim 1, wherein the size of the gap d is 2 μm or more and 500 μm or less. With a plating film, the film conductive surface is brought into contact with the cathode roll through a liquid film while a film having a conductive surface is conveyed, and a plating film is formed on the film conductive surface in a plating bath disposed before or after the film. A method for producing a film with a plating film, wherein the plating film component deposited on the cathode roll is scraped off by a blade and / or an elastic body. The method for producing a film with a plating film according to claim 7, wherein a liquid is continuously or intermittently supplied to the cathode roll and / or the blade and / or the elastic body. The method for producing a film with a plating film according to claim 1, wherein the plating film is copper. The method for producing a film with a plating film according to claim 1, wherein the film is made of a polyimide resin or a polyester resin. The manufacturing method of the circuit board which forms a circuit pattern in the film manufactured by the manufacturing method of the film with a plating film in any one of Claims 1-10.

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