JP3569197B2 - Laminated plate and method of manufacturing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、高周波数電波を用いる機器、特に１ＧＨｚ以上の高周波に適した機器に使用される低誘電正接、低誘電率積層板の製造方法に関する。
【０００２】
【従来の技術】
フッ素樹脂は誘電正接、誘電率が低い樹脂であり、高周波数の用途の基板に適している。その中でも、ＰＴＦＥ（ポリテトラフルオロエチレン）樹脂が高周波数用途に最も適しているため、ガラス基材などの織布に含浸されてプリプレグを形成し、このプリプレグを積層して片面あるいは両面に銅箔を貼り合わせ、積層板を形成している。
【０００３】
しかしながら、この積層板は、加熱加圧時に反りを生じる場合があり、その改善方法が検討されている。例えば、積層板に用いられるガラス基材の縦糸、横糸のテンション（伸び率）の差異が織布とした後にも残存することが、基板の反りの一つの原因と考えられ、これを解消するために、最外層のプリプレグの縦糸を他のプリプレグの縦糸方向に対して交差させた積層板が検討されている（特開平８−１４８７８０号公報）。
【０００４】
しかし、この積層板は、加熱加圧時の反りを抑制するには優れた効果を奏するが、金属箔をエッチング除去したり、積層板に回路形成を行うときには、再び反りが生じるため、ガラス基材の繊維の方向を変えることのみでは、必ずしも効果的であるとは言えない。基板によっては、反りの量が２０ｍｍ近くにも達する値を示し、このような基板では、回路形成ごの電子部品の実装が困難となり、単層基板や両面基板を順次、積層接着して行く多層基板においては、回路形成のためのレジスト膜を一様な厚さに形成できないため、精密な回路形成が不可能となるなどの問題を発生させるばかりでなく、更にレーダー波の受信などの高周波用アンテナなどに使用する場合においては、電波の有効受信面積が設計値通りにえられないという電気特性に係る問題も発生させる。
【０００５】
本発明者の鋭意研究の結果、反りの原因と考えられるのは、ＰＴＦＥと銅箔の線膨張係数の差が大きいことにあると認められた。すなわち、ＰＴＦＥの融点（もしくはゲル化温度）が極端に高く、銅箔とＰＴＦＥ樹脂とを接着するために３８０℃程度の高温加熱接着プレス工程が必要となり、高温加熱工程−冷却工程において銅箔が有する線膨張係数により大きく伸び、大きく収縮しようとするため、ＰＴＦＥ含浸プリプレグもしくはＰＴＦＥ積層板の熱膨張量との差が大きくなり、このＰＴＦＥ含浸プリプレグもしくはそれを使用した積層板と銅箔には残留応力が残存し、従って、回路形成の際エッチング工程で銅箔が除去される、あるいは積層板の上下面の除去率が異なると、積層板の上面、下面における残留応力のバランスが崩れ、反りが発生することが知見された。
【０００６】
これを解決するためには、線膨張係数が銅の線膨張係数に近い樹脂をプリプレグに含浸して用いればよいが、金属箔と同程度の線膨張係数をもつフッ素樹脂は現在知られておらず、反りの発生を有効に防止できる可能性はない。
【０００７】
また、基板の厚さを厚くすることにより反りを防止する方法も考えられるが、この方法では、同一のインピーダンスを得るために厚さに対して自然対数倍の基板の面積が必要であり、基板を小型化できないと言う問題がある。
【０００８】
さらに、反りを抑制する方法として、高温伸び箔と言われる銅箔を用いる方法が考えられるが、高温伸び箔は、通常用いられる銅箔の２〜３倍の価格であるため、コスト的に採用されにくい。
【０００９】
【発明が解決しようとする課題】
そこで、銅箔のエッチングにより回路を形成したときにおいても反りが少ない積層板およびその製造方法が求められている。
【００１０】
【課題を解決するための手段】
本発明は、ＰＴＦＥ樹脂を含浸してなる１枚または２枚以上のプリプレグの最外層の両面に銅箔を有し、該プリプレグと該銅箔との間に溶融時の粘度が１０７ポワズ以下の溶融フッ素樹脂が２μｍから該銅箔厚みの２倍以下の厚みで配置されることを特徴とする積層板に関する。
【００１１】
好ましい実施態様においては、前記溶融フッ素樹脂層の厚みが銅箔の厚み以下である。
【００１２】
また、好ましい実施態様においては、前記溶融フッ素樹脂が、ＰＦＡ、ＦＥＰ、ＥＴＦＥ、ＰＶＤＦ、ＥＣＴＦＥ、ＰＣＴＦＥ、ＰＶＦまたはこれらの混合物からなる群から選択される。
【００１３】
本発明は、さらに、ＰＴＦＥ樹脂を含浸してなる１枚または２枚以上のプリプレグの最外層の両面に溶融時またはゲル化時の粘度が１０７ポワズ以下の溶融フッ素樹脂を配置し、該溶融フッ素樹脂上に銅箔を配置した後、減圧雰囲気の圧力下において、常温から前記ＰＴＦＥ樹脂の融点よりやや高い成形温度まで昇温する昇温工程と、該成形温度を所定時間保持し、該成形温度からＰＴＦＥの溶融開始前温度までを緩慢に降温する第１降温工程と、該ＰＴＦＥの溶融開始前温度から常温までをやや緩慢に冷却する第２降温工程とを有し、該溶融フッ素樹脂が２μｍから該銅箔厚みの２倍以下の厚みとなるように加圧成形することを特徴とする、積層板の製造方法に関する。
【００１４】
【発明の実施の形態】
本発明に用いられるプリプレグは、ＰＴＦＥを含浸したプリプレグであれば特に制限はないが、強度と好ましい誘電正接を得るためには、ガラス繊維などの織布にＰＴＦＥが含浸されたプリプレグであることが好ましい。
【００１５】
本発明の積層板は、上面、下面またはその一方に回路を形成する単層板あるいは両面板であってもよく、一層以上の内層回路が積層された多層板であってもよい。この積層板の最外層の両面には銅箔が接合されている。用いる銅箔の厚みには特に制限がないが、一般に用いられる１８μｍから３６μｍの厚みが好ましく用いられる。
【００１６】
本発明においては、プリプレグと銅箔との間に溶融時の粘度が１０７ポワズ以下の溶融フッ素樹脂がプリプレグの塗布層もしくは樹脂シートとして配置され、溶融フッ素樹脂層の厚みが２μｍから該銅箔厚みの２倍以下の厚みとなるように加圧成形する点に特徴がある。本発明に用いられる溶融フッ素樹脂は、３８０℃以下で溶融するフッ素含有樹脂をいう。溶融フッ素樹脂としては、溶融時の粘度が１０７ポワズ以下であればどのようなフッ素樹脂でもよい。例えば、ＰＦＡ（テトラフルオロエチレンパープロロアルキルビニルエーテル共重合体）、ＦＥＰ（テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体）、ＥＴＦＥ（エチレン−テトラフルオロエチレン共重合体）、ＰＶＤＦ（ポリビニリデンフルオライド）、ＥＣＴＦＥ（エチレンクロロトリフルオロエチレン）、ＰＣＴＦＥ（ポリクロリネートトリフルオロエチレン）、ＰＶＦ（ポリビニルフルオライド）などが挙げられる。これらの樹脂は単独で用いても良く、また、これらの混合樹脂も溶融時の粘度が１０７ポワズ以下であれば、好ましく用いられる。溶融時における好ましい粘度は１０３以上であり、１０７〜１０３ポワズが好ましく、１０５〜１０３ポワズがより好ましく、１０５〜１０４ポワズがさらに好ましい。
【００１７】
溶融フッ素樹脂は、銅箔とプリプレグとの間にあり、溶融フッ素樹脂層の厚みが２μｍから銅箔厚みの２倍以下の厚みとなるように加圧成形される。２μｍ未満では、十分な接着効果が得られず、反りが大きくなる。銅箔厚みの２倍を超えると、多層回路基板の加圧成形時に溶融フッ素樹脂層が溶融していわゆるスイミング現象を発現し内層回路を形成する銅箔が溶融フッ素樹脂の流動と共にずれる虞があり、好ましくない。特に多層回路基板を構成する場合を考慮すると、溶融フッ素樹脂層の厚みは、銅箔厚さ以下であることがより好ましい。
【００１８】
加圧条件には特に制限がなく、プリプレグに銅箔を接着させる際に当業者が一般的に用いる方法を用いてもよいが、以下の方法を用いることが好ましい。すなわち、減圧雰囲気の圧力下において、まず、常温からＰＴＦＥ樹脂の融点よりやや高い成形温度まで昇温し、ついで、この成形温度を所定時間保持する。降温は、第１および第２の降温工程の２段階で行うことが好ましい。第１降温工程は、成形温度からＰＴＦＥの溶融開始前温度までを緩慢に降温する工程であり、第２降温工程は、ＰＴＦＥの溶融開始前温度から常温までをやや緩慢に冷却する工程である。
【００１９】
具体的には、例えば、
（ｉ）温度条件：常温からＰＣＴＦの溶融温度より高温である３８５℃までを６０〜９０分で昇温し、３８５℃で６０〜９０分保持し、３８５℃からＰＴＦＥの溶融開始前の温度である２８５℃までを、８０〜１２０分で冷却し、２８５℃から常温まで２０〜６０分で冷却する；
（ｉｉ）成形面圧条件：昇温開始１０〜３０分後から、１０〜７０Ｋｇ／ｃｍ２の面圧を負荷し、これを冷却終了まで継続する； および
（ｉｉｉ）真空度条件：昇温開始と同時に真空度を上昇させ、５〜２０分後に７００〜７５０ｍｍＨｇとし、冷却終了まで継続する；
ことが好ましい。
【００２０】
このような加圧条件で加圧することにより、エッチング処理したときに反りが小さく、回路のずれも小さい積層板が提供される。特に精密なプレスが要求される多層回路基板や回路線幅の小さい積層板においては、回路のずれや反りは導通不良や回路の断線を発生させ、致命的な欠陥となるため、エッチング処理後の反り、回路のずれがない積層板は、特に有用である。本発明でいう反りが１０ｍｍ以下であれば、精密な多層回路の構成が可能である。
【００２１】
本発明でいう積層板の反りとは、２００×１５０ｍｍ、厚さ０．６ｍｍの大きさの積層板の片面の全面をエッチングして銅箔を除去したときの反りをいう。なお、「２００×１５０ｍｍの大きさの積層板」は、本発明の積層板の大きさを規定するわけではなく、反りの測定のために用いる積層板の大きさを規定しているにすぎない。
【００２２】
本発明において、「積層板の反り」は、以下の方法で測定される。すなわち、成形プレスして得られた２００×１５０ｍｍ、厚さ０．６ｍｍの積層板、あるいは成形プレスして得られた積層板から切り出した２００×１５０ｍｍ、厚さ０．６ｍｍの積層板をエッチングにより片面の銅箔を除去し、２５℃、４時間放置した後、図１に示すように積層板を平面台の上に置き、積層板と台との最長距離ｈ（単位ｍｍ）を測定する。測定枚数は３枚で、平均値で示す。反りが１０ｍｍ以下となる積層板が、以降の工程に好ましく使用される。
【００２３】
なお、プリプレグを積層する場合、各プリプレグ間に、上記３８０℃で特定の粘度範囲を有する溶融フッ素樹脂を接着剤として用いてもよい。
【００２４】
【作用】
本発明の積層板は、ＰＴＦＥと銅箔との間に、３８０℃における溶融粘度が特定範囲のフッ素樹脂を特定の厚みで配置するので、このＰＴＦＥ含浸プリプレグと銅箔の間を強固に接着するとともに、冷却の際の残留応力を吸収し、銅とフッ素樹脂との間の接着性を向上させると考えられる。従って、回路形成の際エッチング工程で銅箔が除去される、あるいは積層板の上下面の除去率が異なっても、積層板の上面、下面における残留応力のバランスが保たれ、反りの防止を抑制すると考えられる。
【００２５】
【実施例】
以下に実施例を挙げて本発明を説明するが、本発明はこの実施例に限定されない。
【００２６】
（実施例１）
株式会社有沢製作所製の厚さ０．１８５ｍｍ、秤量２１５ｇ／ｍ２のガラスクロス（Ｍ７６２８−５４５ Ｓ−６５０）２枚を基材として用いた。これにＰＴＦＥ（三井デュポンフロロケミカル（株）製３４４３ Ｊ）を６２．４％（質量％）含浸させた。得られたＰＴＦＥ含浸プリプレグに、溶融フッ素樹脂として、ＰＦＡ（三井デュポンフロロケミカル（株）製３３４ Ｊ）を３．６％（質量％）含浸させた。得られたプリプレグのガラス布織糸の方向を揃えて、両側に厚さ１８μｍの銅箔（（株）ジャパンエナジー製標準箔 ＪＴＣ箔）を載せ、成形プレスした。
【００２７】
成形プレスの条件は以下の通りである：
（ｉ）温度条件：常温から３８５℃までを７０分で昇温し、３８５℃で８０分保持し、３８５℃から２８５℃までを、１００分で冷却し、２８５℃から常温まで４０分で冷却した；
（ｉｉ）成形面圧条件：昇温開始２０後から、５０ｋｇ／ｃｍ２の面圧を負荷し、これを冷却終了まで継続した； および
（ｉｉｉ）真空度条件：昇温開始と同時に真空度を上昇させ、１０分後に７４０ｍｍＨｇとし、冷却終了まで継続した。
【００２８】
この加圧成形プレスにより、銅箔とＰＴＦＥプリプレグとの間に約５μｍのＰＦＡ層（溶融フッ素樹脂層）を有する、厚みが０．６ｍｍの積層板を得た。
【００２９】
（実施例２）
溶融フッ素樹脂として、ＦＥＰ（三井デュポンフロロケミカル（株）製１２０Ｊ）を用いた以外は実施例１と同じ材料を用い、同じ加圧成形条件で、銅箔とＰＴＦＥプリプレグとの間に約５μｍのＦＥＰ樹脂層（溶融フッ素樹脂層）を有する、厚みが０．６ｍｍの積層板を得た。
【００３０】
（実施例３）
ＰＴＦＥ樹脂を４７．１％（質量％）含浸させたプリプレグを用い、溶融フッ素樹脂として、ＰＦＡを１８．９％（質量％）含浸させた以外は実施例１と同じ材料を用い、同じ加圧成形条件で、銅箔とＰＴＦＥプリプレグとの間に約２８μｍのＰＦＡ樹脂層（溶融フッ素樹脂層）を有する、厚みが０．６ｍｍの積層板を得た。
【００３１】
（実施例４）
ＰＴＦＥ樹脂を５７．５％（質量％）含浸させたプリプレグを用い、溶融フッ素樹脂として２５μｍの厚さのＰＦＡシート（株式会社東レ製）を配置した以外は実施例１と同じ材料を用い、同じ加圧成形条件で、銅箔とＰＴＦＥプリプレグとの間に約２５μｍのＰＦＡ樹脂層（溶融フッ素樹脂層）を有する、厚みが０．６ｍｍの積層板を得た。
【００３２】
（実施例５）
ＰＴＦＥプリプレグの布織糸方向を交差させて積層した以外は、実施例１と同様にして積層板を作成した。すなわち、ＰＴＦＥ樹脂を６２．４％（質量％）含浸させたＰＴＦＥ含浸プリプレグに、ＰＦＡ樹脂を３．６％（質量％）含浸させた。得られたプリプレグのガラス布織糸の方向を交差させて、両側に厚さ１８μｍの銅箔を載せ、加圧成形することにより、銅箔とＰＴＦＥプリプレグとの間に約５μｍのＰＦＡ樹脂層を有する、厚みが０．６ｍｍの積層板を得た。
【００３３】
（比較例１）
実施例１と同じ材料を用いて、溶融フッ素樹脂を使用しなかった点以外は実施例１と同様にして積層板を得た。すなわち、ＰＴＦＥ樹脂を６６％（質量％）含浸させたプリプレグのガラス布織糸の方向を揃えて積層し、両側に銅箔を載せて実施例１と同じ条件で加圧成形を行い、銅箔とＰＴＦＥプリプレグが直接接着した（すなわち、溶融フッ素樹脂層が介在しない）、厚みが０．６ｍｍの積層板を得た。
【００３４】
（比較例２）
実施例１と同じ材料を用いて、ＰＴＦＥ樹脂を６５．２％（質量％）含浸させたＰＴＦＥプリプレグを用い、溶融フッ素樹脂としてＰＦＡ樹脂を０．８％（質量％）含浸させた以外は実施例１と同じ加圧成形条件で、銅箔とＰＴＦＥプリプレグとの間に約１μｍのＰＦＡ樹脂層（溶融フッ素樹脂層）を有する、厚みが０．６ｍｍの積層板を得た。
【００３５】
（比較例３）
ＰＴＦＥ樹脂を６６％（質量％）含浸させたプリプレグのガラス布織糸の方向を交差させて積層した以外は比較例１と同様にして積層板を作成した。すなわち、得られたＰＴＦＥプリプレグのガラス布織糸の方向を交差させて積層し、両側に銅箔を載せて実施例１と同じ条件で加圧成形を行い、銅箔とＰＴＦＥプリプレグが直接接着した（すなわち、溶融フッ素樹脂層が介在しない）、厚みが０．６ｍｍの積層板を得た。
【００３６】
（参考例）
比較例１の銅箔の代りに、三井金属工業（株）製高温伸び箔３ＥＣ−ＴＨＥ箔、厚み１８μｍの銅箔を用い、実施例１と同じ条件で加圧成形した。
【００３７】
実施例１〜５、比較例１〜３、および参考例の積層板を、それぞれ２００×１５０ｍｍに切り出し、塩化第２鉄溶液でエッチングを行い、片面の銅箔を除去し、２５℃で４時間放置し、反り量を求めた。結果を表１に示す。
【００３８】
【表１】
表１の結果は、本発明の方法で得られた積層板は、いずれも反りが１０ｍｍ以下であり、高温伸び銅箔を用いるよりも反り防止効果が得られたことを示している。他方、溶融フッ素樹脂を用いない比較例１および比較例３、溶融フッ素樹脂の厚みが２μｍ未満の比較例２では、反りは改善されなかった。プリプレグのガラス布織糸方向を交差させた比較例３の積層板は、比較例１と比べて反りはわずかに小さくなるものの、やはり、反りは改善されていない。比較例１と３との相違は、プリプレグのガラス布織糸方向がそろっているか、交差しているかであるから、この差が反りの改善に寄与しているとは考えられない。
他方、比較例３と同様、プリプレグのガラス布織糸方向を交差させ、溶融フッ素樹脂層を有する実施例５の反りは改善されている。また、比較例１と同様、プリプレグのガラス布織糸方向をそろえ、溶融フッ素樹脂層を有する実施例１の反りも改善されている。このことから、プリプレグのガラス布織糸方向を交差させるか否かは積層板の反りの改善には寄与する度合いが少なく、積層板の反りの解消には、ＰＴＦＥと銅箔の間に溶融フッ素樹脂を介在させること、すなわち、銅箔とＰＴＦＥの熱膨張率の差に起因する残留応力を解消することが本質的に必要であると知見される。
【００４０】
（実施例６）
この実施例では、上記実施例と同じ材料を用いた。ガラスクロス２枚を基材とし、ＰＴＦＥを６２．４％含浸させ、これに、ＰＦＡを表２に記載された厚みとなるようにガラス布織糸方向をそろえて配置し、その上に表２に記載の厚みの銅箔を配置して、上記と同じ条件で加圧成形した。得られた積層板を２００×１５０ｍｍの大きさに切り出し、それぞれ、図２に模式図として示す１ｍｍの幅で同心方状に銅箔が残るエッチングパターンを図３に示すように８個等分配置して形成した。図２および３において、破線は銅箔部が残存している部分である。このエッチングした積層板にＰＦＡシートを配置し、さらに１２μｍの銅箔を配置して、再び同じ条件で加圧成形し、さらに最外層の銅箔をエッチング処理して全て除いた。
得られた積層板の回路のずれを、対角線にずれが生じるか否かで判断した。結果を表２に示す。表２中の数字は、回路にずれが生じなかった積層板の個数を表す。７個以上を合格とした。
【００４１】
【表２】
表２の結果からわかるように、銅箔の厚みが１８μｍおよび３６μｍのとき、銅箔厚み以下のＰＦＡ層を有する積層板は、すべて、回路の反りを生じることがなかった。また、銅箔厚みが１２μｍの場合を含め、銅箔厚みの２倍以下の場合も、ほとんど回路にずれは生じなかった
【００４３】
（実施例７）
ＰＴＦＥを４７．１％含浸させたプリプレグを用いた以外は、実施例６と同様に積層板を形成し、実施例６と同様に評価した。結果を表３に示す。
【００４４】
【表３】
表３の結果も、実施例６と同様、銅箔厚みの２倍以下のＰＦＡ厚みでは、回路のずれはほとんど生じず、銅箔厚み以下では、回路のずれは全くなかった。
【００４６】
【発明の効果】
本発明により、銅箔のエッチング除去による回路形成後においても反りが少ない積層板が得られた。この積層板は、反りが少ないため、電子部品の実装に支障をきたすこともなく、一様なレジスト膜を形成することも可能となるため、その後の回路形成工程がスムーズに進行し、製造効率の向上に大きく寄与するとともに、アンテナなどに使用する場合においても設計値を忠実に反映させることができる安定した電気特性を確保できる基板を提供できる。
【図面の簡単な説明】
【図１】積層板の反りを測定する方法を示す図である。
【図２】積層板の回路のずれを判定するためのエッチングパターンを示す図である。
【図３】回路のずれを判定するエッチングパターンが形成された積層板の模式図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a low dielectric loss tangent and low dielectric constant laminate used for equipment using high frequency radio waves, particularly equipment suitable for high frequencies of 1 GHz or more.
[0002]
[Prior art]
Fluororesin is a resin having a low dielectric loss tangent and a low dielectric constant, and is suitable for a substrate for high frequency use. Among them, PTFE (polytetrafluoroethylene) resin is most suitable for high-frequency applications, so it is impregnated into a woven fabric such as a glass substrate to form a prepreg, and the prepreg is laminated to form a copper foil on one or both surfaces. Are laminated to form a laminate.
[0003]
However, this laminate may be warped when heated and pressed, and methods for improving the warpage are being studied. For example, the fact that the difference in the tension (elongation) between the warp and the weft of the glass base material used for the laminated board remains even after the woven fabric is considered to be one cause of the warpage of the substrate, In addition, a laminate in which the warp of the outermost prepreg crosses the warp direction of another prepreg has been studied (Japanese Patent Laid-Open No. 8-148780).
[0004]
However, although this laminated plate is excellent in suppressing warpage during heating and pressurizing, it is warped again when metal foil is removed by etching or when a circuit is formed on the laminated plate. Changing the fiber orientation of the material alone is not always effective. Depending on the substrate, the amount of warpage reaches a value close to 20 mm. With such a substrate, it is difficult to mount electronic components such as a circuit, and a multilayer substrate in which a single-layer substrate or a double-sided substrate is sequentially laminated and bonded. On the substrate, the resist film for forming the circuit cannot be formed to a uniform thickness, which not only causes problems such as the inability to form a precise circuit, but also for high-frequency applications such as radar wave reception. In the case where the antenna is used for an antenna or the like, a problem relating to electrical characteristics that an effective reception area of a radio wave cannot be obtained as designed value also occurs.
[0005]
As a result of earnest studies by the present inventors, it was recognized that the cause of the warpage was a large difference in linear expansion coefficient between PTFE and the copper foil. That is, the melting point (or gelation temperature) of PTFE is extremely high, and a high-temperature heat bonding press step of about 380 ° C. is required to bond the copper foil and the PTFE resin. Because of its large expansion and contraction due to its linear expansion coefficient, the difference from the thermal expansion of the PTFE-impregnated prepreg or the PTFE laminate becomes large, and the PTFE-impregnated prepreg or the laminate using the same and the laminate and copper foil remain. Stress remains, and therefore, if the copper foil is removed in the etching step during circuit formation, or if the removal rates of the upper and lower surfaces of the laminate differ, the balance of the residual stress on the upper and lower surfaces of the laminate is lost, and warpage occurs. It was found to occur.
[0006]
In order to solve this, a resin having a linear expansion coefficient close to that of copper may be impregnated and used in the prepreg, but a fluororesin having a linear expansion coefficient similar to that of a metal foil is not known at present. Therefore, there is no possibility that the occurrence of warpage can be effectively prevented.
[0007]
A method of preventing warpage by increasing the thickness of the substrate is also conceivable. However, this method requires a natural logarithmic multiple times the area of the substrate to obtain the same impedance. There is a problem that cannot be reduced in size.
[0008]
Furthermore, as a method of suppressing warpage, a method using a copper foil referred to as a high-temperature stretched foil is conceivable. However, since a high-temperature stretched foil is two to three times as expensive as a commonly used copper foil, it is employed in terms of cost. It is hard to be done.
[0009]
[Problems to be solved by the invention]
Therefore, there is a demand for a laminate having a small warpage even when a circuit is formed by etching a copper foil, and a method of manufacturing the laminate.
[0010]
[Means for Solving the Problems]
The present invention, on both sides of the outermost layer of one or two or more prepregs obtained by impregnating the PTFE resin has a copper foil, the viscosity during melt between the prepreg and the copper foil 10 7 poise or less Wherein the molten fluororesin is disposed at a thickness of 2 μm to twice or less the thickness of the copper foil.
[0011]
In a preferred embodiment, the thickness of the molten fluororesin layer is equal to or less than the thickness of the copper foil.
[0012]
In a preferred embodiment, the molten fluororesin is selected from the group consisting of PFA, FEP, ETFE, PVDF, ECTFE, PCTFE, PVF or a mixture thereof.
[0013]
The present invention further viscosity during melting or during gelation on both sides of the outermost layer of one or two or more prepregs obtained by impregnating the PTFE resin is placed 10 7 poise or less of the melting fluorine resin, the molten After arranging the copper foil on the fluororesin, under a pressure of a reduced pressure atmosphere, a temperature raising step of raising the temperature from room temperature to a molding temperature slightly higher than the melting point of the PTFE resin, and holding the molding temperature for a predetermined time, A first temperature lowering step for slowly lowering the temperature from the temperature to the temperature before the start of melting of PTFE, and a second temperature lowering step for slightly cooling the temperature from the temperature before the start of melting of the PTFE to normal temperature. The present invention relates to a method for manufacturing a laminated board, which comprises performing pressure molding so as to have a thickness of 2 μm to twice or less the thickness of the copper foil.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The prepreg used in the present invention is not particularly limited as long as it is a prepreg impregnated with PTFE, but in order to obtain strength and a preferable dielectric tangent, prepreg in which PTFE is impregnated into a woven fabric such as glass fiber may be used. preferable.
[0015]
The laminated board of the present invention may be a single-layer board or a double-sided board that forms a circuit on the upper surface, the lower surface, or one of them, or may be a multilayer board in which one or more inner-layer circuits are laminated. Copper foil is bonded to both surfaces of the outermost layer of the laminate. The thickness of the copper foil used is not particularly limited, but a commonly used thickness of 18 μm to 36 μm is preferably used.
[0016]
In the present invention, arranged as a coating layer or a resin sheet with a viscosity of 10 7 poise or less of the melting fluorine resin during melt prepreg between the prepreg and the copper foil, copper foil thickness of the molten fluororesin layer is from 2μm It is characterized in that pressure molding is performed so as to have a thickness of twice or less the thickness. The molten fluororesin used in the present invention refers to a fluorine-containing resin that melts at 380 ° C. or lower. The melt fluororesin, may be any fluoroplastic long 10 7 poise or less viscosity at the time of melting. For example, PFA (tetrafluoroethylene perproloalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride), ECTFE (ethylene chlorotrifluoroethylene), PCTFE (polychlorinate trifluoroethylene), PVF (polyvinyl fluoride) and the like. These resins may be used alone, also viscosity during even a mixed molten resin is not more 10 7 poise or less is preferably used. Preferred viscosity at the time of melting is 10 3 or more, preferably 107 to 3 poise, more preferably 105 to 3 poise, more preferably 105 to 4 poise.
[0017]
The molten fluororesin is located between the copper foil and the prepreg, and is pressure-formed so that the thickness of the molten fluororesin layer is from 2 μm to twice or less the thickness of the copper foil. If it is less than 2 μm, a sufficient adhesive effect cannot be obtained, and the warpage becomes large. If the thickness exceeds twice the thickness of the copper foil, the molten fluororesin layer melts during the pressure molding of the multilayer circuit board, so that a so-called swimming phenomenon may occur and the copper foil forming the inner layer circuit may shift with the flow of the molten fluororesin. Is not preferred. In particular, considering the case of forming a multilayer circuit board, the thickness of the molten fluororesin layer is more preferably equal to or less than the thickness of the copper foil.
[0018]
The pressing conditions are not particularly limited, and a method generally used by those skilled in the art when bonding a copper foil to a prepreg may be used, but the following method is preferably used. That is, under the pressure of a reduced-pressure atmosphere, first, the temperature is raised from room temperature to a molding temperature slightly higher than the melting point of the PTFE resin, and then the molding temperature is maintained for a predetermined time. The cooling is preferably performed in two stages of the first and second cooling processes. The first temperature lowering step is a step of slowly lowering the temperature from the molding temperature to the temperature before the start of melting of PTFE, and the second temperature lowering step is a step of slightly cooling the temperature from the temperature before the start of melting of PTFE to the normal temperature.
[0019]
Specifically, for example,
(I) Temperature condition: The temperature is raised from room temperature to 385 ° C., which is higher than the melting temperature of PCTF, in 60 to 90 minutes, held at 385 ° C. for 60 to 90 minutes, and maintained at 385 ° C. before the start of PTFE melting. Cooling to a certain 285 ° C. in 80-120 minutes and cooling from 285 ° C. to room temperature in 20-60 minutes;
(Ii) Surface pressure for molding: 10 to 30 minutes after the start of temperature rise, a surface pressure of 10 to 70 Kg / cm 2 is applied, and this is continued until the end of cooling; and (iii) vacuum condition: Start of temperature rise At the same time, the degree of vacuum is increased to 700 to 750 mmHg after 5 to 20 minutes and continued until the end of cooling;
Is preferred.
[0020]
By applying pressure under such pressurizing conditions, a laminated board which has a small warpage and a small circuit shift when etched is provided. In particular, in the case of a multilayer circuit board or a laminated board with a small circuit line width, which requires precise pressing, circuit misalignment and warping can cause conduction failure and circuit disconnection, and become fatal defects. Laminates without warpage or circuit displacement are particularly useful. If the warpage in the present invention is 10 mm or less, a precise multilayer circuit can be formed.
[0021]
The term “warpage of the laminate” as used in the present invention means the warpage when the copper foil is removed by etching the entire surface of one side of the laminate having a size of 200 × 150 mm and a thickness of 0.6 mm. The “laminate having a size of 200 × 150 mm” does not specify the size of the laminate of the present invention, but merely defines the size of the laminate used for measuring the warpage. .
[0022]
In the present invention, the “warpage of the laminate” is measured by the following method. That is, a 200 × 150 mm, 0.6 mm thick laminated plate obtained by molding press, or a 200 × 150 mm, 0.6 mm thick laminated plate cut from a laminated plate obtained by molding press is etched. After the copper foil on one side is removed and left at 25 ° C. for 4 hours, the laminate is placed on a flat table as shown in FIG. 1, and the longest distance h (unit: mm) between the laminate and the table is measured. The number of sheets measured is three, and the average value is shown. A laminate having a warpage of 10 mm or less is preferably used in the subsequent steps.
[0023]
When prepregs are laminated, a molten fluororesin having a specific viscosity range at 380 ° C. may be used as an adhesive between the prepregs.
[0024]
[Action]
In the laminate of the present invention, a fluorine resin having a melt viscosity at 380 ° C. in a specific range is disposed at a specific thickness between the PTFE and the copper foil, so that the PTFE-impregnated prepreg and the copper foil are firmly bonded to each other. At the same time, it is considered that the residual stress at the time of cooling is absorbed and the adhesiveness between copper and the fluororesin is improved. Therefore, even if the copper foil is removed in the etching step during circuit formation, or the removal rates of the upper and lower surfaces of the laminate are different, the balance of the residual stress on the upper and lower surfaces of the laminate is maintained, and the prevention of warpage is suppressed. It is thought that.
[0025]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
[0026]
(Example 1)
Two glass cloths (M7628-545 S-650) having a thickness of 185 g / m 2 and a thickness of 0.185 mm manufactured by Arisawa Seisakusho Co., Ltd. were used as the base material. This was impregnated with 62.4% (mass%) of PTFE (3443 J manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.). The obtained PTFE-impregnated prepreg was impregnated with PFA (334 J, manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) as a molten fluororesin at 3.6% (mass%). An 18 μm-thick copper foil (a standard foil JTC foil manufactured by Japan Energy Co., Ltd.) was placed on both sides of the obtained prepreg with the directions of the glass cloth yarns aligned, and formed and pressed.
[0027]
The conditions of the forming press are as follows:
(I) Temperature condition: the temperature is raised from room temperature to 385 ° C. in 70 minutes, held at 385 ° C. for 80 minutes, cooled from 385 ° C. to 285 ° C. in 100 minutes, and cooled from 285 ° C. to room temperature in 40 minutes. did;
(Ii) Molding surface pressure condition: A surface pressure of 50 kg / cm 2 was applied from 20 after the start of temperature rise, and this was continued until the end of cooling; and (iii) vacuum degree condition: The degree of vacuum was simultaneously increased with the start of temperature rise. The temperature was raised to 740 mmHg after 10 minutes and continued until the cooling was completed.
[0028]
By this press forming press, a laminate having a thickness of 0.6 mm having a PFA layer (molten fluororesin layer) of about 5 μm between the copper foil and the PTFE prepreg was obtained.
[0029]
(Example 2)
The same material as in Example 1 was used as the molten fluororesin except that FEP (120J manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) was used. Under the same pressure molding conditions, a gap of about 5 μm was formed between the copper foil and the PTFE prepreg. A laminate having an FEP resin layer (molten fluororesin layer) and a thickness of 0.6 mm was obtained.
[0030]
(Example 3)
A prepreg impregnated with 47.1% (% by mass) of PTFE resin was used, and the same material as in Example 1 was used, except that 18.9% (% by mass) of PFA was impregnated as a molten fluorine resin. Under the molding conditions, a laminate having a thickness of 0.6 mm having a PFA resin layer (molten fluororesin layer) of about 28 μm between the copper foil and the PTFE prepreg was obtained.
[0031]
(Example 4)
A prepreg impregnated with 57.5% (mass%) of a PTFE resin was used, and the same material as in Example 1 was used except that a PFA sheet (manufactured by Toray Industries, Inc.) having a thickness of 25 μm was arranged as a molten fluorine resin. Under pressure molding conditions, a laminate having a thickness of 0.6 mm having a PFA resin layer (molten fluororesin layer) of about 25 μm between the copper foil and the PTFE prepreg was obtained.
[0032]
(Example 5)
A laminated board was prepared in the same manner as in Example 1 except that the PTFE prepregs were laminated with the cloth yarn directions crossed. That is, the PTFE-impregnated prepreg impregnated with 62.4% (% by mass) of the PTFE resin was impregnated with 3.6% (% by mass) of the PFA resin. The direction of the glass cloth yarn of the obtained prepreg was crossed, and a copper foil having a thickness of 18 μm was placed on both sides and pressed to form a PFA resin layer of about 5 μm between the copper foil and the PTFE prepreg. Thus, a laminate having a thickness of 0.6 mm was obtained.
[0033]
(Comparative Example 1)
A laminate was obtained using the same materials as in Example 1, except that no molten fluororesin was used. That is, prepreg impregnated with 66% (mass%) of PTFE resin is laminated with the direction of the glass cloth woven yarn aligned, and copper foil is placed on both sides and pressure-molded under the same conditions as in Example 1 to obtain a copper foil. And a PTFE prepreg were directly adhered (that is, a molten fluororesin layer was not interposed), and a laminate having a thickness of 0.6 mm was obtained.
[0034]
(Comparative Example 2)
Using the same material as in Example 1, a PTFE prepreg impregnated with 65.2% (% by mass) of PTFE resin was used, and the same procedure was performed except that 0.8% (% by mass) of PFA resin was impregnated as a molten fluororesin. Under the same pressure molding conditions as in Example 1, a laminate having a thickness of 0.6 mm having a PFA resin layer (molten fluororesin layer) of about 1 μm between the copper foil and the PTFE prepreg was obtained.
[0035]
(Comparative Example 3)
A laminated board was prepared in the same manner as in Comparative Example 1, except that the prepreg impregnated with 66% (mass%) of PTFE resin was laminated so that the directions of the glass cloth yarns were crossed. That is, the obtained PTFE prepregs were laminated with the directions of the glass cloth yarns intersecting with each other, copper foil was placed on both sides, and pressure molding was performed under the same conditions as in Example 1, and the copper foil and the PTFE prepreg were directly bonded. A laminate having a thickness of 0.6 mm was obtained (that is, no molten fluororesin layer was interposed).
[0036]
(Reference example)
Instead of the copper foil of Comparative Example 1, a high-temperature stretched foil 3EC-THE foil manufactured by Mitsui Kinzoku Kogyo KK and a copper foil having a thickness of 18 μm were pressed and formed under the same conditions as in Example 1.
[0037]
The laminated boards of Examples 1 to 5, Comparative Examples 1 to 3, and Reference Example were cut into 200 × 150 mm, respectively, and etched with a ferric chloride solution to remove a copper foil on one side, and then at 25 ° C. for 4 hours. It was left and the amount of warpage was determined. Table 1 shows the results.
[0038]
[Table 1]
The results in Table 1 show that the laminates obtained by the method of the present invention each had a warpage of 10 mm or less, and that a higher warp prevention effect was obtained than when a high-temperature stretched copper foil was used. On the other hand, in Comparative Examples 1 and 3 where no molten fluororesin was used, and in Comparative Example 2 where the thickness of the molten fluororesin was less than 2 μm, the warpage was not improved. The laminate of Comparative Example 3 in which the directions of the glass cloth yarns of the prepreg were intersected was slightly smaller than that of Comparative Example 1, but the warp was not improved. The difference between Comparative Examples 1 and 3 is whether the glass cloth yarn direction of the prepreg is uniform or intersects. Therefore, it is not considered that this difference contributes to the improvement of the warpage.
On the other hand, as in Comparative Example 3, the direction of the glass cloth yarn of the prepreg was crossed, and the warpage of Example 5 having the molten fluororesin layer was improved. Further, similarly to Comparative Example 1, the direction of the glass cloth yarn of the prepreg was aligned, and the warpage of Example 1 having the molten fluororesin layer was also improved. Therefore, whether or not the direction of the glass cloth yarn of the prepreg intersects little contributes to the improvement of the warpage of the laminate, and to eliminate the warp of the laminate, the molten fluorine is used between the PTFE and the copper foil. It is found that it is essentially necessary to interpose a resin, that is, to eliminate the residual stress caused by the difference in the coefficient of thermal expansion between the copper foil and PTFE.
[0040]
(Example 6)
In this example, the same material as in the above example was used. Two glass cloths were used as a base material, impregnated with 62.4% of PTFE, and PFA was arranged on the glass cloth so as to have the thickness shown in Table 2 in the same direction as the glass cloth yarn. Was placed under pressure and molded under the same conditions as above. The obtained laminated board is cut into a size of 200 × 150 mm, and each of the etching patterns is concentrically provided with a copper foil having a width of 1 mm as schematically shown in FIG. 2 and eight equally arranged as shown in FIG. Formed. In FIGS. 2 and 3, the dashed line is the portion where the copper foil portion remains. A PFA sheet was placed on the etched laminate, a copper foil of 12 μm was further placed, pressure molding was performed again under the same conditions, and the outermost copper foil was removed by etching.
The shift of the circuit of the obtained laminated board was determined based on whether or not a shift occurred in the diagonal line. Table 2 shows the results. The numbers in Table 2 represent the number of laminated boards in which no shift occurred in the circuit. Seven or more pieces were accepted.
[0041]
[Table 2]
As can be seen from the results in Table 2, when the thickness of the copper foil was 18 μm and 36 μm, all the laminates having a PFA layer having a thickness equal to or less than the copper foil thickness did not cause circuit warpage. In addition, even when the thickness of the copper foil was 12 μm or less, even when the thickness of the copper foil was twice or less, there was almost no deviation in the circuit.
(Example 7)
A laminate was formed in the same manner as in Example 6, except that a prepreg impregnated with 47.1% of PTFE was used, and evaluated in the same manner as in Example 6. Table 3 shows the results.
[0044]
[Table 3]
Also in the results of Table 3, as in the case of Example 6, there was almost no circuit displacement when the PFA thickness was twice or less the copper foil thickness, and no circuit displacement occurred below the copper foil thickness.
[0046]
【The invention's effect】
According to the present invention, a laminate having less warpage even after a circuit is formed by etching and removing a copper foil was obtained. Since the laminated board has a small warpage, it does not hinder the mounting of electronic components, and it is possible to form a uniform resist film. It is possible to provide a substrate which can greatly contribute to improvement of the performance and can secure stable electric characteristics capable of faithfully reflecting design values even when used for an antenna or the like.
[Brief description of the drawings]
FIG. 1 is a diagram showing a method for measuring the warpage of a laminated plate.
FIG. 2 is a diagram showing an etching pattern for determining a shift of a circuit of a laminated board.
FIG. 3 is a schematic view of a laminated plate on which an etching pattern for determining a circuit shift is formed.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000148439A JP3569197B2 (en) | 2000-05-19 | 2000-05-19 | Laminated plate and method of manufacturing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000148439A JP3569197B2 (en) | 2000-05-19 | 2000-05-19 | Laminated plate and method of manufacturing the same |
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| Publication Number | Publication Date |
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| JP2001328205A JP2001328205A (en) | 2001-11-27 |
| JP3569197B2 true JP3569197B2 (en) | 2004-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2000148439A Expired - Fee Related JP3569197B2 (en) | 2000-05-19 | 2000-05-19 | Laminated plate and method of manufacturing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11903127B2 (en) * | 2020-10-26 | 2024-02-13 | Nan Ya Plastics Corporation | Fluoride-based resin prepreg and circuit substrate using the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003273630A (en) * | 2002-03-13 | 2003-09-26 | Daikin Ind Ltd | Antenna element |
| EP3339016A4 (en) * | 2015-08-20 | 2019-05-01 | AGC Inc. | Multilayer base and method for producing molded body of same |
| CN108859326B (en) * | 2018-06-07 | 2021-01-05 | 南京大学 | Copper-clad method of PTFE (polytetrafluoroethylene) -based PCB (printed Circuit Board) copper-clad plate |
| TWI680871B (en) * | 2018-09-27 | 2020-01-01 | 南亞塑膠工業股份有限公司 | Fluorine resin composition, prepreg and copper foil substrate using the composition |
| US10889741B2 (en) | 2018-11-28 | 2021-01-12 | Nan Ya Plastics Corporation | Fluorocarbon resin composition and prepreg and copper foil substrate using the same |
| CN109849477A (en) * | 2019-02-22 | 2019-06-07 | 昆山华阳新材料股份有限公司 | Composite material with electro-magnetic screen function |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62216742A (en) * | 1986-03-19 | 1987-09-24 | 日立化成工業株式会社 | Manufacture of aluminum-core copper lined laminated plate |
| JPS63173638A (en) * | 1987-01-14 | 1988-07-18 | 松下電工株式会社 | Laminated board |
| JPS63199636A (en) * | 1987-02-14 | 1988-08-18 | 松下電工株式会社 | Laminated board |
| JPH0379343A (en) * | 1989-08-23 | 1991-04-04 | Fujikura Ltd | Metal-foiled laminated sheet and preparation thereof |
| JP2548879Y2 (en) * | 1991-08-14 | 1997-09-24 | 中興化成工業株式会社 | Laminated materials for printed wiring boards |
| JPH05138741A (en) * | 1991-11-19 | 1993-06-08 | Nitto Denko Corp | Adhesive sheet for printed circuit board and board using the same |
| JPH0818403B2 (en) * | 1993-06-03 | 1996-02-28 | 日本ピラー工業株式会社 | Laminates and green composite films for laminates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11903127B2 (en) * | 2020-10-26 | 2024-02-13 | Nan Ya Plastics Corporation | Fluoride-based resin prepreg and circuit substrate using the same |
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| JP2001328205A (en) | 2001-11-27 |
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