JP3899398B2 - Resin composition - Google Patents
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- JP3899398B2 JP3899398B2 JP05811099A JP5811099A JP3899398B2 JP 3899398 B2 JP3899398 B2 JP 3899398B2 JP 05811099 A JP05811099 A JP 05811099A JP 5811099 A JP5811099 A JP 5811099A JP 3899398 B2 JP3899398 B2 JP 3899398B2
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- polyimide
- resin composition
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Description
【０００１】
【発明の属する技術分野】
本発明は、比較的低温で接着硬化でき、溶媒に可溶で耐熱性及び接着性に優れた樹脂組成物に関する。本発明の樹脂組成物は、フレキシブル印刷回路基板、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ ｂｏｎｄｉｎｇ）用テープ、複合リードフレーム、積層材料等に用いられる耐熱性接着性に優れた接着剤として有用である。
【０００２】
【従来の技術】
近年、電子機器の高機能化、高性能化、小型化が進んでおり、それらに伴って用いられる電子部品に対する小型化、軽量化が求められてきている。そのため半導体素子パッケージ方法やそれらを実装する配線材料または配線部品も、より高密度、高機能、かつ高性能なものが求められるようになってきた。特に、半導体パッケージ、ＣＯＬ及びＬＯＣパッケージ、ＭＣＭ（Multi Chip Module ）等の高密度実装材料や多層ＦＰＣ等のプリント配線板材料、さらには航空宇宙材料として好適に用いることのできる、良好な接着性を示す材料が求められている。
【０００３】
従来、半導体パッケージやその他実装材料において、良好な機械的特性や耐熱性、絶縁性を示す接着材料として、アクリル系、フェノール系、エポキシ系、ポリイミド系等の接着剤が知られている。
【０００４】
ところが、フェノール系及びエポキシ系の接着剤は、接着性は優れているが、柔軟性に劣る。柔軟性のあるアクリル系の接着剤は耐熱性が低いという問題が生じる。これを解決するために、ポリイミドが用いられている。ポリイミドは、種々の有機ポリマーの中でも耐熱性に優れているため、宇宙、航空分野まで幅広く用いられ、接着材料としても用いられている。しかし、耐熱性の高いポリイミド系接着剤は接着するために３００℃前後の高温と高圧力を要し、接着力もそれほど高いとはいえない。また、従来のポリイミド系接着剤は吸水率が高く、例えば、このポリイミド系接着剤を使用したリードフレームを半田浴に浸漬する際、膨れ等を生じやすいといった問題を有していた。
【０００５】
【発明が解決しようとする課題】
そこで本発明者らは、上記課題を解決し、半田耐熱性、耐熱性および接着性に優れ、特に２５０℃以下の低温で接着可能な樹脂組成物を提供することを目的とし、鋭意研究を行った結果、本発明を完成するに至った。
【０００６】
【課題を解決するための手段】
本発明にかかる樹脂組成物の要旨とするところは、ポリイミド樹脂とエポキシ樹脂を含有し、硬化反応後の吸水率が、１．５％以下であり得る。
【０００７】
また、前記ポリイミド樹脂が、一般式（１）化５
【０００８】
【化５】
で表されるエステル酸二無水物と
一般式（２）化６
【００１０】
【化６】
（式中、Ｙは脂肪族の二価の基、または、化７
【００１２】
【化７】
（式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 は水素またはアルキル基、Ａは二価の有機基を示す。ベンゼン環の水素は、置換されない。）から選択される二価の基を示す。）
で表されるジイソシアナートとを反応させて得られるポリイミド樹脂であり得る。
【００１４】
さらに、前記ジイソシアナートが、一般式（３）化８
【００１５】
【化８】
（式中Ｚは、−Ｃ（＝Ｏ）−、−ＳＯ２−、−Ｏ−、−Ｓ−、−（ＣＨ２）ｍ−、−ＮＨＣＯ−、−Ｃ（ＣＨ３）２−、−Ｃ（ＣＦ３）２−、−Ｃ（＝Ｏ）Ｏ−、または結合であり、ｍ、ｎは１以上１０以下の整数である。）で示されるジイソシアナートであり得る。
【００１７】
ここで、「樹脂組成物の硬化反応後」とは、例えば樹脂組成物をシート状に成形し、１００℃で１０分間、１５０℃で２０分間乾燥させた後、１５０℃で３時間加熱硬化させた後をいう。すなわち樹脂組成物中のエポキシ樹脂が硬化した状態とした後をいう。
【００１８】
【発明の実施の形態】
以下、本発明を詳細に説明する。本発明の樹脂組成物は、ポリイミド樹脂とエポキシ樹脂を混合したものであり、硬化反応後の吸水率が、１．５％以下であり得る樹脂組成物である。
【００１９】
かかる、樹脂組成物に用いられるポリイミド樹脂は、上記特性を有していれば基本的には限定されないが、特には一般式（１）化９
【００２０】
【化９】
（式中、Ｘは芳香環を含む二価の基を示す。）で表されるエステル酸二無水物を構成成分として含むポリイミド樹脂を用いると、優れた低吸水率を発現するため、半田耐熱性に優れた特性を有する。
【００２２】
本発明に用いられる一般式（１）で表されるエステル酸二無水物の好ましい例としては、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物、ｐ−フェニレンビス（トリメリット酸モノエステル無水物）、３，３’，４，４’−エチレングリコールベンゾエートテトラカルボン酸二無水物、４，４’−ビフェニレンビス（トリメリット酸モノエステル無水物）、１，４−ナフタレンビス（トリメリット酸モノエステル無水物）、１，２−エチレンビス（トリメリット酸モノエステル無水物）、１，３−トリメチレンビス（トリメリット酸モノエステル無水物）、１，４−テトラメチレンビス（トリメリット酸モノエステル無水物）、１，５−ペンタメチレンビス（トリメリット酸モノエステル無水物）、１，６−ヘキサメチレンビス（トリメリット酸モノエステル無水物）等が挙げられるがこれらに限定するものではない。これらのうちの１種または２種以上を組み合わせて用い得る。
【００２３】
さらに、一般式（２）化１０
【００２４】
【化１０】
（式中、Ｙは脂肪族の二価の基、または、化１１
【００２６】
【化１１】
（式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 は水素またはアルキル基、Ａは二価の有機基を示す。ベンゼン環の水素は、置換されない。）から選択される二価の基を示す。）で表されるジイソシアナートを用いると上記エステル酸二無水物との組み合わせにより、優れた低吸水率を発現することができる。
【００２８】
一般式（２）で表されるジイソシアナートの好ましい例としては、ジフェニルメタンジイソシアナート、パラフェニレンジイソシアナート、２−クロロ−１，４−フェニルジイソシアナート、２，４−トルエンジイソシアナート、２，６−トルエンジイソシアナート、１，５−ナフタレンジイソシアナート、ヘキサメチレンジイソシアナート、イソフォロンジイソシアナート、キシリレンジイソシアナート、リジンジイソシアナート、テトラメチルキシレンジイソシアナート、トリメチルヘキサメチレンジイソシアナート等が挙げられるがこれに限定するものではない。これらのうち、一般式（３）化１２
【００２９】
【化１２】
（式中Ｚは、−Ｃ（＝Ｏ）−、−ＳＯ２−、−Ｏ−、−Ｓ−、−（ＣＨ２）ｍ−、−ＮＨＣＯ−、−Ｃ（ＣＨ３）２−、−Ｃ（ＣＦ３）２−、−Ｃ（＝Ｏ）Ｏ−、または結合であり、ｍ、ｎは１以上１０以下の整数である。）
で表される、例えばジフェニルメタンジイソシアナート等が特に好ましく用いられる。本発明にかかる樹脂組成物には、上記のジイソシアナートのうちいずれか１種を用いる。
【００３１】
本発明にかかる樹脂組成物に含まれるポリイミド樹脂は、特には上記一般式（１）で表されるエステル酸二無水物及び上記一般式（２）で表されるジイソシアナート成分を有機極性溶媒中で重合して得られる。この場合の配合割合は、エステル酸二無水物と全ジイソシアナートとが実質的に等モルになるように使用するのが好ましいが、エステル酸二無水物を全ジイソシアナートに対して８０〜９８モル％とし分子量及び分子末端をコントロールすることも可能である。
【００３２】
上記ポリイミド樹脂を製造するには、当業者公知の種々の方法により製造することができるが、具体的に示すと、このポリイミドは、まず、アルゴン、窒素などの不活性雰囲気中において、一般式（２）で表されるジイソシアナート及び一般式（１）で表されるエステル酸二無水物より選択される酸二無水物を有機極性溶媒中に溶解または拡散させて加熱反応させることにより得られる。
【００３３】
各モノマーの添加順序は特に限定されず、酸二無水物を有機極性溶媒中に先に加えておき、ジイソシアナート成分である上記一般式（２）を添加し、ポリイミド溶液としても良いし、ジイソシアナート成分を有機極性溶媒中に先に適量加えて、次に酸二無水物を加え、最後に残りのジイソシアナート成分を加えて、ポリイミド溶液としても良い。この他にも、当業者に公知の種々の添加方法を用い得る。
【００３４】
ポリアミド酸溶液の生成反応に用いられる有機極性溶媒としては、例えば、ジメチルスルホキシド、ジエチルスルホキシド等のスルホキシド系溶媒、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド等のホルムアミド系溶媒、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド等のアセトアミド系溶媒、Ｎ−メチル−２−ピロリドン等のピロリドン系溶媒、フェノール、ｏ−，ｐ−，ｍ−またはｐ−クレゾール、キシノール、ハロゲン化フェノール、カテコール等のフェノール系溶媒、あるいはヘキサメチルホスホルアミド、γ−ブチロラクトン等を挙げることができる。更に必要に応じて、これらの有機極性溶媒とキシレンあるいはトルエン等の芳香族炭化水素とを組み合わせて用いることもできる。
【００３５】
一般に、酸二無水物とジアミンからポリイミドを生成する場合、発生する水が加水分解を起こしポリアミド酸のイミド化を阻害することを防止するために、発生する水の影響を極力小さくするための工夫や、脱水剤等によりイミド化を積極的に進める等の種々の処理を行っていた。しかし、上記一般式（１）で表されるエステル酸二無水物及び一般式（２）で表されるジイソシアナートからなるポリイミド樹脂では、酸二無水物とジアミンを用いた場合に生じる重合反応時の水の発生を伴わないため、重合時の分子量低下の危険性が少なくなり、安定した分子量のポリイミド樹脂を得ることができる。
【００３６】
上記のポリイミド樹脂およびエポキシ樹脂を用いたポリイミド樹脂は、上記一般式（１）で表されるエステル酸二無水物を用いているため、さらに一般式（２）で表されるジイソシアナートとに組み合わせによって、特に優れた低吸水性を有し、またガラス転移温度が比較的低温であるため、低吸湿性及び低温接着を可能とする優れた接着材料となり得る。
【００３７】
また、本発明にかかる樹脂組成物に用い得るエポキシ樹脂としては、ビスフェノール系エポキシ樹脂、ハロゲン化ビスフェノール系エポキシ樹脂、フェノールノボラック系エポキシ樹脂、ハロゲン化フェノールノボラック系エポキシ樹脂、アルキルフェノールノボラック系エポキシ樹脂、ポリフェノール系エポキシ樹脂、ポリグリコール系エポキシ樹脂、環状脂肪族エポキシ樹脂、クレゾールノボラック系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ウレタン変性エポキシ樹脂、ゴム変性エポキシ樹脂、エポキシ変性ポリシロキサン等が用いることができる。
【００３８】
エポキシ樹脂をポリイミド樹脂に混合する場合、混合割合は、ポリイミド１００重量部に対して、１〜５０重量部、好ましくは５〜３０重量部である。エポキシ樹脂を加えることにより接着性が増加するが、１重量部より少ない場合は接着強度が低く、５０重量部より多くなると可撓性、耐熱性等の特性が劣る場合がある。また、用いるエポキシ樹脂の吸水特性の影響および有機溶媒への溶解性、ポリイミド樹脂との組み合わせの観点より、吸水率１．５％以下の吸水率を満たす本発明にかかる樹脂組成物中のエポキシ樹脂の混合割合は、上記範囲内において種々選択し得る。
【００３９】
本発明の樹脂組成物は、上記のようにして得られた優れた特性を有するポリイミド樹脂からなるため、１．５％以下、好ましくは１．２％以下、さらに好ましくは１．０％以下という優れた低吸水率が発現され得る。また、本発明にかかる樹脂組成物は、さらにエポキシ樹脂を含有するため、ポリイミドの有する優れた耐熱性及び低吸水率等の特性に、さらに良好な接着性が付与されている。
【００４０】
また、本発明の樹脂組成物には、さらに種々の材料を添加し得る。具体的には、吸水性、耐熱性、接着性等の特性付与のため必要に応じて、酸二無水物系、アミン系、イミダゾール系等の一般に用いられるエポキシ硬化剤、促進剤や種々のカップリング剤を併用しうる。また、エポキシ樹脂以外の熱硬化性樹脂、ビスマレイミド、ビスアリルナジイミド、フェノール樹脂、シアナート樹脂等を更に加えて本発明の樹脂組成物を得ることも可能である。
【００４１】
本発明の樹脂組成物は、ポリイミド樹脂、エポキシ樹脂、さらにエポキシ硬化剤及びその他の成分を均一に撹拌混合することにより得られる。この際、ポリイミド溶液にそのままエポキシ化合物、エポキシ硬化剤、およびその他の成分を添加し、樹脂組成物溶液とし得る。あるいは、ポリイミド溶液に低沸点溶媒を添加し、更にエポキシ樹脂、エポキシ硬化剤等を加えて、撹拌混合して本発明の樹脂組成物を調整し得る。
【００４２】
この他に、ポリアミド酸の重合に用いた溶媒を充分に溶解するがポリイミドが溶解しにくい貧溶媒中に、ポリイミド溶液を投入して、ポリイミド樹脂を析出させて未反応モノマーを取り除いて精製し、乾燥させ固形のポリイミド樹脂としてから、適宜、本発明の樹脂組成物とすることもできる。貧溶媒としては、アセトン、メタノール、エタノール、イソプロパノール、ベンゼン、メチルセロソルブ、メチルエチルケトン等が例として挙げられるが、これに限定されない。
【００４３】
また、このようにして得られた精製したポリイミド樹脂を他のエポキシ樹脂と共に再び有機溶媒に溶解し、濾過精製ワニスの状態とすることもできが、これに限定されない。この時使用される有機溶媒は特に限定されず、当業者に公知のいずれの有機溶媒でも使用できる。
【００４４】
従来のポリイミド系接着剤は、銅箔等の金属及びポリイミド等の樹脂フィルムに対して接着性が十分でなく、またエポキシ樹脂との混合はその難溶性より困難であったが、本発明にかかる樹脂組成物は、銅箔等の金属箔やポリイミドフィルムとの接着性が良好であり、またその有機溶媒に対する溶解性が良好であるという特性をも併せ持ち、使用に際し加工性に優れる。
【００４５】
本発明の樹脂組成物は、特に接着剤としての使用に適し、その具体的な使用態様は、当業者が実施しうる範囲内で種々の方法があるが、例えば、あらかじめシート状に成形しておき、シート状接着剤として用い得る。また、本発明の樹脂組成物は、ガラス布、ガラスマット、芳香族ポリアミド繊維布、芳香族ポリアミド繊維マット等にワニスとして含浸し、樹脂を半硬化させ繊維強化型のシート状接着剤として用いることも可能である。
【００４６】
さらに、本発明の樹脂組成物は、ワニスとしてそのまま用いることもできる。具体的にはフィルムの片面もしくは両面に、本発明の樹脂組成物を溶解したワニスを塗布、乾燥し、銅箔・アルミ箔・４２合金等の金属箔や別のフィルム、印刷回路基板等を加熱加圧して接着しても良い。この場合のフィルムの種類は特に限定されず、例えばポリイミドフィルム及びポリエステルフィルム等が挙げられる。また、この場合の接着条件としては、接着硬化するために必要十分である接着条件であれば良く、具体的には加熱温度１５０℃〜２５０℃、圧力０．１〜１０ＭＰａで加熱時間５〜２０分程度の条件で加熱加圧することが好ましい。
【００４７】
上記のようにして得られる本発明にかかる樹脂組成物は、ＴＡＢ用テープ、複合リードフレーム、積層材料等に好適に用いられ得る特性を有する。すなわち、具体的には、硬化反応後の吸水率が、１．５％以下、好ましくは、１．３％以下、特に好ましくは、１．０％以下という優れた耐吸水率を示し、また半田耐熱性に優れ、且つ耐熱性、接着性ともに優れており、接着剤として使用する際約２５０℃以下の温度さらには２００℃以下の温度において接着可能である。
【００４８】
【実施例】
【００４９】
（実施例１）
容量５００ｍｌのガラス製フラスコにジメチルホルムアミド（ＤＭＦ）２８０ｇにジフェニルメタンジイソシアナート３７．１８ｇ（０．１４８７ｍｏｌ）を加え、窒素雰囲気下、１３０℃で加熱しながら、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物（以下、ＥＳＤＡという）８５．７ｇ（０．１４８７ｍｏｌ）を粘度に注目しながら徐々に添加した。粘度が１５００poise に達したところでＥＳＤＡの添加をやめポリイミド溶液を得た。
【００５０】
このポリイミド溶液に１０３ｇにエピコート８２８（油化シェル社製）を５ｇ、４，４’−ジアミノジフェニルスルフォン（４，４’−ＤＤＳ）３ｇを溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１３０℃で１０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５１】
（実施例２）
ジイソシアナート成分をヘキサメチレンジイソシアナート２４．３９ｇ（０．１４８７ｍｏｌ）に変更する以外は、実施例１と同様にポリイミド溶液を得た。
【００５２】
このポリイミド溶液に１０３ｇにエピコート８２８（油化シェル社製）を５ｇ、４，４’−ジアミノジフェニルスルフォン（４，４’−ＤＤＳ）３ｇを溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１３０℃で１０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５３】
（実施例３）
実施例１で得られたポリイミド溶液に１０３ｇにエピコート１０３２Ｈ６０（油化シェル社製）を５ｇ、４，４’−ジアミノジフェニルスルフォン（４，４’−ＤＤＳ）３ｇを溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１３０℃で１０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５４】
（比較例１）
容量５００ｍｌのガラス製フラスコにジメチルホルムアミド（ＤＭＦ）２８０ｇにジフェニルメタンジイソシアナート３７．１８ｇ（０．１４８７ｍｏｌ）を仕込み、窒素雰囲気下、１３０℃で加熱しながら、ベンゾフェノンテトラカルボン酸二無水物（以下、ＢＴＤＡという）４７．８８ｇ（０．１４８７ｍｏｌ）を粘度に注目しながら徐々に添加した。粘度が１５００poise に達したところでＢＴＤＡの添加をやめポリイミド溶液を得た。
【００５５】
上記で得たポリイミド溶液を１０３ｇ、エピコート８２８（油化シェル社製）を５ｇ、４，４’−ＤＤＳ３ｇを溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５６】
( 比較例２)
実施例１で得たポリイミド溶液をガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５７】
( 比較例３)
プラタボンドＭ１２７６（共重合ナイロン、日本リルサン社製）を１０ｇ、エピコート８２８（油化シェル社製）を２０ｇ、ジアミノジフェニルスルフォン１ｇを８３ｇのＤＭＦに溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥がし、鉄枠に固定しさらに１３０℃で１０分乾燥し、厚み２５μｍのシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μｍの銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分間加熱加圧し、銅張フレキシブル積層板を得た。
【００５８】
以上の各実施例及び比較例で得られたフレキシブル銅張積層板について引き剥し強度、半田耐熱性（２６０℃半田浴に１０秒浸漬したときの外観評価）を評価した。また、各接着シートの吸水率も併せて評価した。その結果を表１に示す。
【００５９】
【表１】
【発明の効果】
本発明の樹脂組成物は、接着剤として使用するときに２５０℃以下の温度で接着することが可能である。従来の耐熱接着剤と異なり、接着に高温を要せず、ポリイミドフィルムに対しても高い接着力を示し、高温まで高い接着力を保持する。さらに低吸水率であるため、半田浴に浸漬する際の膨れ等を生じない半田耐熱性を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition that can be adhesively cured at a relatively low temperature, is soluble in a solvent, and has excellent heat resistance and adhesiveness. The resin composition of the present invention is useful as an adhesive excellent in heat-resistant adhesive used for flexible printed circuit boards, TAB (Tape Automated Bonding) tapes, composite lead frames, laminated materials and the like.
[0002]
[Prior art]
In recent years, electronic devices have been improved in function, performance, and size, and accordingly, electronic components used are required to be reduced in size and weight. Therefore, semiconductor device packaging methods and wiring materials or wiring components for mounting them have been required to have higher density, higher functionality, and higher performance. In particular, it has good adhesion that can be suitably used as a semiconductor package, COL and LOC packages, high-density mounting materials such as MCM (Multi Chip Module), printed wiring board materials such as multilayer FPC, and aerospace materials. There is a need for materials to show.
[0003]
Conventionally, acrylic, phenolic, epoxy, and polyimide adhesives are known as adhesive materials that exhibit good mechanical properties, heat resistance, and insulation in semiconductor packages and other mounting materials.
[0004]
However, phenolic and epoxy adhesives are excellent in adhesiveness but inferior in flexibility. A flexible acrylic adhesive has a problem of low heat resistance. In order to solve this, polyimide is used. Polyimide is excellent in heat resistance among various organic polymers, and thus is widely used in the space and aviation fields, and is also used as an adhesive material. However, polyimide adhesives with high heat resistance require a high temperature of about 300 ° C. and a high pressure for bonding, and the adhesive strength is not so high. Further, the conventional polyimide adhesive has a high water absorption rate, and has a problem that, for example, when a lead frame using this polyimide adhesive is immersed in a solder bath, it tends to swell.
[0005]
[Problems to be solved by the invention]
Therefore, the present inventors have conducted extensive research with the aim of solving the above-mentioned problems and providing a resin composition that is excellent in solder heat resistance, heat resistance, and adhesiveness, and can be bonded particularly at a low temperature of 250 ° C. or lower. As a result, the present invention has been completed.
[0006]
[Means for Solving the Problems]
The gist of the resin composition according to the present invention includes a polyimide resin and an epoxy resin, and the water absorption after the curing reaction may be 1.5% or less.
[0007]
Further, the polyimide resin is represented by the general formula (1)
[0008]
[Chemical formula 5]
An ester dianhydride represented by the general formula (2)
[0010]
[Chemical 6]
Wherein Y is an aliphatic divalent group or
[0012]
[Chemical 7]
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 are hydrogen or an alkyl group, A represents a divalent organic group, and hydrogen in the benzene ring is not substituted). The group of is shown. )
The polyimide resin obtained by making it react with the diisocyanate represented by these may be used.
[0014]
Further, the diisocyanate is represented by the general formula (3)
[0015]
[Chemical 8]
(In the formula, Z represents —C (═O) —, —SO 2 —, —O—, —S—, — (CH 2) m —, —NHCO—, —C (CH 3) 2 —, —C (CF 3). 2-, —C (═O) O—, or a bond, and m and n are integers of 1 or more and 10 or less.
[0017]
Here, “after the curing reaction of the resin composition” means, for example, that the resin composition is formed into a sheet, dried at 100 ° C. for 10 minutes and 150 ° C. for 20 minutes, and then heated and cured at 150 ° C. for 3 hours. After. That is, after the epoxy resin in the resin composition has been cured.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. The resin composition of the present invention is a resin composition in which a polyimide resin and an epoxy resin are mixed, and the water absorption after the curing reaction can be 1.5% or less.
[0019]
The polyimide resin used in the resin composition is not basically limited as long as it has the above-described characteristics, but in particular, the general formula (1)
[0020]
[Chemical 9]
(In the formula, X represents a divalent group containing an aromatic ring.) When a polyimide resin containing an ester dianhydride represented by the formula is used as a component, an excellent low water absorption rate is exhibited. It has excellent properties.
[0022]
Preferable examples of the ester dianhydride represented by the general formula (1) used in the present invention include 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-. Tetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 3,3 ′, 4,4′-ethylene glycol benzoate tetracarboxylic dianhydride, 4,4′-biphenylenebis (tri Merit acid monoester anhydride), 1,4-naphthalenebis (trimellitic acid monoester anhydride), 1,2-ethylenebis (trimellitic acid monoester anhydride), 1,3-trimethylenebis (trimerit Acid monoester anhydride), 1,4-tetramethylene bis (trimellitic acid monoester anhydride), 1,5-pentamethylene bis (trimellitic acid Ester anhydrides), 1,6-hexamethylene bis (trimellitic acid monoester anhydride), and the are exemplified not limited thereto. One or more of these may be used in combination.
[0023]
Furthermore, the general formula (2)
[0024]
[Chemical Formula 10]
Wherein Y is an aliphatic divalent group or
[0026]
Embedded image
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 are hydrogen or an alkyl group, A represents a divalent organic group, and hydrogen in the benzene ring is not substituted). The group of is shown. When the diisocyanate represented by (2) is used, an excellent low water absorption rate can be expressed by the combination with the above ester dianhydride.
[0028]
Preferred examples of the diisocyanate represented by the general formula (2) include diphenylmethane diisocyanate, paraphenylene diisocyanate, 2-chloro-1,4-phenyl diisocyanate, and 2,4-toluene diisocyanate. 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, trimethylhexa Examples include, but are not limited to, methylene diisocyanate. Of these, general formula (3)
[0029]
Embedded image
(In the formula, Z represents —C (═O) —, —SO 2 —, —O—, —S—, — (CH 2) m —, —NHCO—, —C (CH 3) 2 —, —C (CF 3). 2-, -C (= O) O-, or a bond, and m and n are integers of 1-10.)
For example, diphenylmethane diisocyanate represented by the formula is particularly preferably used. In the resin composition according to the present invention, any one of the above diisocyanates is used.
[0031]
In particular, the polyimide resin contained in the resin composition according to the present invention contains an ester dianhydride represented by the general formula (1) and a diisocyanate component represented by the general formula (2) as an organic polar solvent. Obtained by polymerization in The blending ratio in this case is preferably such that the ester dianhydride and the total diisocyanate are substantially equimolar, but the ester dianhydride is 80 to 80% of the total diisocyanate. It is also possible to control the molecular weight and molecular end by making it 98 mol%.
[0032]
In order to produce the polyimide resin, it can be produced by various methods known to those skilled in the art. Specifically, the polyimide is firstly represented by the general formula (1) in an inert atmosphere such as argon or nitrogen. It can be obtained by dissolving or diffusing an acid dianhydride selected from the diisocyanate represented by 2) and the ester dianhydride represented by the general formula (1) in an organic polar solvent and subjecting it to a heat reaction. .
[0033]
The order of addition of each monomer is not particularly limited, and acid dianhydride is previously added to an organic polar solvent, and the above general formula (2) which is a diisocyanate component is added, and a polyimide solution may be used. A suitable amount of the diisocyanate component is first added to the organic polar solvent, then acid dianhydride is added, and finally the remaining diisocyanate component is added to form a polyimide solution. In addition, various addition methods known to those skilled in the art can be used.
[0034]
Examples of the organic polar solvent used for the reaction for forming the polyamic acid solution include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N. -Acetamide solvents such as dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, phenol, o-, p-, m- or p-cresol, xinol, halogenated phenol, Phenol solvents such as catechol, hexamethylphosphoramide, γ-butyrolactone and the like can be mentioned. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.
[0035]
In general, when producing polyimide from acid dianhydride and diamine, in order to prevent the generated water from hydrolyzing and inhibiting imidization of the polyamic acid, a device for minimizing the effect of the generated water In addition, various treatments such as positively proceeding with imidization with a dehydrating agent or the like were performed. However, in the polyimide resin comprising the ester dianhydride represented by the general formula (1) and the diisocyanate represented by the general formula (2), a polymerization reaction that occurs when the acid dianhydride and diamine are used. Since there is no generation of water at the time, there is less risk of molecular weight reduction during polymerization, and a polyimide resin having a stable molecular weight can be obtained.
[0036]
Since the polyimide resin using the above polyimide resin and epoxy resin uses the ester dianhydride represented by the general formula (1), the diisocyanate represented by the general formula (2) is used. The combination has a particularly excellent low water absorption and a relatively low glass transition temperature, so that it can be an excellent adhesive material capable of low moisture absorption and low temperature bonding.
[0037]
Examples of the epoxy resin that can be used in the resin composition according to the present invention include bisphenol epoxy resin, halogenated bisphenol epoxy resin, phenol novolac epoxy resin, halogenated phenol novolac epoxy resin, alkylphenol novolac epoxy resin, polyphenol. Epoxy resin, polyglycol epoxy resin, cycloaliphatic epoxy resin, cresol novolac epoxy resin, glycidylamine epoxy resin, urethane modified epoxy resin, rubber modified epoxy resin, epoxy modified polysiloxane, and the like can be used.
[0038]
When the epoxy resin is mixed with the polyimide resin, the mixing ratio is 1 to 50 parts by weight, preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyimide. Addition of an epoxy resin increases adhesion, but if it is less than 1 part by weight, the adhesive strength is low, and if it exceeds 50 parts by weight, properties such as flexibility and heat resistance may be inferior. Moreover, the epoxy resin in the resin composition according to the present invention satisfying the water absorption rate of 1.5% or less from the viewpoint of the effect of the water absorption property of the epoxy resin to be used, the solubility in an organic solvent, and the combination with the polyimide resin. The mixing ratio can be variously selected within the above range.
[0039]
Since the resin composition of the present invention comprises the polyimide resin having excellent characteristics obtained as described above, it is 1.5% or less, preferably 1.2% or less, more preferably 1.0% or less. Excellent low water absorption can be expressed. Moreover, since the resin composition concerning this invention contains an epoxy resin further, the adhesiveness is further provided to the characteristics, such as the outstanding heat resistance and low water absorption which a polyimide has.
[0040]
Various materials can be further added to the resin composition of the present invention. Specifically, as necessary for imparting properties such as water absorption, heat resistance, adhesiveness, etc., generally used epoxy curing agents, accelerators and various cups such as acid dianhydrides, amines and imidazoles A ring agent may be used in combination. It is also possible to obtain a resin composition of the present invention by further adding a thermosetting resin other than an epoxy resin, bismaleimide, bisallylnadiimide, phenol resin, cyanate resin, or the like.
[0041]
The resin composition of the present invention can be obtained by uniformly stirring and mixing a polyimide resin, an epoxy resin, an epoxy curing agent, and other components. At this time, an epoxy compound, an epoxy curing agent, and other components can be directly added to the polyimide solution to obtain a resin composition solution. Alternatively, the resin composition of the present invention can be prepared by adding a low boiling point solvent to the polyimide solution, further adding an epoxy resin, an epoxy curing agent, etc., and stirring and mixing.
[0042]
In addition to this, in a poor solvent that dissolves the solvent used for the polyamic acid polymerization sufficiently but the polyimide is difficult to dissolve, the polyimide solution is added, and the polyimide resin is precipitated to remove the unreacted monomer and purified, After drying to obtain a solid polyimide resin, the resin composition of the present invention can be appropriately used. Examples of the poor solvent include, but are not limited to, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, methyl ethyl ketone, and the like.
[0043]
Further, the purified polyimide resin thus obtained can be dissolved again in an organic solvent together with other epoxy resins to form a filtered and purified varnish, but is not limited thereto. The organic solvent used at this time is not particularly limited, and any organic solvent known to those skilled in the art can be used.
[0044]
Conventional polyimide adhesives have insufficient adhesion to metals such as copper foil and resin films such as polyimide, and mixing with an epoxy resin is more difficult than its poor solubility, but the present invention is applied. The resin composition has good adhesion to a metal foil such as a copper foil or a polyimide film, and also has a good solubility in an organic solvent, and is excellent in workability when used.
[0045]
The resin composition of the present invention is particularly suitable for use as an adhesive, and there are various methods for its specific use within the range that can be carried out by those skilled in the art. It can be used as a sheet-like adhesive. In addition, the resin composition of the present invention is impregnated as a varnish in glass cloth, glass mat, aromatic polyamide fiber cloth, aromatic polyamide fiber mat, etc., and the resin is semi-cured to be used as a fiber-reinforced sheet adhesive. Is also possible.
[0046]
Furthermore, the resin composition of the present invention can be used as it is as a varnish. Specifically, a varnish in which the resin composition of the present invention is dissolved is applied to one side or both sides of the film and dried to heat a metal foil such as copper foil, aluminum foil or 42 alloy, another film, or a printed circuit board. You may pressurize and adhere. The kind of film in this case is not specifically limited, For example, a polyimide film, a polyester film, etc. are mentioned. Further, the bonding conditions in this case may be any bonding conditions that are necessary and sufficient for adhesive curing. Specifically, the heating temperature is 150 ° C. to 250 ° C., the pressure is 0.1 to 10 MPa, and the heating time is 5 to 20. It is preferable to heat and press under conditions of about a minute.
[0047]
The resin composition according to the present invention obtained as described above has characteristics that can be suitably used for TAB tapes, composite lead frames, laminated materials and the like. Specifically, the water absorption after the curing reaction is 1.5% or less, preferably 1.3% or less, and particularly preferably 1.0% or less. It is excellent in heat resistance and excellent in both heat resistance and adhesiveness. When used as an adhesive, it can be bonded at a temperature of about 250 ° C. or lower, further 200 ° C. or lower.
[0048]
【Example】
[0049]
Example 1
To a glass flask having a capacity of 500 ml, 37.18 g (0.1487 mol) of diphenylmethane diisocyanate was added to 280 g of dimethylformamide (DMF), and heated at 130 ° C. in a nitrogen atmosphere while 2,2-bis (4-hydroxyphenyl) was added. ) 85.7 g (0.1487 mol) of propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as ESDA) was gradually added while paying attention to the viscosity. When the viscosity reached 1500 poise, the addition of ESDA was stopped to obtain a polyimide solution.
[0050]
In 103 g of this polyimide solution, 5 g of Epicoat 828 (manufactured by Yuka Shell) and 3 g of 4,4′-diaminodiphenyl sulfone (4,4′-DDS) were dissolved. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 130 ° C. for 10 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0051]
(Example 2)
A polyimide solution was obtained in the same manner as in Example 1 except that the diisocyanate component was changed to 24.39 g (0.1487 mol) of hexamethylene diisocyanate.
[0052]
In 103 g of this polyimide solution, 5 g of Epicoat 828 (manufactured by Yuka Shell) and 3 g of 4,4′-diaminodiphenyl sulfone (4,4′-DDS) were dissolved. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 130 ° C. for 10 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0053]
(Example 3)
5 g of Epicoat 1032H60 (manufactured by Yuka Shell) and 3 g of 4,4′-diaminodiphenylsulfone (4,4′-DDS) were dissolved in 103 g of the polyimide solution obtained in Example 1. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 130 ° C. for 10 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0054]
(Comparative Example 1)
A glass flask having a capacity of 500 ml was charged with 280 g of dimethylformamide (DMF) with 37.18 g (0.1487 mol) of diphenylmethane diisocyanate, and heated at 130 ° C. in a nitrogen atmosphere while benzophenone tetracarboxylic dianhydride (hereinafter, 47.88 g (0.1487 mol) (referred to as BTDA) was gradually added while paying attention to the viscosity. When the viscosity reached 1500 poise, the addition of BTDA was stopped to obtain a polyimide solution.
[0055]
103 g of the polyimide solution obtained above, 5 g of Epicoat 828 (manufactured by Yuka Shell), and 3 g of 4,4′-DDS were dissolved. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0056]
(Comparative Example 2)
The polyimide solution obtained in Example 1 was cast on a glass plate, dried at 100 ° C. for 10 minutes, then peeled off from the glass plate, fixed to an iron frame and further dried at 150 ° C. for 20 minutes, and a sheet having a thickness of 25 μm was formed. Obtained. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0057]
(Comparative Example 3)
Platabond M1276 (copolymerized nylon, manufactured by Nippon Rilsan) was dissolved in 10 g, Epicoat 828 (manufactured by Yuka Shell) in 20 g, and 1 g of diaminodiphenylsulfone was dissolved in 83 g of DMF. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 130 ° C. for 10 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0058]
The flexible copper-clad laminates obtained in the above Examples and Comparative Examples were evaluated for peel strength and solder heat resistance (appearance evaluation when immersed in a 260 ° C. solder bath for 10 seconds). Moreover, the water absorption rate of each adhesive sheet was also evaluated. The results are shown in Table 1.
[0059]
[Table 1]
【The invention's effect】
The resin composition of the present invention can be bonded at a temperature of 250 ° C. or lower when used as an adhesive. Unlike conventional heat-resistant adhesives, it does not require high temperature for bonding, exhibits high adhesion to polyimide films, and maintains high adhesion to high temperatures. Furthermore, since it has a low water absorption rate, it has solder heat resistance that does not cause swelling or the like when immersed in a solder bath.
Claims (2)
【００００】The diisocyanate is represented by the general formula (3)
0000
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