JP3605556B2 - Resin composite having quasi-homogeneous compatible structure - Google Patents
Resin composite having quasi-homogeneous compatible structure Download PDFInfo
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- JP3605556B2 JP3605556B2 JP2000282729A JP2000282729A JP3605556B2 JP 3605556 B2 JP3605556 B2 JP 3605556B2 JP 2000282729 A JP2000282729 A JP 2000282729A JP 2000282729 A JP2000282729 A JP 2000282729A JP 3605556 B2 JP3605556 B2 JP 3605556B2
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Description
【０００１】
【産業上の利用分野】
本発明は、熱硬化性樹脂と熱可塑性樹脂とからなる新規な樹脂複合体に関し、特に、エポキシ樹脂とポリスルホン（PSF）とからなる樹脂複合体についての提案である。
【０００２】
【従来の技術】
樹脂複合体の技術は、熱硬化性樹脂に熱可塑性樹脂を混合して複合させることにより、この熱硬化性樹脂の物性を改善する技術などが代表的である。例えば、エポキシ樹脂とポリエーテルスルホン（以下、「ＰＥＳ」で示す）との混合系（ＰＥＳ変成エポキシ樹脂）において、エポキシ樹脂とＰＥＳとが形成する共連続構造により、エポキシ樹脂の靱性を改善する技術がそれである（Ｋｅｉｚｏ Ｙａｍａｎａｋａ ａｎｄ Ｔａｋａｓｈｉ Ｉｎｏｕｅ， Ｐｏｌｙｍｅｒ， ｖｏｌ．３０， Ｐ６６２（１９８９）参照）。
【０００３】
２種の樹脂を混合してなる上記ＰＥＳ変性エポキシ樹脂は、エポキシ樹脂単独のものに比べて、樹脂の靱性が向上する。この理由は、このＰＥＳ変性エポキシ樹脂が以下に述べるような樹脂構造を形成するからである。すなわち、ビスフェノールＡ型エポキシ樹脂などのエポキシ樹脂とＰＥＳとの混合系は、エポキシ樹脂を高温で硬化すると、エポキシ樹脂とＰＥＳとが完全に溶け合った状態（相溶状態）とはならず、スピノーダル分解を起こしてエポキシ樹脂とＰＥＳが分離状態で混合している状態（相分離状態）となる。
このような相分離状態は、混合する樹脂の最初の分散状態における非相溶の度合いに依存するもので、非相溶の度合いが大きい場合には球状ドメイン構造となり、非相溶の度合いが小さい場合には、共連続構造となる。
上記「球状ドメイン構造」とは、ＰＥＳを主とする樹脂マトリックス中に、エポキシ樹脂を主とする樹脂からなる球状ドメインが互いに独立し、あるいはそれらの一部が連結して分散している状態の構造を指し、「共連続構造」とは、主として、ＰＥＳを主とする樹脂マトリックス中に、エポキシ樹脂を主とする樹脂からなる球状ドメインが互いに連結し合い、かつ規則正しく分散している状態の構造を指す。
このような構造は、構成樹脂のそれぞれが完全に分離しているのではなく、ＰＥＳの中にもエポキシ樹脂が含有されていて、その比率は圧倒的にＰＥＳが高く、一方、エポキシ樹脂の中にも、ＰＥＳが含有されていて、その比率はエポキシ樹脂が高いような構造であり、それぞれの樹脂が完全に相分離しているのではなく、互いに一部が相溶している。
【０００４】
【発明が解決しようとする課題】
ところが、上記共連続構造は、エポキシ樹脂とＰＥＳとが相分離状態となることによって形成されるものであり、スピノーダル分解によって生成するエポキシ樹脂の球状ドメインが単にＰＥＳマトリックス中に分散しているだけの構造である。そのため、エポキシ樹脂に、ＰＥＳを分散導入する効果はあるものの、ＰＥＳ本来の物性よりも高くすることはできない。この理由は、共連続構造を形成した複合体のガラス転移温度を動的粘弾性測定により測定すると、ガラス転移温度のピーク数が２つであることが認められることから、エポキシ樹脂とマトリックスであるＰＥＳとの相互作用が弱いためと考えられる。
上述したような共連続構造に関する知見は、感光性樹脂と熱可塑性樹脂との混合系、例えばアクリル系樹脂とポリエーテルスルホンとの混合系（ＰＥＳ変成アクリル系樹脂）についても同様であった。
【０００５】
本発明の目的は、エポキシ樹脂などの熱硬化性樹脂が示す特有の物性、例えば耐熱性を具えると共に、ＰＥＳなどの熱可塑性樹脂が示す本来の物性よりもさらに高い物性値を示す新規な樹脂複合体およびその製造技術を提供することにある。
【０００６】
【課題を解決するための手段】
発明者らは、上記の目的を実現すべく、まず、樹脂複合体の１つの混合系である熱硬化性樹脂と熱可塑性樹脂との系について研究した。熱硬化性樹脂と熱可塑性樹脂との混合系，例えば、エポキシ樹脂／ＰＥＳ混合系において、エポキシ樹脂とＰＥＳは、図１に示すように、低温では相溶するが高温では２相分離する，いわゆるＬＣＳＴ型（Ｌｏｗ Ｃｒｉｔｉｃａｌ Ｓｏｌｕｔｉｏｎ Ｔｅｍｐｅｒａｔｕｒｅ ）の相図を示す。
しかし、エポキシ樹脂が、硬化反応に伴って高分子化され、その樹脂のガラス転移温度（Ｔｇ ）が高くなって硬化温度以上になると、その温度において分子運動が凍結され相分離できなくなる。なぜなら、相分離するには分子の運動，拡散が必要だからである。
【０００７】
本発明は、このような事実に着目して鋭意研究した結果完成されたものであり、熱硬化性樹脂と熱可塑性樹脂とが相分離することによって明確な共連続構造あるいは球状ドメイン構造を形成しないように、硬化速度や相分離速度を制御して樹脂を硬化させ複合化させることにより、上記目的を実現することができる。
【０００８】
すなわち、本発明は、熱硬化性樹脂と熱可塑性樹脂とからなる樹脂複合体、即ち、エポキシ樹脂とポリスルホン（PSF）とからなる樹脂複合体であって、その樹脂複合体は、相分離して共連続構造や球状ドメイン構造が形成されないように硬化されることによって得られる擬似均一相溶構造を有してなることを特徴とする樹脂複合体であり、上記擬似均一相溶構造を形成する構成樹脂粒子の粒径が透過型電子顕微鏡（以下、「ＴＥＭ」で示す）観察による測定値で 0.1μｍ以下であり、かつ昇温速度５℃／分、振動周波数６．２８ rad／secの条件で測定した動的粘弾性測定による樹脂のガラス転移温度のピーク数が１つである特性を示すものであることを特徴とする。
【００１１】
そして、上述したような本発明の樹脂複合体を製造する方法は、第１に、熱可塑性樹脂と混合した熱硬化性樹脂を硬化することにより熱硬化性樹脂と熱可塑性樹脂とを複合化するに当たり、熱硬化性樹脂と熱可塑性樹脂との場合は、熱硬化性樹脂の硬化温度、硬化剤の種類のうちから選ばれる１種または２種の因子によって決定される擬似均一相形成点を超える硬化速度で硬化させることを特徴とする。
第２に、熱可塑性樹脂と混合した熱硬化性樹脂を硬化することにより熱硬化性樹脂と熱可塑性樹脂とを複合化するに当たり、未硬化熱硬化性樹脂の架橋密度または分子量のいずれか１種以上の因子によって決定される擬似均一相形成点を超えない相分離速度で硬化させることを特徴とする。
第３に、熱可塑性樹脂と混合した熱硬化性樹脂を硬化することにより熱硬化性樹脂と熱可塑性樹脂とを複合化するに当たり、上記擬似均一相形成点を超える硬化速度で、かつ上記擬似均一相形成点を超えない相分離速度で硬化させることを特徴とする。
ここで、熱硬化性樹脂と熱可塑性樹脂の配合比を、熱可塑性樹脂の含有量で15〜50wt％とすることが望ましい。
【００１２】
【作用】
本発明の熱硬化性樹脂と熱可塑性樹脂とからなる樹脂複合体の特徴は、熱硬化性樹脂と熱可塑性樹脂とが擬似均一相溶構造を形成してなる点にある。
この擬似均一相溶構造は、発明者らが考え出した新しい概念であり、以下に説明する構造をいう。
すなわち、擬似均一相溶構造は、エポキシ樹脂などの熱硬化性樹脂が示す特有の物性を具えると共に、ＰＥＳなどの熱可塑性樹脂本来の物性よりも高い物性値を示す、より均質な構造をいい、動的粘弾性測定によるガラス転移温度ピーク値が１つであり、熱硬化性樹脂あるいは感光性樹脂と熱可塑性樹脂間との相互作用が極めて強いものである。
したがって、本発明の樹脂複合体は、図２(a)の走査型電子顕微鏡（以下、「ＳＥＭ」で示す。）写真に示すような構造を有し、図２(b)のＳＥＭ写真に示す従来の共連続粒子構造とは明らかに相違するものである。しかも、この樹脂複合体は、ＴＥＭ観察（図２(c)参照）による構成樹脂粒子の粒径が 0.1μｍ以下であって、より均質となっているものである。このような均質な樹脂複合体であるため、有機溶剤などにより熱可塑性樹脂が溶出されにくく、耐薬品性に優れる。従来技術において説明した共連続構造では、塩化メチレンによりＰＥＳが溶出して、表面が凹凸になるが(図２(b)図面代用写真参照)、本発明では、塩化メチレンによってもＰＥＳなどの熱可塑性樹脂の溶出量は少なく、表面に凹凸が発生することがない。
【００１３】
このような樹脂複合体の構造による効果は、前記複合体における熱可塑性樹脂（例えば、ＰＥＳ）の含有量が固形分で15〜50wt％である場合に特に顕著となる。この理由は、熱可塑性樹脂の含有量が15wt％未満では、樹脂成分の網目に絡み合う熱可塑性樹脂分子が少ないため強靱化の効果が十分に発揮されず、一方、熱可塑性樹脂の含有量が50wt％を超えると、架橋点の減少によって熱硬化性樹脂と熱可塑性樹脂間との相互作用が小さくなるからである。
【００１４】
このような熱硬化性樹脂と熱可塑性樹脂との擬似均一相溶構造は、以下に示す本発明方法によって形成されるものである。すなわち、本発明に係る擬似均一相溶構造は、熱硬化性樹脂と熱可塑性樹脂を必要に応じて溶剤に溶解して均一に混合し、その後、硬化速度を速くすること、および／または相分離速度を遅くすることにより、構成樹脂粒子の粒径をＴＥＭ観察による測定値で 0.1μｍ以下にすることにより、形成される。
【００１５】
具体的には、本発明方法は、第１に、熱硬化性樹脂を用いる場合は、熱硬化性樹脂の硬化温度、硬化剤の種類のうちから選ばれる１種または２種の因子によって決定される擬似均一相形成点を超える硬化速度で硬化させる点に特徴がある。ここでの擬似均一相形成点とは、複合体を構成する樹脂粒子の粒径がＴＥＭ観察による測定値で 0.1μｍ以下である擬似均一相溶構造を得ることができる、硬化速度の下限値を意味する。
【００１６】
また、本発明方法は、第２に、未硬化熱硬化性樹脂の架橋密度または分子量のいずれか１種以上の因子によって決定される擬似均一相形成点を超えない相分離速度で硬化させる点に特徴がある。ここでの擬似均一相形成点とは、複合体を構成する樹脂粒子の粒径がＴＥＭ観察による測定値で 0.1μｍ以下である擬似均一相溶構造を得ることができる、相分離速度の上限値を意味する。
【００１７】
さらに、本発明方法は、第３に、上記擬似均一相形成点を超える硬化速度で、かつ上記擬似均一相形成点を超えない相分離速度で硬化させる点に特徴がある。これは、硬化速度と相分離速度を決定する因子が相互に影響する場合の方法を意味する。
【００１８】
次に、硬化速度または相分離速度を決定する上述した種々の因子の相互関係について説明する。まず、硬化速度を決定する因子については、他の因子条件を一定とすると、
(1).熱硬化性樹脂の硬化温度が高いほど硬化速度は速くなる。
従って、擬似均一相形成点を超える硬化速度を得るのに必要な硬化温度の下限値を超えて熱硬化性樹脂を硬化すると、得られる樹脂複合体の構造は擬似均一相溶構造となる。
(2).ゲル化時間が短い硬化剤ほど硬化速度は速くなる。
従って、擬似均一相形成点を超える硬化速度を得るのに必要なゲル化時間の上限値を超えないような硬化剤を用いて熱硬化性樹脂を硬化すると、得られる樹脂複合体の構造は擬似均一相溶構造となる。
【００１９】
このような事実を考慮すると、熱硬化性樹脂と熱可塑性樹脂の複合化に当たって上記変動因子が１種の場合は、擬似均一相形成点に対応するその因子の値が１点決まる。それ故に、上記変動因子が２種以上の場合には、擬似均一相形成点に対応するその因子の値は種々の組み合わせが考えられる。すなわち、構成樹脂粒子の粒径がＴＥＭ観察による測定値で 0.1μｍ以下となるような硬化速度を示す組み合わせを選定することができる。
【００２０】
次に、相分離速度を決定する因子については、他の因子条件を一定とすると、(1).未硬化熱硬化性樹脂の架橋密度が高いほど相分離は起きにくい（相分離速度は遅くなる）。
従って、擬似均一相形成点を超えない相分離速度を得るのに必要な架橋密度の下限値を超える架橋密度を有する未硬化熱硬化性樹脂を用いて硬化すると、得られる樹脂複合体の構造は擬似均一相溶構造となる。
(2).未硬化熱硬化性樹脂の分子量が大きいほど相分離は起きにくい（相分離速度は遅くなる）。
従って、擬似均一相形成点を超えない相分離速度を得るのに必要な分子量の下限値を超える分子量を有する未硬化熱硬化性樹脂を用いて硬化すると、得られる樹脂複合体の構造は擬似均一相溶構造となる。
【００２１】
このような事実を考慮すると、熱硬化性樹脂と熱可塑性樹脂の複合化に当たって上記変動因子が１種の場合は、擬似均一相形成点に対応するその因子の値が１点決まる。それ故に、上記変動因子が２種の場合には、擬似均一相形成点に対応するその因子の値は種々の組み合わせが考えられる。すなわち、構成樹脂粒子の粒径がＴＥＭ観察による測定値で 0.1μｍ以下となるような相分離速度を示す組み合わせを選定することができる。
【００２２】
以上説明したような本発明方法により得られる樹脂複合体は、エポキシ樹脂などの熱硬化性樹脂が示す特有の物性を具えると共に、ＰＥＳなどの熱可塑性樹脂本来の物性よりもさらに高い物性値を示すことができる。
すなわち、本発明にかかる擬似均一相溶構造を有する樹脂複合体は、ＰＥＳ単独の樹脂強度よりも高くなり、従来にはないエポキシ樹脂の強靱化効果を有するものである。
【００２３】
本発明においては、上述したように熱硬化性樹脂と熱可塑性樹脂とを複合化するに先立って、熱硬化性樹脂と熱可塑性樹脂は、必要に応じて溶剤に溶解することにより均一に混合される。このような溶剤としては、例えば、ジメチルホルムアミド（DMF ）や塩化メチレン、ジメチルスルホキシド（DMSO）、ノルマルメチルピロリドン（NMP ）などが使用できる。また、相分離開始温度未満で、かつ硬化開始温度未満の温度にて、熱硬化性樹脂と熱可塑性樹脂とを加熱溶融させて混合させることも可能である。
【００２４】
本発明において熱硬化性樹脂としては、フェノール樹脂、メラミン樹脂や尿素樹脂などのアミノ樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、ウレタン樹脂、ジアリルフタレート樹脂などが使用できる。
【００２５】
本発明において熱可塑性樹脂としては、フェノキシ樹脂やポリエーテルスルホンの他に、ポリスルホン、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリアセタール、ポリカーボネート、ポリエーテルイミドなどのエンジニアリングプラスチック、ポリスチレン、ポリエチレン、ポリアリレート、ポリアミドイミド、ポリオキシベンゾエート、ポリ塩化ビニル、ポリ酢酸ビニルなどが使用できる。
【００２７】
本発明において、熱硬化性樹脂としてエポキシ樹脂を用いる場合の硬化剤としては、イミダゾール系硬化剤やジアミン、ポリアミン、ポリアミド、無水有機酸、ビニルフェノールなどが使用できる。一方、エポキシ樹脂以外の熱硬化性樹脂を使用する場合は、周知の硬化剤を使用できる。
【００２８】
なお、エポキシ樹脂などの熱硬化性樹脂特有の物性を具えると共に、複合化させるＰＥＳなどの熱可塑性樹脂本来の物性よりもさらに高い物性値を示す、本発明の樹脂複合体は、プリント配線板用接着剤などの無電解めっき用接着剤や、プリント配線板等に用いられる基板材料、レジスト材料およびプリプレグ材料、半導体パッケージの封止材、繊維強化複合材料の母材、射出成形用材料、圧縮成形用材料などさまざまな用途に利用されることが期待される。
【００２９】
以下に、硬化剤の影響（試験１）、硬化温度の影響（試験２）、架橋密度の影響（試験３）、ＰＥＳ配合量の影響（試験４）について説明する。
（試験１：硬化剤の影響）
(1) エポキシ樹脂／ＰＥＳ系において、ゲル化時間（硬化速度）の異なる硬化剤を用い、エポキシ樹脂の硬化剤の種類が上記混合系の樹脂構造および物性にどのような影響を及ぼすかについて調べた。
(2) ゲル化時間の異なる硬化剤としては、表１に示す数種類のイミダゾール系硬化剤（四国化成製）を用いた。
(3) なお、硬化剤の影響を調べるために、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（油化シェル製、商品名：エピコート828 ）を用い、エポキシ樹脂／ＰＥＳの配合比を70／30とし、ＰＥＳを２倍量のジメチルホルムアミド（DMF ）で溶解させ、所定量のエポキシ樹脂と硬化剤を混合して硬化させ、また、エポキシ樹脂のエポキシ当量を184 〜194 、硬化条件を120℃×５時間＋150℃×２時間、と一定条件にした。
【００３０】
得られた樹脂硬化物の構造および物性を調べた結果を図３および表１に示す。図３ (a) 〜(d) は、表１に示すイミダゾール系硬化剤を用いて得られた樹脂硬化物の組織を示すＳＥＭ写真であり、(a)2PHZ-CN, (b)2PZ-OK, (c)2E4MZ-CN, (d)1B2MZを用いた場合を示す。これらの写真および表１に示す結果から明らかなように、硬化速度の遅い硬化剤（ (a) 、 (b) ）を用いると、相分離の進行によって球状ドメイン構造が形成され、樹脂の強度や伸び率が低いことが判った。これに対し、擬似均一相形成点を超える硬化速度を示す硬化剤（ (c) 、 (d) ）で硬化させると、エポキシ樹脂とＰＥＳとが擬似均一相溶構造を形成し、この硬化物の強度および伸び率は共に大きく向上することが判った。
【００３１】
図４は、上記樹脂硬化物のＳＥＭ観察により得られた樹脂の粒径と硬化剤のゲル化時間の関係を示す図である。この図に示す結果から明らかなように、１２０ ℃でのゲル化時間が約５分以下になると、樹脂の粒径が急激に小さくなり、球状ドメイン構造から擬似均一相溶構造になることが判った。すなわち、本実施例の条件下では、硬化剤のゲル化時間によって決定される擬似均一相形成点は、ゲル化時間が５分程度のところに存在することが判る。
【００３２】
【表１】
（試験２：硬化温度の影響）
(1) エポキシ樹脂／ＰＥＳ系において、硬化温度の異なる硬化条件にて硬化することにより、エポキシ樹脂の硬化温度が、得られる樹脂硬化物の樹脂構造にどのような影響を及ぼすかについて調べた。
(2) 硬化温度の異なる硬化条件としては、以下に示す４条件を実施した。
ａ．80℃で６時間ｂ．100℃で６時間ｃ．120℃で５時間ｄ．150℃で４時間
(3) 硬化剤によって、(1).硬化温度が低いほど、擬似均一相溶構造を形成する場合(2)．硬化温度が高いほど、擬似均一相溶構造を形成する場合があるとの知見から、硬化剤としては、(3)．アミン系硬化剤（住友化学製、商品名：DDM ），(4)．イミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）を用いた。
(4) なお、硬化温度の影響を調べるために、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（油化シェル製、商品名：エピコート828 ）を用い、エポキシ樹脂／ＰＥＳ／硬化剤の配合比を、(1)．アミン系硬化剤(DDM) の場合は70／30／20、(2)．イミダゾール系硬化剤(2E4MZ-CN)の場合は70／30／５とし、ＰＥＳを２倍量のジメチルホルムアミド（DMF ）で溶解させ、所定量のエポキシ樹脂と硬化剤を混合して硬化させ、また、エポキシ樹脂のエポキシ当量を184 〜194 、と一定条件にした。
【００３４】
得られた樹脂硬化物の構造を調べた結果を 図５および図６に示す。 図５（ａ） 〜（ｄ） および図６（ａ） 〜（ｄ） はそれぞれ、▲１▼アミン系硬化剤および▲２▼イミダゾール系硬化剤に関するものであり、いずれも、上記種々の硬化温度にて得られた樹脂硬化物の組織を示すＳＥＭ写真であり、（ａ） ８０℃， （ｂ）１００℃ ， （ｃ）１２０ ℃ ， （ｄ）１５０℃の場合を示す。
硬化剤として▲１▼タイプのアミン系硬化剤（ＤＤＭ ）を用いた場合、図５の写真から明らかなように、樹脂構造は、硬化温度が８０℃の時には擬似均一相溶構造を形成したが、硬化温度が１００ ℃以上になると球状ドメイン構造を形成するようになり、その粒子径は０．２ μｍ以上になることが判った。
一方、硬化剤として▲２▼タイプのイミダゾール系硬化剤（２Ｅ４ＭＺ−ＣＮ）を用いた場合、図６の写真から明らかなように、樹脂構造は、逆に硬化温度が１００ ℃以上では擬似均一相溶構造を形成したが、硬化温度が８０℃の時には粒径約０．３ μｍの球状ドメイン構造を形成するようになることが判った。
【００３５】
図７および図８はそれぞれ、上記２つのタイプの硬化剤について、ＳＥＭ観察により得られた樹脂の粒径とエポキシ樹脂の硬化温度の関係を示す図である。これらの図に示す結果から明らかなように、(1)タイプのアミン系硬化剤では、硬化温度が90℃以下になると球状ドメイン構造から擬似均一相溶構造になり、一方、(2)タイプのイミダゾール系硬化剤では、硬化温度が90℃以上になると球状ドメイン構造から擬似均一相溶構造になることが判った。すなわち、本試験例の条件下では、エポキシ樹脂の硬化温度によって決定される擬似均一相形成点は、硬化温度が90℃程度のところに存在することが判る。
【００３６】
（試験３：架橋密度の影響）
(1) エポキシ樹脂／ＰＥＳ系において、骨格構造が同じでエポキシ当量の異なるエポキシ樹脂を硬化することにより、エポキシ樹脂のエポキシ当量が、得られる樹脂硬化物の樹脂構造にどのような影響を及ぼすかについて調べ、これにより樹脂の架橋密度の影響を考察した。
(2) エポキシ当量の異なるエポキシ樹脂としては、表２に示す数種類のビスフェノールＡ型エポキシ樹脂を用いた。
(3) なお、エポキシ当量の影響を調べるために、硬化剤としてイミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）を用い、エポキシ樹脂／ＰＥＳ／硬化剤の配合比を70／30／５とし、ＰＥＳを２倍量のジメチルホルムアミド（DMF ）で溶解させ、所定量のエポキシ樹脂と硬化剤を混合して硬化させ、また、硬化条件を80℃で１時間， 100℃で１時間， 120℃で１時間， 150℃で３時間、と一定条件にした。
【００３７】
得られた樹脂硬化物の構造を調べた結果を図９および表２に示す。図９ (a) 〜(d) は上記種々のエポキシ当量を有するエポキシ樹脂を用いて得られた樹脂硬化物の組織を示すＳＥＭ写真であり、(a) エピコート828, (b)エピコート1001, (c) エピコート1004, (d) エピコート1007の場合を示す。これらの写真および表２に示す結果から明らかなように、エポキシ当量が大きく、言い換えれば架橋密度が低いほど、相分離がし易く、一方、エポキシ当量が小さく、言い換えれば架橋密度が高いほど、その樹脂構造は擬似均一相溶構造となることが判った。すなわち、本試験例の条件下では、エポキシ樹脂のエポキシ当量（または架橋密度）によって決定される擬似均一相形成点は、エポキシ当量が300 前後程度のところに存在することが判る。
【００３８】
【表２】
（試験４：ＰＥＳ配合量の影響）
(1) エポキシ樹脂／ＰＥＳ系において、ＰＥＳ配合量を種々変化させることにより、得られる樹脂硬化物の物性にどのような影響を及ぼすかについて調べた。
(2) ＰＥＳ配合量としては、0 〜 60wt ％まで種々変化させた。
(3) なお、ＰＥＳ配合量の影響を調べるために、エポキシ樹脂としてはクレゾールノボラック型エポキシ樹脂（日本化薬製、商品名：EOCN-103S ）、硬化剤としてはイミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）を用い、ＰＥＳを２倍量のジメチルホルムアミド（DMF ）で溶解させ、所定量のエポキシ樹脂と硬化剤を混合して硬化させ、また、エポキシ樹脂のエポキシ当量を210 〜230 、エポキシ樹脂の硬化条件を80℃で１時間， 100℃で１時間， 120℃で１時間， 150℃で３時間、と一定条件にした。
【００４４】
このようにして得た樹脂硬化物の物性変化を調べた結果を図11に示す。この図に示す結果から明らかなように、ＰＥＳの配合量が増加するにしたがい樹脂の強度が大きくなり、30％ＰＥＳのところで極大値を示し、以降樹脂強度が逆に小さくなった。特に30％ＰＥＳの樹脂硬化物は、エポキシ樹脂単独のみならず、ＰＥＳ単独よりも強度が高い。なお、本試験例の条件下では、得られる樹脂硬化物は、すべての配合組成において擬似均一相溶構造を形成していた。このように本試験例の結果から、エポキシ樹脂／ＰＥＳ系においては、ＰＥＳ配合量は、15〜50wt％，より好ましくは20〜40wt％が望ましいことが判った。
【００４５】
【実施例】
（参考例１）
(1) エポキシ樹脂／ＰＥＳ系において、エポキシ樹脂としてエポキシ当量が184〜194 のビスフェノールＡ型エポキシ樹脂（油化シェル製、商品名：エピコート828 ）、硬化剤としてイミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）を用い、下記組成でDMF を用いて樹脂を混合し、 120℃で５時間， 150℃で２時間の硬化条件にて硬化し、擬似均一相溶構造の樹脂硬化物を得た。なお、120℃での硬化剤のゲル化時間は３分であった。
樹脂組成：エピコート828 ／PES ／2E4MZ-CN＝70／30／５
【００４６】
このようにして得た樹脂硬化物について、下記条件にてＴＥＭ観察を行った。その結果、樹脂硬化物を構成する樹脂の粒径は0.1μｍ以下であった。
〔観察条件〕
(1) ミクロトームを用いて、試料を 70nm の薄片に切り取る。
(2) 切り取った薄片を四酸化オスミウム（ OsO 4 ）のメタノール溶液に 24 時間浸漬させる。
(3) ＴＥＭ観察時の加速電圧を 80kV として観察する。
また、動的粘弾性測定にてガラス転移温度Ｔg を測定した結果、図 10 に示すようにＴg のピークは１つであり、物性的に均質であることが判った。これによって、引張強度や伸び率などの物性値が、構成樹脂成分単独のものよりも高くなるものと推察する。
【００４７】
さらに、得られた樹脂硬化物の引張強度と引張伸び率は、それぞれ８３５ｋｇ／ｃｍ２、８．０ ％であり、構成樹脂成分単独のものより高いことを確認した。なお、同じ硬化剤，硬化条件で作製したエポキシ樹脂のみからなる硬化物の引張強度と引張伸び率は、それぞれ約５００ ｋｇ／ｃｍ２， ４．８ ％であった。
【００４８】
上述したような結果は、硬化剤としてイミダゾール系硬化剤（四国化成製、商品名：１Ｂ２ＭＺ ）を用いた場合でも同様に得られた。この場合、１２０ ℃での硬化剤のゲル化時間は４４秒であった。
【００４９】
（参考例２）
(1) エポキシ樹脂／ＰＥＳ系において、エポキシ樹脂としてエポキシ当量が184〜194 のビスフェノールＡ型エポキシ樹脂（四国化成製、商品名：エピコート828 ）、硬化剤としてイミダゾール系硬化剤（油化シェル製、商品名：2E4MZ-CN）を用い、下記組成でDMF を用いて樹脂を混合し、80℃×１時間＋ 150℃×４時間の硬化条件にて硬化し、擬似均一相溶構造の樹脂硬化物を得た。なお、本参考例は、参考例１とはエポキシ樹脂の硬化温度が相違するだけである。
樹脂組成：エピコート828 ／PES ／2E4MZ-CN＝70／30／５
【００５０】
このようにして得た樹脂硬化物について、参考例１と同様にしてＴＥＭ観察を行った結果、樹脂粒径は0.1 μｍ以下であった。また、動的粘弾性測定にてガラス転移温度Ｔg を測定した結果、参考例１と同様にＴg のピークは１つであった。
【００５１】
さらに、得られた樹脂硬化物の引張強度と引張伸び率は、それぞれ８３５ｋｇ／ｃｍ２、９．１ ％であり、構成樹脂成分単独のものより高いことを確認した。なお、同じ硬化剤，硬化条件で作製したエポキシ樹脂のみからなる硬化物の引張強度と引張伸び率は、それぞれ約５００ ｋｇ／ｃｍ２、 ４．５ ％であった。
【００５２】
（参考例３）
(1) エポキシ樹脂／ＰＥＳ系において、エポキシ樹脂としてエポキシ当量が184〜194 のビスフェノールＡ型エポキシ樹脂（油化シェル製、商品名：エピコート828 ）、硬化剤としてアミン系硬化剤（住友化学製、商品名：DDM ）を用い、下記組成でDMF を用いて樹脂を混合し、80℃で６時間， 150℃で２時間の硬化条件にて硬化し、擬似均一相溶構造の樹脂硬化物を得た。
樹脂組成：エピコート828 ／PES ／DDM ＝70／30／18
【００５３】
このようにして得た樹脂硬化物について、参考例１と同様にしてＴＥＭ観察を行った結果、樹脂粒径は0.1μｍ以下であった。また、動的粘弾性にてガラス転移温度Ｔg を測定した結果、参考例１と同様にＴg のピークは１つであった。
【００５４】
さらに、得られた樹脂硬化物の引張強度と引張伸び率は、それぞれ８６０ｋｇ／ｃｍ２、８．６ ％であり、構成樹脂成分単独のものより高いことを確認した。なお、同じ硬化剤，硬化条件で作製したエポキシ樹脂のみからなる硬化物の引張強度と引張伸び率は、それぞれ約５００ｋｇ／ｃｍ２、５％であった。
【００５５】
（参考例４）
エポキシ樹脂／ＰＥＳ系において、エポキシ樹脂としてエポキシ当量が210 〜230 のクレゾールノボラック型エポキシ樹脂（日本化薬製、商品名：EOCN-103S）、硬化剤としてイミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）を用い、下記組成でDMF を用いて樹脂を混合し、80℃で１時間、150 ℃で４時間の硬化条件にて硬化し、疑似均一相溶構造の硬化物を得た。
樹脂組成：EOCN-103S ／PES ／2E4MZ-CN＝70／30／５
【００５６】
このようにして得た樹脂硬化物について、参考例１と同様にしてＴＥＭ観察を行った結果、樹脂粒径は0.1μｍ以下であった。また、動的粘弾性測定にてガラス転移温度Ｔg を測定した結果、参考例１と同様にＴg 点のピークは、１つであった。
【００５７】
さらに、得られた樹脂硬化物の引張強度と引張伸び率はそれぞれ９９０ ｋｇ／ｃｍ２、６．５ ％であり、構成樹脂成分単独のものより高いことを確認した。なお、同じ硬化剤、硬化条件で作成したエポキシ樹脂のみからなる硬化物の引張強度と引張伸び率は、それぞれ約５５０ ｋｇ／ｃｍ２、２．８ ％であった。
【００５８】
（参考例５：アディティブ配線板用接着剤への適用）
(1) クレゾールノボラック型エポキシ樹脂（日本化薬製）70重量部、ポリエーテルスルホン（ＰＥＳ，ＩＣＩ製）30重量部、イミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）５重量部、およびエポキシ樹脂微粉末（東レ製）を平均粒径5.5μｍのものを25重量部, 平均粒径0.5μｍのものを10重量部を混合した後、ジメチルホルムアミド／ブチルセロソルブ（１／１）混合溶剤を添加しながら、ホモディスパー攪拌機で粘度120cpsに調整し、続いて、３本ロールで混練して接着剤溶液を得た。
(2) この接着剤溶液を、銅箔が貼着されていないガラスエポキシ絶縁板（東芝ケミカル製）上に、ローラーコーターを用いて塗布し、その後、80℃で１時間，100 ℃で１時間，120 ℃で１時間，150 ℃で３時間、乾燥硬化させて厚さ20μｍの接着剤層を形成した。
(3) 接着剤層を形成した上記基板を、クロム酸水溶液（CrO 3 , 500g/l）に70℃15分間浸漬して接着剤層の表面を粗化し、次いで、中和溶液（シプレイ製）に浸漬したのち水洗した。
(4) 接着剤層の表面を粗化した基板にパラジウム触媒（シプレイ製）を付与して接着剤層の表面を活性化させ、その後、表４に示す組成のアディティブ用無電解めっき液に11時間浸漬して、めっき膜の厚さが25μｍの無電解銅めっきを施した。
【００５９】
【表４】
（比較例１：アディティブ配線板用接着剤への適用）
(1) 以下に示す条件以外は参考例５と同様にして、エポキシ樹脂微粉末含有の接着剤溶液を調製し、銅箔が貼着されていないガラスエポキシ絶縁板（東芝ケミカル製）上に、厚さ20μｍの接着剤層とめっき膜の厚さが25μｍの無電解銅めっき膜を形成した。
〔樹脂組成〕
フェノールノボラック型エポキシ樹脂： 100重量部
イミダゾール系硬化剤（四国化成製、商品名：2P4MHZ）：４重量部
〔接着剤層の硬化条件〕
100 ℃で１時間，150 ℃で５時間
【００６１】
参考例５および比較例１にて形成した無電解銅めっき膜のピール強度、ならびに接着剤層の絶縁抵抗とガラス転移点Ｔg を測定した。その結果を表５に示す。この表に示す結果から明らかなように、擬似均一相溶構造を形成する本発明にかかるＰＥＳ変性エポキシ樹脂を配線板用接着剤に適用することにより、接着強度、耐熱性および電気絶縁性が、従来のものに比べ著しく向上することが判った。
【００６２】
【表５】
（参考例６：エポキシ樹脂／ＰＥＳ系）
エポキシ樹脂／ＰＥＳ系において、エポキシ当量が210 〜230 のクレゾールノボラック型エポキシ樹脂（日本化薬製、商品名：ECON-103S ）70重量部、ポリエーテルスルホン（ＰＥＳ，ＩＣＩ製）30重量部およびイミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）５重量部を、ＤＭＦを用いて混合し、その後、80℃で１時間、150 ℃で５時間の硬化条件にて硬化し、疑似均一相溶構造の硬化物を得た。
【００６８】
このようにして得た樹脂硬化物について、参考例１と同様にしてＴＥＭ観察を行った結果、樹脂粒径は0.1μｍ以下であった。また、動的粘弾性測定にてガラス転移温度Ｔg を測定した結果、参考例１と同様にＴg 点のピークは、１つであった。
【００６９】
さらに、得られた樹脂硬化物の引張強度と引張伸び率はそれぞれ９９５ ｋｇ／ｃｍ２，６．４ ％であり、構成樹脂成分単独のものより高いことを確認した。なお、同じ硬化剤，硬化条件で作成したエポキシ樹脂のみからなる硬化物の引張強度と引張伸び率は、それぞれ約５５０ ｋｇ／ｃｍ２ ，３．０ ％であった。
【００７０】
（実施例１：エポキシ樹脂／ＰＳＦ系）
エポキシ樹脂／ポリスルホン（ＰＳＦ）系において、エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（油化シェル製、商品名：エピコート828 ）、硬化剤としてイミダゾール系硬化剤（四国化成製、商品名：2E4MZ-CN）を用い、下記組成でDMF を用いて樹脂を混合し、80℃で１時間、150℃で５時間の硬化条件にて硬化し、疑似均一相溶構造の硬化物を得た。
樹脂組成：エピコート828 ／PSF ／イミダゾール系硬化剤＝70／30／５
【００７１】
このようにして得た樹脂硬化物について、参考例１と同様にしてＴＥＭ観察を行った結果、樹脂粒径は0.1μｍ以下であった。また、動的粘弾性測定にてガラス転移温度Ｔg を測定した結果、参考例１と同様にＴg 点のピークは、１つであった。
【００７２】
さらに、得られた樹脂硬化物の引張強度と引張伸び率はそれぞれ８００ ｋｇ／ｃｍ２，７．８ ％であり、構成樹脂成分単独のものより高いことを確認した。なお、同じ硬化剤，硬化条件で作成したエポキシ樹脂のみからなる硬化物の引張強度と引張伸び率は、それぞれ約５００ ｋｇ／ｃｍ２ ，４．５ ％であった。また、この実施例１３で得られた樹脂は、誘電率が４．０ で、熱膨張率が５．５ ×１０−５／℃であり、シリカ粉などと混合して半導体パッケージの封止樹脂としても使用できる。
【００７８】
なお、上記ピール強度、絶縁抵抗、ガラス転移点Ｔｇ およびヒートサイクル試験の方法または評価方法を説明する。
（１） ピール強度
ＪＩＳ−Ｃ−６４８１
（２） 絶縁抵抗
基板に層間絶縁層を形成し、粗化したのち触媒付与を行い、次いで、めっきレジストを形成してレジストパターンを作成した。その後、無電解めっきを施し、パターン間の絶縁抵抗を測定した。なお、パターン間絶縁性は、Ｌ／Ｓ＝７５／７５ μｍのくしばパターンにて、８０℃／８５％／２４Ｖ，１０００時間後の値を測定した。
（３） ガラス転移点Ｔｇ
動的粘弾性測定により測定した。
（４） ヒートサイクル試験
−６５℃×３０ｍｉｎ 〜１２５ ℃×３０ｍｉｎ のヒートサイクル試験を行い、クラックの発生と層間絶縁層の剥離の有無を調べ、その耐久サイクル数で評価した。
【００７９】
【発明の効果】
以上説明したように本発明によれば、エポキシ樹脂などの熱硬化性樹脂が示す特有の物性、例えば耐熱性を具えると共に、複合化させるＰＥＳなどの熱可塑性樹脂本来の物性よりもさらに高い物性値を示す新規な樹脂複合体を確実に提供することができる。
【図面の簡単な説明】
【図１】熱可塑性樹脂−熱硬化性樹脂の混合系の状態図を示す図である。
【図２】（ａ） 本発明にかかる樹脂複合体の擬似均一相溶構造を示す結晶構造のＳＥＭ写真、 （ｂ） 従来技術にかかる樹脂複合体の共連続粒子構造を示す結晶構造のＳＥＭ写真、および （ｃ）本発明にかかる樹脂複合体の擬似均一相溶構造を示す結晶構造のＴＥＭ写真である。
【図３】各種イミダゾール系硬化剤（ａ）２ＰＨＺ−ＣＮ， （ｂ）２ＰＺ−ＯＫ， （ｃ）２Ｅ４ＭＺ−ＣＮ， （ｄ）１Ｂ２ＭＺを用いて得られた樹脂硬化物の結晶構造を示すＳＥＭ写真である。
【図４】硬化剤のゲル化時間と複合体を構成する樹脂の粒径との関係を示す図である。
【図５】アミン系硬化剤に関し、各種硬化温度（ａ） ８０℃， （ｂ）１００℃ ， （ｃ）１２０ ℃ ， （ｄ）１５０℃にて得られた樹脂硬化物の結晶構造を示すＳＥＭ写真である。
【図６】イミダゾール系硬化剤に関し、各種硬化温度（ａ） ８０℃， （ｂ）１００℃ ， （ｃ）１２０ ℃， （ｄ） １５０℃にて得られた樹脂硬化物の結晶構造を示すＳＥＭ写真である。
【図７】樹脂の硬化温度と複合体を構成する樹脂の粒径との関係を示す図（アミン系硬化剤の場合）である。
【図８】樹脂の硬化温度と複合体を構成する樹脂の粒径との関係を示す図（イミダゾール系硬化剤の場合）である。
【図９】各種エポキシ当量のエポキシ樹脂（ａ） エピコート８２８， （ｂ）エピコート１００１， （ｃ） エピコート１００４， （ｄ） エピコート１００７を用いて得られた樹脂硬化物の結晶構造を示すＳＥＭ写真である。
【図１０】本発明にかかる樹脂複合体の動的粘弾性測定結果を示す図である。
【図１１】本発明にかかる樹脂複合体の強度試験測定結果で、（ａ） 引張強さ，（ｂ）引張伸び率を示す図である。[0001]
[Industrial applications]
The present invention relates to a novel resin composite composed of a thermosetting resin and a thermoplastic resin, and particularly to a proposal of a resin composite composed of an epoxy resin and polysulfone (PSF).
[0002]
[Prior art]
A typical example of a resin composite technique is a technique of improving the physical properties of a thermosetting resin by mixing a thermosetting resin with a thermoplastic resin to form a composite. For example, in a mixed system (PES-modified epoxy resin) of an epoxy resin and polyether sulfone (hereinafter, referred to as “PES”), a technique for improving the toughness of the epoxy resin by a co-continuous structure formed by the epoxy resin and PES. (See Keizo Yamanaka and Takashi Inoue, Polymer, vol. 30, p. 662 (1989)).
[0003]
The PES-modified epoxy resin obtained by mixing two kinds of resins has improved toughness of the resin as compared with the epoxy resin alone. This is because the PES-modified epoxy resin forms a resin structure as described below. In other words, in a mixed system of an epoxy resin such as a bisphenol A type epoxy resin and PES, when the epoxy resin is cured at a high temperature, the epoxy resin and the PES do not completely dissolve (compatibility state) but spinodal decomposition. Is caused and the epoxy resin and PES are mixed in a separated state (phase separated state).
Such a phase separation state depends on the degree of incompatibility in the initial dispersion state of the resin to be mixed, and when the degree of incompatibility is large, a spherical domain structure is formed, and the degree of incompatibility is small. In such a case, a bicontinuous structure is formed.
The "spherical domain structure" refers to a state in which spherical domains composed of a resin mainly composed of an epoxy resin are independent of each other in a resin matrix mainly composed of PES, or a part of them is connected and dispersed. The term "co-continuous structure" refers to a structure in which spherical domains composed mainly of an epoxy resin are connected to each other and regularly dispersed in a resin matrix mainly composed of PES. Point to.
In such a structure, the constituent resins are not completely separated from each other, but the PES also contains the epoxy resin, and the ratio is overwhelmingly high in PES, while the epoxy resin is contained in the epoxy resin. However, PES is contained therein, and the ratio thereof is such that the epoxy resin is high, and the respective resins are not completely phase-separated but are partially compatible with each other.
[0004]
[Problems to be solved by the invention]
However, the co-continuous structure is formed when the epoxy resin and PES are in a phase-separated state, and the spherical domains of the epoxy resin generated by spinodal decomposition are merely dispersed in the PES matrix. Structure. Therefore, although there is an effect of dispersing and introducing PES into the epoxy resin, it cannot be made higher than the original physical properties of PES. The reason for this is that when the glass transition temperature of the composite having a bicontinuous structure is measured by dynamic viscoelasticity measurement, it is recognized that the number of peaks of the glass transition temperature is two, and therefore the epoxy resin and the matrix are used. This is probably because the interaction with PES is weak.
The knowledge about the co-continuous structure as described above was also applied to a mixed system of a photosensitive resin and a thermoplastic resin, for example, a mixed system of an acrylic resin and polyether sulfone (PES-modified acrylic resin).
[0005]
An object of the present invention is to provide a novel resin exhibiting specific physical properties such as a thermosetting resin such as an epoxy resin, for example, having heat resistance and exhibiting higher physical property values than the original physical properties exhibited by a thermoplastic resin such as PES. An object of the present invention is to provide a composite and a technique for producing the composite.
[0006]
[Means for Solving the Problems]
The inventors first studied a system of a thermosetting resin and a thermoplastic resin, which is one mixed system of a resin composite, in order to achieve the above object. In a mixed system of a thermosetting resin and a thermoplastic resin, for example, in an epoxy resin / PES mixed system, as shown in FIG. 1, the epoxy resin and PES are compatible at low temperatures but separate into two phases at high temperatures. The phase diagram of LCST type (Low Critical Solution Temperature) is shown.
However, when the epoxy resin is polymerized with the curing reaction and the glass transition temperature (Tg) of the resin increases and becomes higher than the curing temperature, the molecular motion is frozen at that temperature and the phase separation cannot be performed. This is because phase separation requires the movement and diffusion of molecules.
[0007]
The present invention has been completed as a result of intensive research focusing on such facts, and does not form a clear co-continuous structure or spherical domain structure due to phase separation between a thermosetting resin and a thermoplastic resin. As described above, by controlling the curing rate and the phase separation rate to cure and composite the resin, the above object can be achieved.
[0008]
That is, the present invention is a resin composite composed of a thermosetting resin and a thermoplastic resin, that is, a resin composite composed of an epoxy resin and polysulfone (PSF). A resin composite characterized by having a pseudo-homogeneous compatible structure obtained by being cured so that a bicontinuous structure or a spherical domain structure is not formed, and a structure forming the pseudo-homogeneous compatible structure The particle size of the resin particles is 0.1 μm or less as measured by observation with a transmission electron microscope (hereinafter, referred to as “TEM”), and at a heating rate of 5 ° C./min and a vibration frequency of 6.28 rad / sec. It is characterized by exhibiting the characteristic that the number of peaks of the glass transition temperature of the resin by the measured dynamic viscoelasticity measurement is one.
[0011]
In the method for producing the resin composite of the present invention as described above, first, the thermosetting resin mixed with the thermoplastic resin is cured to form a composite of the thermosetting resin and the thermoplastic resin. In the case of a thermosetting resin and a thermoplastic resin, the curing temperature of the thermosetting resin exceeds the quasi-homogeneous phase formation point determined by one or two factors selected from the types of curing agents. It is characterized by being cured at a curing speed.
Second, when the thermosetting resin mixed with the thermoplastic resin is cured to form a composite of the thermosetting resin and the thermoplastic resin, one of the crosslinking density and the molecular weight of the uncured thermosetting resin is used. Curing is performed at a phase separation rate not exceeding the pseudo-homogeneous phase formation point determined by the above factors.
Third, when the thermosetting resin mixed with the thermoplastic resin is cured to form a composite of the thermosetting resin and the thermoplastic resin, the curing speed is higher than the quasi-uniform phase formation point and the quasi-uniform It is characterized by curing at a phase separation rate not exceeding the phase formation point.
Here, it is desirable that the blending ratio between the thermosetting resin and the thermoplastic resin is 15 to 50 wt% in terms of the content of the thermoplastic resin.
[0012]
[Action]
A feature of the resin composite of the present invention comprising a thermosetting resin and a thermoplastic resin is that the thermosetting resin and the thermoplastic resin form a pseudo-homogeneous compatible structure.
This quasi-homogeneous compatible structure is a new concept devised by the inventors and refers to a structure described below.
In other words, the quasi-homogeneous compatible structure refers to a more uniform structure that has the unique physical properties of a thermosetting resin such as an epoxy resin and exhibits higher physical property values than the original physical properties of a thermoplastic resin such as PES. In addition, the glass transition temperature peak value by dynamic viscoelasticity measurement is one, and the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin is extremely strong.
Therefore, the resin composite of the present invention has a structure as shown in the scanning electron microscope (hereinafter, referred to as “SEM”) photograph of FIG. 2A, and is shown in the SEM photograph of FIG. 2B. This is clearly different from the conventional bicontinuous particle structure. In addition, in the resin composite, the particle diameter of the constituent resin particles observed by TEM (see FIG. 2C) is 0.1 μm or less, and is more uniform. Because of such a homogeneous resin composite, the thermoplastic resin is hardly eluted by an organic solvent or the like, and is excellent in chemical resistance. In the co-continuous structure described in the prior art, PES is eluted by methylene chloride, and the surface becomes uneven (see the drawing substitute photograph in FIG. 2 (b)). In the present invention, however, thermoplastic resin such as PES is also used by methylene chloride. The amount of resin eluted is small, and no irregularities occur on the surface.
[0013]
The effect due to the structure of the resin composite is particularly remarkable when the content of the thermoplastic resin (for example, PES) in the composite is 15 to 50 wt% in solid content. The reason is that if the content of the thermoplastic resin is less than 15% by weight, the effect of toughening is not sufficiently exhibited because the number of thermoplastic resin molecules entangled in the network of the resin component is small, while the content of the thermoplastic resin is 50% by weight. %, The interaction between the thermosetting resin and the thermoplastic resin decreases due to the decrease in the number of crosslinking points.
[0014]
Such a pseudo-homogeneous compatible structure of a thermosetting resin and a thermoplastic resin is formed by the following method of the present invention. That is, the quasi-homogeneous compatible structure according to the present invention can be obtained by dissolving a thermosetting resin and a thermoplastic resin in a solvent as needed and mixing them uniformly, and then increasing the curing speed, and / or phase separation. It is formed by reducing the speed to make the particle diameter of the constituent resin particles 0.1 μm or less as measured by TEM observation.
[0015]
Specifically, in the method of the present invention, first, when a thermosetting resin is used, it is determined by one or two factors selected from the curing temperature of the thermosetting resin and the type of the curing agent. It is characterized in that it is cured at a curing speed exceeding the pseudo-homogeneous phase formation point. The quasi-homogeneous phase formation point is defined as the lower limit of the curing rate at which a quasi-homogeneous compatible structure in which the particle size of the resin particles constituting the composite is 0.1 μm or less as measured by TEM observation can be obtained. means.
[0016]
Second, the method of the present invention is characterized in that the uncured thermosetting resin is cured at a phase separation rate not exceeding a quasi-homogeneous phase formation point determined by one or more factors of the crosslinking density or molecular weight. There are features. Here, the quasi-homogeneous phase formation point is the upper limit of the phase separation rate at which a quasi-homogeneous compatible structure in which the particle size of the resin particles constituting the composite is 0.1 μm or less as measured by TEM observation can be obtained. Means
[0017]
Thirdly, the method of the present invention is characterized in that curing is performed at a curing speed exceeding the above-mentioned quasi-uniform phase formation point and at a phase separation rate not exceeding the above-mentioned quasi-uniform phase formation point. This means a method in which the factors determining the curing rate and the phase separation rate interact.
[0018]
Next, the interrelation of the above-mentioned various factors which determine the curing rate or the phase separation rate will be described. First, regarding the factors that determine the curing speed, assuming that other factor conditions are constant,
(1). The higher the curing temperature of the thermosetting resin, the faster the curing speed.
Therefore, when the thermosetting resin is cured beyond the lower limit of the curing temperature required to obtain a curing rate exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes a quasi-homogeneous compatible structure.
(2). The shorter the gel time, the faster the curing speed.
Therefore, when the thermosetting resin is cured using a curing agent that does not exceed the upper limit of the gelation time required to obtain a curing rate exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes pseudo- A uniform compatible structure results.
[0019]
In consideration of such a fact, in the case of combining the thermosetting resin and the thermoplastic resin with one kind of the above-mentioned variable factor, the value of the factor corresponding to the pseudo-homogeneous phase formation point is determined by one point. Therefore, when there are two or more of the above-mentioned variation factors, various combinations of the values of the factors corresponding to the quasi-homogeneous phase formation points can be considered. That is, it is possible to select a combination showing a curing rate such that the particle diameter of the constituent resin particles is 0.1 μm or less as measured by TEM observation.
[0020]
Next, as for the factors that determine the phase separation speed, if other factors and conditions are fixed, (1). The higher the crosslink density of the uncured thermosetting resin, the less the phase separation occurs (the lower the phase separation speed) ).
Therefore, when cured using an uncured thermosetting resin having a crosslinking density exceeding the lower limit of the crosslinking density required to obtain a phase separation rate not exceeding the quasi-homogeneous phase formation point, the structure of the resulting resin composite becomes A quasi-uniform compatible structure is obtained.
(2). As the molecular weight of the uncured thermosetting resin increases, phase separation hardly occurs (the phase separation speed decreases).
Therefore, when cured using an uncured thermosetting resin having a molecular weight exceeding the lower limit of the molecular weight required to obtain a phase separation rate not exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes quasi-homogeneous. It has a compatible structure.
[0021]
In consideration of such a fact, in the case of combining the thermosetting resin and the thermoplastic resin with one kind of the above-mentioned variable factor, the value of the factor corresponding to the pseudo-homogeneous phase formation point is determined by one point. Therefore, when the above-mentioned variable factors are two kinds, various combinations of the values of the factors corresponding to the quasi-homogeneous phase formation point can be considered. That is, it is possible to select a combination exhibiting a phase separation rate such that the particle diameter of the constituent resin particles is 0.1 μm or less as measured by TEM observation.
[0022]
The resin composite obtained by the method of the present invention as described above has the specific physical properties of a thermosetting resin such as an epoxy resin, and has a higher physical property value than the original physical properties of a thermoplastic resin such as PES. Can be shown.
That is, the resin composite having a pseudo-homogeneous compatible structure according to the present invention has a higher resin strength than PES alone, and has a toughening effect of an epoxy resin that has not existed conventionally.
[0023]
In the present invention, prior to compounding the thermosetting resin and the thermoplastic resin as described above, the thermosetting resin and the thermoplastic resin are uniformly mixed by being dissolved in a solvent as necessary. You. Examples of such a solvent include dimethylformamide (DMF), methylene chloride, dimethylsulfoxide (DMSO), and normal methylpyrrolidone (NMP). At a temperature lower than the phase separation start temperature and lower than the curing start temperature, the thermosetting resin and the thermoplastic resin can be mixed by heating and melting.
[0024]
In the present invention, as the thermosetting resin, phenol resins, amino resins such as melamine resins and urea resins, epoxy resins, unsaturated polyester resins, polyimide resins, urethane resins, diallyl phthalate resins, and the like can be used.
[0025]
In the present invention, as the thermoplastic resin, in addition to phenoxy resin and polyether sulfone, polysulfone, polyphenylene sulfide, polyether ether ketone, polyacetal, polycarbonate, engineering plastics such as polyetherimide, polystyrene, polyethylene, polyarylate, polyamide imide , Polyoxybenzoate, polyvinyl chloride, polyvinyl acetate and the like can be used.
[0027]
In the present invention, as a curing agent when an epoxy resin is used as the thermosetting resin, an imidazole-based curing agent, a diamine, a polyamine, a polyamide, an organic acid anhydride, a vinyl phenol, or the like can be used. On the other hand, when a thermosetting resin other than the epoxy resin is used, a known curing agent can be used.
[0028]
The resin composite of the present invention, which has physical properties unique to a thermosetting resin such as an epoxy resin and exhibits physical properties higher than the original physical properties of a thermoplastic resin such as PES to be composited, is a printed wiring board. Adhesives for electroless plating such as adhesives for substrates, substrate materials used for printed wiring boards, resist materials and prepreg materials, sealing materials for semiconductor packages, base materials for fiber-reinforced composite materials, injection molding materials, compression It is expected to be used for various applications such as molding materials.
[0029]
The effects of the curing agent (test 1), the effects of the curing temperature (test 2), the effects of the crosslink density (test 3),Effect of PES content (Test 4)Will be described.
(Test 1: Effect of curing agent)
(1) Using epoxy resin / PES-based curing agents with different gelling times (curing speeds), investigate how the type of epoxy resin curing agent affects the resin structure and physical properties of the above mixed system. Was.
(2) As the curing agents having different gelling times, several kinds of imidazole-based curing agents (manufactured by Shikoku Chemicals) shown in Table 1 were used.
(3) In order to investigate the effect of the curing agent, a bisphenol A type epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 828) was used as the epoxy resin, and the mixing ratio of epoxy resin / PES was 70/30. PES is dissolved in twice the amount of dimethylformamide (DMF), a predetermined amount of an epoxy resin and a curing agent are mixed and cured, and the epoxy equivalent of the epoxy resin is 184 to 194, and the curing condition is 120 ° C. × 5 hours. The conditions were kept constant at + 150 ° C. × 2 hours.
[0030]
FIG. 3 and Table 1 show the results of examining the structure and physical properties of the obtained cured resin. 3 (a) to 3 (d) are SEM photographs showing the structure of the cured resin obtained using the imidazole-based curing agent shown in Table 1, wherein (a) 2PHZ-CN and (b) 2PZ-OK. , (c) 2E4MZ-CN and (d) 1B2MZ. As is clear from these photographs and the results shown in Table 1, the curing agent having a low curing speed was used.( (a) , (b) )It was found that the use of the compound formed a spherical domain structure due to the progress of phase separation, and the strength and elongation of the resin were low. On the other hand, a curing agent showing a curing speed exceeding the quasi-homogeneous phase formation point( (c) , (d) )It was found that when cured, the epoxy resin and PES formed a pseudo-homogeneous compatible structure, and both the strength and elongation of this cured product were greatly improved.
[0031]
FIG. 4 is a diagram showing the relationship between the particle size of the resin obtained by SEM observation of the cured resin and the gelation time of the curing agent. As is clear from the results shown in this figure, when the gelation time at 120 ° C. becomes about 5 minutes or less, the particle size of the resin sharply decreases, and it becomes clear that the spherical domain structure becomes a pseudo-homogeneous compatible structure. Was. That is, under the conditions of the present example, it can be seen that the quasi-homogeneous phase formation point determined by the gel time of the curing agent exists at a point where the gel time is about 5 minutes.
[0032]
[Table 1]
(test2: Influence of curing temperature)
(1) In the epoxy resin / PES system, the effect of the curing temperature of the epoxy resin on the resin structure of the obtained cured resin was investigated by curing under curing conditions having different curing temperatures.
(2) As the curing conditions having different curing temperatures, the following four conditions were implemented.
a. 6 hours at 80 ° C b. 6 hours at 100 ° C. 5 hours at 120 ° C. 4 hours at 150 ° C
(3) Depending on the curing agent, (1). When the curing temperature is lower, a pseudo-homogeneous compatible structure is formed (2). From the finding that a higher curing temperature may form a pseudo-homogeneous compatible structure in some cases, the curing agent is (3). Amine-based curing agent (Sumitomo Chemical, trade name: DDM), (4). An imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) was used.
(4) In order to investigate the influence of the curing temperature, a bisphenol A type epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 828) was used as the epoxy resin, and the mixing ratio of epoxy resin / PES / curing agent was calculated as follows: 1). 70/30/20 for amine-based curing agent (DDM), (2). In the case of an imidazole-based curing agent (2E4MZ-CN), the ratio is 70/30/5, PES is dissolved in twice the amount of dimethylformamide (DMF), and a predetermined amount of epoxy resin and a curing agent are mixed and cured. The epoxy equivalent of the epoxy resin was 184 to 194, and the conditions were fixed.
[0034]
The results of examining the structure of the obtained cured resin are shown in FIG. 5 and FIG. FIGS. 5 (a) to 5 (d) and FIGS. 6 (a) to 6 (d) relate to (1) amine-based curing agents and (2) imidazole-based curing agents, respectively. 5 is an SEM photograph showing the structure of the cured resin obtained in (a) at 80 ° C., (b) at 100 ° C., (c) at 120 ° C., and (d) at 150 ° C.
When a (1) type amine-based curing agent (DDM) was used as the curing agent, as shown in the photograph of FIG. 5, the resin structure formed a pseudo-homogeneous compatible structure when the curing temperature was 80 ° C. When the curing temperature was 100 ° C. or higher, a spherical domain structure was formed, and the particle diameter was found to be 0.2 μm or more.
On the other hand, when a (2) type imidazole-based curing agent (2E4MZ-CN) is used as the curing agent, the resin structure has a quasi-homogeneous phase at a curing temperature of 100 ° C. or higher, as is clear from the photograph in FIG. Although a melted structure was formed, it was found that when the curing temperature was 80 ° C., a spherical domain structure having a particle size of about 0.3 μm was formed.
[0035]
7 and 8 are diagrams showing the relationship between the particle size of the resin obtained by SEM observation and the curing temperature of the epoxy resin for the above two types of curing agents. As is clear from the results shown in these figures, in the case of the amine type curing agent of the type (1), when the curing temperature is 90 ° C or lower, the spherical domain structure changes to a pseudo-homogeneous compatible structure, while the type (2) type It was found that the imidazole-based curing agent changed from a spherical domain structure to a pseudo-homogeneous compatible structure when the curing temperature was 90 ° C or higher. That is, the booktestUnder the conditions of the example, it can be seen that the quasi-homogeneous phase formation point determined by the curing temperature of the epoxy resin exists at a curing temperature of about 90 ° C.
[0036]
(test3: Influence of crosslink density)
(1) In the epoxy resin / PES system, by curing epoxy resins having the same skeleton structure and different epoxy equivalents, how the epoxy equivalent of the epoxy resin affects the resin structure of the cured resin obtained Was examined, and the effect of the crosslink density of the resin was examined.
(2) Several types of bisphenol A type epoxy resins shown in Table 2 were used as epoxy resins having different epoxy equivalents.
(3) In order to examine the effect of the epoxy equivalent, an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) was used as a curing agent, and the mixing ratio of epoxy resin / PES / curing agent was 70/30. / 5, PES is dissolved in twice the amount of dimethylformamide (DMF), and a predetermined amount of epoxy resin and a curing agent are mixed and cured. The curing conditions are 80 ° C. for 1 hour and 100 ° C. for 1 hour. , 120 ° C for 1 hour and 150 ° C for 3 hours.
[0037]
FIG. 9 and Table 2 show the results of examining the structure of the obtained cured resin. FIGS. 9 (a) to 9 (d) are SEM photographs showing the structure of the cured resin obtained using the epoxy resins having various epoxy equivalents, wherein (a) epicoat 828, (b) epicoat 1001, (b) c) Epicoat 1004, (d) Epicoat 1007. As is clear from these photographs and the results shown in Table 2, the larger the epoxy equivalent, in other words, the lower the crosslink density, the easier the phase separation, while the smaller the epoxy equivalent, in other words, the higher the crosslink density, the higher the epoxy equivalent. It was found that the resin structure was a pseudo-homogeneous compatible structure. That is, the booktestUnder the conditions of the example, it can be seen that the quasi-homogeneous phase formation point determined by the epoxy equivalent (or crosslink density) of the epoxy resin exists at around 300 epoxy equivalent.
[0038]
[Table 2]
(test4: Influence of PES content)
(1) In the epoxy resin / PES system, it was examined how various changes in the amount of PES affect the physical properties of the obtained cured resin.
(2) As the PES compounding amount,0 ~ 60wt %Various changes were made.
(3) In order to investigate the effect of the PES content, a cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name: EOCN-103S) was used as the epoxy resin, and an imidazole-based curing agent (manufactured by Shikoku Chemicals) was used as the curing agent. PES was dissolved in twice the amount of dimethylformamide (DMF) using a trade name of 2E4MZ-CN), and a predetermined amount of an epoxy resin and a curing agent were mixed and cured. The curing conditions of the epoxy resin were fixed at 80 ° C. for 1 hour, at 100 ° C. for 1 hour, at 120 ° C. for 1 hour, and at 150 ° C. for 3 hours.
[0044]
FIG. 11 shows the result of examining the change in the physical properties of the resin cured product thus obtained. As is clear from the results shown in this figure, the strength of the resin increased as the amount of PES increased, showed a maximum value at 30% PES, and thereafter the resin strength decreased. In particular, a cured resin of 30% PES has higher strength than not only epoxy resin but also PES alone. The booktestUnder the conditions of the examples, the obtained cured resin formed a pseudo-homogeneous compatible structure in all the compounding compositions. Book like thistestFrom the results of the examples, it was found that in the epoxy resin / PES system, the PES content is desirably 15 to 50% by weight, more preferably 20 to 40% by weight.
[0045]
【Example】
(Reference example1)
(1) In the epoxy resin / PES system, a bisphenol A type epoxy resin having an epoxy equivalent of 184 to 194 (manufactured by Yuka Shell, trade name: Epicoat 828) as an epoxy resin, and an imidazole-based curing agent (manufactured by Shikoku Chemicals) as a curing agent. (Product name: 2E4MZ-CN), resin is mixed with DMF with the following composition and cured at 120 ° C for 5 hours and at 150 ° C for 2 hours to obtain a cured resin with a pseudo-homogeneous compatible structure. Got. The gel time of the curing agent at 120 ° C. was 3 minutes.
Resin composition: Epicoat 828 / PES / 2E4MZ-CN = 70/30/5
[0046]
About the resin cured product obtained in this way,TEM observation was performed under the following conditions. As a result, the particle diameter of the resin constituting the cured resin was 0.1 μm or less.
[Observation conditions)
(1) Using a microtome, 70nm And cut into slices.
(2) Osmium tetroxide ( OsO Four ) In methanol solution twenty four Let soak for hours.
(3) Acceleration voltage for TEM observation 80kV Observe as
In addition, the glass transition temperature T was determined by dynamic viscoelasticity measurement.gAs a result of measuringFigure Ten As shownTgHas one peak,It turned out to be homogeneous in physical properties. Due to this, it is assumed that physical properties such as tensile strength and elongation are higher than those of the constituent resin component alone..
[0047]
Furthermore, the tensile strength and the tensile elongation of the obtained cured resin are 835 kg / cm, respectively.2, 8.0%, which was higher than that of the constituent resin component alone. The tensile strength and tensile elongation of a cured product made of only an epoxy resin produced under the same curing agent and curing conditions are about 500 kg / cm.2, 4.8%.
[0048]
The results described above were similarly obtained when an imidazole-based curing agent (Shikoku Chemicals, trade name: 1B2MZ) was used as the curing agent. In this case, the gel time of the curing agent at 120 ° C. was 44 seconds.
[0049]
(Reference example2)
(1) In the epoxy resin / PES system, a bisphenol A type epoxy resin having an epoxy equivalent of 184 to 194 (manufactured by Shikoku Chemicals, trade name: Epicoat 828) as an epoxy resin, and an imidazole-based curing agent (manufactured by Yuka Shell Co., Ltd.) as a curing agent (Product name: 2E4MZ-CN), resin is mixed with DMF with the following composition, and cured under the curing conditions of 80 ° C x 1 hour + 150 ° C x 4 hours to obtain a cured resin with a pseudo-homogeneous compatible structure Got. The bookReference exampleIsReference exampleThe only difference from 1 is the curing temperature of the epoxy resin.
Resin composition: Epicoat 828 / PES / 2E4MZ-CN = 70/30/5
[0050]
About the resin cured product obtained in this way,Reference Example 1As a result of TEM observation in the same manner as in the above, the resin particle size was 0.1 μm or less. In addition, the glass transition temperature T was determined by dynamic viscoelasticity measurement.gAs a result of measuringReference Example 1As in TgHad one peak.
[0051]
Furthermore, the tensile strength and the tensile elongation of the obtained cured resin are 835 kg / cm, respectively.2, 9.1%, which was higher than that of the constituent resin component alone. The tensile strength and tensile elongation of a cured product made of only an epoxy resin produced under the same curing agent and curing conditions are about 500 kg / cm.2, 4.5%.
[0052]
(Reference example3)
(1) In an epoxy resin / PES system, a bisphenol A type epoxy resin having an epoxy equivalent of 184 to 194 (manufactured by Yuka Shell, trade name: Epicoat 828) as an epoxy resin, and an amine curing agent (manufactured by Sumitomo Chemical Co., Ltd.) as a curing agent (Product name: DDM), resin is mixed with DMF with the following composition and cured at 80 ° C for 6 hours and at 150 ° C for 2 hours to obtain a cured resin having a quasi-homogeneous compatible structure. Was.
Resin composition: Epicoat 828 / PES / DDM = 70/30/18
[0053]
About the resin cured product obtained in this way,Reference Example 1As a result of TEM observation in the same manner as in the above, the resin particle size was 0.1 μm or less. The glass transition temperature T is determined by dynamic viscoelasticity.gAs a result of measuringReference Example 1As in TgHad one peak.
[0054]
Further, the tensile strength and the tensile elongation of the obtained cured resin are 860 kg / cm, respectively.28.6%, which was higher than that of the constituent resin component alone. In addition, the tensile strength and the tensile elongation of a cured product made of only an epoxy resin produced under the same curing agent and curing conditions are about 500 kg / cm, respectively.2Was 5%.
[0055]
(Reference example4)
In the epoxy resin / PES system, a cresol novolak type epoxy resin having an epoxy equivalent of 210 to 230 (Nippon Kayaku, trade name: EOCN-103S) as an epoxy resin, and an imidazole type hardener (Shikoku Chemicals, trade name, as a curing agent) : 2E4MZ-CN), DMF was mixed with the following composition, and cured at 80 ° C for 1 hour and 150 ° C for 4 hours to obtain a cured product having a pseudo-homogeneous compatible structure. .
Resin composition: EOCN-103S / PES / 2E4MZ-CN = 70/30/5
[0056]
About the resin cured product obtained in this way,Reference Example 1As a result of TEM observation in the same manner as in the above, the resin particle size was 0.1 μm or less. In addition, the glass transition temperature T was determined by dynamic viscoelasticity measurement.gAs a result of measuringReference Example 1As in TgThere was one point peak.
[0057]
Furthermore, the tensile strength and the tensile elongation of the obtained cured resin are 990 kg / cm, respectively.2, 6.5%, which was higher than that of the constituent resin component alone. In addition, the tensile strength and the tensile elongation of a cured product made of only the epoxy resin prepared under the same curing agent and curing conditions are about 550 kg / cm, respectively.22.8%.
[0058]
(Reference example5: Application to adhesive for additive wiring board)
(1) 70 parts by weight of cresol novolac type epoxy resin (manufactured by Nippon Kayaku), 30 parts by weight of polyether sulfone (manufactured by PES, ICI), 5 parts by weight of imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) And 25 parts by weight of an epoxy resin fine powder (manufactured by Toray) having an average particle diameter of 5.5 μm, and 10 parts by weight of an epoxy resin fine powder having an average particle diameter of 0.5 μm. A mixed solvent of dimethylformamide / butyl cellosolve (1/1) While adding the mixture, the viscosity was adjusted to 120 cps with a homodisper stirrer, and then kneaded with three rolls to obtain an adhesive solution.
(2) This adhesive solution is applied on a glass epoxy insulating plate (manufactured by Toshiba Chemical) on which no copper foil is stuck, using a roller coater, and then at 80 ° C. for 1 hour and at 100 ° C. for 1 hour. After drying and curing at 120 ° C. for 1 hour and at 150 ° C. for 3 hours, an adhesive layer having a thickness of 20 μm was formed.
(3) The above substrate having the adhesive layer formed thereon is treated with a chromic acid aqueous solutionThree, 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then immersed in a neutralizing solution (manufactured by Shipley) and then washed with water.
(4) A palladium catalyst (manufactured by Shipley) was applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer. After immersion for an hour, electroless copper plating with a plating film thickness of 25 μm was performed.
[0059]
[Table 4]
(Comparative Example 1: Application to an additive for an additive wiring board)
(1) Except for the following conditionsReference exampleIn the same manner as in 5, an epoxy resin fine powder-containing adhesive solution was prepared, and a 20 μm-thick adhesive layer and a plating film were formed on a glass epoxy insulating plate (manufactured by Toshiba Chemical Co.) on which no copper foil was stuck. An electroless copper plating film having a thickness of 25 μm was formed.
(Resin composition)
Phenol novolak type epoxy resin: 100 parts by weight
Imidazole-based curing agent (Shikoku Chemicals, trade name: 2P4MHZ): 4 parts by weight
(Curing conditions of adhesive layer)
1 hour at 100 ° C, 5 hours at 150 ° C
[0061]
Reference example5 and the peel strength of the electroless copper plating film formed in Comparative Example 1, the insulation resistance of the adhesive layer and the glass transition point TgWas measured. Table 5 shows the results. As is clear from the results shown in this table, by applying the PES-modified epoxy resin according to the present invention that forms a quasi-homogeneous compatible structure to the adhesive for wiring boards, the adhesive strength, heat resistance and electrical insulation properties are improved. It turned out that it is remarkably improved as compared with the conventional one.
[0062]
[Table 5]
(Reference example6: epoxy resin / PES type)
In an epoxy resin / PES system, 70 parts by weight of a cresol novolak type epoxy resin having an epoxy equivalent of 210 to 230 (manufactured by Nippon Kayaku, trade name: ECON-103S), 30 parts by weight of polyether sulfone (PES, ICI) and imidazole 5 parts by weight of a system-based curing agent (trade name: 2E4MZ-CN, manufactured by Shikoku Chemicals Co., Ltd.) are mixed using DMF, and then cured under the curing conditions of 80 ° C. for 1 hour and 150 ° C. for 5 hours, resulting in pseudo-homogeneous A cured product having a compatible structure was obtained.
[0068]
About the resin cured product obtained in this way,Reference Example 1As a result of TEM observation in the same manner as in the above, the resin particle size was 0.1 μm or less. In addition, the glass transition temperature T was determined by dynamic viscoelasticity measurement.gAs a result of measuringReference Example 1As in TgThere was one point peak.
[0069]
Furthermore, the tensile strength and the tensile elongation of the obtained cured resin were 995 kg / cm, respectively.2, 6.4%, which was higher than that of the resin component alone. The tensile strength and tensile elongation of a cured product made of only the epoxy resin prepared under the same curing agent and curing conditions are about 550 kg / cm, respectively.2 , 3.0%.
[0070]
(Example1: Epoxy resin / PSF type)
In the epoxy resin / polysulfone (PSF) system, a bisphenol A type epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 828) as an epoxy resin, and an imidazole curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) as a curing agent And a resin having the following composition and mixed with DMF, and cured at 80 ° C. for 1 hour and at 150 ° C. for 5 hours to obtain a cured product having a pseudo-homogeneous compatible structure.
Resin composition: Epicoat 828 / PSF / imidazole-based curing agent = 70/30/5
[0071]
About the resin cured product obtained in this way,Reference Example 1As a result of TEM observation in the same manner as in the above, the resin particle size was 0.1 μm or less. In addition, the glass transition temperature T was determined by dynamic viscoelasticity measurement.gAs a result of measuringReference Example 1As in TgThere was one point peak.
[0072]
Further, the tensile strength and the tensile elongation of the obtained cured resin are 800 kg / cm, respectively.2, 7.8%, which was higher than that of the constituent resin component alone. The tensile strength and the tensile elongation of a cured product made of only an epoxy resin prepared under the same curing agent and curing conditions are about 500 kg / cm, respectively.2 , 4.5%. The resin obtained in Example 13 had a dielectric constant of 4.0 and a coefficient of thermal expansion of 5.5 × 10-5/ ° C, and can be used as a sealing resin for a semiconductor package by mixing with silica powder or the like.
[0078]
The peel strength, insulation resistance, glass transition point Tg and heat cycle test method or evaluation method will be described.
(1) Peel strength
JIS-C-6481
(2) Insulation resistance
An interlayer insulating layer was formed on the substrate, and after roughening, a catalyst was applied, and then a plating resist was formed to form a resist pattern. Thereafter, electroless plating was performed, and the insulation resistance between the patterns was measured. The inter-pattern insulation was measured at a temperature of 80 ° C./85%/24 V for 1000 hours using a comb pattern of L / S = 75/75 μm.
(3) Glass transition point Tg
It was measured by dynamic viscoelasticity measurement.
(4) Heat cycle test
A heat cycle test at −65 ° C. × 30 min to 125 ° C. × 30 min was performed, and the occurrence of cracks and the presence or absence of peeling of the interlayer insulating layer were examined.
[0079]
【The invention's effect】
As described above, according to the present invention, a thermosetting resin such as an epoxy resin exhibits unique physical properties, such as heat resistance, and further higher physical properties than the original physical properties of a thermoplastic resin such as PES to be compounded. It is possible to reliably provide a novel resin composite showing a value.
[Brief description of the drawings]
FIG. 1 is a diagram showing a phase diagram of a mixed system of a thermoplastic resin and a thermosetting resin.
FIG. 2A is an SEM photograph of a crystal structure showing a pseudo-homogeneous compatible structure of the resin composite according to the present invention, and FIG. 2B is an SEM photograph of a crystal structure showing a co-continuous particle structure of the resin composite according to the prior art And (c) is a TEM photograph of a crystal structure showing a pseudo-homogeneous compatible structure of the resin composite according to the present invention.
FIG. 3 is an SEM photograph showing the crystal structure of a cured resin obtained using various imidazole-based curing agents (a) 2PHZ-CN, (b) 2PZ-OK, (c) 2E4MZ-CN, and (d) 1B2MZ. It is.
FIG. 4 is a diagram showing the relationship between the gelation time of a curing agent and the particle size of a resin constituting a composite.
FIG. 5 is an SEM showing the crystal structure of a cured resin obtained at various curing temperatures (a) 80 ° C., (b) 100 ° C., (c) 120 ° C., and (d) 150 ° C. It is a photograph.
FIG. 6 is an SEM showing the crystal structure of a cured resin obtained at various curing temperatures (a) 80 ° C., (b) 100 ° C., (c) 120 ° C., and (d) 150 ° C. with respect to the imidazole-based curing agent. It is a photograph.
FIG. 7 is a diagram showing the relationship between the curing temperature of the resin and the particle size of the resin constituting the composite (in the case of an amine-based curing agent).
FIG. 8 is a diagram showing the relationship between the curing temperature of the resin and the particle size of the resin constituting the composite (in the case of an imidazole-based curing agent).
FIG. 9 is an SEM photograph showing a crystal structure of a cured resin obtained by using epoxy resins (a) epicoat 828, (b) epicoat 1001, (c) epicoat 1004, and (d) epicoat 1007 with various epoxy equivalents. is there.
FIG. 10 is a view showing the results of measuring dynamic viscoelasticity of the resin composite according to the present invention.
FIG. 11 is a diagram showing (a) tensile strength and (b) tensile elongation as a result of a strength test measurement of the resin composite according to the present invention.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000282729A JP3605556B2 (en) | 1993-02-24 | 2000-09-18 | Resin composite having quasi-homogeneous compatible structure |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5807893 | 1993-02-24 | ||
| JP5-139168 | 1993-05-19 | ||
| JP13916893 | 1993-05-19 | ||
| JP5-58078 | 1993-05-19 | ||
| JP2000282729A JP3605556B2 (en) | 1993-02-24 | 2000-09-18 | Resin composite having quasi-homogeneous compatible structure |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05271192A Division JP3142425B2 (en) | 1993-02-24 | 1993-10-05 | Resin composite having pseudo-homogeneous compatible structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001114981A JP2001114981A (en) | 2001-04-24 |
| JP3605556B2 true JP3605556B2 (en) | 2004-12-22 |
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| JP2000282729A Expired - Lifetime JP3605556B2 (en) | 1993-02-24 | 2000-09-18 | Resin composite having quasi-homogeneous compatible structure |
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| JP3949676B2 (en) | 2003-07-22 | 2007-07-25 | 三井金属鉱業株式会社 | Copper foil with ultrathin adhesive layer and method for producing the copper foil with ultrathin adhesive layer |
| RU2013139854A (en) * | 2011-01-28 | 2015-03-10 | Торэй Индастриз, Инк. | EPOXY POLYMERIC COMPOSITION FOR FIBER REINFORCED COMPOSITE MATERIALS, PREGREG AND FIBER REINFORCED COMPOSITE MATERIAL |
| EP3757148A4 (en) | 2018-02-22 | 2021-07-07 | Hitachi Chemical Company, Ltd. | EPOXY RESINS, EPOXY RESIN COMPOSITION, CURED EPOXY RESIN AND MANUFACTURING METHODS THEREFORE, COMPOSITE MATERIAL, INSULATION ELEMENT, ELECTRONIC DEVICE, STRUCTURAL MATERIAL AND MOVING OBJECT |
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