JP2004083783A - Epoxy resin composition, molded cured product thereof, semiconductor encapsulating material, and resin composition for electronic circuit board - Google Patents

Abstract

A semiconductor sealing material, a resin composition for an electronic circuit board, a resin casting material, an adhesive, an interlayer insulating material for a build-up board, a coating material such as an insulating paint, etc., which require excellent heat resistance and moisture resistance. To provide an epoxy resin composition, a molded cured product thereof, a semiconductor encapsulating material, and a resin composition for an electronic circuit board, which can be suitably used as a resin.
SOLUTION: It is derived from a tetrasubstituted dihydroxybenzene (a) having at least one substituent selected from the group consisting of a benzyl group, a 1-phenylethyl group and a 1-methyl-1-phenylethyl group, and epihalohydrin. An epoxy resin composition, comprising a cured epoxy resin (A) and a curing agent (B), a cured cured product thereof, a semiconductor sealing material, and a resin composition for an electronic circuit board.
[Selection diagram] None.

Description

〔式中、Ｒ^１〜Ｒ^６は、それぞれ独立にヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のシクロアルキル基、アリール基、ハロゲン原子または下記一般式（２）
【化４】

（式中、Ｒ^７、Ｒ^８はそれぞれ独立に水素原子、或いはメチル基を示す。）
で表される置換基を示し、かつ、これら置換基のうち２つは必ずヒドロキシ基であり、１つは必ず上記一般式（２）で示される基である。〕
で表されるものが挙げられる。
【０００９】
これらの中でも、２個のヒドロキシ基および１個の上記一般式（２）で示される置換基以外の３個の置換基がいずれもメチル基である化合物が好ましく、例えば、以下の構造式（３−１）〜（３−５）で表される化合物が挙げられる。
【化５】

【００１０】
前記４置換ジヒドロキシベンゼン類（ａ）の製造方法は特に限定されるものではないが、例えば、３置換ジヒドロキシベンゼン化合物（ａ１）と、芳香族性モノビニル化合物（ａ２）或いはベンジル位に脱離基を有するベンジル化合物（ａ３）とを反応させることによって得ることができる。
【００１１】
前記３置換ジヒドロキシベンゼン化合物（ａ１）としては、その構造が特に限定されるものではなく、例えば下記一般式（４）
【化６】

（式中、Ｒ^９〜Ｒ^１２はそれぞれ独立に炭素数１〜６のアルキル基、炭素数１〜６のシクロアルキル基、アリール基またはハロゲン原子を示し、且つそのうち１つは必ずヒドロキシ基である。）
で表される化合物が挙げられる。
【００１２】
前記３置換ジヒドロキシベンゼン化合物（ａ１）の具体的な例としては、トリメチルハイドロキノン、２，４，５−トリメチルレゾルシン、４，５，６−トリメチルレゾルシン、３，４，５−トリメチルカテコール、３，５，６−トリメチルカテコール、トリエチルハイドロキノン、２，４，５−トリエチルレゾルシン、４，５，６−トリエチルレゾルシン、３，４，５−トリエチルカテコール、３，５，６−トリエチルカテコール、トリプロピルハイドロキノン、２，４，５−トリプロピルレゾルシン、４，５，６−トリプロピルレゾルシン、３，４，５−トリプロピルカテコール、３，５，６−トリプロピルカテコール、トリブチルハイドロキノン、２，４，５−トリブチルレゾルシン、４，５，６−トリブチルレゾルシン、３，４，５−トリブチルカテコール、３，５，６−トリブチルカテコールなどのトリアルキル置換ジヒドロキシベンゼン類、トリフェニルハイドロキノン、２，４，５−トリフェニルレゾルシンなどのトリアリール置換ハイドキノン類、トリブロモハイドロキノンなどのトリハロゲン置換ジヒドロキシベンゼン類などが挙げられるが、これらの中でも、耐熱性と耐湿性のバランスに優れることからトリメチルハイドロキノンが特に好ましい。
【００１３】
前記芳香族性モノビニル化合物（ａ２）としては、芳香環にビニル基が１個結合している化合物であれば特に限定されるものではなく、スチレン、メチルスチレン等が挙げられ、ベンジル位に脱離基を有するベンジル化合物（ａ３）としては、塩化ベンジル、臭化ベンジル、沃化ベンジル等のハロゲン化ベンジル化合物或いは、ベンジルアルコール、ベンジルメトキサイド等が挙げられる。
【００１４】
これら芳香族性モノビニル化合物（ａ２）、ベンジル位に脱離基を有するベンジル化合物（ａ３）の中でも、工業的に入手し易く、且つ、副反応が起こりにくいことからスチレン、塩化ベンジル、臭化ベンジルが好ましい。
【００１５】
前記３置換ジヒドロキシベンゼン化合物（ａ１）と、芳香族性モノビニル化合物（ａ２）或いはベンジル位に脱離基を有するベンジル化合物（ａ３）との反応について以下に説明する。
【００１６】
まず、３置換ジヒドロキシベンゼン化合物（ａ１）と芳香族性モノビニル化合物（ａ２）を仕込み、必要に応じて反応触媒や有機溶媒を用いて、３置換ジヒドロキシベンゼン化合物（ａ１）の芳香環上の置換基のない１箇所とビニル基を付加反応させる。
【００１７】
また、３置換ジヒドロキシベンゼン化合物（ａ１）とベンジル位に脱離基を有するベンジル化合物（ａ３）を反応させる場合も同様に、３置換ジヒドロキシベンゼン化合物（ａ１）とベンジル位に脱離基を有するベンジル化合物（ａ３）を仕込み、必要に応じて反応触媒や有機溶媒を用いて、３置換ジヒドロキシベンゼン化合物（ａ１）の芳香環上の置換基のない１箇所とベンジル位とを、脱水、脱ハロゲン、脱アルコール反応等の縮合反応させる。
【００１８】
前記反応の終了後、必要に応じて、苛性ソーダ、重炭酸ソーダ、アンモニア、トリエチルアミン等の塩基性化合物を用いて中和、或いは水洗などして反応触媒を失活させた後に、有機溶媒を蒸留などによって除去し、再結晶などを行って精製し、４置換ジヒドロキシベンゼン類（ａ）を得ることができる。
【００１９】
前記触媒としては、例えば、塩酸、硫酸、無水硫酸、ｐ−トルエンスルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸、シユウ酸、ギ酸、リン酸、トリクロロ酢酸、トリフルオロ酢酸、三弗化硼素エーテル錯体、三弗化硼素フェノール錯体等が挙げられ、これらの中でも、反応速度が速い点からｐ−トルエンスルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸が好ましい。前記触媒の添加量としては、３置換ジヒドロキシベンゼン化合物（ａ１）と、芳香族性モノビニル化合物（ａ２）或いはベンジル位に脱離基を有するベンジル化合物（ａ３）との総量１００重量部に対して、０．０１〜１０重量部の範囲であることが好ましい。
【００２０】
また前記有機溶媒としては、３置換ジヒドロキシベンゼン化合物（ａ１）と、芳香族性モノビニル化合物（ａ２）或いはベンジル位に脱離基を有するベンジル化合物（ａ３）、並びに生成物を溶解し、それらに対して不活性であれば特に制限されるものではないが、例えば、ベンゼン、トルエン、キシレンなどの芳香族性有機溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系有機溶媒、メタノール、エタノール、イソプロピルアルコール、ノルマルブタノールなどのアルコール系有機溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン、メトキシエタノールなどのエーテル系有機溶媒等が挙げられ、用いる原料や生成物の溶解度などの性状や反応条件や経済性等を考慮して適宜選択することが出来るが、特に芳香族性有機溶媒、ケトン系有機溶媒が好ましい。
【００２１】
前記有機溶媒の使用量としては、特に制限されるものではないが、３置換ジヒドロキシベンゼン化合物（ａ１）と、芳香族性モノビニル化合物（ａ２）或いはベンジル位に脱離基を有するベンジル化合物（ａ３）との総量１００重量部に対して、１０〜５００重量部の範囲が好ましい。反応条件としては、室温〜２００℃、好ましくは、５０〜１５０℃の温度にて、０．５〜３０時間加熱撹拌する。
【００２２】
本発明で用いるエポキシ樹脂（Ａ）は、前述のようにして得られた４置換ジヒドロキシベンゼン類（ａ）とエピハロヒドリンから誘導されるものであり、その構造が特に限定されるものではないが、例えば、下記構造式（５−１）〜（５−２）で表されるものが挙げられる。
【００２３】
【化７】

（式中、ｎは繰り返し数を示す。）
【００２４】
前記構造式中のｎは該エポキシ樹脂の用途に応じて適宜設定し合成されるものであるが、０〜１０が好ましく、粘度が低く取り扱いが容易であることから０〜３が特に好ましい。
【００２５】
前記エポキシ樹脂（Ａ）を製造する方法は、特に限定されるものではないが、例えば、前述の方法で得られた４置換ジヒドロキシベンゼン類（ａ）とエピハロヒドリンとの溶解混合物にアルカリ金属水酸化物を添加し、または添加しながら２０〜１２０℃で１〜１０時間反応させ、必要に応じて、溶媒を用いてグリシジル化反応を行う方法が挙げられる。
【００２６】
前記エピハロヒドリンとしては特に限定されるものではないが、例えば、エピクロルヒドリン、β−メチルエピクロルヒドリン、エピブロモヒドリン、β−メチルエピブロモヒドリン等が挙げられる。これらの中でも反応性の点からエピクロルヒドリンが好ましい。
【００２７】
前記エピハロヒドリンの添加量は、原料の４置換ジヒドロキシベンゼン類（ａ）中の水酸基１当量に対して、０．３〜１０当量の範囲が好ましく、前記エポキシ樹脂（Ａ）の所望の特性に応じて、エピハロヒドリンの量を適宜調節することが出来るが、例えば、エピハロヒドリンが２．５当量よりも少ない場合には、エポキシ基と未反応の４置換ジヒドロキシベンゼン類（ａ）との反応が起こり、−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−を多く含む高分子量物が得られ、２．５当量以上の場合には、低分子量物、例えば上記構造式（５−１）、（５−２）中のｎ＝０の化合物の含有量が高くなり、低粘度の液状エポキシ樹脂が得られる。
【００２８】
前記アルカリ金属水酸化物としては特に限定されるものではないが、水酸化カリウム、水酸化ナトリウム、水酸化バリウム、酸化マグネシウム、炭酸ナトリウム、炭酸カリウム等が挙げられ、これらの中でも水酸化カリウム、水酸化ナトリウムが好ましい。また、これらは水溶液、固形のいずれでも好適に用いることが出来る。
【００２９】
前記アルカリ金属水酸化物を水溶液として使用する場合は、該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に減圧下、または常圧下連続的に水及びエピハロヒドリンを留出させ、更に分液し水は除去しエピハロヒドリンは反応系内に連続的に戻す方法が挙げられる。
【００３０】
前記溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、ブタノールなどのアルコール類、アセトン、メチルエチルケトンなどのケトン類、ジオキサンなどのエーテル類、ジメチルスルホン、ジメチルスルホキシド等の非プロトン性極性溶媒などが挙げられる。
【００３１】
前記アルコール類、エーテル類を溶媒とする場合の使用量は、エピハロヒドリン１００重量部対し、通常５〜５０重量部、特に１０〜３０重量部であることが好ましい。また非プロトン性極性溶媒を用いる場合の使用量は、エピハロヒドリン１００重量部に対し、通常５〜１００重量部、特に１０〜６０重量部であることが好ましい。
【００３２】
また、４置換ジヒドロキシベンゼン類（ａ）とエピハロヒドリンの溶解混合物にテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の４級アンモニウム塩を触媒として添加し、５０〜１５０℃で１〜５時間反応させて得られる４置換ジヒドロキシベンゼン類（ａ）のハロヒドリンエーテル化物に、前記アルカリ金属水酸化物の固体または水溶液を加え、再び２０〜１２０℃で１〜１０時間反応させ脱ハロゲン化水素（閉環）させる方法でもよい。
【００３３】
次いで、前述のグリシジル化反応で得られた反応物を水洗後、または水洗無しに加熱減圧下、１１０〜２５０℃、圧力１０ｍｍＨｇ以下でエピハロヒドリンや他の添加溶媒などを除去することにより、粗エポキシ樹脂が得られる。
【００３４】
更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、エピハロヒドリン等を回収した後に得られる前記粗エポキシ樹脂を再びトルエン、メチルイソブチルケトンなどの溶剤に溶解し、前記アルカリ金属水酸化物の水溶液を加えて更に反応させて閉環を確実なものにする、再閉環反応を行うこともできる。この場合、アルカリ金属水酸化物の使用量は粗エポキシ樹脂中に残存する加水分解性塩素１モルに対して、０．５〜１０モル、特に１．２〜５．０モル使用することが好ましい。
【００３５】
前記再閉環反応の反応条件は特に限定されるものではないが、反応温度は５０〜１２０℃、反応時間は０．５〜３時間であることが好ましい。更に反応速度の向上を目的として、４級アンモニウム塩やクラウンエーテル等の相関移動触媒を用いることも出来る。前記相関移動触媒を使用する場合のその使用量は、粗エポキシ樹脂１００重量部に対して０．１〜３．０重量部の範囲が好ましい。
【００３６】
再閉環反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトンなどの溶剤を留去することにより高純度化することが出来る。
【００３７】
本発明で用いる硬化剤（Ｂ）は、種々のエポキシ樹脂用硬化剤が使用でき、アミン系化合物、酸無水物系化合物、アミド系化合物、フェノ−ル系化合物などのエポキシ樹脂用硬化剤が挙げられる。
【００３８】
具体的には、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニル変性フェノールアラルキル樹脂、フェノールトリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂、アミノトリアジン変性フェノール樹脂等を始めとする多価フェノール化合物、及びこれらの変性物、イミダゾ−ル、ＢＦ_３−アミン錯体、並びにグアニジン誘導体などが挙げられる。またこれらの硬化剤は単独で用いてもよく、２種以上を混合してもよい。
【００３９】
これらの硬化剤のなかでも、特に耐熱性が優れる点では、例えば、フェノールノボラック樹脂、ナフトールノボラック樹脂、フェノールトリメチロールメタン樹脂が特に好ましく、耐湿性が優れる点では、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニル変性フェノールアラルキル樹脂が特に好ましく、難燃性が優れる点では、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニル変性フェノールアラルキル樹脂、アミノトリアジン変性フェノール樹脂が特に好ましい。
【００４０】
前記硬化剤（Ｂ）の使用量は、硬化反応が充分で、硬化物性が良好となる点から、エポキシ樹脂のエポキシ基１当量に対して、硬化剤中の活性水素基が０．７〜１．５当量になる範囲が好ましい。
【００４１】
また、硬化促進剤を適宜使用することもできる。硬化促進剤としては特に限定されるものではなく、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。半導体封止材料、電子回路基板用樹脂組成物として使用する場合は、リン系化合物ではトリフェニルフォスフィン、第３級アミンでは１，８−ジアザビシクロ−［５，４，０］−ウンデセン（ＤＢＵ）などが、硬化性、耐熱性、電気特性、耐湿信頼性などが優れるために好ましい。
【００４２】
本発明のエポキシ樹脂組成物には、上記した各成分に加え、更にその他のエポキシ樹脂を併用して使用することもできる。併用する場合の混合比は、得られる硬化物の耐熱性と耐湿性のバランスが良好である点から、エポキシ樹脂（Ａ）の全エポキシ樹脂に占める割合が３０〜９０重量％が好ましく、特に４０〜８０重量％が好ましい。
【００４３】
前記その他のエポキシ樹脂としては、特に制限されるものではなく、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、レゾルシン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、カテコール型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂等の液状エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂、ブロム化フェノールノボラック型エポキシ樹脂などが挙げられ、これらの中でも粘度が低く、且つ硬化性が良好である点から、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂が好ましい。またこれらのその他のエポキシ樹脂は単独で用いてもよく、２種以上を混合してもよい。
【００４４】
また本発明のエポキシ樹脂組成物は必要に応じて、無機充填剤、難燃付与剤、顔料、シランカップリング剤、離型剤等の種々の配合剤を添加することができる。
【００４５】
前記無機充填材としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。該充填材の配合量を特に大きくする場合は溶融シリカを用いるのが好ましく、溶融シリカとしては破砕状、球状のいずれでも使用可能であるが、配合量を高め且つ成形材料の溶融粘度の上昇を抑制するためには、球状のものを主に用いる方が特に好ましい。更に球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調製し、平均粒径が５〜３０μｍにすることが好ましい。その充填率は難燃性が良好となる点から、エポキシ樹脂組成物の全体量に対して６５〜９２重量％が特に好ましい。また導電ペーストなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることもできる。
【００４６】
前記難燃付与剤としては特に制限されるものではなく、ハロゲン化合物、燐原子含有化合物や窒素原子含有化合物や無機系難燃化合物などが挙げられる。具体的には、テトラブロモビスフェノールＡ型エポキシ樹脂などのハロゲン化合物、赤燐、燐酸エステル化合物などの燐原子含有化合物、メラミンなどの窒素原子含有化合物、水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、硼酸カルシウムなどの無機系難燃化合物が挙げられる。
【００４７】
本発明のエポキシ樹脂組成物の使用用途としては、半導体封止材料、積層板や電子回路基板等に用いられる樹脂組成物、樹脂注型材料、接着剤、ビルドアップ基板用層間絶縁材料、絶縁塗料等のコーティング材料等が挙げられ、これらの中でも、半導体封止材料、電子回路基板用樹脂組成物に好適に用いることができる。
【００４８】
前記半導体封止材材料は、本発明のエポキシ樹脂組成物及び前述の無機充填材、必要に応じその他の成分を押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合して製造することができる。ここで用いる充填剤は、シリカが好ましい。また、無機充填材の使用量は通常、充填率３０〜９５重量％となる範囲であり、難燃性や耐湿性や耐ハンダクラック性の向上、線膨張係数の低下を図るためには、好ましくは７０〜９５重量％、それらの効果を顕著なものとするには８０〜９５重量％であることが特に好ましい。
【００４９】
前記電子回路基板用樹脂組成物は、本発明のエポキシ樹脂組成物をトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン等の溶剤に溶解させることにより製造することができる。この際の溶剤の使用量は、前記電子回路基板用樹脂組成物中、通常１０〜７０重量％であり、好ましくは１５〜６５重量％、特に好ましくは３５〜６５重量％なる範囲である。なお、前記電子回路基板は、具体的には、プリント配線基板、プリント回路板、フレキシブルプリント配線板、ビルドアップ配線板等が挙げられる。
【００５０】
また、本発明のエポキシ樹脂組成物を接着剤や塗料等のコーティング材料として使用する場合は、該組成物を溶融してコーティングしても良いし、該組成物を前記溶剤に溶解したものを通常の方法でコーティングした後、溶剤を乾燥除去させ硬化させても良い。この際、必要に応じて、前記硬化触媒を使用してもよい。また、前記の無機フィラー等を混合しても良い。
【００５１】
本発明の成形硬化物は、前記エポキシ樹脂組成物を成形熱硬化させて得ることができる。該硬化物は積層物、注型物、接着剤、塗膜、フィルムとして使用できる。例えば、半導体封止材料の硬化物を得る方法としては、該組成物を注型、或いはトランスファ−成形機、射出成形機などを用いて成形し、さらに８０〜２００℃で２〜１０時間に加熱する方法が挙げられる。また、電子回路基板用樹脂組成物の硬化物を得る方法としては、電子回路基板用樹脂組成物をガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させ加熱乾燥してプリプレグを得て積層した後、それを熱プレス成形する方法が挙げられる。
【００５２】
【実施例】
次に本発明を実施例、比較例により具体的に説明するが、以下において部、％は特に断わりのない限り重量基準である。
【００５３】
実施例１
▲１▼４置換ジヒドロキシベンゼンの合成
温度計、滴下ロート、冷却および撹拌機を取り付けたフラスコに窒素ガスパージを施しながら、トリメチルハイドロキノン１５２ｇ（１．０モル）をメチルイソブチルケトン１５０ｇに溶解し、パラトルエンスルホン酸１水和物１．５ｇを加えて８０℃まで昇温した後に、スチレンモノマー１１４ｇ（１．１モル）を発熱に注意しながら１時間要して滴下した。滴下終了後、１３５℃で１０時間反応を続けた後に、５％ＮａＯＨを添加して触媒を中和失活させた。その後、水洗によって、系内から副生塩を除去し、最後にメチルイソブチルケトンを蒸留除去することにより、下記構造式（６）で示される、４置換ジヒドロキシベンゼン２０５ｇを得た。
【化８】

【００５４】
▲２▼エポキシ樹脂の合成
温度計、滴下ロート、冷却管および撹拌機を取り付けたフラスコに窒素ガスパージを施しながら、▲１▼で得られた４置換ジヒドロキシベンゼン１２８ｇ（水酸基１．０当量）、エピクロルヒドリン４６３ｇ（５．０モル）、ジメチルスルホキシド５３ｇを仕込み溶解させた。６５℃に昇温した後に、共沸する圧力までに減圧して、４９％水酸化ナトリウム水溶液８２ｇ（１．０モル）を５時間かけて滴下した、次いでこの条件下で０．５時間撹拌を続けた。この間、共沸で留出してきた留出分をディーンスタークトラップで分離して、水層を除去し、有機層を反応系内に戻しながら反応した。その後、未反応のエピクロルヒドリンを減圧蒸留して留去させた。それで得られた粗エポキシ樹脂にメチルイソブチルケトン５５０ｇを加えて溶解し、水１００ｇを用いた水洗を５回繰り返してジメチルスルホキシドを除去した。次いでそれにｎ−ブタノール５５ｇを加え溶解した。更にこの溶液に１０％水酸化ナトリウム水溶液１５ｇを添加して８０℃で２時間反応させた後に洗浄液のＰＨが中性となるまで水１００ｇを用いた水洗を３回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去して下記構造式（７）で示されるエポキシ樹脂（α）１７０ｇを得た。得られたエポキシ樹脂は、常温で粘凋液体であり、そのエポキシ当量は２０８ｇ／ｅｑ．であった。エポキシ当量から式中のｎは０．１６であることが確認された。
【化９】

【００５５】
▲３▼エポキシ樹脂組成物の調製
▲２▼で得られたエポキシ樹脂（α）１９９部、硬化剤として、フェノールノボラック樹脂（ＰＨＥＮＯＬＩＴＥ　ＴＤ−２１３１：大日本インキ化学工業（株）製、軟化点８０℃、水酸基当量１０４ｇ／ｅｑ．）１０４部、硬化促進剤として、トリフェニルフォスフィン（ＴＰＰ）３部を配合し、１００℃の温度で激しく撹拌混練して目的のエポキシ樹脂組成物（ｉ）を得た。
【００５６】
比較例１
エポキシ樹脂（α）１９９部の代わりにビスフェノールＡ型エポキシ樹脂（ＥＰＩＣＬＯＮ　８５０Ｓ：大日本インキ化学工業（株）製、エポキシ当量１８８ｇ／ｅｑ．）１８３部を用いた以外は、実施例１―▲３▼と同様にして、エポキシ樹脂組成物（ｉｉ）を得た。
【００５７】
比較例２
エポキシ樹脂（α）１９９部の代わりにジヒドロキシナフタレン型エポキシ樹脂（ＥＰＩＣＬＯＮ　ＨＰ−４０３２、エポキシ当量１６０ｇ／ｅｑ．）１６０部を用いた以外は、実施例１−▲３▼と同様にしてエポキシ樹脂組成物（ｉｉｉ）を得た。
【００５８】
試験例１および比較試験例１〜２
実施例１、比較例１〜２で得られた組成物をそれぞれ１５０℃で１０分間プレス成形し，その後１７５℃で５時間さらに硬化せしめた後に試験片（サイズ　２．５ｍｍ×２５ｍｍ×７５ｍｍ）を作成した。得られた試験片のガラス転移温度（動的粘弾性法）と吸湿率の試験結果を第１表に示す。なお、吸湿率は８５℃・８５％ＲＨの恒温恒湿機内で３００時間処理し、その後の重量増加量を処理前の重量で除した値である。
【表１】

【００５９】
【発明の効果】
本発明によれば、優れた耐熱性と耐湿性が求められる、半導体封止材料、電子回路基板用マトリックス樹脂、樹脂注型材料、接着剤、ビルドアップ基板用層間絶縁材料、絶縁塗料等のコーティング材料等として好適に用いることができるエポキシ樹脂組成物、その成形硬化物、半導体封止材料および電子回路基板用樹脂組成物を提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is a coating material such as a semiconductor sealing material, a resin composition for an electronic circuit board, a resin casting material, an adhesive, an interlayer insulating material for a build-up board, an insulating paint, etc., which require excellent heat resistance and moisture resistance. The present invention relates to an epoxy resin composition, a molded cured product thereof, a semiconductor encapsulating material, and a resin composition for an electronic circuit board, which can be suitably used as such.
[0002]
[Prior art]
Epoxy resins can be cured with various curing agents to give cured products with excellent mechanical properties, moisture resistance, chemical resistance, heat resistance, and electrical properties. It is used in a wide range of fields such as materials and casting materials. Above all, low-viscosity epoxy resin is excellent in workability, fluidity, etc., and in addition to the above general-purpose fields, liquid sealing materials such as glove top materials and underfill materials for semiconductor devices, die attach materials for semiconductors, It is also used for members requiring high reliability, such as a conductive paste material for electrical connection between layers of a density circuit board. A typical example of the low-viscosity epoxy resin is a bisphenol A-type epoxy resin. In addition, as a special epoxy resin having excellent heat resistance, a dihydroxynaphthalene-type epoxy resin is also used in a special field (Japanese Patent Application Laid-Open No. 2001-2001). No. 11286). In recent years, in the field of electronics such as semiconductor encapsulants and printed wiring boards, there has been a strong demand for epoxy resins having both excellent heat resistance and moisture resistance in a well-balanced manner.
[0003]
However, the bisphenol A type epoxy resin described above has poor heat resistance and cannot satisfy the above requirements. Further, the above-mentioned dihydroxynaphthalene type epoxy resin has high heat resistance, but has a high moisture absorption rate, and the balance between the heat resistance and the moisture resistance is not at a satisfactory level.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a semiconductor sealing material, a resin composition for an electronic circuit board, a resin casting material, an adhesive, an interlayer insulating material for a build-up board, an insulating paint, etc., which are required to have excellent heat resistance and moisture resistance. An object of the present invention is to provide an epoxy resin composition which can be suitably used as a coating material and the like, a molded cured product thereof, a semiconductor encapsulating material and a resin composition for an electronic circuit board.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve such problems, and as a result, an epoxy resin composition containing an epoxy resin derived from a tetrasubstituted dihydroxy compound having a specific molecular structure has particularly excellent heat resistance and moisture resistance. It has been found that a cured product having both properties is provided, and the present invention has been completed.
[0006]
That is, the present invention relates to a method for preparing a 4-substituted dihydroxybenzenes (a) having at least one substituent selected from the group consisting of a benzyl group, a 1-phenylethyl group, and a 1-methyl-1-phenylethyl group and epihalohydrin. An epoxy resin composition comprising an epoxy resin (A) to be derived and a curing agent (B).
Further, the present invention provides a molded cured product obtained by molding and curing the epoxy resin composition, and a semiconductor encapsulating material and a resin composition for electronic circuit boards, characterized by containing the epoxy resin composition. Is what you do.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the epoxy resin composition of the present invention is 4-substituted having at least one substituent selected from the group consisting of a benzyl group, a 1-phenylethyl group, and a 1-methyl-1-phenylethyl group. An epoxy resin derived from dihydroxybenzenes (a) and epihalohydrin may be used, and is not particularly limited.
[0008]
Although the structure of the 4-substituted dihydroxybenzenes (a) is not particularly limited, for example, the following general formula (1)
Embedded image

[Wherein, R ¹ ~ R ⁶ Is independently a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 1 to 6 carbon atoms, an aryl group, a halogen atom, or the following general formula (2)
Embedded image

(Where R ⁷ , R ⁸ Each independently represents a hydrogen atom or a methyl group. )
And two of these substituents are always hydroxy groups, and one is always a group represented by the general formula (2). ]
Are represented.
[0009]
Among them, a compound in which two hydroxy groups and one substituent other than one substituent represented by the above general formula (2) are all methyl groups is preferable, and for example, a compound represented by the following structural formula (3) -1) to (3-5).
Embedded image

[0010]
The method for producing the 4-substituted dihydroxybenzenes (a) is not particularly limited. For example, a 3-substituted dihydroxybenzene compound (a1) and an aromatic monovinyl compound (a2) or a leaving group at the benzyl position may be used. By reacting the compound with the benzyl compound (a3).
[0011]
The structure of the trisubstituted dihydroxybenzene compound (a1) is not particularly limited, and for example, the following general formula (4)
Embedded image

(Where R ⁹ ~ R ¹² Each independently represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 1 to 6 carbon atoms, an aryl group or a halogen atom, and one of them is always a hydroxy group. )
The compound represented by is mentioned.
[0012]
Specific examples of the trisubstituted dihydroxybenzene compound (a1) include trimethylhydroquinone, 2,4,5-trimethylresorcin, 4,5,6-trimethylresorcin, 3,4,5-trimethylcatechol, and 3,5 2,6-trimethylcatechol, triethylhydroquinone, 2,4,5-triethylresorcin, 4,5,6-triethylresorcin, 3,4,5-triethylcatechol, 3,5,6-triethylcatechol, tripropylhydroquinone, 2 4,4,5-tripropyl resorcinol, 4,5,6-tripropyl resorcinol, 3,4,5-tripropyl catechol, 3,5,6-tripropyl catechol, tributyl hydroquinone, 2,4,5-tributyl resorcinol , 4,5,6-tributylresorcin, 3,4,5 Trialkyl-substituted dihydroxybenzenes such as tributylcatechol and 3,5,6-tributylcatechol; triarylsubstituted hydroquinones such as triphenylhydroquinone and 2,4,5-triphenylresorcin; and trihalogen-substituted dihydroxy such as tribromohydroquinone. Examples thereof include benzenes. Among them, trimethylhydroquinone is particularly preferable because of its excellent balance between heat resistance and moisture resistance.
[0013]
The aromatic monovinyl compound (a2) is not particularly limited as long as it is a compound in which one vinyl group is bonded to an aromatic ring, and examples thereof include styrene and methylstyrene. Examples of the benzyl compound having a group (a3) include benzyl halide compounds such as benzyl chloride, benzyl bromide, and benzyl iodide, benzyl alcohol, and benzyl methoxide.
[0014]
Among these aromatic monovinyl compounds (a2) and benzyl compounds having a leaving group at the benzyl position (a3), styrene, benzyl chloride, benzyl bromide are preferred because they are industrially available and hardly cause side reactions. Is preferred.
[0015]
The reaction between the trisubstituted dihydroxybenzene compound (a1) and the aromatic monovinyl compound (a2) or the benzyl compound having a leaving group at the benzyl position (a3) will be described below.
[0016]
First, a trisubstituted dihydroxybenzene compound (a1) and an aromatic monovinyl compound (a2) are charged, and a substituent on an aromatic ring of the trisubstituted dihydroxybenzene compound (a1) is added as necessary using a reaction catalyst or an organic solvent. Addition reaction with one of the groups without the vinyl group.
[0017]
Similarly, when the trisubstituted dihydroxybenzene compound (a1) is reacted with a benzyl compound (a3) having a leaving group at the benzyl position, the benzyl compound having a leaving group at the benzyl position is also reacted with the trisubstituted dihydroxybenzene compound (a1). The compound (a3) was charged, and if necessary, a reaction catalyst or an organic solvent was used to dehydrate, dehalogenate, and remove one unsubstituted position on the aromatic ring of the 3-substituted dihydroxybenzene compound (a1) from the benzyl position. A condensation reaction such as a dealcoholation reaction is performed.
[0018]
After the completion of the reaction, if necessary, neutralize with a basic compound such as caustic soda, sodium bicarbonate, ammonia, and triethylamine, or deactivate the reaction catalyst by washing or the like, and then remove the organic solvent by distillation or the like. Then, the resultant is purified by recrystallization or the like to obtain the 4-substituted dihydroxybenzenes (a).
[0019]
Examples of the catalyst include hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, and boron trifluoride etherate And boron trifluoride phenol complex. Among them, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid are preferred from the viewpoint of a high reaction rate. The amount of the catalyst added is 100 parts by weight based on the total amount of the trisubstituted dihydroxybenzene compound (a1) and the aromatic monovinyl compound (a2) or the benzyl compound having a leaving group at the benzyl position (a3). It is preferably in the range of 0.01 to 10 parts by weight.
[0020]
As the organic solvent, a trisubstituted dihydroxybenzene compound (a1), an aromatic monovinyl compound (a2) or a benzyl compound having a leaving group at the benzyl position (a3), and a product are dissolved. It is not particularly limited as long as it is inert, for example, benzene, toluene, aromatic organic solvents such as xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone organic solvents such as cyclohexanone, methanol, ethanol, Examples include alcohol-based organic solvents such as isopropyl alcohol and normal butanol, and ether-based organic solvents such as diethyl ether, tetrahydrofuran, dioxane, and methoxyethanol. Select accordingly Although Rukoto can, especially aromatic organic solvents, ketone-based organic solvents preferably used.
[0021]
The amount of the organic solvent to be used is not particularly limited, but a trisubstituted dihydroxybenzene compound (a1) and an aromatic monovinyl compound (a2) or a benzyl compound having a leaving group at the benzyl position (a3) Is preferably in the range of 10 to 500 parts by weight with respect to 100 parts by weight in total. As reaction conditions, the mixture is heated and stirred at a temperature of room temperature to 200 ° C, preferably 50 to 150 ° C for 0.5 to 30 hours.
[0022]
The epoxy resin (A) used in the present invention is derived from the tetrasubstituted dihydroxybenzenes (a) obtained as described above and epihalohydrin, and the structure thereof is not particularly limited. And those represented by the following structural formulas (5-1) to (5-2).
[0023]
Embedded image

(In the formula, n indicates the number of repetitions.)
[0024]
N in the above structural formula is appropriately set and synthesized according to the use of the epoxy resin, but is preferably from 0 to 10, and particularly preferably from 0 to 3 since viscosity is low and handling is easy.
[0025]
The method for producing the epoxy resin (A) is not particularly limited. For example, an alkali metal hydroxide may be added to the dissolved mixture of the tetrasubstituted dihydroxybenzenes (a) and epihalohydrin obtained by the above method. Or a reaction at 20 to 120 ° C. for 1 to 10 hours while adding glycidylation reaction, if necessary, using a solvent.
[0026]
The epihalohydrin is not particularly restricted but includes, for example, epichlorohydrin, β-methylepichlorohydrin, epibromohydrin, β-methylepibromohydrin and the like. Of these, epichlorohydrin is preferred from the viewpoint of reactivity.
[0027]
The addition amount of the epihalohydrin is preferably in the range of 0.3 to 10 equivalents relative to 1 equivalent of the hydroxyl group in the raw material of the 4-substituted dihydroxybenzenes (a), depending on the desired properties of the epoxy resin (A). The amount of epihalohydrin can be appropriately adjusted. For example, when epihalohydrin is less than 2.5 equivalents, a reaction between the epoxy group and the unreacted 4-substituted dihydroxybenzenes (a) occurs, and -CH ₂ CH (OH) CH ₂ A high molecular weight product containing a large amount of-is obtained, and when it is 2.5 equivalents or more, the content of a low molecular weight product, for example, the compound of n = 0 in the above structural formulas (5-1) and (5-2) And a low-viscosity liquid epoxy resin is obtained.
[0028]
The alkali metal hydroxide is not particularly limited, but includes potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate and the like. Among these, potassium hydroxide, water Sodium oxide is preferred. In addition, these can be suitably used as either an aqueous solution or a solid.
[0029]
When the alkali metal hydroxide is used as an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system under reduced pressure, or water and epihalohydrin are continuously distilled off under normal pressure, Further, there is a method in which water is separated and epihalohydrin is continuously returned into the reaction system.
[0030]
Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane; and aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide. .
[0031]
When the alcohols or ethers are used as the solvent, the amount used is generally 5 to 50 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of epihalohydrin. When the aprotic polar solvent is used, the amount used is usually preferably 5 to 100 parts by weight, particularly preferably 10 to 60 parts by weight, per 100 parts by weight of epihalohydrin.
[0032]
A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the 4-substituted dihydroxybenzenes (a) and epihalohydrin, and the mixture is added at 50 to 150 ° C. for 1 to 5 times. A solid or aqueous solution of the above alkali metal hydroxide is added to the halohydrin etherified product of the tetrasubstituted dihydroxybenzenes (a) obtained by reacting for 4 hours, and the mixture is reacted again at 20 to 120 ° C. for 1 to 10 hours to dehalogenate. A method of hydrogen (ring closure) may be used.
[0033]
Next, after washing the reaction product obtained in the above-mentioned glycidylation reaction with water or without heating, under heating and reduced pressure at 110 to 250 ° C. and at a pressure of 10 mmHg or less, epihalohydrin and other additional solvents are removed to obtain a crude epoxy resin. Is obtained.
[0034]
Further, in order to make the epoxy resin less hydrolyzable halogen, the crude epoxy resin obtained after collecting epihalohydrin and the like is dissolved again in a solvent such as toluene and methyl isobutyl ketone, and an aqueous solution of the alkali metal hydroxide is added. In addition, a re-closure reaction may be carried out to further secure the ring closure. In this case, the amount of the alkali metal hydroxide to be used is preferably 0.5 to 10 mol, particularly preferably 1.2 to 5.0 mol, per mol of the hydrolyzable chlorine remaining in the crude epoxy resin. .
[0035]
The reaction conditions for the ring closure reaction are not particularly limited, but the reaction temperature is preferably 50 to 120 ° C., and the reaction time is preferably 0.5 to 3 hours. For the purpose of further improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether can be used. When the phase transfer catalyst is used, its use amount is preferably in the range of 0.1 to 3.0 parts by weight based on 100 parts by weight of the crude epoxy resin.
[0036]
After completion of the ring closure reaction, the resulting salt is removed by filtration, washing with water, or the like, and the solvent can be further purified by distilling off a solvent such as toluene or methyl isobutyl ketone under reduced pressure with heating.
[0037]
As the curing agent (B) used in the present invention, various curing agents for epoxy resins can be used, and examples thereof include curing agents for epoxy resins such as amine compounds, acid anhydride compounds, amide compounds and phenol compounds. Can be
[0038]
Specifically, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromethylene anhydride Modified melitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin Phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified Enol aralkyl resins, phenol trimethylol methane resins, tetraphenylol ethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, aminotriazine-modified phenol resins and the like Polyhydric phenol compounds, their modified products, imidazole, BF ₃ -Amine complexes, and guanidine derivatives. These curing agents may be used alone or in combination of two or more.
[0039]
Among these curing agents, particularly in terms of excellent heat resistance, for example, phenol novolak resin, naphthol novolak resin, phenol trimethylol methane resin is particularly preferred, and in terms of excellent moisture resistance, phenol aralkyl resin, cresol aralkyl resin, A naphthol aralkyl resin and a biphenyl-modified phenol aralkyl resin are particularly preferred, and phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, biphenyl-modified phenol aralkyl resins, and aminotriazine-modified phenol resins are particularly preferred in terms of excellent flame retardancy.
[0040]
The amount of the curing agent (B) used is such that the amount of the active hydrogen groups in the curing agent is 0.7 to 1 with respect to one equivalent of the epoxy group of the epoxy resin, since the curing reaction is sufficient and the cured properties are good. A range of 0.5 equivalent is preferred.
[0041]
Further, a curing accelerator can be appropriately used. The curing accelerator is not particularly limited, and examples thereof include a phosphorus compound, a tertiary amine, imidazole, a metal salt of an organic acid, a Lewis acid, and an amine complex. When used as a semiconductor sealing material or a resin composition for an electronic circuit board, triphenylphosphine is used for a phosphorus compound, and 1,8-diazabicyclo- [5,4,0] -undecene (DBU) is used for a tertiary amine. And the like are preferable because of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability and the like.
[0042]
In the epoxy resin composition of the present invention, in addition to the above-described components, other epoxy resins can be used in combination. When used in combination, the proportion of the epoxy resin (A) in the total epoxy resin is preferably 30 to 90% by weight, and particularly preferably 40 to 40, because the balance between the heat resistance and the moisture resistance of the obtained cured product is good. ~ 80% by weight is preferred.
[0043]
The other epoxy resin is not particularly limited. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, resorcinol epoxy resin, hydroquinone epoxy resin Liquid epoxy resin such as resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetra Phenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy Resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolak epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin epoxy resin, biphenyl-modified novolak epoxy resin, tetrabromo Bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin and the like can be mentioned. Among them, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoint of low viscosity and good curability. These other epoxy resins may be used alone or in combination of two or more.
[0044]
The epoxy resin composition of the present invention may contain various additives such as an inorganic filler, a flame retardant, a pigment, a silane coupling agent, and a release agent, if necessary.
[0045]
Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. When the blending amount of the filler is particularly large, it is preferable to use fused silica. As the fused silica, any of crushed and spherical forms can be used, but the blending amount is increased and the melt viscosity of the molding material is increased. In order to suppress this, it is particularly preferable to mainly use spherical particles. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica so that the average particle diameter is 5 to 30 μm. The filling rate is particularly preferably 65 to 92% by weight based on the total amount of the epoxy resin composition, since the flame retardancy becomes good. When used for applications such as conductive paste, conductive fillers such as silver powder and copper powder can also be used.
[0046]
The flame retardant is not particularly limited, and examples thereof include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specifically, halogen compounds such as tetrabromobisphenol A type epoxy resin, phosphorus atom-containing compounds such as red phosphorus and phosphoric ester compounds, nitrogen atom-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, boric acid Inorganic flame retardant compounds such as calcium.
[0047]
Uses of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminated boards and electronic circuit boards, resin casting materials, adhesives, interlayer insulating materials for build-up boards, insulating paints And the like, and among them, these can be suitably used for a semiconductor sealing material and a resin composition for an electronic circuit board.
[0048]
The semiconductor encapsulant material is thoroughly mixed with the epoxy resin composition of the present invention, the above-mentioned inorganic filler, and other components as necessary, using an extruder, a kneader, a roll, or the like, until they become uniform. Can be manufactured. The filler used here is preferably silica. The amount of the inorganic filler is usually in the range of 30 to 95% by weight, and is preferably used in order to improve flame retardancy, moisture resistance, solder crack resistance, and decrease the coefficient of linear expansion. Is particularly preferably from 70 to 95% by weight, and more preferably from 80 to 95% by weight in order to make their effects remarkable.
[0049]
The resin composition for an electronic circuit board can be produced by dissolving the epoxy resin composition of the present invention in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, and methyl isobutyl ketone. The amount of the solvent used at this time is usually 10 to 70% by weight, preferably 15 to 65% by weight, particularly preferably 35 to 65% by weight in the resin composition for an electronic circuit board. The electronic circuit board specifically includes a printed wiring board, a printed circuit board, a flexible printed wiring board, a build-up wiring board, and the like.
[0050]
When the epoxy resin composition of the present invention is used as a coating material such as an adhesive or a paint, the composition may be melted and coated, or a composition obtained by dissolving the composition in the solvent is usually used. After coating by the method described above, the solvent may be removed by drying to be cured. At this time, the curing catalyst may be used as needed. Further, the above-mentioned inorganic filler and the like may be mixed.
[0051]
The molded cured product of the present invention can be obtained by molding and thermosetting the epoxy resin composition. The cured product can be used as a laminate, a cast, an adhesive, a coating, or a film. For example, as a method of obtaining a cured product of a semiconductor encapsulating material, the composition is cast or molded using a transfer molding machine, an injection molding machine, and the like, and further heated at 80 to 200 ° C. for 2 to 10 hours. Method. As a method for obtaining a cured product of the resin composition for an electronic circuit board, a method of impregnating the resin composition for an electronic circuit board into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and heating. After drying to obtain a prepreg and laminating it, there is a method of hot press molding.
[0052]
【Example】
Next, the present invention will be described in detail with reference to Examples and Comparative Examples. In the following, parts and percentages are by weight unless otherwise specified.
[0053]
Example 1
(1) Synthesis of 4-substituted dihydroxybenzene
While applying a nitrogen gas purge to a flask equipped with a thermometer, a dropping funnel, a cooling and a stirrer, 152 g (1.0 mol) of trimethylhydroquinone was dissolved in 150 g of methyl isobutyl ketone, and 1.5 g of paratoluenesulfonic acid monohydrate was obtained. Was added and the temperature was raised to 80 ° C., and 114 g (1.1 mol) of styrene monomer was added dropwise over 1 hour while paying attention to heat generation. After completion of the dropwise addition, the reaction was continued at 135 ° C. for 10 hours, and then 5% NaOH was added to neutralize and deactivate the catalyst. Thereafter, by-product salts were removed from the system by washing with water, and finally methyl isobutyl ketone was distilled off to obtain 205 g of a 4-substituted dihydroxybenzene represented by the following structural formula (6).
Embedded image

[0054]
(2) Synthesis of epoxy resin
A nitrogen gas purge was applied to a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, while 128 g of the 4-substituted dihydroxybenzene obtained in (1) (1.0 equivalent of hydroxyl group) and 463 g (5.0 mol) of epichlorohydrin were obtained. And 53 g of dimethyl sulfoxide were charged and dissolved. After the temperature was raised to 65 ° C., the pressure was reduced to an azeotropic pressure, and 82 g (1.0 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Then, stirring was performed under these conditions for 0.5 hour. Continued. During this period, the distillate distilled off azeotropically was separated by a Dean-Stark trap, and the aqueous layer was removed, and the reaction was performed while returning the organic layer into the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 550 g of methyl isobutyl ketone was added to and dissolved in the obtained crude epoxy resin, and washing with 100 g of water was repeated 5 times to remove dimethyl sulfoxide. Next, 55 g of n-butanol was added and dissolved therein. Further, 15 g of a 10% aqueous sodium hydroxide solution was added to the solution, and the mixture was reacted at 80 ° C. for 2 hours. Thereafter, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Then, the system was dehydrated by azeotropic distillation and after microfiltration, the solvent was distilled off under reduced pressure to obtain 170 g of an epoxy resin (α) represented by the following structural formula (7). The obtained epoxy resin is a viscous liquid at room temperature and has an epoxy equivalent of 208 g / eq. Met. From the epoxy equivalent, it was confirmed that n in the formula was 0.16.
Embedded image

[0055]
(3) Preparation of epoxy resin composition
199 parts of the epoxy resin (α) obtained in (2), and a phenol novolak resin (PHENOLITE TD-2131: manufactured by Dainippon Ink and Chemicals, softening point 80 ° C, hydroxyl equivalent 104 g / eq.) As a curing agent 104 parts and 3 parts of triphenylphosphine (TPP) as a curing accelerator were blended and vigorously stirred and kneaded at a temperature of 100 ° C. to obtain a desired epoxy resin composition (i).
[0056]
Comparative Example 1
Example 1- ▲ 3, except that 183 parts of a bisphenol A type epoxy resin (EPICLON 850S: manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 188 g / eq.) Was used instead of 199 parts of the epoxy resin (α). In the same manner as in ▼, an epoxy resin composition (ii) was obtained.
[0057]
Comparative Example 2
An epoxy resin composition was prepared in the same manner as in Example 1-3 except that 199 parts of the epoxy resin (α) was replaced by 160 parts of a dihydroxynaphthalene-type epoxy resin (EPICLON HP-4032, epoxy equivalent: 160 g / eq.). The product (iii) was obtained.
[0058]
Test Example 1 and Comparative Test Examples 1-2
Each of the compositions obtained in Example 1 and Comparative Examples 1 and 2 was press-molded at 150 ° C. for 10 minutes, and further cured at 175 ° C. for 5 hours, and then a test piece (size 2.5 mm × 25 mm × 75 mm) was obtained. Created. Table 1 shows the test results of the glass transition temperature (dynamic viscoelasticity method) and the moisture absorption rate of the obtained test pieces. The moisture absorption rate is a value obtained by treating for 300 hours in a thermo-hygrostat at 85 ° C. and 85% RH, and then dividing the weight increase by the weight before the treatment.
[Table 1]

[0059]
【The invention's effect】
According to the present invention, coating of a semiconductor sealing material, a matrix resin for an electronic circuit board, a resin casting material, an adhesive, an interlayer insulating material for a build-up board, an insulating paint, etc., in which excellent heat resistance and moisture resistance are required. An epoxy resin composition, a molded cured product thereof, a semiconductor encapsulating material, and a resin composition for electronic circuit boards that can be suitably used as a material or the like can be provided.

Claims (5)

Epoxy resin derived from a tetrasubstituted dihydroxybenzenes (a) having at least one substituent selected from the group consisting of a benzyl group, a 1-phenylethyl group and a 1-methyl-1-phenylethyl group, and epihalohydrin ( An epoxy resin composition comprising A) and a curing agent (B). 4-substituted dihydroxybenzenes (a) are represented by the following general formula (1)

[Wherein, R ^{1 to} R ⁶ each independently represent a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 1 to 6 carbon atoms, an aryl group, a halogen atom, or the following general formula (2)

(In the formula, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.)
And two of them are always hydroxy groups, and one is always a group represented by the general formula (2). ]
The epoxy resin composition according to claim 1, which is a compound represented by the formula: A molded cured product obtained by molding and curing the epoxy resin composition according to claim 1. A semiconductor encapsulating material comprising the epoxy resin composition according to claim 1. A resin composition for an electronic circuit board, comprising the epoxy resin composition according to claim 1.