JP4771445B2 - Insulating resin composition for electronic parts and adhesive sheet - Google Patents
Insulating resin composition for electronic parts and adhesive sheet Download PDFInfo
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- JP4771445B2 JP4771445B2 JP2001210262A JP2001210262A JP4771445B2 JP 4771445 B2 JP4771445 B2 JP 4771445B2 JP 2001210262 A JP2001210262 A JP 2001210262A JP 2001210262 A JP2001210262 A JP 2001210262A JP 4771445 B2 JP4771445 B2 JP 4771445B2
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Description
【0001】
【発明の属する技術分野】
本発明は、電子部品の組み立てに用いられる絶縁樹脂組成物に関する。
【0002】
【従来の技術】
電子部品用絶縁樹脂組成物には、従来エポキシ樹脂、硬化剤からなるエポキシ樹脂組成物が用いられている。
【0003】
【発明が解決しようとする課題】
近年チップ抵抗器、チップコンデンサ、チップインダクタなどの電子部品の小型化、軽量化に伴い、電子部品を構成する基材との接着性に優れ、熱接着時に接着層の形状変形が小さく、なお且つ硬化前後においてフレキシブル性があり、工程中取り扱いに優れる材料が求められている。
【0004】
【課題を解決するための手段】
本発明者らは前記した課題を解決すべく鋭意研究を重ねた結果、上記性能を同時に満足させる電子部品用絶縁樹脂組成物が得られることを見出し本発明を完成した。即ち、本発明は、
(1)エポキシ樹脂(a)、硬化剤(b)、並びに平均粒子径が1μm以下のコアシェル構造架橋ゴム(c)を含有し、コアシェル構造架橋ゴム(c)の含有量が樹脂分総量に対して60重量%以上95重量%以下であることを特徴とする電子部品用絶縁樹脂組成物、
(2)コアシェル構造架橋ゴム(c)のコア層が架橋ポリブタジエンであり、シェル層がアクリル酸アルキル−メタクリル酸アルキル共重合物である(1)に記載の電子部品用絶縁樹脂組成物、
(3)コアシェル構造架橋ゴム(c)のコア層が架橋ポリブタジエンであり、シェル層がメタクリル酸アルキル−スチレン共重合物である(1)に記載の電子部品用絶縁樹脂組成物、
(4)コアシェル構造架橋ゴム(c)のコア層が架橋アクリル酸アルキル共重合物であり、シェル層がアクリル酸アルキル共重合物である請求項(1)に記載の電子部品用絶縁樹脂組成物、
(5)(1)乃至(4)の何れか1項に記載の電子部品用絶縁樹脂組成物のシート、
(6)シートの厚みが5μm以上50μm以下で、なお且つ150℃、1MPaで加熱、加圧したときの辺部の樹脂変形量が100μm以下である(5)に記載の電子部品用絶縁樹脂組成物のシート、
(7)(1)乃至(6)の何れか一項に記載の電子部品用絶縁樹脂組成物又はシートの硬化物
に関する。
【0005】
【発明の実施の形態】
本発明の電子部品用絶縁樹脂組成物はエポキシ樹脂(a)、硬化剤(b)、並びに平均粒子径が1μm以下のコアシェル構造架橋ゴム(c)を含有する。
【0006】
本発明で用いられるエポキシ樹脂(a)は、分子内に2個以上のエポキシ基を持つ化合物であればどのようなものでも良く、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、脂環式エポキシ樹脂、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、グリシジルエステル系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ハロゲン化フェノール類をグリシジル化したエポキシ樹脂、エポキシ化ポリブタジエン等があげられるが、特にビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、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が好ましく、これらを2種類以上併用することも出来る。
【0007】
本発明で用いられる硬化剤(b)としては、例えばフタル酸無水物、トリメリット酸無水物、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物、エチレングリコール無水トリメリット酸無水物、ビフェニルテトラカルボン酸無水物等の芳香族カルボン酸無水物、アゼライン酸、セバシン酸、ドデカン二酸等の脂肪族カルボン酸の無水物、テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、ナジック酸無水物、ヘット酸無水物、ハイミック酸無水物等の脂環式カルボン酸無水物、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン、ジアミノジフェニルエーテル、p−フェニレンジアミン、m−フェニレンジアミン、o−フェニレンジアミン、1,5−ジアミノナフタレン、m−キシリレンジアミン等の芳香族アミン、エチレンジアミン、ジエチレンジアミン、イソフォロンジアミン、ビス(4−アミノ−3−メチルジシクロヘキシル)メタン、ポリエーテルジアミン等の脂肪族アミン、ジシアンジアミド、1−(o−トリル)ビグアニド等のグアニジン類、エポキシ樹脂のアミンアダクト、ビスフェノールA、ビスフェノールF、ビスフェノールS、4,4’−ビフェニルフェノール、テトラメチルビスフェノールA、ジメチルビスフェノールA、テトラメチルビスフェノールF、ジメチルビスフェノールF、テトラメチルビスフェノールS、ジメチルビスフェノールS、テトラメチル−4,4’−ビフェノール、ジメチル−4,4’−ビフェニルフェノール、1−(4−ヒドロキシフェニル)−2−[4−(1,1−ビス−(4−ヒドロキシフェニル)エチル)フェニル]プロパン、2,2’−メチレン−ビス(4−メチル−6−tert−ブチルフェノール)、4,4’−ブチリデン−ビス(3−メチル−6−tert−ブチルフェノール)、トリスヒドロキシフェニルメタン、レゾルシノール、ハイドロキノン、ピロガロール、ジイソプロピリデン骨格を有するフェノール類、1,1−ジ−4−ヒドロキシフェニルフルオレン等のフルオレン骨格を有するフェノール類、フェノール化ポリブタジエン、フェノール、クレゾール類、エチルフェノール類、ブチルフェノール類、オクチルフェノール類、ビスフェノールA、ビスフェノールF、ビスフェノールS、ナフトール類等の各種フェノールを原料とするノボラック樹脂、キシリレン骨格含有フェノールノボラック樹脂、ジシクロペンタジエン骨格含有フェノールノボラ・メチルイミダゾールイソシアヌル酸の2:3付加物、2−フェニルイミダゾールイソシアヌル酸付加物、2−フェニル−3,5−ジヒドロキシメチルイミダゾール、2−フェニル−4−ヒドロキシメチル−5−メチルイミダゾール、1−シアノエチル−2−フェニル−3,5−ジシアノエトキシメチルイミダゾールの各種イミダゾール類、及び、それらイミダゾール類とフタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸、ナフタレンジカルボン酸、マレイン酸、蓚酸等の多価カルボン酸との塩類、ジヒドラジド類、ルイス酸、ブレンステッド酸塩類、ポリメルカプトン類、イソシアネート類、ブロックイソシアネート類等が挙げられる。
【0008】
これら硬化剤のうち、どの硬化剤を用いるかは接着剤に要求される特性によって適宜選択されるが、好ましくはエポキシ樹脂のアミンアダクト、ジヒドラジド類である。
【0009】
これら硬化剤(b)の使用量はエポキシ樹脂(a)のエポキシ基に対する硬化剤の当量比において通常0.3〜2.0、好ましくは0.4〜1.6、更に好ましくは0.5〜1.3の範囲で用いられる。上記硬化剤は2種以上を混合して用いることもできる。また、必要に応じて硬化促進剤を配合しても良い。硬化促進剤としてはエポキシ樹脂の硬化を促進するものであればどのようなものでも良く、例えばイミダゾール類、有機リン化合物、第三級アミン、第四級アンモニウム塩などがある。
【0010】
本発明で使用するコアシェル構造架橋ゴム(c)は、2層又は3層構造であり、コア層がゴム弾性を示す架橋ゴムであり、コア層をゴム弾性を示さない架橋ポリマーで被覆した構造であればどのようなものでも良い。コア層としては架橋ポリブタジエン、架橋アクリル酸アルキル共重合物、架橋ポリイソプレンなどが挙げられ、シェル層としてはアクリル酸アルキル−メタクリル酸アルキル共重合物、メタクリル酸アルキル−スチレン共重合物、アクリル酸アルキル共重合物などが挙げられる。
これらのうちコア層とシェル層の好ましい組み合わせとしては、コア層が架橋ポリブタジエンであり、シェル層がアクリル酸アルキル−メタクリル酸アルキル共重合物又はメタクリル酸アルキル−スチレン共重合物である組み合わせ、コア層が架橋アクリル酸アルキル共重合物であり、シェル層がアクリル酸アルキル共重合物である組み合わせが挙げられる。
コアシェル構造架橋ゴムの平均粒子径は、1μm以下が好ましい。平均粒子径が1μmより大きいと熱接着時に接着層の形状変形が大きくなる傾向がある。また、粒子径が小さすぎると凝集しやすくなるため、平均粒子径は0.1μm以上が好ましい。
【0011】
本発明の電子部品用絶縁樹脂組成物中のコアシェル構造架橋ゴムの添加量は絶縁樹脂組成物中、樹脂分総量に対して60重量%以上95重量%以下であり、好ましくは80重量%以上90重量%以下である。60重量%より少ない場合、熱接着時に接着層の形状変化が生じ、95重量%より多い場合、接着信頼性が低下する。
【0012】
本発明の電子部品用絶縁樹脂組成物には、必要に応じて、他の添加物を加えることができる。例えば天然ワックス類、合成ワックス類および長鎖脂肪族酸の金属塩類等の可塑剤、酸アミド類、エステル類、パラフィン類などの離型剤、ニトリルゴム、ブタジエンゴム等の応力緩和剤、三酸化アンチモン、五酸化アンチモン、酸化錫、水酸化錫、酸化モリブデン、硼酸亜鉛、メタ硼酸バリウム、赤燐、水酸化アルミニウム、水酸化マグネシウム、アルミン酸カルシウム等の無機難燃剤、テトラブロモビスフェノールA、テトラブロモ無水フタル酸、ヘキサブロモベンゼン、ブロム化フェノールノボラック等の臭素系難燃剤、シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤等のカップリング剤、溶融シリカ、結晶性シリカ、低α線シリカ、ガラスフレーク、ガラスビーズ、ガラスバルーン、タルク、アルミナ、ケイ酸カルシウム、水酸化アルミニウム、炭酸カルシウム、硫酸バリウム、マグネシア、窒化ケイ素、窒化ホウ素、フェライト、希土コバルト、金、銀、ニッケル、銅、鉛、鉄粉、酸化鉄、砂鉄等の金属粉、黒鉛、カーボン、弁柄、黄鉛等の無機質充填剤または導電性粒子等、染料や顔料等の着色剤、炭素繊維、ガラス繊維、ボロン繊維、シリコンカーバイト繊維、アルミナ繊維、シリカアルミナ繊維などの無機系繊維、アラミド繊維、ポリエステル繊維、セルロース繊維、炭素繊維などの有機系繊維、酸化安定剤、光安定剤、耐湿性向上剤、チキソトロピー付与剤、希釈剤、消泡剤、他の各種の樹脂、粘着付与剤、帯電防止剤、滑剤、紫外線吸収剤等を配合することもできる。
【0013】
本発明の電子部品用絶縁樹脂組成物は各成分を均一に混合するため、溶剤を加えワニスとすることが好ましい。溶剤はエポキシ樹脂を溶解するものであればどのようなものでも良いが、特にメチルエチルケトン、トルエン、キシレン、酢酸エチル、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、シクロヘキサノン、プロピレングリコールジアセテート、エチレングリコールモノメチルエーテル等がエポキシ樹脂の溶解性に優れるため好ましい。これらの溶剤の配合量は樹脂が溶解し、コアシェル構造架橋ゴムを混合できる量であれば特に制限はないが、エポキシ樹脂、硬化剤及びコアシェル構造架橋ゴムの総量100重量部に対して、30〜200重量部が好ましい。尚、コアシェル構造架橋ゴムを均一に分散する為、らいかい機、ホモジナイザー、三本ロール等を用いることが有効である。
【0014】
本発明の電子部品用絶縁樹脂組成物のシートは、シートの厚みが5μm以上100μm以下で、なお且つ150℃、1MPaで加熱、加圧したときの辺部の樹脂変形量が100μm以下であるものが好ましい。この場合の樹脂の変形量とはシートを直径5mmの円形に打ち抜いたものを2枚のガラス板の間にはさみ、150℃1MPaで1時間加熱、加圧して硬化させたときの直径の変形量である。
本発明のシートは、支持体となるフィルム上に形成される。形成方法としては、前記電子部品用絶縁樹脂組成物のワニスをフィルム上に塗布、溶剤を乾燥するのが良いが、これに限定されるものではない。乾燥後のシート厚みは、用途にもよるが、実用上5μm以上100μm以下がよい。支持体となるフィルムとしては、乾燥工程に耐える耐熱性を有したものであることが必要である。これを満足しコスト的にも安価なものとしてはポリエチレンテレフタレート(PET)フィルム等が挙げられる。接着シートの剥離性を良くする為、支持体フィルムの表面には離型処理を施してあることが好ましい。
【0015】
本発明の電子部品用絶縁樹脂組成物の硬化条件については、どのような条件でも構わないが、その温度は120〜250℃が好ましい。120℃より低い温度では樹脂の硬化が不十分になり、250℃より高い温度では樹脂の熱分解が起きる為好ましくない。
【0016】
【実施例】
以下、更に実施例を以て本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例および比較例中、%および部は、特記しない限り重量基準である。
実施例1
RE−310S(液状ビスフェノールAエポキシ樹脂、日本化薬株式会社製、エポキシ当量182g/eq)50部、YD−012(固形ビスフェノールAエポキシ樹脂、東都化成株式会社製、エポキシ当量670g/eq)50部、アミキュアMY−H(エポキシ樹脂のアミンアダクト、味の素株式会社製)20部、パラロイドEXL−2602(コアシェル構造架橋ゴム、呉羽化学工業株式会社製、コア層:架橋ポリブタジエン、シェル層:アクリル酸アルキル−メタクリル酸アルキル共重合物、平均粒子径200nm)600部、プロピレングリコールジアセテート800部を秤量し、プラネタリーミキサーで予備混合後、更に3本ロールにて混練してワニスを得た。このワニスをPETフィルム#3811(リンテック株式会社製、離型処理品)に乾燥後の厚みが25μmになるように塗布し、140℃で3分間乾燥して電子部品用絶縁樹脂組成物のシートを得た。得られたシートは硬化前後においてフレキシブル性を有していた。得られたシートを直径5mmの円形に打ち抜いたものを2枚のガラス板にはさみ、150℃、1MPaで1時間加熱、加圧して硬化させたときの直径の変形量は50μmであった。また、接着したガラスの垂直方向の引き剥がし強度は5MPaと良好であった。
【0017】
実施例2
RE−310S(液状ビスフェノールAエポキシ樹脂、日本化薬株式会社製、エポキシ当量182g/eq)50部、YD−012(固形ビスフェノールAエポキシ樹脂、東都化成株式会社製、エポキシ当量670g/eq)50部、アミキュアMY−H(エポキシ樹脂のアミンアダクト、味の素株式会社製)20部、パラロイドEXL−2655(コアシェル構造架橋ゴム、呉羽化学工業株式会社製、コア層:架橋ポリブタジエン、シェル層:メタクリル酸アルキル−スチレン共重合物、平均粒子径200nm)600部、プロピレングリコールジアセテート800部を秤量し、プラネタリーミキサーで予備混合後、更に3本ロールにて混練してワニスを得た。このワニスをPETフィルム#3811(リンテック株式会社製、離型処理品)に乾燥後の厚みが25μmになるように塗布し、140℃で3分間乾燥して電子部品用絶縁樹脂組成物のシートを得た。得られたシートは硬化前後においてフレキシブル性を有していた。得られたシートを直径5mmの円形に打ち抜いたものを2枚のガラス板にはさみ、150℃、1MPaで1時間加熱、加圧して硬化させたときの直径の変形量は50μmであった。また、接着したガラスの垂直方向の引き剥がし強度は5MPaと良好であった。
【0018】
実施例3
RE−310S(液状ビスフェノールAエポキシ樹脂、日本化薬株式会社製、エポキシ当量182g/eq)50部、YD−012(固形ビスフェノールAエポキシ樹脂、東都化成株式会社製、エポキシ当量670g/eq)50部、アミキュアVDH(1,3−ビス(ヒドラジノカルボエチル)−5−イソプロピルヒダントイン、味の素株式会社製)20部、ゼオンF351(コアシェル構造架橋ゴム、日本ゼオン株式会社製、コア層:架橋アクリル酸アルキル共重合、シェル層:アクリル酸アルキル共重合物、平均粒子径300nm)600部、プロピレングリコールジアセテート800部を秤量し、プラネタリーミキサーで予備混合後、更に3本ロールにて混練してワニスを得た。このワニスをPETフィルム#3811(リンテック株式会社製、離型処理品)に乾燥後の厚みが25μmになるように塗布し、140℃で3分間乾燥して電子部品用絶縁樹脂組成物のシートを得た。得られたシートは硬化前後においてフレキシブル性を有していた。得られたシートを直径5mmの円形に打ち抜いたものを2枚のガラス板にはさみ、150℃、1MPaで1時間加熱、加圧して硬化させたときの直径の変形量は70μmであった。また、接着したガラスの垂直方向の引き剥がし強度は4MPaと良好であった。
【0019】
実施例4
RE−310S(液状ビスフェノールAエポキシ樹脂、日本化薬株式会社製、エポキシ当量182g/eq)50部、YD−012(固形ビスフェノールAエポキシ樹脂、東都化成株式会社製、エポキシ当量670g/eq)50部、アミキュアMY−H(エポキシ樹脂のアミンアダクト、味の素株式会社製)20部、SG−2000(タルク微粉末、日本タルク株式会社製)200部、パラロイドEXL−2655(コアシェル構造架橋ゴム、呉羽化学工業株式会社製、コア層:架橋ポリブタジエン、シェル層:メタクリル酸アルキル−スチレン共重合物、平均粒子径200nm)600部、プロピレングリコールジアセテート800部を秤量し、プラネタリーミキサーで予備混合後、更に3本ロールにて混練してワニスを得た。このワニスをPETフィルム#3811(リンテック株式会社製、離型処理品)に乾燥後の厚みが25μmになるように塗布し、140℃で3分間乾燥して電子部品用絶縁樹脂組成物のシートを得た。得られたシートは硬化前後においてフレキシブル性を有していた。得られたシートを直径5mmの円形に打ち抜いたものを2枚のガラス板にはさみ、150℃、1MPaで1時間加熱、加圧して硬化させたときの直径の変形量は30μmであった。また、接着したガラスの垂直方向の引き剥がし強度は5MPaと良好であった。
【0020】
【発明の効果】
本発明の電子部品用絶縁樹脂組成物は、電子部品を構成する基材との接着性に優れ、熱接着時に接着層の形状変形が小さく、なお且つ硬化前後においてフレキシブル性があるため工程中の取り扱いに優れる。従って、本発明のシートは、電子部品の絶縁用シートとして極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an insulating resin composition used for assembling electronic components.
[0002]
[Prior art]
Conventionally, an epoxy resin composition composed of an epoxy resin and a curing agent is used for the insulating resin composition for electronic parts.
[0003]
[Problems to be solved by the invention]
In recent years, as electronic components such as chip resistors, chip capacitors, and chip inductors have become smaller and lighter, it has excellent adhesiveness with the base materials that make up electronic components, and the deformation of the adhesive layer during thermal bonding is small. There is a demand for a material that is flexible before and after curing and that is excellent in handling during the process.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an insulating resin composition for electronic parts that satisfies the above performances at the same time can be obtained, thereby completing the present invention. That is, the present invention
(1) An epoxy resin (a), a curing agent (b), and a core-shell structure crosslinked rubber (c) having an average particle diameter of 1 μm or less are contained, and the content of the core-shell structure crosslinked rubber (c) is based on the total resin content 60% by weight or more and 95% by weight or less of an insulating resin composition for electronic parts,
(2) The insulating resin composition for electronic components according to (1), wherein the core layer of the core-shell structure crosslinked rubber (c) is crosslinked polybutadiene, and the shell layer is an alkyl acrylate-alkyl methacrylate copolymer,
(3) The insulating resin composition for electronic components according to (1), wherein the core layer of the core-shell structure crosslinked rubber (c) is a crosslinked polybutadiene and the shell layer is an alkyl methacrylate-styrene copolymer.
(4) The insulating resin composition for electronic parts as set forth in claim 1, wherein the core layer of the core-shell structure crosslinked rubber (c) is a crosslinked alkyl acrylate copolymer and the shell layer is an alkyl acrylate copolymer. ,
(5) The sheet of the insulating resin composition for electronic parts according to any one of (1) to (4),
(6) The insulating resin composition for electronic components according to (5), wherein the thickness of the sheet is 5 μm or more and 50 μm or less, and the amount of resin deformation at the side when heated and pressurized at 150 ° C. and 1 MPa is 100 μm or less. Sheet of things,
(7) The present invention relates to the insulating resin composition for electronic parts or the cured product of the sheet according to any one of (1) to (6).
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The insulating resin composition for electronic parts of the present invention contains an epoxy resin (a), a curing agent (b), and a core-shell structure crosslinked rubber (c) having an average particle size of 1 μm or less.
[0006]
The epoxy resin (a) used in the present invention may be any compound as long as it has two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Epoxy resin, cycloaliphatic epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxy resin obtained by glycidylation of halogenated phenols, epoxidized polybutadiene, etc. In particular, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are preferable, and two or more kinds thereof can be used in combination.
[0007]
Examples of the curing agent (b) used in the present invention include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyltetracarboxylic anhydride. Aromatic carboxylic acid anhydrides such as acid anhydrides, anhydrides of aliphatic carboxylic acids such as azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, nadic acid anhydride, head Aliphatic carboxylic acid anhydrides such as acid anhydrides and hymic acid anhydrides, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, Fragrance such as m-xylylenediamine Amines, ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, aliphatic amines such as polyetherdiamine, dicyandiamide, guanidines such as 1- (o-tolyl) biguanide, epoxy resins Amine adducts, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl -4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxypheny ) Ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenyl Methane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenolated polybutadiene, phenol, cresols, ethylphenols, Novolak resins made from various phenols such as butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, phenol novolac resins containing xylylene skeleton, dicyclopenta 2: 3 adduct of ene skeleton-containing phenol nobola methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5- Various imidazoles of methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid And salts with polyvalent carboxylic acids such as maleic acid and succinic acid, dihydrazides, Lewis acids, Bronsted acid salts, polymercaptons, isocyanates, and blocked isocyanates.
[0008]
Among these curing agents, which curing agent is used is appropriately selected depending on the properties required for the adhesive, and is preferably an amine adduct or dihydrazide of an epoxy resin.
[0009]
The amount of these curing agents (b) used is usually 0.3 to 2.0, preferably 0.4 to 1.6, more preferably 0.5 in the equivalent ratio of the curing agent to the epoxy group of the epoxy resin (a). Used in the range of ~ 1.3. Two or more of the above curing agents can be mixed and used. Moreover, you may mix | blend a hardening accelerator as needed. Any curing accelerator may be used as long as it accelerates the curing of the epoxy resin. Examples thereof include imidazoles, organic phosphorus compounds, tertiary amines, and quaternary ammonium salts.
[0010]
The core-shell structure crosslinked rubber (c) used in the present invention has a two-layer or three-layer structure, the core layer is a crosslinked rubber exhibiting rubber elasticity, and the core layer is coated with a crosslinked polymer that does not exhibit rubber elasticity. Anything is acceptable. Examples of the core layer include cross-linked polybutadiene, cross-linked alkyl acrylate copolymer, cross-linked polyisoprene, and the shell layer includes alkyl acrylate-alkyl methacrylate copolymer, alkyl methacrylate-styrene copolymer, alkyl acrylate. Examples include copolymers.
Among these, a preferable combination of the core layer and the shell layer is a combination in which the core layer is a crosslinked polybutadiene and the shell layer is an alkyl acrylate-alkyl methacrylate copolymer or an alkyl methacrylate-styrene copolymer, Is a crosslinked alkyl acrylate copolymer, and the shell layer is an alkyl acrylate copolymer.
The average particle diameter of the core-shell structure crosslinked rubber is preferably 1 μm or less. When the average particle diameter is larger than 1 μm, the shape deformation of the adhesive layer tends to increase during thermal bonding. Moreover, since it will become easy to aggregate when a particle diameter is too small, 0.1 micrometer or more is preferable for an average particle diameter.
[0011]
The addition amount of the core-shell structure crosslinked rubber in the insulating resin composition for electronic parts of the present invention is 60% by weight or more and 95% by weight or less, preferably 80% by weight or more and 90% by weight or less with respect to the total resin content in the insulating resin composition. % By weight or less. When the amount is less than 60% by weight, a change in the shape of the adhesive layer occurs at the time of thermal bonding.
[0012]
If necessary, other additives can be added to the insulating resin composition for electronic parts of the present invention. For example, plasticizers such as natural waxes, synthetic waxes and metal salts of long chain aliphatic acids, release agents such as acid amides, esters and paraffins, stress relaxation agents such as nitrile rubber and butadiene rubber, trioxide Inorganic flame retardants such as antimony, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, tetrabromobisphenol A, anhydrous tetrabromo Brominated flame retardants such as phthalic acid, hexabromobenzene, brominated phenol novolak, silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, fused silica, crystalline silica, low α Wire silica, glass flakes, glass beads, glass balloons, talc Alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, lead, iron powder, iron oxide, iron sand, etc. Powders, graphite, carbon, petals, inorganic fillers such as yellow lead or conductive particles, coloring agents such as dyes and pigments, carbon fibers, glass fibers, boron fibers, silicon carbide fibers, alumina fibers, silica alumina fibers Inorganic fibers such as aramid fibers, polyester fibers, cellulose fibers, carbon fibers and other organic fibers, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropy imparting agents, diluents, antifoaming agents, and other various types These resins, tackifiers, antistatic agents, lubricants, ultraviolet absorbers and the like can also be blended.
[0013]
In the insulating resin composition for electronic parts of the present invention, it is preferable to add a solvent to obtain a varnish in order to uniformly mix the components. Any solvent may be used as long as it dissolves the epoxy resin, and in particular, methyl ethyl ketone, toluene, xylene, ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, cyclohexanone, propylene glycol diacetate, Ethylene glycol monomethyl ether and the like are preferable because of excellent solubility of the epoxy resin. The amount of these solvents is not particularly limited as long as the resin can be dissolved and the core-shell structure crosslinked rubber can be mixed, but the amount of the epoxy resin, the curing agent, and the core-shell structure crosslinked rubber is 30 to 30 parts by weight. 200 parts by weight is preferred. In order to uniformly disperse the core-shell structure crosslinked rubber, it is effective to use a raking machine, a homogenizer, a triple roll, or the like.
[0014]
The sheet of the insulating resin composition for electronic parts according to the present invention has a sheet thickness of 5 μm or more and 100 μm or less, and a resin deformation amount of the side portion when heated and pressed at 150 ° C. and 1 MPa is 100 μm or less. Is preferred. The amount of deformation of the resin in this case is the amount of deformation of the diameter when a sheet punched into a circle having a diameter of 5 mm is sandwiched between two glass plates and heated and pressurized at 150 ° C. and 1 MPa for 1 hour to cure. .
The sheet | seat of this invention is formed on the film used as a support body. As a forming method, the varnish of the insulating resin composition for electronic parts is preferably applied on the film and the solvent is dried, but is not limited thereto. Although the sheet thickness after drying depends on the use, it is practically 5 μm or more and 100 μm or less. The film to be a support needs to have heat resistance that can withstand the drying process. A polyethylene terephthalate (PET) film etc. is mentioned as what is satisfying this and cheap also in terms of cost. In order to improve the peelability of the adhesive sheet, the surface of the support film is preferably subjected to a release treatment.
[0015]
The curing condition of the insulating resin composition for electronic parts of the present invention may be any condition, but the temperature is preferably 120 to 250 ° C. When the temperature is lower than 120 ° C., the resin is not sufficiently cured, and when the temperature is higher than 250 ° C., the resin is thermally decomposed.
[0016]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In Examples and Comparative Examples,% and parts are based on weight unless otherwise specified.
Example 1
50 parts of RE-310S (liquid bisphenol A epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 182 g / eq), 50 parts of YD-012 (solid bisphenol A epoxy resin, Toto Kasei Co., Ltd., epoxy equivalent 670 g / eq) , Amicure MY-H (epoxy resin amine adduct, manufactured by Ajinomoto Co., Inc.), 20 parts, Paraloid EXL-2602 (core shell structure crosslinked rubber, manufactured by Kureha Chemical Industry Co., Ltd., core layer: crosslinked polybutadiene, shell layer: alkyl acrylate- 600 parts of alkyl methacrylate copolymer (average particle diameter 200 nm) and 800 parts of propylene glycol diacetate were weighed, premixed with a planetary mixer, and then kneaded with three rolls to obtain a varnish. This varnish was applied to PET film # 3811 (manufactured by Lintec Co., Ltd., release-treated product) so that the thickness after drying was 25 μm, and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts. Obtained. The obtained sheet had flexibility before and after curing. When the obtained sheet was punched into a circle having a diameter of 5 mm and sandwiched between two glass plates and heated and pressurized at 150 ° C. and 1 MPa for 1 hour, the deformation amount of the diameter was 50 μm. Further, the peel strength in the vertical direction of the adhered glass was as good as 5 MPa.
[0017]
Example 2
50 parts of RE-310S (liquid bisphenol A epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 182 g / eq), 50 parts of YD-012 (solid bisphenol A epoxy resin, Toto Kasei Co., Ltd., epoxy equivalent 670 g / eq) , Amicure MY-H (epoxy resin amine adduct, manufactured by Ajinomoto Co., Inc.), 20 parts, Paraloid EXL-2655 (core shell structure crosslinked rubber, manufactured by Kureha Chemical Industry Co., Ltd., core layer: crosslinked polybutadiene, shell layer: alkyl methacrylate- Styrene copolymer (average particle size 200 nm) 600 parts and propylene glycol diacetate 800 parts were weighed, premixed with a planetary mixer, and then kneaded with three rolls to obtain a varnish. This varnish was applied to PET film # 3811 (manufactured by Lintec Co., Ltd., release-treated product) so that the thickness after drying was 25 μm, and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts. Obtained. The obtained sheet had flexibility before and after curing. When the obtained sheet was punched into a circle having a diameter of 5 mm and sandwiched between two glass plates and heated and pressurized at 150 ° C. and 1 MPa for 1 hour, the deformation amount of the diameter was 50 μm. Further, the peel strength in the vertical direction of the adhered glass was as good as 5 MPa.
[0018]
Example 3
50 parts of RE-310S (liquid bisphenol A epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 182 g / eq), 50 parts of YD-012 (solid bisphenol A epoxy resin, Toto Kasei Co., Ltd., epoxy equivalent 670 g / eq) 20 parts of Amicure VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, manufactured by Ajinomoto Co., Inc.), ZEON F351 (core-shell structure crosslinked rubber, manufactured by ZEON CORPORATION, core layer: crosslinked alkyl acrylate) Copolymerization, shell layer: 600 parts of alkyl acrylate copolymer, average particle diameter 300 nm) and 800 parts of propylene glycol diacetate are weighed, premixed with a planetary mixer, and then kneaded with three rolls to obtain a varnish. Obtained. This varnish was applied to PET film # 3811 (manufactured by Lintec Co., Ltd., release-treated product) so that the thickness after drying was 25 μm, and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts. Obtained. The obtained sheet had flexibility before and after curing. When the obtained sheet was punched out into a circle having a diameter of 5 mm and sandwiched between two glass plates and heated and pressurized at 150 ° C. and 1 MPa for 1 hour, the amount of deformation of the diameter was 70 μm. Further, the peel strength in the vertical direction of the adhered glass was as good as 4 MPa.
[0019]
Example 4
50 parts of RE-310S (liquid bisphenol A epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 182 g / eq), 50 parts of YD-012 (solid bisphenol A epoxy resin, Toto Kasei Co., Ltd., epoxy equivalent 670 g / eq) Amycure MY-H (Amine Adduct of Epoxy Resin, Ajinomoto Co., Ltd.) 20 parts, SG-2000 (talc fine powder, Nihon Talc Co., Ltd.) 200 parts, Paraloid EXL-2655 (Core-shell structure cross-linked rubber, Kureha Chemical Industries) Co., Ltd., core layer: cross-linked polybutadiene, shell layer: alkyl methacrylate-styrene copolymer, average particle size 200 nm) 600 parts, propylene glycol diacetate 800 parts were weighed, premixed with a planetary mixer, and further 3 The varnish was obtained by kneading with this roll. This varnish was applied to PET film # 3811 (manufactured by Lintec Co., Ltd., release-treated product) so that the thickness after drying was 25 μm, and dried at 140 ° C. for 3 minutes to obtain an insulating resin composition sheet for electronic parts Obtained. The obtained sheet had flexibility before and after curing. When the obtained sheet was punched out into a circle having a diameter of 5 mm and sandwiched between two glass plates and heated and pressurized at 150 ° C. and 1 MPa for 1 hour, the deformation amount of the diameter was 30 μm. Further, the peel strength in the vertical direction of the adhered glass was as good as 5 MPa.
[0020]
【The invention's effect】
The insulating resin composition for electronic parts of the present invention is excellent in adhesiveness with the base material constituting the electronic parts, has a small shape deformation of the adhesive layer during thermal bonding, and is flexible before and after curing. Excellent handling. Therefore, the sheet of the present invention is extremely useful as an insulating sheet for electronic components.
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PL2049611T3 (en) | 2006-07-31 | 2019-04-30 | Henkel Ag & Co Kgaa | Curable epoxy resin-based adhesive compositions |
JP2008038070A (en) * | 2006-08-09 | 2008-02-21 | Toshiba Corp | Epoxy adhesive, cast-molded product using the same, and method for producing the cast-molded product using the same |
WO2008045270A1 (en) | 2006-10-06 | 2008-04-17 | Henkel Ag & Co. Kgaa | Pumpable epoxy paste adhesives resistant to wash-off |
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