JP4250988B2 - High thermal conductive epoxy resin composition and semiconductor device - Google Patents
High thermal conductive epoxy resin composition and semiconductor device Download PDFInfo
- Publication number
- JP4250988B2 JP4250988B2 JP2003083940A JP2003083940A JP4250988B2 JP 4250988 B2 JP4250988 B2 JP 4250988B2 JP 2003083940 A JP2003083940 A JP 2003083940A JP 2003083940 A JP2003083940 A JP 2003083940A JP 4250988 B2 JP4250988 B2 JP 4250988B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- particle size
- resin composition
- formula
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、高熱伝導エポキシ樹脂組成物及びこれを用いた半導体装置に関するものである。
【０００２】
【従来の技術】
最近の半導体デバイスの性能向上に伴う要求として、半導体素子をフェイスダウン構造で回路が形成されたマザーボードあるいはドーターボードに実装される方法（フリップチップ方式）が注目されている。これは従来から用いられている方式、例えば半導体素子から金線でリードフレーム上にコンタクトをとりパッケージングされた形態でマザーボードあるいはドーターボードに実装する方法では、回路による情報伝達の遅れ、クロストークによる情報伝達エラー等が生ずる、という問題が発生していることに起因する。一方フリップチップ方式においては、互いの線膨張係数が異なる半導体素子と回路基板とをダイレクトに電気接続を行うことから、接続部分の信頼性が問題となっている。この対策としては、半導体素子と回路基板との空隙に液状樹脂を注入し硬化させて、電気接続部に集中する応力を樹脂にも分散させることにより接続信頼性を向上させる方法がとられている。しかしながら液状樹脂は、毛細管現象を利用して半導体素子と回路基板との空隙に注入されるため、注入に多くの時間を要する。生産性を向上させるためには液状樹脂の早い充填が必要であるが、早い充填は未充填、ボイドを引き起こし易く、半導体装置の信頼性も低下させるため、画期的に生産性を向上させることは難しい。また常温で液状であることが制約条件となり、無機充填材の充填量が低く、吸湿し易いために、固形エポキシ、固形硬化剤をつかったエポキシ樹脂組成物に比べて信頼性が劣る。
この様な問題から、半導体装置における回路基板と半導体素子との間の空隙を確実に充填し、生産性に優れ、なおかつ接続部分に高い信頼性を付与できる固形エポキシ、固形硬化剤をつかったエポキシ樹脂組成物が求められており、更には高速回路による発熱のため、エポキシ樹脂組成物に高熱伝導性も付与する必要がある。
【０００３】
固形エポキシ、固形硬化剤をつかったエポキシ樹脂組成物を用いる場合において、半導体装置における回路基板と半導体素子との間の空隙を確実に充填するために、最大粒径を２４μｍ以下、成形温度での溶融温度を２００ポイズ以下にする方法（例えば、特許文献１参照。）、最大粒径を２０μｍ以下、メジアン径を０．２〜３μｍにする方法（例えば、特許文献２参照。）が知られているが、無機充填材としては最大粒径のみにしか着目しておらず、粒子の種類、粒度分布には触れられていない。
また、無機充填材としてアルミナを必須成分とした時の流動性を向上させるために、０．４〜０．７μｍ、１２〜１８μｍ、３０〜３８μｍに粒度分布の極大点をもたせる方法（例えば、特許文献３参照。）、粒度分布の形状に着目してロジン・ラムラー式を用いた方法（例えば、特許文献４参照。）が知られているが、フリップチップ方式の様な狭い空隙の充填に有利な方法には触れられていない。
さらに前述特許文献のいずれについても、接続部分に高い信頼性を付与するエポキシ樹脂、フェノール樹脂硬化剤の種類については触れられていない。
【０００４】
【特許文献１】
特開平１１−２８８９７９号公報（第２〜９頁）
【特許文献２】
特開２０００−２９０４７１号公報（第２〜１０頁）
【特許文献３】
特開平７−２７８４１５号公報（第２〜９頁）
【特許文献４】
特開平７−１１８５０６号公報（第２〜６頁）
【０００５】
【発明が解決しようとする課題】
本発明は、半導体装置における回路基板と半導体素子との間の空隙を確実に充填し、生産性に優れ、なおかつ接続部分に高い信頼性を付与する高熱伝導エポキシ樹脂組成物及びこれを用いた半導体装置を提供するものである。
【０００６】
【課題を解決するための手段】
本発明は、（Ａ）一般式（１）で示される多官能フェノール樹脂（ａ）と一般式（２）で示される結晶性エポキシ樹脂の前駆体であるフェノール類（ｂ）とを重量比（ａ）／（ｂ）が４〜９で混合してグリシジルエーテル化したエポキシ樹脂を、全エポキシ樹脂中の８０重量％以上含むエポキシ樹脂、（Ｂ）一般式（１）で示される多官能フェノール樹脂硬化剤を、全フェノール樹脂硬化剤中の８０重量％以上含むフェノール樹脂硬化剤、（Ｃ）硬化促進剤及び（Ｄ）無機充填材として０．５μｍ〜１２μｍに粒度分布の極大点を２つ以上有し、なおかつ最大粒径が２４μｍ以下であるアルミナを必須成分とする高熱伝導エポキシ樹脂組成物、及びこれを用いた半導体装置である。
【化３】
【０００７】
【化４】
【０００８】
【発明の実施の形態】
本発明は、所定のエポキシ樹脂、所定のフェノール樹脂硬化剤、硬化促進剤及び無機充填材として所定の粒度分布及び最大粒径のアルミナを含有してなることを特徴とする高熱伝導エポキシ樹脂組成物、及びこれを用いた半導体装置についてである。
【０００９】
本発明における一般式（１）で示される多官能フェノール樹脂（ａ）と一般式（２）で示される結晶性エポキシ樹脂の前駆体であるフェノール類（ｂ）とを重量比（ａ）／（ｂ）が４〜９で混合してグリシジルエーテル化したエポキシ樹脂は、エポキシ樹脂組成物のガラス転移温度を高くするために配合している。
【００１０】
【化５】
【化６】
一般式（１）で示される多官能フェノール樹脂（ａ）に結晶性エポキシ樹脂の前駆体であるフェノール類（ｂ）を混合することにより、エポキシ樹脂組成物をより低粘度化することが可能となる。しかし重量比（ａ）／（ｂ）が下限値未満の場合は、エポキシ樹脂組成物のガラス転移温度低下を招いて接続信頼性において不利になり、重量比（ａ）／（ｂ）が上限値を超える場合は、エポキシ樹脂組成物の低粘度化への寄与が小さくなり、流動性において不利になる。
一般式（１）で示される多官能フェノール樹脂としては、式（３）、式（４）等が挙げられるが、入手のし易さ、性能等の面から式（３）が好ましい。また結晶性エポキシ樹脂の前駆体であるフェノール類としては、４，４−ジヒドロキシビフェニル、４，４−ジヒドロキシ−３，３，５，５−テトラメチルビフェニル、４，４−ジヒドロキシ−３，３，５，５−テトラターシャルブチルビフェニル、等が挙げられるが、入手のし易さ、性能等の点から４，４−ジヒドロキシビフェニルが好ましい。
【００１３】
【化７】
【化８】
なおここで用いるエポキシ樹脂による効果を損なわない範囲で、他のエポキシ樹脂を併用できる。併用できるエポキシ樹脂としては、例えばビフェニル型エポキシ、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、スチルベン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、テルペン変性フェノール型エポキシ樹脂、ハイドロキノン型エポキシ樹脂等が挙げられるが、これらに限定されるものではない。しかし本発明における一般式（１）で示される多官能フェノール樹脂（ａ）と一般式（２）で示される結晶性エポキシ樹脂の前駆体であるフェノール類（ｂ）を混合してグリシジルエーテル化したエポキシ樹脂が全エポキシ樹脂中の８０重量％未満になると、エポキシ樹脂組成物のガラス転移温度低下を招き易くなり接続信頼性において不利になる。
【００１６】
本発明における一般式（１）で示される多官能フェノール樹脂硬化剤は同様に、エポキシ樹脂組成物のガラス転移温度を高くするために配合しており、式（３）、式（４）等が挙げられるが、入手のし易さ、性能等の面から式（３）が好ましい。
【００１７】
【化９】
【化１０】
なおここで用いるフェノール樹脂硬化剤による効果を損なわない範囲で、他のフェノール樹脂硬化剤を併用できる。例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂、フェノールアラルキル樹脂、テルペン変性フェノール樹脂等が挙げられるが、これらに限定されるものではない。しかし本発明における一般式（１）で示される多官能フェノール樹脂硬化剤が、全フェノール樹脂硬化剤中の８０重量％未満になると、エポキシ樹脂の場合と同様にガラス転移温度の低下を招いてしまう。
【００２０】
本発明における硬化促進剤としては、エポキシ基とフェノール性水酸基との硬化反応を促進させるものであればよく、一般に封止材料に使用するものを用いることができ、例えば１，８−ジアザビシクロ（５，４，０）ウンデセン−７、トリフェニルホスフィン、ベンジルジメチルアミン、２−メチルイミダゾール等が挙げられ、これらは単独でも混合して用いてもよい。
【００２１】
本発明における無機充填材は、最大粒径が小さく、かつ所定の粒度分布を有することに一つの特徴がある。半導体装置における回路基板と半導体素子との間の空隙を確実に充填する、という点では、無機充填材の粒子径は小さいほど望ましい。しかし粒子径の小さい無機充填材のみでは空隙を充填するのに十分な流動性を得ることが出来ず、十分な流動性を得ようとして無機充填材量を低減すると、十分な信頼性及び熱伝導性を得ることが出来ない。そのため、０．５μｍ〜１２μｍに粒度分布の極大点を２つ以上有するアルミナを用い、なおかつ狭路の充填性を阻害する比較的大きめの粒子を取り除く必要がある。粒度分布の極大点が下限値未満に存在すると流動性が著しく低下し、極大点が上限値を超えて存在すると、流路によってはいくら最大粒径を制御しても充填性が損なわれ易くなる。また、例え極大点が０．５μｍ〜１２μｍの範囲内であったとしても、極大点が１つであると、比較的大きめの無機充填材の隙間に比較的小さめの粒子を配置させるという充填理論が適用出来ないことから、極大点の粒子径によらず流動性が著しく低下してしまう。
なお流路によって充填を阻害する粒径は異なるため、「充填を阻害する粒径」に明確な基準があるわけではなく、半導体装置における回路基板と半導体素子との間の空隙の大きさを考慮して、従来公知の分級法を適宜用いて調整すればよい。ただ最大粒径を２４μｍ以下とすることによって、多くの場合の充填性に対応出来るものと思われる。
【００２２】
ここでの無機充填材の粒度分布は、ＪＩＳ Ｍ８１００ 粉塊混合物−サンプリング方法通則に準じて無機充填材を採取し、ＪＩＳ Ｒ １６２２−１９９５ファインセラミックス原料粒子径分布測定のための試料調整通則に準じて、無機充填材を測定用試料として調整し、ＪＩＳ Ｒ １６２９−１９９７ ファインセラミックス原料のレーザー回折・散乱法による粒子径分布測定方法に準じて(株)島津製作所・製のレーザー回折式粒度分布測定装置ＳＡＬＤ−７０００（レーザー波長：４０５ｎｍ）を用いて、溶媒に水を用い無機充填材の屈折率が実数部１．８０、虚数部１．００の条件のもと測定した値である。
また比表面積は、ＪＩＳ Ｒ １６２６−１９９６ ファインセラミックス粉体の気体吸着ＢＥＴ法による比表面積の測定方法に準じて、窒素を吸着質として用い、ＢＥＴ１点法によって測定した値である。
【００２３】
本発明に用いるエポキシ樹脂組成物は、（Ａ）〜（Ｄ）成分の他、必要に応じて臭素化エポキシ樹脂、酸化アンチモン等の難燃剤、酸化ビスマス水和物等の無機イオン交換体、γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック、ベンガラ等の着色剤、シリコーンオイル、シリコーンゴム等の低応力成分、天然ワックス、合成ワックス、高級脂肪酸及びその金属塩類もしくはパラフィン等の離型剤、酸化防止剤等の各種添加剤を適宜配合してもよい。更に必要に応じて無機充填材をカップリング剤やエポキシ樹脂あるいはフェノール樹脂で予め処理して用いてもよく、処理の方法としては、溶媒を用いて混合した後に溶媒を除去する方法や、直接無機充填材に添加し、混合機を用いて処理する方法等がある。
【００２４】
本発明に用いるエポキシ樹脂組成物は、（Ａ）〜（Ｄ）成分、その他の添加剤等をミキサーを用いて常温混合し、ロール、ニーダー等の押出機等の混練機で溶融混練し、冷却後粉砕して得られる。
【００２５】
【実施例】
以下に、実施例を挙げて本発明を説明するが、これらの実施例に限定されるものではない。
実施例１
アルミナＡ（平均粒径８．２μｍ、比表面積１．１ｍ２／ｇ、極大点の粒径９．８μｍ、最大粒径２４μｍ以下） ６４．００重量％
アルミナＤ（平均粒径０．７μｍ、比表面積７．９ｍ２／ｇ、極大点の粒径０．７μｍ、最大粒径２４μｍ以下） ２０．００重量％
式（３）であらわされる多官能フェノール樹脂（ａ）と式（５）であらわされるフェノール類（ｂ）を重量比（ａ）／（ｂ）＝４で混合してグリシジルエーテル化したもの（ジャパンエポキシレジン（株）製、エピコートＹＬ６６７７、エポキシ当量１６３。以下、エポキシ樹脂１という。） ８．１８重量％
【００２６】
【化１１】
【化１２】
式（３）であらわされる多官能フェノール樹脂硬化剤（明和化成（株）製、ＭＥＨ−７５００−３Ｓ、軟化点８３℃、水酸基当量１０３） ５．３２重量％
γ−グリシドキシプロピルトリメトキシシラン ０．２０重量％
１，８−ジアザビシクロ（５，４，０）ウンデセン−７（以下、ＤＢＵという） ０．２０重量％
臭素化ビスフェノールＡ型エポキシ樹脂（軟化点６３℃、エポキシ基当量３５９、臭素含有量４８重量％） ０．５０重量％
三酸化アンチモン １．００重量％
カルナバワックス ０．３０重量％
カーボンブラック ０．３０重量％
を、常温においてミキサーで混合し、７０〜１２０℃で２本ロールにより混練し、冷却後粉砕してエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を以下の方法で評価した。結果を表１に示す。
【００２９】
評価方法
スパイラルフロー：ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用の金型を用い、金型温度１７５℃、注入圧力６．９ＭＰａ、硬化時間２分で測定した。単位はｃｍ。
スリット充填性：４０μｍ、６０μｍ、８０μｍの流路厚を有する金型を用いて、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間２分でトランスファー成形し、各流路の充填距離を測定した。単位はｍｍ。
模擬金型充填性：長さ１４５ｍｍ、幅１５ｍｍ、厚み０．５ｍｍの矩形型流路中に、９ｍｍ×９ｍｍ×０．４２ｍｍ（厚み）の四角柱を６個有する（四角柱と四角柱の間隔は３ｍｍ）狭路充填を想定した評価用金型、及び長さ１４５ｍｍ、幅１５ｍｍ、厚み０．５ｍｍの矩形型流路中に、９ｍｍ×９ｍｍ×０．４５ｍｍ（厚み）の四角柱を６個有する（四角柱と四角柱の間隔は３ｍｍ）狭路充填を想定した評価用金型を用いて、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間２分でトランスファー成形し、８０μｍ及び５０μｍギャップの充填性（未充填、ボイドの有無）を判定した。
ガラス転移温度：トランスファー成形機を用い、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間２分で、４ｍｍ×４ｍｍ×１５ｍｍの大きさに成形した試験片を１７５℃、８時間で後硬化し、熱機械分析装置（セイコー電子工業（株）製、ＴＭＡ１００）を用いて測定温度範囲０〜３２０℃、昇温速度５℃／分で測定した時のチャートより、α１、α２を決定し、その延長線の交点をガラス転移温度とした。単位は℃。
【００３０】
実施例２〜９、比較例１〜８
表１、表２の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得、同様に評価した。これらの評価結果を表１、表２に示す。
実施例１以外で用いたアルミナ及びエポキシ樹脂、フェノール樹脂を以下に示す。
アルミナＢ（平均粒径５．０μｍ、比表面積２．８ｍ２／ｇ、極大点の粒径５．０μｍ、最大粒径２４μｍ以下）
アルミナＣ（平均粒径４．０μｍ、比表面積３．１ｍ２／ｇ、極大点の粒径５．０μｍ、最大粒径１２μｍ以下）
アルミナＥ（平均粒径０．７μｍ、比表面積７．９ｍ２／ｇ、極大点の粒径０．７μｍ、最大粒径１２μｍ以下）
アルミナＦ（平均粒径１３．０μｍ、比表面積１．０ｍ２／ｇ、極大点の粒径１５．０μｍ、最大粒径２４μｍ以下）
アルミナＧ（平均粒径０．１μｍ、比表面積３０ｍ２／ｇ、極大点の粒径０．１μｍ、最大粒径２４μｍ以下）
アルミナＨ（平均粒径７．７μｍ、比表面積１．０ｍ２／ｇ、極大点の粒径９．８μｍ、最大粒径４５μｍ）
アルミナＩ（平均粒径０．７μｍ、比表面積７．９ｍ２／ｇ、極大点の粒径０．７μｍ、最大粒径４５μｍ）
エポキシ樹脂２：式（３）であらわされる多官能フェノール樹脂（ａ）と式（５）であらわされるフェノール類（ｂ）を重量比（ａ）／（ｂ）＝９で混合してグリシジルエーテル化したもの（エポキシ当量１６５）
エポキシ樹脂３：式（３）であらわされる多官能フェノール樹脂（ａ）と式（５）であらわされるフェノール類（ｂ）を重量比（ａ）／（ｂ）＝１．５で混合してグリシジルエーテル化したもの（エポキシ当量１６０）
エポキシ樹脂４：式（３）であらわされる多官能フェノール樹脂（ａ）と式（５）であらわされるフェノール類（ｂ）を重量比（ａ）／（ｂ）＝２０で混合してグリシジルエーテル化したもの（エポキシ当量１６６）
ビフェニル型エポキシ樹脂（ジャパンエポキシレジン（株）製、ＹＸ４０００、融点１０８℃、エポキシ当量１８５）
オルソクレゾールノボラック型エポキシ樹脂（日本化薬（株）製、ＥＯＣＮ−１０２０−５５、軟化点５５℃、エポキシ当量１９６）
フェノールノボラック樹脂（住友ベークライト（株）製、ＰＲ−ＨＦ３、軟化点８０℃、水酸基当量１０５）
フェノールアラアルキル樹脂（三井化学（株）製、ＸＬＣ−４Ｌ、軟化点６２℃、水酸基当量１６８）
【００３１】
【表１】
【表２】
【発明の効果】
本発明に従うと、高熱伝導エポキシ樹脂組成物は、半導体装置における回路基板と半導体素子との間の空隙を確実に充填し、生産性に優れ、なおかつ接続部分に高い信頼性を付与できることから、産業上有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a high thermal conductive epoxy resin composition and a semiconductor device using the same.
[0002]
[Prior art]
As a demand accompanying the recent improvement in performance of semiconductor devices, a method (flip chip method) in which a semiconductor element is mounted on a mother board or a daughter board on which a circuit is formed with a face-down structure has attracted attention. This is a conventional method, for example, a method in which a contact is made on a lead frame with a gold wire from a semiconductor element and mounted in a packaged form on a mother board or a daughter board. This is due to the occurrence of a problem that an information transmission error or the like occurs. On the other hand, in the flip chip method, since the semiconductor element and the circuit board having different linear expansion coefficients are directly electrically connected, the reliability of the connection portion is a problem. As a countermeasure against this, a method of improving the connection reliability by injecting a liquid resin into the gap between the semiconductor element and the circuit board and curing the resin to disperse the stress concentrated on the electrical connection portion also in the resin is taken. . However, since the liquid resin is injected into the gap between the semiconductor element and the circuit board using the capillary phenomenon, it takes a long time for the injection. In order to improve productivity, quick filling of liquid resin is necessary, but fast filling is not filled, it is easy to cause voids, and the reliability of semiconductor devices is also reduced, so that productivity can be dramatically improved. Is difficult. Moreover, since it is liquidity at normal temperature, the filling amount of the inorganic filler is low, and it is easy to absorb moisture. Therefore, the reliability is inferior compared with the epoxy resin composition using the solid epoxy and the solid curing agent.
Due to these problems, solid epoxy that can reliably fill the gap between the circuit board and the semiconductor element in the semiconductor device, has excellent productivity, and can give high reliability to the connection part, epoxy using a solid curing agent There is a demand for a resin composition, and furthermore, due to heat generation by a high-speed circuit, it is necessary to impart high thermal conductivity to the epoxy resin composition.
[0003]
In the case of using an epoxy resin composition using a solid epoxy and a solid curing agent, the maximum particle size is 24 μm or less at a molding temperature in order to reliably fill the gap between the circuit board and the semiconductor element in the semiconductor device. A method of making the melting temperature 200 poise or less (for example, see Patent Document 1), a method for making the maximum particle size 20 μm or less, and the median diameter 0.2 to 3 μm (for example, see Patent Document 2) are known. However, as the inorganic filler, attention is paid only to the maximum particle size, and the particle type and particle size distribution are not mentioned.
Moreover, in order to improve the fluidity | liquidity when an alumina is an essential component as an inorganic filler, the method of giving the maximum point of a particle size distribution to 0.4-0.7micrometer, 12-18micrometer, 30-38micrometer (for example, patent A method using the Rosin-Rammler method (for example, see Patent Document 4) is known by paying attention to the shape of the particle size distribution, but it is advantageous for filling a narrow gap like a flip chip method. It is not touched on the method.
Furthermore, none of the above-mentioned patent documents mentions the types of epoxy resin and phenol resin curing agent that impart high reliability to the connection portion.
[0004]
[Patent Document 1]
JP-A-11-288879 (pages 2 to 9)
[Patent Document 2]
JP 2000-290471 A (pages 2 to 10)
[Patent Document 3]
JP-A-7-278415 (pages 2-9)
[Patent Document 4]
JP-A-7-118506 (pages 2-6)
[0005]
[Problems to be solved by the invention]
The present invention relates to a highly thermally conductive epoxy resin composition that reliably fills a gap between a circuit board and a semiconductor element in a semiconductor device, has excellent productivity, and imparts high reliability to a connection portion, and a semiconductor using the same A device is provided.
[0006]
[Means for Solving the Problems]
In the present invention, (A) a polyfunctional phenol resin (a) represented by the general formula (1) and a phenol (b) which is a precursor of the crystalline epoxy resin represented by the general formula (2) are mixed in a weight ratio ( an epoxy resin containing 80% by weight or more of an epoxy resin in which a) / (b) is mixed in 4 to 9 to form glycidyl ether, and (B) a polyfunctional phenol resin represented by the general formula (1) As a phenol resin curing agent containing 80% by weight or more of the curing agent in the total phenol resin curing agent, (C) a curing accelerator, and (D) two or more maximum points of particle size distribution in 0.5 μm to 12 μm. A highly heat-conductive epoxy resin composition having an essential component of alumina having a maximum particle size of 24 μm or less, and a semiconductor device using the same.
[Chemical 3]
[0007]
[Formula 4]
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises a high thermal conductive epoxy resin composition comprising a predetermined epoxy resin, a predetermined phenol resin curing agent, a curing accelerator, and alumina having a predetermined particle size distribution and a maximum particle size as an inorganic filler. And a semiconductor device using the same.
[0009]
In the present invention, the polyfunctional phenol resin (a) represented by the general formula (1) and the phenols (b) which are precursors of the crystalline epoxy resin represented by the general formula (2) are mixed in a weight ratio (a) / ( The epoxy resin which b) mixed by 4-9 and glycidyl-etherified is mix | blended in order to make the glass transition temperature of an epoxy resin composition high.
[0010]
[Chemical formula 5]
[Chemical 6]
It is possible to lower the viscosity of the epoxy resin composition by mixing phenols (b), which are precursors of crystalline epoxy resins, into the polyfunctional phenol resin (a) represented by the general formula (1). Become. However, when the weight ratio (a) / (b) is less than the lower limit value, the glass transition temperature of the epoxy resin composition is lowered, which is disadvantageous in connection reliability, and the weight ratio (a) / (b) is the upper limit value. If it exceeds 1, the contribution to lowering the viscosity of the epoxy resin composition is reduced, which is disadvantageous in fluidity.
Examples of the polyfunctional phenol resin represented by the general formula (1) include the formula (3) and the formula (4), and the formula (3) is preferable from the viewpoint of easy availability and performance. Examples of phenols that are precursors of crystalline epoxy resins include 4,4-dihydroxybiphenyl, 4,4-dihydroxy-3,3,5,5-tetramethylbiphenyl, 4,4-dihydroxy-3,3, 5,5-tetratertiarybutylbiphenyl and the like can be mentioned, and 4,4-dihydroxybiphenyl is preferable from the viewpoint of availability and performance.
[0013]
[Chemical 7]
[Chemical 8]
In addition, another epoxy resin can be used together in the range which does not impair the effect by the epoxy resin used here. Examples of the epoxy resin that can be used in combination include biphenyl type epoxy, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, naphthol novolak type epoxy resin, dicyclo Examples include, but are not limited to, pentadiene-modified phenolic epoxy resins, terpene-modified phenolic epoxy resins, and hydroquinone epoxy resins. However, the polyfunctional phenol resin (a) represented by the general formula (1) in the present invention and the phenol (b) which is a precursor of the crystalline epoxy resin represented by the general formula (2) were mixed to form glycidyl ether. When the epoxy resin is less than 80% by weight based on the total epoxy resin, the glass transition temperature of the epoxy resin composition tends to be lowered, which is disadvantageous in connection reliability.
[0016]
Similarly, the polyfunctional phenol resin curing agent represented by the general formula (1) in the present invention is blended in order to increase the glass transition temperature of the epoxy resin composition, and the formula (3), the formula (4), etc. Although mentioned, Formula (3) is preferable from surfaces, such as availability and performance.
[0017]
[Chemical 9]
[Chemical Formula 10]
In addition, another phenol resin hardening | curing agent can be used together in the range which does not impair the effect by the phenol resin hardening | curing agent used here. Examples include phenol novolac resins, cresol novolac resins, dicyclopentadiene modified phenol resins, phenol aralkyl resins, terpene modified phenol resins, and the like, but are not limited thereto. However, when the polyfunctional phenol resin curing agent represented by the general formula (1) in the present invention is less than 80% by weight in the total phenol resin curing agent, the glass transition temperature is lowered as in the case of the epoxy resin. .
[0020]
As a hardening accelerator in this invention, what is necessary is just to accelerate | stimulate the hardening reaction of an epoxy group and a phenolic hydroxyl group, and what is generally used for a sealing material can be used, for example, 1, 8- diazabicyclo (5 , 4, 0) Undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like, and these may be used alone or in combination.
[0021]
One feature of the inorganic filler in the present invention is that it has a small maximum particle size and a predetermined particle size distribution. The smaller the particle diameter of the inorganic filler, the more desirable is that the gap between the circuit board and the semiconductor element in the semiconductor device is surely filled. However, it is not possible to obtain sufficient fluidity to fill the voids only with an inorganic filler having a small particle size. If the amount of inorganic filler is reduced in order to obtain sufficient fluidity, sufficient reliability and heat conduction can be obtained. I can't get sex. Therefore, it is necessary to use alumina having two or more maximum points of particle size distribution at 0.5 μm to 12 μm, and to remove relatively large particles that impede the filling of narrow paths. If the maximum point of the particle size distribution is below the lower limit value, the fluidity is significantly lowered, and if the maximum point is higher than the upper limit value, the filling property is liable to be impaired even if the maximum particle size is controlled depending on the flow path. . In addition, even if the maximum point is in the range of 0.5 μm to 12 μm, if there is only one maximum point, a relatively small particle is arranged in a gap between relatively large inorganic fillers. Therefore, the fluidity is remarkably lowered regardless of the maximum particle size.
Since the particle size that inhibits filling differs depending on the flow path, there is no clear standard for “particle size that inhibits filling”, and the size of the gap between the circuit board and the semiconductor element in the semiconductor device is considered. Then, it may be adjusted by appropriately using a conventionally known classification method. However, it seems that the filling property in many cases can be coped with by setting the maximum particle size to 24 μm or less.
[0022]
Here, the particle size distribution of the inorganic filler is obtained by collecting the inorganic filler in accordance with JIS M8100 powder mixture-sampling method general rule, and in accordance with the sample preparation general rule for fine particle size distribution measurement of JIS R 1622-1995. Then, an inorganic filler is prepared as a measurement sample, and a laser diffraction particle size distribution measurement manufactured by Shimadzu Corporation in accordance with a particle size distribution measurement method by a laser diffraction / scattering method of a JIS R 1629-1997 fine ceramic raw material. This is a value measured using an apparatus SALD-7000 (laser wavelength: 405 nm) under the conditions that the refractive index of the inorganic filler is real part 1.80 and imaginary part 1.00 using water as the solvent.
The specific surface area is a value measured by the BET 1-point method using nitrogen as an adsorbate in accordance with the method for measuring the specific surface area of the fine ceramic powder by the gas adsorption BET method of JIS R 1626-1996.
[0023]
In addition to the components (A) to (D), the epoxy resin composition used in the present invention includes a brominated epoxy resin, a flame retardant such as antimony oxide, an inorganic ion exchanger such as bismuth oxide hydrate, γ -Coupling agents such as glycidoxypropyltrimethoxysilane, colorants such as carbon black and bengara, low stress components such as silicone oil and silicone rubber, natural waxes, synthetic waxes, higher fatty acids and their metal salts or paraffins You may mix | blend various additives, such as a mold release agent and antioxidant, suitably. Further, if necessary, the inorganic filler may be used after being treated with a coupling agent, an epoxy resin or a phenol resin in advance, and as a treatment method, a method of removing the solvent after mixing with a solvent or a direct inorganic filler may be used. There is a method of adding to a filler and processing using a mixer.
[0024]
The epoxy resin composition used in the present invention is obtained by mixing the components (A) to (D) and other additives at room temperature using a mixer, melt-kneading with a kneader such as an extruder such as a roll or kneader, and cooling. Obtained by post-grinding.
[0025]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Example 1
Alumina A (average particle size 8.2 .mu.m, specific surface area 1.1 m 2 / g, the particle size of the maximum point 9.8 .mu.m, or smaller than the maximum particle size 24 [mu] m) 64.00 wt%
Alumina D (average particle size 0.7 [mu] m, a specific surface area of 7.9 m 2 / g, the maximum point particle size 0.7 [mu] m, or less than the maximum particle size 24 [mu] m) 20.00 wt%
A polyfunctional phenol resin (a) represented by the formula (3) and a phenol (b) represented by the formula (5) mixed at a weight ratio (a) / (b) = 4 to form glycidyl ether (Japan) Manufactured by Epoxy Resin Co., Ltd., Epicoat YL6677, epoxy equivalent 163. Hereinafter referred to as Epoxy Resin 1) 8.18% by weight
[0026]
Embedded image
Embedded image
Multifunctional phenol resin curing agent represented by formula (3) (Maywa Kasei Co., Ltd., MEH-7500-3S, softening point 83 ° C., hydroxyl group equivalent 103) 5.32% by weight
γ-glycidoxypropyltrimethoxysilane 0.20% by weight
1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU) 0.20% by weight
Brominated bisphenol A type epoxy resin (softening point 63 ° C., epoxy group equivalent 359, bromine content 48% by weight) 0.50% by weight
Antimony trioxide 1.00% by weight
Carnauba wax 0.30% by weight
Carbon black 0.30% by weight
Were mixed at a normal temperature with a mixer, kneaded with two rolls at 70 to 120 ° C., cooled and pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.
[0029]
Evaluation method Spiral flow: Using a mold for spiral flow measurement according to EMMI-1-66, measurement was performed at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes. The unit is cm.
Slit filling: Using molds with channel thicknesses of 40 μm, 60 μm, and 80 μm, transfer molding is performed at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, a curing time of 2 minutes, and the filling distance of each channel is measured. did. The unit is mm.
Simulated mold filling property: Six rectangular columns of 9 mm × 9 mm × 0.42 mm (thickness) are provided in a rectangular flow channel having a length of 145 mm, a width of 15 mm, and a thickness of 0.5 mm (the interval between the rectangular columns and the rectangular columns). 3 mm) 6 square prisms of 9 mm x 9 mm x 0.45 mm (thickness) in an evaluation die assuming narrow path filling and a rectangular flow channel of length 145 mm, width 15 mm, thickness 0.5 mm (Evaluation is performed using a mold for evaluation, assuming a narrow path filling, with a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, a curing time of 2 minutes, and 80 μm and 50 μm) Gap filling properties (unfilled, presence of voids) were determined.
Glass transition temperature: Using a transfer molding machine, a test piece molded into a size of 4 mm × 4 mm × 15 mm with a mold temperature of 175 ° C., an injection pressure of 9.8 MPa and a curing time of 2 minutes is post-cured at 175 ° C. for 8 hours. Then, α1 and α2 are determined from a chart when measured with a thermomechanical analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd., TMA100) at a measurement temperature range of 0 to 320 ° C. and a heating rate of 5 ° C./min. The intersection of the extended lines was defined as the glass transition temperature. The unit is ° C.
[0030]
Examples 2-9, Comparative Examples 1-8
According to the composition of Table 1 and Table 2, an epoxy resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner. These evaluation results are shown in Tables 1 and 2.
The alumina, epoxy resin and phenol resin used in other than Example 1 are shown below.
Alumina B (average particle size 5.0 μm, specific surface area 2.8 m 2 / g, maximum point particle size 5.0 μm, maximum particle size 24 μm or less)
Alumina C (average particle size 4.0 μm, specific surface area 3.1 m 2 / g, maximum point particle size 5.0 μm, maximum particle size 12 μm or less)
Alumina E (average particle size 0.7 [mu] m, a specific surface area of 7.9 m 2 / g, the maximum point particle size 0.7 [mu] m, or less than the maximum particle size of 12 [mu] m)
Alumina F (average particle diameter 13.0, specific surface area 1.0 m 2 / g, the particle size of the maximum point 15.0 .mu.m, less than or equal to the maximum particle size of 24 [mu] m)
Alumina G (average particle size 0.1 [mu] m, a specific surface area of 30 m 2 / g, the maximum point particle size 0.1 [mu] m, or less than the maximum particle size of 24 [mu] m)
Alumina H (average particle size 7.7 μm, specific surface area 1.0 m 2 / g, maximum point particle size 9.8 μm, maximum particle size 45 μm )
Alumina I (average particle size 0.7 [mu] m, a specific surface area of 7.9 m 2 / g, the maximum point particle size 0.7 [mu] m, maximum particle size 45 [mu] m)
Epoxy resin 2: Polyfunctional phenol resin (a) represented by formula (3) and phenols (b) represented by formula (5) are mixed at a weight ratio (a) / (b) = 9 to form glycidyl ether. (Epoxy equivalent 165)
Epoxy resin 3: Polyfunctional phenol resin (a) represented by formula (3) and phenols (b) represented by formula (5) were mixed at a weight ratio (a) / (b) = 1.5 to give glycidyl. Etherified (epoxy equivalent 160)
Epoxy resin 4: Polyfunctional phenol resin (a) represented by formula (3) and phenols (b) represented by formula (5) are mixed at a weight ratio (a) / (b) = 20 to form glycidyl ether. (Epoxy equivalent 166)
Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YX4000, melting point 108 ° C., epoxy equivalent 185)
Orthocresol novolac type epoxy resin (Nippon Kayaku Co., Ltd., EOCN-1020-55, softening point 55 ° C., epoxy equivalent 196)
Phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF3, softening point 80 ° C., hydroxyl equivalent 105)
Phenol araalkyl resin (Mitsui Chemicals, XLC-4L, softening point 62 ° C., hydroxyl equivalent 168)
[0031]
[Table 1]
[Table 2]
【The invention's effect】
According to the present invention, the high thermal conductive epoxy resin composition reliably fills the gap between the circuit board and the semiconductor element in the semiconductor device, is excellent in productivity, and can impart high reliability to the connection portion. It is useful above.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003083940A JP4250988B2 (en) | 2003-03-25 | 2003-03-25 | High thermal conductive epoxy resin composition and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003083940A JP4250988B2 (en) | 2003-03-25 | 2003-03-25 | High thermal conductive epoxy resin composition and semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004292515A JP2004292515A (en) | 2004-10-21 |
| JP4250988B2 true JP4250988B2 (en) | 2009-04-08 |
Family
ID=33399231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003083940A Expired - Fee Related JP4250988B2 (en) | 2003-03-25 | 2003-03-25 | High thermal conductive epoxy resin composition and semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4250988B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5830974B2 (en) * | 2010-07-02 | 2015-12-09 | 日立化成株式会社 | Resin composition, B stage sheet, metal foil with resin, metal substrate and LED substrate |
| JP2012224799A (en) * | 2011-04-22 | 2012-11-15 | Sumitomo Bakelite Co Ltd | Liquid sealing resin composition and semiconductor device using the same |
| JP6187455B2 (en) * | 2012-03-29 | 2017-08-30 | 住友ベークライト株式会社 | Resin composition and semiconductor device |
| CN102633990A (en) * | 2012-04-05 | 2012-08-15 | 广东生益科技股份有限公司 | Epoxy resin composition, prepreg made of epoxy resin composition and copper-coated laminate made of epoxy resin composition |
| JP2014031460A (en) * | 2012-08-06 | 2014-02-20 | Panasonic Corp | Epoxy resin composition for encapsulation and semiconductor device using the same |
| CN112226041A (en) * | 2020-10-12 | 2021-01-15 | 江苏华海诚科新材料股份有限公司 | High-thermal-conductivity epoxy resin composition and preparation method thereof |
-
2003
- 2003-03-25 JP JP2003083940A patent/JP4250988B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004292515A (en) | 2004-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5019251B2 (en) | Epoxy resin composition and semiconductor device | |
| KR20080069264A (en) | Sealing epoxy resin forming material and electronic component device | |
| JP4250988B2 (en) | High thermal conductive epoxy resin composition and semiconductor device | |
| JP4622221B2 (en) | Epoxy resin composition and semiconductor device | |
| JPS6259626A (en) | Epoxy resin composition | |
| JP4496740B2 (en) | Epoxy resin composition and semiconductor device | |
| JP4411853B2 (en) | High thermal conductive epoxy resin composition and semiconductor device | |
| JP2018177858A (en) | Carbon black-dispersed phenolic resin, epoxy resin composition and method for producing the same | |
| JP2004352894A (en) | Epoxy resin composition and semiconductor device | |
| JP2003277585A (en) | Epoxy resin composition and semiconductor device | |
| JP2003213084A (en) | Epoxy resin composition and semiconductor device | |
| JP5275697B2 (en) | Epoxy resin composition for sealing and method for producing the same | |
| JP5124930B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
| JP2006225464A (en) | Epoxy resin composition and semiconductor device | |
| JP2005154717A (en) | Epoxy resin composition and semiconductor device | |
| JP3582771B2 (en) | Epoxy resin composition and semiconductor device | |
| JP2004277509A (en) | High-heat conductive epoxy resin composition and semiconductor apparatus | |
| JP2002241581A (en) | Epoxy resin composition and semiconductor device | |
| JP5067994B2 (en) | Epoxy resin composition and semiconductor device | |
| JP3986917B2 (en) | Epoxy resin composition and semiconductor device | |
| JP5093977B2 (en) | Area mounted semiconductor device | |
| JP4687195B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
| JPH05125159A (en) | Epoxy resin composition, its cured product and semiconductor device | |
| JP2000309678A (en) | Epoxy resin composition and semiconductor device | |
| JP2003089718A (en) | Epoxy resin composition and semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051128 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080411 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080527 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080722 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081224 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090106 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4250988 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120130 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130130 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140130 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |