JP4348775B2 - Epoxy resin composition - Google Patents

Description

（Ｒ²、Ｒ³は炭素数１〜３０の一価の炭化水素基、Ｒ⁴、Ｒ⁵は炭素数１〜２０の二価の炭化水素基、ｎは１〜３の整数を各々示す。） 」である。
【００１６】
【発明の実施の形態】
以下、本発明の構成を詳述する。
【００１７】
本発明におけるエポキシ樹脂（Ａ）は１分子中にエポキシ基を２個以上有するものであれば特に限定されず、これらの具体例としては、たとえばクレゾールノボラック型エポキシ樹脂、ビスヒドロキシビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、線状脂肪族型エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、ハロゲン化エポキシ樹脂およびスピロ環含有エポキシ樹脂などがあげられる。用途によっては２種以上のエポキシ樹脂を併用しても良いが、半導体装置封止用としては耐熱性の点からクレゾールノボラック型エポキシ樹脂またはビスヒドロキシビフェニル型エポキシ樹脂を含有することが好ましく、そのエポキシ当量は５００以下が好ましく、特に３００以下が好ましい。これらクレゾールノボラック型エポキシ樹脂またはビスヒドロキシビフェニル型エポキシ樹脂の含有量は、全エポキシ樹脂（Ａ）中に50重量％以上含むことが好ましい。
【００１８】
本発明において、エポキシ樹脂（Ａ）の配合量は、通常エポキシ系樹脂組成物中に５〜２５重量％の範囲が好適である。かかる範囲内とすることにより成形性や接着性が十分であり、線膨張係数が小さく、低応力性に優れたエポキシ系樹脂組成物が得られる。
【００１９】
本発明における硬化剤（Ｂ）は、エポキシ樹脂（Ａ）と反応して硬化させるものであれば特に限定されず、それらの具体例としては、例えばフェノールノボラック、クレゾールノボラックなどのノボラック樹脂、ビスフェノールＡなどのビスフェノール化合物、無水マレイン酸、無水フタル酸、無水ピロメリット酸などの酸無水物およびメタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどの芳香族アミンなどがあげられる。
【００２０】
なかでも、半導体装置封止用としては、耐熱性、耐湿性および保存性の点から、フェノールノボラック、クレゾールノボラックなどのノボラック樹脂が好ましく用いられ、用途によっては２種以上の硬化剤を併用しても良い。
【００２１】
本発明において、エポキシ樹脂（Ａ）と硬化剤（Ｂ）の配合比は、機械的性質および耐湿性の点から、エポキシ樹脂（Ａ）に対する硬化剤（Ｂ）の化学当量比が０．５〜１．６、特に０．８〜１．３の範囲にあることが好ましい。
【００２２】
また、本発明においてエポキシ樹脂（Ａ）と硬化剤（Ｂ）の硬化反応を促進するため硬化触媒を用いても良い。硬化触媒は硬化反応を促進するものであれば特に限定されず、たとえば２−メチルイミダゾール、２，４−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−ヘプタデシルイミダゾールなどのイミダゾール化合物、トリエチルアミン、ベンジルジメチルアミン、α−メチルベンジルメチルアミン、２−（ジメチルアミノメチル）フェノール、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）ウンデセン−７などの３級アミン化合物、ジルコニウムテトラメトキシド、ジルコニウムテトラプロポキシド、テトラキス（アセチルアセトナト）ジルコニウム、トリ（アセチルアセトナト）アルミニウムなどの有機金属化合物およびトリフェニルホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリ（ｐ−メチルフェニル）ホスフィン、トリ（ノニルフェニル）ホスフィンなどの有機ホスフィン化合物（Ｆ）があげられる。なかでも信頼性および成形性の点から有機ホスフィン化合物（Ｆ）が好ましく、トリフェニルホスフィンが特に好ましく用いられる。
【００２３】
これらの硬化触媒は、用途によっては二種以上を併用してもよく、その添加量はエポキシ樹脂（Ａ）１００重量部に対して０．１〜１０重量部の範囲が望ましい。
【００２４】
本発明における充填材（Ｃ）としては、溶融シリカ、結晶性シリカ、炭酸カルシウム、炭酸マグネシウム、アルミナ、マグネシア、クレー、タルク、ケイ酸カルシウム、酸化チタン、アスベスト、ガラス繊維などがあげられる。なかでも溶融シリカは線膨張係数を低下させる効果が大きく、低応力化に有効なために好ましく用いられる。
【００２５】
本発明においては、充填材（Ｃ）の割合を全体の８５〜９５重量％とするものである。かかる充填剤（Ｃ）の割合が８５重量％に満たない場合には半田耐熱性の点で問題があり、一方、９５重量％を超える場合には成形性の問題がある。
【００２６】
本発明におけるシランカップリング剤（Ｄ）としては、アミノ基を含有し、かつ該アミノ基がすべて二級アミノ基であるシラン化合物（ｄ′）と下記化学式（Ｉ）で表されるシラン化合物（ｄ″）とを併用することが重要である。これによって、耐湿性などの信頼性および流動性、熱時硬度、バリなどの成形性を保ちつつ、銀メッキとの接着性が向上する。
【００２７】
【化６】

（Ｒ²、Ｒ³は炭素数１〜３０の一価の炭化水素基、Ｒ⁴、Ｒ⁵は炭素数１〜２０の二価の炭化水素基、ｎは１〜３の整数を各々示す。）
【００２８】
アミノ基を含有し、かつ該アミノ基がすべて二級アミノ基であるシラン化合物（ｄ′）の具体例としては、下記式（II）または（III）で表されるものがあげられる。
【００２９】
【化７】

（Ｒ¹、Ｒ²、Ｒ³は炭素数１〜３０の一価の炭化水素基、Ｒ⁴、Ｒ⁵は炭素数１〜２０の二価の炭化水素基、ｎは１〜３の整数を各々示す。）
【００３０】
【化８】

（Ｒ¹、Ｒ²、Ｒ³は炭素数１〜３０の一価の炭化水素基、Ｒ⁴、Ｒ⁵は炭素数１〜２０の二価の炭化水素基、ｎは１〜３の整数を各々示す。）
【００３１】
なかでも、式（Ｉ）においてＲ¹がフェニル基、Ｒ²およびＲ³がメチル基またはエチル基、Ｒ⁴がプロピレン基でｎは２または３のシラン化合物（ｄ′）が成形性および信頼性の改良効果が大きいため、好ましく用いられる。
【００３２】
シラン化合物（ｄ″）については、式（Ｉ）中でＲ²およびＲ³がメチル基またはエチル基、Ｒ⁴がプロピレン基でｎは２または３のシラン化合物（ｄ″）が銀メッキへの接着性の改良の効果が大きいので好ましく用いられる。
【００３３】
本発明においてはシランカップリング剤（Ｄ）中のシラン化合物（ｄ′）と（ｄ″）との混合比（ｄ′：ｄ″）を重量比で８５：１５〜５０：５０の範囲にするものである。かかる範囲内とすることにより成形性および信頼性の改良効果を優れたものとすることができる。混合比（ｄ′：ｄ″）がかかる範囲外であると成形性や信頼性の改良効果が不十分なものとなる。なお、銀メッキへの接着性の改良効果を大きくする観点から、混合比（ｄ′：ｄ″）は３０：７０〜５０：５０の範囲にあることが更に好ましい。
【００３４】
このシランカップリング剤（Ｄ）の添加量は、成形性と信頼性の点から、通常充填材１００重量部に対して０．１〜５重量部、好ましくは０．２〜３重量部、更に好ましくは０．３〜１．５重量部である。本発明において充填材（Ｃ）をシランカップリング剤（Ｄ）であらかじめ表面処理することが、信頼性、接着性の向上の点で好ましい。
【００３５】
本発明のエポキシ系樹脂組成物にはハロゲン化エポキシ樹脂などのハロゲン化合物、リン化合物などの難燃剤、三酸化アンチモンなどの難燃助剤、カーボンブラック、酸化鉄などの着色剤、シリコーンゴム、スチレン系ブロック共重合体、オレフィン系重合体、変性ニトリルゴム、変性ポリブタジエンゴムなどのエラストマー、ポリスチレンなどの熱可塑性樹脂、チタネートカップリング剤などのカップリング剤、長鎖脂肪酸、長鎖脂肪酸の金属塩、長鎖脂肪酸のエステル、長鎖脂肪酸のアミド、パラフィンワックスなどの離型剤および有機過酸化物など架橋剤を任意に添加することができる。
【００３６】
本発明のエポキシ系樹脂組成物は溶融混練することが好ましく、たとえばバンバリーミキサー、ニーダー、ロール、単軸もしくは二軸の押出機およびコニーダーなどの公知の混練方法を用いて溶融混練することにより、製造される。
【００３７】
本発明のエポキシ系樹脂組成物は特に銀メッキとの接着性が良好であり、リードフレーム部分を銀メッキしたパッケージを成形するにあたって特に有用である。
【００３８】
【実施例】
以下、実施例により本発明を具体的に説明する。なお、実施例中の％は重量％を示す。
なお、本発明で使用した原材料は以下の通りである。なお、組成物への配合量は全組成物中の重量％で示し、硬化促進剤、着色剤および離型剤以外配合量は表１に記載した。
【００３９】
〈エポキシ樹脂Ｉ〉エポキシ当量２００のオルソクレゾールノボラック型エポキシ樹脂
〈エポキシ樹脂II〉４，４−ビス（２，３−エポキシプロポキシ）−３，３，５，５−テトラメチルビフェニル
〈硬化剤Ｉ〉水酸基当量１０７のフェノールノボラック樹脂
〈硬化剤II〉下記式で示されるフェノール化合物
【化９】

（ただし、ｍが１〜３の成分を９０重量％含む）
〈無機質充填材〉平均粒径２３μｍの非晶性溶融シリカ
〈シランカップリング剤Ｉ〉Ｎ−フェニルアミノプロピルトリメトキシシラン
〈シランカップリング剤II〉γ−ウレイドプロピルトリエトキシシラン
〈シランカップリング剤III〉γ−グリシジロキシプロピルトリメトキシシラン
（シランカップリング剤は前もって無機充填材と混合しておいた。なおシランカップリング剤Ｉとシランカップリング剤IIを同時に使用する場合にはシランカップリング剤同士を混合してから無機充填材と混合した。）
〈難燃剤〉エポキシ当量４００、臭素含有量５０重量％のブロム化ビスフェノールＡ型エポキシ樹脂
〈難燃助剤〉三酸化アンチモン
〈硬化促進剤〉トリフェニルホスフィン（０．１重量％）
〈着色剤〉カーボンブラック（０．２重量％）
〈離型剤〉カルナバワックス（０．３重量％）
【００４０】
各成分を、表１に示した組成比で、ミキサーによりドライブレンドした。これを、ロール表面温度９０℃のミキシングロールを用いて５分間加熱混練後、冷却、粉砕して半導体封止用のエポキシ系樹脂組成物を製造した。
【００４１】
【表１】

【００４２】
この樹脂組成物を用いて、低圧トランスファー成形法により１７５℃、キュアータイム２分間の条件で成形し、１８０℃、５時間の条件でポストキュアーして下記の物性測定法により各樹脂組成物の物性を評価した。なお、特に示さない限り成形条件は１７５℃、キュアタイム２分間であり、ポストキュアーは１８０℃、５時間とした。
【００４３】
半田耐熱性：表面にAl蒸着した模擬素子を搭載し、リードフレーム部分を銀メッキしたチップサイズ１２×１２ｍｍの１６０ｐｉｎＱＦＰ（クアッドフラットパッケージ）を２０個成形し、８５℃／８５％ＲＨで１６８時間加湿後、最高温度２４５℃のＩＲリフロー炉で加熱処理し、外部クラックの発生数を調べた。表２には試験を行ったパッケージ２０個の内、外部クラックの発生したパッケージ数を示す。
【００４４】
接着性：半田耐熱性試験に用いたのと同様の１６０ｐｉｎＱＦＰを８５℃／８５％ＲＨで１６８時間加湿後、最高温度２４５℃のＩＲリフロー炉で２分間加熱処理したのち、リードフレームの銀メッキ部分の剥離状況を超音波探傷器（日立建機株式会社製 ｍｉ−ｓｃｏｐｅ１０）で観測し、剥離の発生数を調べた。表２には試験を行ったパッケージ２０個の内、剥離の発生したパッケージ数を示す。
【００４５】
吸水率：半田耐熱性試験に用いいたのと同様の１６０ｐｉｎＱＦＰについて乾燥後の重量と８５℃／８５％ＲＨで１６８時間加湿後の重量の比較から樹脂組成物の吸水率（％）を測定した。表２には２０個の平均値を示す。
【００４６】
ＰＫＧ充填性：半田耐熱試験に用いたのと同様の１６０ｐｉｎＱＦＰを成形後に目視および顕微鏡を用いて観察し、未充填・ボイドの有無を調べた。表２に結果を示す。未充填・ボイドのあるものを不良、未充填・ボイドの見られないものを良好と判断した。
【００４７】
表２に評価結果を示す。
【００４８】
【表２】

【００４９】
表２に見られるように本発明のエポキシ系樹脂組成物は半田耐熱性、接着性、ＰＫＧ充填性に優れている。
【００５０】
これに対してシランカップリング剤Ｉを単独で使用した場合は接着性が、シランカップリング剤IIを単独で使用した場合は半田耐熱性が、シランカップリング剤IIIを単独で使用した場合は半田耐熱性と接着性が劣っている。
シランカップリング剤Ｉとシランカップリング剤IIの混合比が重量比で８５：１５〜５０：５０の範囲を外れる場合は接着性および半田耐熱性が劣っている。
【００５１】
充填材の量が８５重量％未満、あるいは９５重量％を越える場合は接着性および半田耐熱性が劣っている。
【００５２】
【発明の効果】
シランカップリング剤として特定の二種のシランカップリング剤を特定の重量比で混合し、半導体用封止樹脂に含有させることによって、銀メッキとの接着性が向上し、また高い半田耐熱性、良好な成形性が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin composition excellent in moldability, reliability, and adhesiveness, and particularly suitable for semiconductor encapsulation.
[0002]
[Prior art]
Epoxy resins are excellent in heat resistance, moisture resistance, electrical characteristics, adhesiveness, and the like, and can be added with various characteristics depending on the formulation, and thus are used as industrial materials such as paints, adhesives, and electrical insulating materials.
[0003]
As sealing methods for electronic circuit components such as semiconductor devices, hermetic sealing with metals and ceramics and resin sealing with phenol resin, silicone resin, epoxy resin, etc. have been proposed. The resin used is called a sealing material resin. Among them, resin sealing with an epoxy resin is most actively performed from the viewpoint of the balance between economy, productivity, and physical properties. As a sealing method using an epoxy resin, a method in which a composition obtained by adding a curing agent, a filler or the like to an epoxy resin is used, and a semiconductor element is set in a mold and sealed by a transfer molding method or the like is generally performed. It has been broken.
[0004]
The properties required for the epoxy resin composition for semiconductor encapsulation include reliability, moldability, and adhesiveness. Reliability is moisture resistance, solder heat resistance, etc., and moldability is fluidity, heat, etc. Hardness, burr, etc. are raised.
[0005]
Moisture resistance as used herein means that when a resin-encapsulated semiconductor device is left in a high-temperature, high-humidity environment, moisture penetrates through the interface between the encapsulating resin and the encapsulating resin and the lead frame. This is to prevent the device from failing. In recent years, the degree of integration of semiconductor elements has been improved, and higher moisture resistance has been required.
[0006]
In order to improve the moisture resistance of the sealing resin, a silane coupling agent is usually added. Specifically, a method of adding epoxy silane (Japanese Patent Publication No. Sho 62-17640), a method of adding mercaptosilane (Japanese Patent Laid-Open No. 55-153357) and a method of adding an aminosilane having a secondary amino group (Japanese Patent Laid-Open No. 2-218736) have been proposed.
[0007]
It has also been proposed to improve moisture resistance by reducing impurities contained in components such as epoxy resins and curing agents and increasing the purity of the sealing resin (Japanese Patent Laid-Open No. 57-212224). .
[0008]
Recently, the mounting of semiconductor device packages on printed circuit boards has been increasing in density and automation, and instead of the conventional “insertion mounting method” in which lead pins are inserted into holes in the substrate, semiconductor device packages are mounted on the substrate surface. Soldering "surface mounting method" has become popular. Accordingly, semiconductor device packages are also shifting from conventional DIP (dual in-line package) to thin FPP (flat plastic package) suitable for high-density mounting and surface mounting.
[0009]
Among packages suitable for such “surface mounting method”, TSOP, TQFP, and LQFP having a thickness of 2 mm or less are becoming mainstream due to the advancement of microfabrication technology. Therefore, it becomes more susceptible to external influences such as humidity and temperature, and reliability such as solder heat resistance, high temperature reliability and heat resistance reliability will become increasingly important in the future.
[0010]
In surface mounting, mounting is usually performed by solder reflow. In this method, semiconductor device packages are placed on a substrate, and these are exposed to a high temperature of 200 ° C. or higher, and solder previously applied to the substrate is melted to adhere the semiconductor device package to the substrate surface. In such a mounting method, since the entire semiconductor device package is exposed to a high temperature, if the adhesiveness between the resin and the lead frame is poor, peeling occurs, and a phenomenon occurs in which a crack is generated from the space formed at that time. Therefore, the adhesiveness with the metal used as a frame in the semiconductor sealing resin is very important.
[0011]
Moreover, peeling is more likely to occur from the silver-plated portion of the frame. This is because the silver-plated portion is inferior in adhesiveness to the resin as compared with 42 alloy or copper. Therefore, it is very important to improve the adhesiveness with the silver-plated portion, which is a cause of peeling.
[0012]
[Problems to be solved by the invention]
However, the addition of a silane coupling agent to the sealing resin is effective for improving moisture resistance, but now it is required to improve the adhesion with silver plating and to have solder heat resistance. However, a problem that the conventional silane coupling agent is insufficient is revealed. Therefore, the object of the present invention is to solve the problems of the epoxy resin composition described above, and improve the adhesiveness with silver plating in addition to reliability such as moisture resistance and fluidity, moldability such as hot hardness and burrs. It is to enable a thinner and highly integrated resin-encapsulated semiconductor by providing a resin composition having excellent solder heat resistance.
[0013]
[Means for Solving the Problems]
The inventors of the present invention have found that an epoxy resin composition suitable for the purpose can be obtained by adding a silane coupling agent having a specific structure, thereby achieving the present invention. .
[0014]
The present invention mainly has the following configuration. That is,
“An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), a filler (C) and a silane coupling agent (D), wherein the proportion of the filler (C) is 85 to 85% of the total. The silane coupling agent (D) is 95% by weight, and the silane coupling agent (D) contains an amino group and all of the amino groups are secondary amino groups, and is represented by the following chemical formula (I): And a mixing ratio (d ′: d ″) in a weight ratio of 85:15 to 50:50.
[0015]
[Chemical formula 5]

(R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3, respectively. )
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0017]
The epoxy resin (A) in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples thereof include, for example, a cresol novolac type epoxy resin, a bishydroxybiphenyl type epoxy resin, Examples thereof include bisphenol A type epoxy resins, linear aliphatic type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, and spiro ring-containing epoxy resins. Depending on the application, two or more types of epoxy resins may be used in combination, but it is preferable to contain a cresol novolac type epoxy resin or a bishydroxybiphenyl type epoxy resin from the viewpoint of heat resistance for sealing a semiconductor device. The equivalent is preferably 500 or less, particularly preferably 300 or less. The content of these cresol novolac type epoxy resins or bishydroxybiphenyl type epoxy resins is preferably 50% by weight or more in the total epoxy resin (A).
[0018]
In the present invention, the blending amount of the epoxy resin (A) is usually preferably in the range of 5 to 25% by weight in the epoxy resin composition. By setting it within such a range, it is possible to obtain an epoxy resin composition having sufficient moldability and adhesiveness, a small linear expansion coefficient, and excellent low stress property.
[0019]
The curing agent (B) in the present invention is not particularly limited as long as it is cured by reacting with the epoxy resin (A). Specific examples thereof include novolak resins such as phenol novolak and cresol novolak, and bisphenol A. Bisphenol compounds such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and the like, and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
[0020]
Among them, novolak resins such as phenol novolak and cresol novolak are preferably used for sealing semiconductor devices from the viewpoint of heat resistance, moisture resistance and storage, and two or more kinds of curing agents may be used in combination depending on applications. Also good.
[0021]
In the present invention, the compounding ratio of the epoxy resin (A) and the curing agent (B) is such that the chemical equivalent ratio of the curing agent (B) to the epoxy resin (A) is 0.5 to 0.5 from the viewpoint of mechanical properties and moisture resistance. It is preferable that it exists in the range of 1.6, especially 0.8-1.3.
[0022]
In the present invention, a curing catalyst may be used to accelerate the curing reaction between the epoxy resin (A) and the curing agent (B). The curing catalyst is not particularly limited as long as it accelerates the curing reaction. For example, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Imidazole compounds such as methylimidazole and 2-heptadecylimidazole, triethylamine, benzyldimethylamine, α-methylbenzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1 , 8-diazabicyclo (5,4,0) undecene-7 and other tertiary amine compounds, zirconium tetramethoxide, zirconium tetrapropoxide, tetrakis (acetylacetonato) zirconium, tri (acetylacetonato) aluminum, etc. Machine metal compound and triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (p- methylphenyl) phosphine, tri organic phosphine compounds such as (nonylphenyl) phosphine (F) and the like. Of these, the organic phosphine compound (F) is preferable from the viewpoint of reliability and moldability, and triphenylphosphine is particularly preferably used.
[0023]
These curing catalysts may be used in combination of two or more depending on the application, and the addition amount is desirably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
[0024]
Examples of the filler (C) in the present invention include fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, asbestos, and glass fiber. Among them, fused silica is preferably used because it has a large effect of reducing the linear expansion coefficient and is effective in reducing stress.
[0025]
In this invention, the ratio of a filler (C) shall be 85 to 95 weight% of the whole. When the proportion of the filler (C) is less than 85% by weight, there is a problem in terms of solder heat resistance, whereas when it exceeds 95% by weight, there is a problem with formability.
[0026]
As the silane coupling agent (D) in the present invention, a silane compound (d ′) containing an amino group and all of the amino groups being secondary amino groups and a silane compound represented by the following chemical formula (I) ( In combination with d ″), it is important to improve the adhesion to silver plating while maintaining the reliability and fluidity such as moisture resistance, the moldability such as hot hardness and burrs.
[0027]
[Chemical 6]

(R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3, respectively. )
[0028]
Specific examples of the silane compound (d ′) containing an amino group and all of the amino groups being secondary amino groups include those represented by the following formula (II) or (III).
[0029]
[Chemical 7]

(R ¹ , R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3. Each is shown.)
[0030]
[Chemical 8]

(R ¹ , R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3. Each is shown.)
[0031]
Among them, a silane compound (d ′) in which R ¹ is a phenyl group, R ² and R ³ are a methyl group or an ethyl group, R ⁴ is a propylene group, and n is 2 or 3 in the formula (I) is moldability and reliability. Since the improvement effect of is large, it is preferably used.
[0032]
As for the silane compound (d ″), in formula (I), R ² and R ³ are methyl or ethyl groups, R ⁴ is a propylene group, and n is 2 or 3 silane compound (d ″) to silver plating. Since the effect of improving adhesiveness is great, it is preferably used.
[0033]
In the present invention, the mixing ratio (d ′: d ″) of the silane compounds (d ′) and (d ″) in the silane coupling agent (D) is in the range of 85:15 to 50:50 by weight. Is. By making it within such a range, the effect of improving moldability and reliability can be made excellent. If the mixing ratio (d ′: d ″) is outside this range, the effect of improving the formability and reliability will be insufficient. From the viewpoint of increasing the effect of improving the adhesiveness to silver plating, mixing The ratio (d ′: d ″) is more preferably in the range of 30:70 to 50:50.
[0034]
The amount of the silane coupling agent (D) added is usually 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, more preferably 100 parts by weight, from the viewpoint of moldability and reliability. Preferably it is 0.3-1.5 weight part. In the present invention, the surface treatment of the filler (C) with the silane coupling agent (D) in advance is preferable in terms of improving reliability and adhesiveness.
[0035]
The epoxy resin composition of the present invention includes halogen compounds such as halogenated epoxy resins, flame retardants such as phosphorus compounds, flame retardant aids such as antimony trioxide, colorants such as carbon black and iron oxide, silicone rubber, styrene Block copolymers, olefin polymers, elastomers such as modified nitrile rubber and modified polybutadiene rubber, thermoplastic resins such as polystyrene, coupling agents such as titanate coupling agents, long chain fatty acids, metal salts of long chain fatty acids, Release agents such as esters of long chain fatty acids, amides of long chain fatty acids, paraffin wax, and crosslinking agents such as organic peroxides can be optionally added.
[0036]
The epoxy resin composition of the present invention is preferably melt-kneaded. For example, it is produced by melt-kneading using a known kneading method such as a Banbury mixer, a kneader, a roll, a single-screw or twin-screw extruder and a kneader. Is done.
[0037]
The epoxy resin composition of the present invention has particularly good adhesion to silver plating, and is particularly useful in molding a package having a lead frame portion plated with silver.
[0038]
【Example】
Hereinafter, the present invention will be described specifically by way of examples. In addition,% in an Example shows weight%.
The raw materials used in the present invention are as follows. In addition, the compounding quantity to a composition was shown in the weight% in all the compositions, and compounding quantities other than a hardening accelerator, a coloring agent, and a mold release agent were described in Table 1.
[0039]
<Epoxy resin I> Orthocresol novolac type epoxy resin having an epoxy equivalent of 200 <Epoxy resin II> 4,4-bis (2,3-epoxypropoxy) -3,3,5,5-tetramethylbiphenyl <Curing agent I> Phenolic novolak resin having a hydroxyl equivalent weight of 107 <Curing agent II> A phenol compound represented by the following formula:

(However, 90% by weight of the component where m is 1-3)
<Inorganic filler> Amorphous fused silica having an average particle size of 23 [mu] m <Silane coupling agent I> N-phenylaminopropyltrimethoxysilane <Silane coupling agent II> [gamma] -ureidopropyltriethoxysilane <Silane coupling agent III > Γ-Glycidyloxypropyltrimethoxysilane (Silane coupling agent was previously mixed with inorganic filler. Silane coupling agent when Silane coupling agent I and Silane coupling agent II are used simultaneously) After mixing each other, it was mixed with inorganic filler.)
<Flame Retardant> Brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 and bromine content of 50% by weight <Flame retardant aid> Antimony trioxide <Curing accelerator> Triphenylphosphine (0.1% by weight)
<Colorant> Carbon black (0.2% by weight)
<Release agent> Carnauba wax (0.3% by weight)
[0040]
Each component was dry blended with a mixer at the composition ratio shown in Table 1. This was heated and kneaded for 5 minutes using a mixing roll having a roll surface temperature of 90 ° C., then cooled and ground to produce an epoxy resin composition for semiconductor encapsulation.
[0041]
[Table 1]

[0042]
Using this resin composition, it was molded under the conditions of 175 ° C. and a cure time of 2 minutes by the low-pressure transfer molding method, post-cured under the conditions of 180 ° C. and 5 hours, and the physical properties of each resin composition by the following physical property measurement method Evaluated. Unless otherwise indicated, the molding conditions were 175 ° C. and a cure time of 2 minutes, and the post cure was 180 ° C. and 5 hours.
[0043]
Solder heat resistance: 20 160pinQFP (quad flat package) chips with a 12x12mm chip size, mounted with a simulated element with Al vapor deposition on the surface, and silver-plated on the lead frame are molded and humidified at 85 ° C / 85% RH for 168 hours Thereafter, heat treatment was performed in an IR reflow furnace having a maximum temperature of 245 ° C., and the number of occurrences of external cracks was examined. Table 2 shows the number of packages in which external cracks occurred among the 20 packages tested.
[0044]
Adhesiveness: 160pinQFP similar to that used for solder heat resistance test was humidified at 85 ° C / 85% RH for 168 hours, then heat-treated in an IR reflow oven at a maximum temperature of 245 ° C for 2 minutes, and then the silver plating part of the lead frame The state of peeling was observed with an ultrasonic flaw detector (mi-scope 10 manufactured by Hitachi Construction Machinery Co., Ltd.), and the number of occurrences of peeling was examined. Table 2 shows the number of peeled packages among the 20 tested packages.
[0045]
Water absorption: The water absorption (%) of the resin composition was measured from a comparison of the weight after drying and the weight after humidification at 85 ° C./85% RH for 168 hours for the same 160pinQFP used in the solder heat resistance test. Table 2 shows the average value of 20 pieces.
[0046]
PKG filling property: 160 pinQFP similar to that used in the solder heat resistance test was observed visually and using a microscope after molding to examine the presence or absence of unfilled voids. Table 2 shows the results. An unfilled / voided product was judged to be defective, and an unfilled / voided product was judged to be good.
[0047]
Table 2 shows the evaluation results.
[0048]
[Table 2]

[0049]
As seen in Table 2, the epoxy resin composition of the present invention is excellent in solder heat resistance, adhesiveness, and PKG fillability.
[0050]
In contrast, when the silane coupling agent I is used alone, the adhesiveness is obtained, when the silane coupling agent II is used alone, the solder heat resistance is obtained, and when the silane coupling agent III is used alone, the solder is used. Heat resistance and adhesiveness are inferior.
When the mixing ratio of the silane coupling agent I and the silane coupling agent II is out of the range of 85:15 to 50:50 by weight, the adhesiveness and solder heat resistance are inferior.
[0051]
When the amount of the filler is less than 85% by weight or more than 95% by weight, the adhesiveness and solder heat resistance are inferior.
[0052]
【The invention's effect】
By mixing two specific silane coupling agents at a specific weight ratio as a silane coupling agent and including them in a semiconductor sealing resin, the adhesion with silver plating is improved, and high solder heat resistance, Good moldability is obtained.

Claims (4)

An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), a filler (C) and a silane coupling agent (D), wherein the ratio of the filler (C) is 85 to 95 of the whole. The silane coupling agent (D) is an amino group, and the silane coupling agent (D) is represented by the following chemical formula (I): An epoxy resin composition for semiconductor encapsulation, comprising a silane compound (d ″) and a mixing ratio (d ′: d ″) of 85:15 to 50:50 by weight.

(R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3, respectively. ) 2. The semiconductor encapsulation according to claim 1, wherein the silane compound (d ′) containing an amino group and all of the amino groups being secondary amino groups is represented by the following chemical formula (II) or (III): An epoxy resin composition for stopping.

(R ¹ , R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3. Each is shown.)

(R ¹ , R ² and R ³ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, R ⁴ and R ⁵ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 1 to 3. Each is shown.) The epoxy resin composition for semiconductor encapsulation according to claim 1 or 2, wherein the curing agent (B) contains a phenol compound represented by the following chemical formula (IV).

(In the formula, R may be the same or different, and represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. M represents an integer of 0 or more.) The semiconductor device sealed with the epoxy resin composition for semiconductor sealing in any one of Claims 1-3.