JP3056634B2 - Epoxy resin composition for semiconductor encapsulation - Google Patents
Epoxy resin composition for semiconductor encapsulationInfo
- Publication number
- JP3056634B2 JP3056634B2 JP6159994A JP6159994A JP3056634B2 JP 3056634 B2 JP3056634 B2 JP 3056634B2 JP 6159994 A JP6159994 A JP 6159994A JP 6159994 A JP6159994 A JP 6159994A JP 3056634 B2 JP3056634 B2 JP 3056634B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- epoxy resin
- phenol
- weight
- resin composition
- 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 - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Description
【０００１】[0001]
【産業上の利用分野】本発明は常温保存性、硬化性に優
れた半導体封止用エポキシ樹脂組成物に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for semiconductor encapsulation having excellent storage stability at room temperature and curability.
【０００２】[0002]
【従来の技術】エポキシ樹脂は耐熱性、耐湿性、電気特
性、接着性などに優れており、電気絶縁材料、塗料、接
着剤など幅広い分野で使用されている。ダイオード、ト
ランジスタ、集積回路等の電子部品についても熱硬化性
樹脂が使われ、特に集積回路では耐熱性、耐湿性に優れ
たオルソクレゾールノボラックエポキシ樹脂をノボラッ
ク型フェノール樹脂で硬化させたエポキシ樹脂組成物が
一般的に用いられている。しかしながら近年集積回路の
高集積化に伴いチップが大型化され、またパッケージは
表面実装化により小型、薄型化されてきている。このた
めクラックの発生、クラックに起因した耐湿性の劣化等
の問題が生じている。また保存性が乏しいため室温で長
時間放置した場合、成形時に流動性（スパイラルフロ
ー）が低下し未充填などの問題が生じている。2. Description of the Related Art Epoxy resins are excellent in heat resistance, moisture resistance, electric properties, adhesiveness and the like, and are used in a wide range of fields such as electric insulating materials, paints and adhesives. Thermosetting resins are also used for electronic components such as diodes, transistors, and integrated circuits.Especially for integrated circuits, epoxy resin compositions obtained by curing orthocresol novolak epoxy resin, which has excellent heat resistance and moisture resistance, with a novolac phenol resin Is generally used. However, in recent years, chips have been increased in size with the increase in integration of integrated circuits, and packages have been reduced in size and thickness by surface mounting. For this reason, there are problems such as generation of cracks and deterioration of moisture resistance due to the cracks. In addition, when stored at room temperature for a long time due to poor preservability, the fluidity (spiral flow) is reduced during molding, causing problems such as unfilling.
【０００３】クラックの問題を解決するために、 エ
ポキシ樹脂として式（４）で示されるエポキシ樹脂の使
用、 溶融シリカ粉末の配合量の増加、 エポキ
シ樹脂硬化剤として式（２）、式（３）で示される可撓
性フェノール硬化剤の使用が提案されている。しかしな
がら可撓性硬化剤は熱時硬化度が低く、離型性が劣ると
いった問題点があり、これらの問題に対する解決手段と
して、 硬化促進剤の増加、 可撓性硬化剤と硬化
促進剤の溶融混合が提案されている。一方保存性の問題
についてはテトラ置換ホスホニウム・テトラ置換ボレー
ト化合物を配合する方法があるが、最近盛んに用いられ
ているマルチプランジャー成形対応としては、速硬化が
主流となっているため硬化性の点でいまだ不充分であ
る。従って、常温保存性と硬化性を両立させた材料の要
求が高まっている。In order to solve the problem of cracks, use of an epoxy resin represented by the formula (4) as an epoxy resin, an increase in the blending amount of fused silica powder, and formulas (2) and (3) as epoxy resin curing agents The use of a flexible phenolic curing agent represented by However, flexible curing agents have problems such as a low degree of hardening when heated and inferior releasability. As a solution to these problems, increasing the number of curing accelerators, melting of the flexible curing agent and melting of the curing accelerator. Mixing has been proposed. On the other hand, there is a method of blending a tetra-substituted phosphonium / tetra-substituted borate compound with regard to the problem of storage stability. The point is still insufficient. Therefore, there is an increasing demand for a material having both room temperature storage stability and curability.
【０００４】[0004]
【発明が解決しようとする課題】本発明は従来の常温保
存性と硬化性の両立という問題点を解決するため種々の
検討の結果なされたもので、その目的とするところは電
気的特性及び他の諸特性を劣化させることなく、常温保
存性、硬化性が優れた半導体封止用エポキシ樹脂組成物
を提供することにある。DISCLOSURE OF THE INVENTION The present invention has been made as a result of various studies in order to solve the conventional problems of compatibility between ordinary temperature storability and curability. An object of the present invention is to provide an epoxy resin composition for semiconductor encapsulation having excellent room temperature storage property and curability without deteriorating the various characteristics of the above.
【０００５】[0005]
【課題を解決するための手段】本発明は、（Ａ）式
（１）で示されるトリフェニルホスフィン・トリフェニ
ルボランとThe present invention relates to (A) triphenylphosphine / triphenylborane represented by the formula (1):
【０００６】[0006]
【化５】 Embedded image
【０００７】（Ｂ）式（２）及び／または式（３）で示
される可撓性フェノール樹脂硬化剤とを予め加熱溶融さ
れてなる溶融混合物、(B) a molten mixture obtained by previously heating and melting a flexible phenol resin curing agent represented by the formula (2) and / or the formula (3);
【０００８】[0008]
【化６】 Embedded image
【０００９】[0009]
【化７】 （式（２）中のＲはパラキシリレン、式（３）中のＲは
ジシクロペンタジエンとフェノールを付加反応したジシ
クロペンタジエンジフェノール、テルペン類とフェノー
ルを付加反応したテルペン類ジフェノール、シクロペン
タジエンとフェノールを付加反応したシクロペンタジエ
ンジフェノール及びシクロヘキサノンとフェノールを付
加縮合したシクロヘキサノンジフェノールの各々の２個
のフェノール部を除いた残基の中から選択される１種、
ｎの値は０〜１０）Embedded image (R in the formula (2) is paraxylylene, R in the formula (3) is dicyclopentadiene diphenol obtained by addition reaction of dicyclopentadiene and phenol, terpene diphenol obtained by addition reaction of terpenes with phenol, and cyclopentadiene. One kind selected from residues excluding two phenol moieties of cyclopentadiene diphenol obtained by addition reaction of phenol and cyclohexanone diphenol obtained by addition condensation of cyclohexanone and phenol,
The value of n is 0-10)
【００１０】（Ｃ）式（４）で示されるエポキシ樹脂(C) an epoxy resin represented by the formula (4)
【００１１】[0011]
【化８】 （式中のＲ1〜Ｒ8は水素、ハロゲン、アルキル基の中か
ら選択される同一もしくは異なる原子または基）Embedded image (Wherein R 1 to R 8 are the same or different atoms or groups selected from hydrogen, halogen, and alkyl groups)
【００１２】を総エポキシ樹脂量に対して５０〜１００
重量％を含むエポキシ樹脂及び（Ｃ）無機充填材を必須
成分とし、特に全樹脂組成物中にトリフェニルホスフィ
ン・トリフェニルボランを０．３〜１．５重量％含む半
導体封止用エポキシ樹脂組成物である。[0012] 50 to 100 with respect to the total amount of epoxy resin
% By weight of an epoxy resin and (C) an inorganic filler as essential components, in particular, an epoxy resin composition for semiconductor encapsulation containing 0.3 to 1.5% by weight of triphenylphosphine / triphenylborane in the total resin composition. Things.
【００１３】以下本発明について詳細に説明する。本発
明に用いる溶融混合物は、式（１）で示されるトリフェ
ニルホスフィン・トリフェニルボランと式（２）及び／
または式（３）の可撓性フェノール樹脂硬化剤からな
る。式（２）及び式（３）の構造で示されるフェノール
樹脂硬化剤は分子構造中に比較的柔軟な構造を有する可
撓性フェノール樹脂硬化剤であり、フェノールノボラッ
ク樹脂硬化剤に比べて高温での弾性率の低下とリードフ
レーム及び半導体チップとの密着性を向上せしめること
ができる。従って、半田付け時の発生応力の低下と、そ
れに伴う半導体チップ等との剥離不良の防止に有効であ
る。更に式（２）中のＲはパラキシリレン、式（３）中
のＲはジシクロペンタジエンとフェノールを付加反応し
たジシクロペンタジエンジフェノール、テルペン類とフ
ェノールを付加反応したテルペン類ジフェノール、シク
ロペンタジエンとフェノール付加反応したシクロペンタ
ジエンジフェノール及びシクロヘキサンとフェノールを
付加縮合したシクロヘキサノンジフェノールの各々の２
個のフェノール部を除いた残基の中から選択される１種
で、これらの中ではテルペン類とフェノールを付加反応
したテルペン類ジフェノールの２個のフェノール部を除
いた残基が好ましい。式（２）及び式（３）のｎの値は
０〜１０である。ｎが１０を越えるとトランスファー成
形時での流動性が低下し、成形性が劣る傾向がある。Hereinafter, the present invention will be described in detail. The molten mixture used in the present invention comprises triphenylphosphine / triphenylborane represented by the formula (1) and formula (2) and / or
Or it consists of a flexible phenolic resin curing agent of the formula (3). The phenolic resin curing agents represented by the structures of the formulas (2) and (3) are flexible phenolic resin curing agents having a relatively flexible structure in the molecular structure, and are higher in temperature than phenol novolak resin curing agents. And the adhesion to the lead frame and the semiconductor chip can be improved. Therefore, it is effective in preventing a reduction in stress generated at the time of soldering and associated peeling failure from a semiconductor chip or the like. R in the formula (2) is paraxylylene, R in the formula (3) is dicyclopentadiene diphenol obtained by addition reaction of dicyclopentadiene and phenol, terpene diphenol obtained by addition reaction of terpenes and phenol, and cyclopentadiene. Each of cyclopentadiene diphenol subjected to phenol addition reaction and cyclohexanone diphenol obtained by addition condensation of cyclohexane and phenol
And one of the residues excluding phenol moieties, and among these, the residues excluding two phenol moieties of terpenes diphenol obtained by addition reaction of terpenes and phenol are preferable. The value of n in the expressions (2) and (3) is 0 to 10. If n exceeds 10, the fluidity during transfer molding tends to decrease, and moldability tends to be poor.
【００１４】本発明に用いるトリフェニルホスフィン・
トリフェニルボランは硬化促進剤であり、この硬化促進
剤の配合量は全樹脂組成物中に０．３〜１．５重量％
で、好ましくは０．６〜１．０重量％である。０．３重
量％未満だと、硬化不足により離型性が悪いという問題
があり、１．５重量％を越えると保存性が劣化するとい
う問題を生じる。本発明の特徴は、式（２）及び／また
は式（３）で示される可撓性フェノール樹脂硬化剤に硬
化促進剤であるトリフェニルホスフィン・トリフェニル
ボランを予め溶融混合した溶融混合物を用いることであ
る。可撓性フェノール樹脂硬化剤と硬化促進剤の溶融混
合手順は、例えば以下のようなものであるが、これに限
定されるものではない。予め加熱溶融させた可撓性フェ
ノール樹脂硬化剤を攪拌しながら、徐々に硬化促進剤を
添加し溶融混合物を得る。この際溶融混合温度は可撓性
フェノール樹脂硬化剤の軟化点及び硬化促進剤の融点を
越える温度で行うことが好ましい。溶融混合時間は、特
に限定するものではないが溶融混合系が透明になってか
ら、３０分間程度であれば通常充分である。この溶融混
合物はフェノールノボラック樹脂硬化剤と併用してもよ
い。併用するフェノールノボラック樹脂硬化剤は、フェ
ノール類とホルムアルデヒド等のアルデヒド源との重縮
合反応により合成される１分子中に２個以上のフェノー
ル性水酸基を有する通常の樹脂、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である。The triphenylphosphine used in the present invention
Triphenylborane is a curing accelerator, and the compounding amount of this curing accelerator is 0.3 to 1.5% by weight in the whole resin composition.
And preferably 0.6 to 1.0% by weight. If it is less than 0.3% by weight, there is a problem that the releasability is poor due to insufficient curing, and if it exceeds 1.5% by weight, there arises a problem that storage stability is deteriorated. A feature of the present invention is to use a melt mixture obtained by previously melt-mixing triphenylphosphine / triphenylborane as a curing accelerator with a flexible phenol resin curing agent represented by the formula (2) and / or the formula (3). It is. The melt mixing procedure of the flexible phenol resin curing agent and the curing accelerator is, for example, as follows, but is not limited thereto. While stirring the flexible phenol resin curing agent that has been heated and melted in advance, a curing accelerator is gradually added to obtain a molten mixture. At this time, it is preferable that the melting and mixing temperature be higher than the softening point of the flexible phenol resin curing agent and the melting point of the curing accelerator. Although the melt mixing time is not particularly limited, it is usually sufficient that the melt mixing time is about 30 minutes after the melt mixing system becomes transparent. This molten mixture may be used in combination with a phenol novolak resin curing agent. The phenol novolak resin curing agent to be used in combination is an ordinary resin having two or more phenolic hydroxyl groups in one molecule synthesized by a polycondensation reaction of a phenol and an aldehyde source such as formaldehyde, such as a phenol novolak resin and a cresol novolak. Resin.
【００１５】この溶融混合物の量を調節することによ
り、耐半田ストレス性を最大限に引きだすことができ
る。耐半田ストレス性の効果を引きだすためには、溶融
混合物中の式（２）及び／または式（３）で示される可
撓性フェノール樹脂硬化剤を総フェノール樹脂硬化剤量
に対して３０重量％以上、更に好ましくは５０重量％以
上使用するのが望ましい。使用量が３０重量％未満だと
低弾性及びリードフレーム、半導体チップとの密着力が
不充分で耐半田ストレス性の向上が望めない。フェノー
ルノボラック樹脂硬化剤に比べて、エポキシ樹脂との反
応速度が遅い可撓性フェノール樹脂硬化剤に硬化促進剤
を溶融混合して得られる溶融混合物を用いることによ
り、フェノールノボラック樹脂硬化剤と同等の反応速度
を得ることができる。これによりフェノールノボラック
樹脂と併用しても、反応速度の差による硬化後のエポキ
シ樹脂組成物中の未反応の可撓性フェノール樹脂硬化剤
の残留を防ぐことができ、成形品表面に未反応成分によ
る白色斑点の存在、熱時硬度の低下等の諸問題を解決す
ることができる。溶融混合物の使用として、別々に製造
した２種以上の溶融混合物をエポキシ樹脂組成物の製造
時に用いてもよい。By adjusting the amount of the molten mixture, the solder stress resistance can be maximized. In order to obtain the effect of resistance to soldering stress, the flexible phenolic resin curing agent represented by the formula (2) and / or (3) in the molten mixture is added in an amount of 30% by weight based on the total amount of the phenolic resin curing agent. More preferably, it is desirable to use 50% by weight or more. If the amount is less than 30% by weight, low elasticity and insufficient adhesion to the lead frame and semiconductor chip cannot be expected to improve solder stress resistance. Compared to the phenol novolak resin curing agent, by using a molten mixture obtained by melt-mixing a curing accelerator with a flexible phenol resin curing agent having a slower reaction rate with the epoxy resin, the same as the phenol novolak resin curing agent Reaction rates can be obtained. This can prevent the unreacted flexible phenolic resin curing agent from remaining in the epoxy resin composition after curing due to the difference in reaction rate, even when used in combination with the phenol novolak resin, and the unreacted components remain on the molded product surface. Problems such as the presence of white spots and a decrease in hardness when heated can be solved. As the use of the molten mixture, two or more separately prepared molten mixtures may be used at the time of producing the epoxy resin composition.
【００１６】本発明に用いる式（４）の構造で示される
ビフェニル型エポキシ樹脂は１分子中に２個のエポキシ
基を有する２官能性エポキシ樹脂で、従来の多官能性エ
ポキシ樹脂に比べ溶融粘度が低く、トランスファー成形
時の流動性に優れる。従って組成物の溶融シリカ粉末を
多く配合することができ、低熱膨張化及び低吸水化が図
られ、耐半田ストレス性に優れるエポキシ樹脂組成物を
得ることができる。このビフェニル型エポキシ樹脂の使
用量はこれを調節することにより耐半田ストレス性を最
大限に引きだすことができ、総エポキシ樹脂量の５０重
量％以上、好ましくは７０重量％以上使用するのが望ま
しい。５０重量％未満だと低熱膨張化及び低吸水性が得
られず、耐半田ストレス性が不十分である。更に式中の
Ｒ1〜Ｒ4はメチル基、Ｒ5〜Ｒ8は水素原子が好ましい。
ビフェニル型エポキシ樹脂以外に他のエポキシ樹脂を併
用する場合、用いるエポキシ樹脂はビスフェノール型エ
ポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フ
ェノールノボラック型エポキシ樹脂、トリフェノールメ
タン型エポキシ樹脂及びアルキル変性トリフェノールメ
タン型エポキシ樹脂等の３官能型エポキシ樹脂、トリア
ジン核含有エポキシ樹脂がある。The biphenyl type epoxy resin represented by the structure of the formula (4) used in the present invention is a bifunctional epoxy resin having two epoxy groups in one molecule, and has a higher melt viscosity than a conventional polyfunctional epoxy resin. And excellent fluidity during transfer molding. Therefore, a large amount of the fused silica powder of the composition can be blended, an epoxy resin composition having low thermal expansion and low water absorption, and having excellent solder stress resistance can be obtained. By adjusting the amount of the biphenyl type epoxy resin, solder stress resistance can be maximized by adjusting the amount of the biphenyl epoxy resin, and it is desirable to use 50% by weight or more, preferably 70% by weight or more of the total epoxy resin amount. If it is less than 50% by weight, low thermal expansion and low water absorption cannot be obtained, and the solder stress resistance is insufficient. Further, in the formula, R 1 to R 4 are preferably a methyl group, and R 5 to R 8 are preferably a hydrogen atom.
When other epoxy resins are used in addition to the biphenyl type epoxy resin, the epoxy resin used is bisphenol type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin. There are trifunctional epoxy resins such as resins and epoxy resins containing triazine nuclei.
【００１７】本発明で用いる無機充填材としては、溶融
シリカ粉末、球状シリカ粉末、結晶シリカ粉末、２次凝
集シリカ粉末、多孔質シリカ粉末、２次凝集シリカ粉末
または多孔質シリカ粉末を粉砕したシリカ粉末、アルミ
ナ等が挙げられ、特に溶融シリカ粉末、球状シリカ粉末
及び溶融シリカ粉末と球状シリカ粉末との混合物が好ま
しい。また無機充填材の配合量としては耐半田ストレス
性と成形性のバランスから全組成物中に７０〜９０重量
％含むことが好ましい。７０重量％未満だと耐半田スト
レス性が低下し、９０重量％を越えると流動性が低下し
充填不良が生じることから成形性が問題となる。The inorganic filler used in the present invention includes fused silica powder, spherical silica powder, crystalline silica powder, secondary aggregated silica powder, porous silica powder, secondary aggregated silica powder or silica obtained by grinding porous silica powder. Examples thereof include powder, alumina, and the like, and particularly preferred are fused silica powder, spherical silica powder, and a mixture of fused silica powder and spherical silica powder. The amount of the inorganic filler is preferably 70 to 90% by weight in the whole composition in view of the balance between solder stress resistance and moldability. If it is less than 70% by weight, the solder stress resistance decreases, and if it exceeds 90% by weight, the fluidity decreases and poor filling occurs, so that moldability is a problem.
【００１８】本発明の半導体封止用エポキシ樹脂組成物
は、エポキシ樹脂、可撓性フェノール樹脂硬化剤とトリ
フェニルホスフィン・トリフェニルボランとの溶融混合
物及び無機充填材を必須成分とするが、これ以外に必要
に応じて、シランカップリング剤、ブロム化エポキシ樹
脂、三酸化アンチモン、ヘキサブロムベンゼン等の難燃
剤、カーボンブラック、ベンガラ等の着色剤、天然ワッ
クス、合成ワックス等の離型剤及びシリコーンオイル、
ゴム等の低応力添加剤等の種々の添加剤を適宜配合して
も差し支えがない。また、本発明の封止用エポキシ樹脂
組成物を成形材料として製造するには、エポキシ樹脂、
溶融混合物、無機充填材、その他の添加剤をミキサー等
によって充分に均一に混合した後、さらに熱ロール又は
ニーダー等で溶融混練し、冷却後粉砕して成形材料とす
ることができる。これらの成形材料は電子部品あるいは
電気部品の封止、被覆、絶縁等に適用することができ
る。The epoxy resin composition for semiconductor encapsulation of the present invention comprises epoxy resin, a molten mixture of a flexible phenol resin curing agent and triphenylphosphine / triphenylborane, and an inorganic filler as essential components. Other than necessary, silane coupling agents, brominated epoxy resins, flame retardants such as antimony trioxide, hexabromobenzene, coloring agents such as carbon black and red iron, release agents such as natural wax and synthetic wax, and silicones oil,
Various additives such as low-stress additives such as rubber may be appropriately compounded. Further, to produce the sealing epoxy resin composition of the present invention as a molding material, epoxy resin,
After the molten mixture, the inorganic filler, and other additives are sufficiently and uniformly mixed by a mixer or the like, the mixture is further melt-kneaded by a hot roll or a kneader, cooled, and ground to obtain a molding material. These molding materials can be applied to sealing, coating, insulating and the like of electronic parts or electric parts.
【００１９】溶融混合物の製造例 溶融混合物１ 式（５）で示される可撓性フェノール樹脂硬化剤（軟化
点７５℃、水酸基当量１７５ｇ／ｅｑ、ｎが１〜４の混
合物であり、重量割合でｎ＝１が２０、ｎ＝２が４０、
ｎ＝３が３０、ｎ＝４が１０）６００重量部とトリフェ
ニルホスフィン・トリフェニルボラン４０重量部を１８
０℃で６０分間溶融混合した。（以下溶融混合物Ａとす
る）。Production Example of Melt Mixture Melt Mixture 1 A flexible phenolic resin curing agent represented by the formula (5) (a mixture having a softening point of 75 ° C., a hydroxyl equivalent of 175 g / eq, and n of 1 to 4; n = 1 is 20, n = 2 is 40,
n = 3 = 30, n = 4 = 10) 600 parts by weight and triphenylphosphine / triphenylborane 40 parts by weight
Melt mixed at 0 ° C. for 60 minutes. (Hereinafter referred to as a molten mixture A).
【００２０】[0020]
【化９】 Embedded image
【００２１】溶融混合物２ 式（５）で示される可撓性フェノール樹脂硬化剤（軟化
点７５℃、水酸基当量１７５ｇ／ｅｑ、ｎが１〜４の混
合物であり、重量割合でｎ＝１が２０、ｎ＝２が４０、
ｎ＝３が３０、ｎ＝４が１０）６００重量部とトリフェ
ニルホスフィン・トリフェニルボラン１３０重量部を１
８０℃で６０分間溶融混合した。（以下溶融混合物Ｂと
する）。 溶融混合物３ 式（６）で示される可撓性フェノール樹脂硬化剤（軟化
点１２０℃、水酸基当量１７０ｇ／ｅｑ、ｎが０〜３の
混合物であり、重量割合でｎ＝０が１０、ｎ＝１が４
０、ｎ＝２が３０、ｎ＝３が２０）６００重量部とトリ
フェニルホスフィン・トリフェニルボラン４０重量部を
１８０℃で６０分間溶融混合した。（以下溶融混合物Ｃ
とする）。Melt mixture 2 A flexible phenolic resin curing agent represented by the formula (5) (a mixture having a softening point of 75 ° C., a hydroxyl equivalent of 175 g / eq, n = 1 to 4, and n = 1 = 1 to 20 by weight). , N = 2 is 40,
n = 3 = 30, n = 4 = 10) 600 parts by weight and triphenylphosphine / triphenylborane 130 parts by weight
Melt mixed at 80 ° C. for 60 minutes. (Hereinafter referred to as a melt mixture B). Melt mixture 3 A flexible phenol resin curing agent represented by the formula (6) (a mixture having a softening point of 120 ° C., a hydroxyl equivalent of 170 g / eq, and n of 0 to 3, and n = 0 = 10 and n = 1 is 4
0, n = 2 = 30 and n = 3 = 20) 600 parts by weight and 40 parts by weight of triphenylphosphine / triphenylborane were melt-mixed at 180 ° C. for 60 minutes. (Hereafter, molten mixture C
And).
【００２２】[0022]
【化１０】 Embedded image
【００２３】溶融混合物４ 式（６）で示される可撓性フェノール樹脂硬化剤（軟化
点１２０℃、水酸基当量１７０ｇ／ｅｑ、ｎが０〜３の
混合物であり、重量割合でｎ＝０が１０、ｎ＝１が４
０、ｎ＝２が３０、ｎ＝３が２０）６００重量部とトリ
フェニルホスフィン・トリフェニルボラン１３０重量部
を１８０℃で６０分間溶融混合した。（以下溶融混合物
Ｄとする）。 溶融混合物５ 式（５）で示される可撓性フェノール樹脂硬化剤（軟化
点７５℃、水酸基当量１７５ｇ／ｅｑ、ｎが１〜４の混
合物であり、重量割合でｎ＝１が２０、ｎ＝２が４０、
ｎ＝３が３０、ｎ＝４が１０）６００重量部とトリフェ
ニルホスフィン・トリフェニルボラン２０重量部を１８
０℃で６０分間溶融混合した。（以下溶融混合物Ｅとす
る）。 溶融混合物６ 式（５）で示される可撓性フェノール樹脂硬化剤（軟化
点７５℃、水酸基当量１７５ｇ／ｅｑ、ｎが１〜４の混
合物であり、重量割合でｎ＝１が２０、ｎ＝２が４０、
ｎ＝３が３０、ｎ＝４が１０）６００重量部とトリフェ
ニルホスフィン・トリフェニルボラン１６０重量部を１
８０℃で６０分間溶融混合した。（以下溶融混合物Ｆと
する）。Melt mixture 4 A flexible phenol resin curing agent represented by the formula (6) (a mixture having a softening point of 120 ° C., a hydroxyl equivalent of 170 g / eq, n of 0 to 3, and n = 0 to 10 by weight ratio). , N = 1 is 4
0, n = 2 = 30, n = 3 = 20) 600 parts by weight and 130 parts by weight of triphenylphosphine / triphenylborane were melt-mixed at 180 ° C. for 60 minutes. (Hereinafter referred to as a molten mixture D). Melt mixture 5 A flexible phenolic resin curing agent represented by the formula (5) (a mixture having a softening point of 75 ° C., a hydroxyl equivalent of 175 g / eq, and n of 1 to 4, and n = 1 = 20 and n = 2 is 40,
n = 3 = 30, n = 4 = 10) 600 parts by weight and 20 parts by weight of triphenylphosphine / triphenylborane
Melt mixed at 0 ° C. for 60 minutes. (Hereinafter referred to as a melt mixture E). Melt mixture 6 A flexible phenol resin curing agent represented by the formula (5) (a mixture having a softening point of 75 ° C., a hydroxyl equivalent of 175 g / eq, and n of 1 to 4; 2 is 40,
n = 3 = 30, n = 4 = 10) 600 parts by weight and triphenylphosphine / triphenylborane 160 parts by weight
Melt mixed at 80 ° C. for 60 minutes. (Hereinafter referred to as a molten mixture F).
【００２４】溶融混合物７ 式（６）で示される可撓性フェノール樹脂硬化剤（軟化
点１２０℃、水酸基当量１７０ｇ／ｅｑ、ｎが０〜３の
混合物であり、重量割合でｎ＝０が１０、ｎ＝１が４
０、ｎ＝２が３０、ｎ＝３が２０）６００重量部とトリ
フェニルホスフィン・トリフェニルボラン２０重量部を
１８０℃で６０分間溶融混合した。（以下溶融混合物Ｇ
とする）。 溶融混合物８ 式（６）で示される可撓性フェノール樹脂硬化剤（軟化
点１２０℃、水酸基当量１７０ｇ／ｅｑ、ｎが０〜３の
混合物であり、重量割合でｎ＝０が１０、ｎ＝１が４
０、ｎ＝２が３０、ｎ＝３が２０）６００重量部とトリ
フェニルホスフィン・トリフェニルボラン１６０重量部
を１８０℃で６０分間溶融混合した。（以下溶融混合物
Ｈとする）。 溶融混合物９ 溶融混合物１で用いた可撓性フェノール樹脂硬化剤６０
０重量部とトリフェニルホスフィン２０重量部を１８０
℃で６０分間溶融混合した（以下溶融混合物Ｉとす
る）。Melt mixture 7 A flexible phenol resin curing agent represented by the formula (6) (a mixture having a softening point of 120 ° C., a hydroxyl equivalent of 170 g / eq, n of 0 to 3, and n = 0 to 10 by weight ratio) , N = 1 is 4
0, n = 2 = 30 and n = 3 = 20) 600 parts by weight and 20 parts by weight of triphenylphosphine / triphenylborane were melt-mixed at 180 ° C. for 60 minutes. (Hereafter, the molten mixture G
And). Melt mixture 8 A flexible phenol resin curing agent represented by the formula (6) (a mixture having a softening point of 120 ° C., a hydroxyl equivalent of 170 g / eq, and n of 0 to 3, and n = 0 = 10 and n = 1 is 4
0, n = 2 = 30, n = 3 = 20) 600 parts by weight and 160 parts by weight of triphenylphosphine / triphenylborane were melt-mixed at 180 ° C. for 60 minutes. (Hereinafter referred to as a molten mixture H). Melt Mixture 9 Flexible phenolic resin curing agent 60 used in Melt Mixture 1
0 parts by weight and 20 parts by weight of triphenylphosphine are added to 180 parts by weight.
The resulting mixture was melt-mixed at 60 ° C. for 60 minutes (hereinafter referred to as “melt mixture I”).
【００２５】以下本発明の実施例で具体的に説明する。 実施例１ ３，３’，５，５’−テトラメチルビフェノールジグリシジルエーテル （融点１０７℃、エポキシ当量１９０ｇ／ｅｑ） １２重量部 溶融混合物Ａ ６．４重量部 フェノールノボラック樹脂硬化剤 （軟化点１０５℃、水酸基当量１０４ｇ／ｅｑ） ２重量部 溶融シリカ粉末 ７８．６重量部 カーボンブラック ０．５重量部 カルナバワックス ０．５重量部 をミキサーで常温で混合し、７０〜１００℃で２軸ロー
ルにより混練し、冷却後粉砕し成形材料とした。得られ
た成形材料をタブレット化し、低圧トランスファー成形
機にて１７５℃、７０ｋｇ／ｃｍ2、１２０秒の条件で
半田クラック試験用として６×６ｍｍのチップを５２ｐ
パッケージに封止した。封止したテスト用素子について
下記の半田クラック試験を行った。評価結果を表１に示
す。Now, the present invention will be described in detail with reference to Examples. Example 1 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether (melting point 107 ° C., epoxy equivalent 190 g / eq) 12 parts by weight Melt mixture A 6.4 parts by weight Phenol novolak resin curing agent (softening point 105 ° C, hydroxyl equivalent 104g / eq) 2 parts by weight Fused silica powder 78.6 parts by weight Carbon black 0.5 parts by weight Carnauba wax 0.5 parts by weight at room temperature with a mixer, and mixed at 70-100 ° C with a biaxial roll. It was kneaded, cooled and pulverized to obtain a molding material. The obtained molding material was tableted, and a 6 × 6 mm chip was used for solder crack test at 175 ° C., 70 kg / cm 2 and 120 seconds by a low-pressure transfer molding machine in a size of 52 p.
It was sealed in a package. The following solder crack test was performed on the sealed test element. Table 1 shows the evaluation results.
【００２６】評価試験 半田クラック試験：封止したテスト用素子を８５℃、８
５％ＲＨの環境下で４８時間及び７２時間処理し、その
後２６０℃の半田槽に１０秒間浸漬後、顕微鏡で外部ク
ラックを観察した。 成形性試験：１７５℃、７０ｋｇ／ｃｍ2の条件でトラ
ンスファー成形機を用いて、１６ｐＤＩＰを成形し、離
型１０秒後にバコール硬度を測定した。得られた成形品
によりバリ（ベント）、離型性、外観のチェックを行っ
た。 スパイラルフロー残存率：成形材料にした直後のスパイ
ラルフローをＥＭＭＩ−Ｉ−６６に準じてた金型を用
い、測定し測定値をＡとし、得られた同一の成形材料を
２５℃で１週間保存した後のスパイラルフローを測定し
測定値Ｂとする。以下の式よりスパイラルフロー残存率
を算出する。 スパイラルフロー残存率（％）＝〔（測定値Ｂ）／（測
定値Ａ）〕×１００ ゲルタイム：１７５℃の熱盤上で測定。Evaluation test Solder crack test: A sealed test element was heated at 85 ° C. for 8 hours.
The treatment was performed for 48 hours and 72 hours in an environment of 5% RH, and then immersed in a solder bath at 260 ° C. for 10 seconds, and external cracks were observed with a microscope. Moldability test: 16 pDIP was molded using a transfer molding machine under the conditions of 175 ° C. and 70 kg / cm 2 , and the Bacol hardness was measured 10 seconds after release from the mold. The obtained molded product was checked for burrs (vent), releasability, and appearance. Spiral flow residual ratio: The spiral flow immediately after forming the molding material was measured using a mold according to EMMI-I-66, and the measured value was set to A. The same molding material obtained was stored at 25 ° C. for one week. After that, the spiral flow is measured, and the measured value is set as a measured value B. The spiral flow residual rate is calculated from the following equation. Spiral flow residual ratio (%) = [(measured value B) / (measured value A)] × 100 Gel time: Measured on a hot plate at 175 ° C.
【００２７】実施例２〜４ 表１の処方に従って配合し、実施例１と同様にして成形
材料を得た。この成形材料で試験用の封止した成形品を
得、実施例１と同様に評価試験を行った。評価結果を表
１に示す。 比較例１〜９ 表１の処方に従って配合し、実施例１と同様にして成形
材料を得た。比較例５，６で用いられる可撓性フェノー
ル樹脂硬化剤は式（５）で示されるものである（軟化点
７５℃、水酸基当量１７５ｇ／ｅｑ、ｎが１〜４の混合
物であり、重量割合でｎ＝１が２０、ｎ＝２が４０、ｎ
＝３が３０、ｎ＝４が１０）。比較例８，９に用いられ
る可撓性フェノール樹脂硬化剤は式（６）で示されるも
のである（軟化点１２０℃、水酸基当量１７０ｇ／ｅ
ｑ、ｎが０〜３の混合物であり、重量割合でｎ＝０が１
０、ｎ＝１が４０、ｎ＝２が３０、ｎ＝３が２０）。こ
の成形材料で試験用に封止した成形品を得、この成形品
を用いて実施例１と同様に評価試験を行った。評価結果
を表１に示す。Examples 2 to 4 Compounded according to the formulation shown in Table 1, and a molding material was obtained in the same manner as in Example 1. A sealed molded product for a test was obtained from this molding material, and an evaluation test was performed in the same manner as in Example 1. Table 1 shows the evaluation results. Comparative Examples 1 to 9 Compounded according to the formulation in Table 1, and a molding material was obtained in the same manner as in Example 1. The flexible phenolic resin curing agent used in Comparative Examples 5 and 6 is represented by the formula (5) (a mixture having a softening point of 75 ° C., a hydroxyl equivalent of 175 g / eq, n of 1 to 4, and a weight ratio of Where n = 1 is 20, n = 2 is 40, n
= 3 = 30, n = 4 = 10). The flexible phenol resin curing agent used in Comparative Examples 8 and 9 is represented by the formula (6) (softening point: 120 ° C., hydroxyl equivalent: 170 g / e).
q, n is a mixture of 0 to 3;
0, n = 1 is 40, n = 2 is 30, and n = 3 is 20). A molded article sealed with this molding material for a test was obtained, and an evaluation test was performed using this molded article in the same manner as in Example 1. Table 1 shows the evaluation results.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【発明の効果】本発明に従うと、従来技術では得ること
ができなかった常温保存性及び硬化性の両立が可能とな
り、半導体封止材料の中でも特に常温保管のできるマル
チプランジャー成形対応材料として好適である。According to the present invention, it is possible to achieve both room temperature storage property and curability which could not be obtained by the prior art, and it is particularly suitable as a multi-plunger molding material which can be stored at room temperature among semiconductor encapsulation materials. It is.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ｃ Ｈ０１Ｌ 23/29 Ｈ０１Ｌ 23/30 Ｒ 23/31 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI C08L 63/00 C08L 63/00 C H01L 23/29 H01L 23/30 R 23/31
Claims (3)
ホスフィン・トリフェニルボランと 【化１】 （Ｂ）式（２）及び／または式（３）で示される可撓性
フェノール樹脂硬化剤とを予め加熱溶融されてなる溶融
混合物、 【化２】 【化３】 （式（２）中のＲはパラキシリレン、式（３）中のＲは
ジシクロペンタジエンとフェノールを付加反応したジシ
クロペンタジエンジフェノール、テルペン類とフェノー
ルを付加反応したテルペン類ジフェノール、シクロペン
タジエンとフェノールを付加反応したシクロペンタジエ
ンジフェノール及びシクロヘキサノンとフェノールを付
加縮合したシクロヘキサノンジフェノールの各々の２個
のフェノール部を除いた残基の中から選択される１種、
ｎの値は０〜１０）（Ｃ）式（４）で示されるエポキシ
樹脂 【化４】 （式中のＲ1〜Ｒ8は水素、ハロゲン、アルキル基の中か
ら選択される同一もしくは異なる原子または基）を総エ
ポキシ樹脂量に対して５０〜１００重量％を含むエポキ
シ樹脂及び（Ｃ）無機充填材を必須成分とすることを特
徴とする半導体封止用エポキシ樹脂組成物。(A) Triphenylphosphine / triphenylborane represented by the formula (1): (B) a molten mixture obtained by previously heating and melting a flexible phenolic resin curing agent represented by the formula (2) and / or the formula (3); Embedded image (R in the formula (2) is paraxylylene, R in the formula (3) is dicyclopentadiene diphenol obtained by addition reaction of dicyclopentadiene and phenol, terpene diphenol obtained by addition reaction of terpenes with phenol, and cyclopentadiene. One kind selected from residues excluding two phenol moieties of cyclopentadiene diphenol obtained by addition reaction of phenol and cyclohexanone diphenol obtained by addition condensation of cyclohexanone and phenol,
The value of n is from 0 to 10) (C) an epoxy resin represented by the formula (4) (R 1 to R 8 in the formula are the same or different atoms or groups selected from hydrogen, halogen and alkyl groups) epoxy resin containing 50 to 100% by weight based on the total epoxy resin amount; An epoxy resin composition for semiconductor encapsulation, comprising an inorganic filler as an essential component.
ン・トリフェニルボランを０．３〜１．５重量％含む請
求項１記載のエポキシ樹脂組成物。2. The epoxy resin composition according to claim 1, wherein the total resin composition contains 0.3 to 1.5% by weight of triphenylphosphine / triphenylborane.
を付加反応したテルペン類ジフェノールの２個のフェノ
ール部を除いた残基である請求項１又は請求項２記載の
エポキシ樹脂組成物。3. The epoxy resin composition according to claim 1, wherein R in the formula (3) is a residue obtained by removing two phenol moieties of a terpene diphenol obtained by addition reaction of a terpene with phenol. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6159994A JP3056634B2 (en) | 1994-03-30 | 1994-03-30 | Epoxy resin composition for semiconductor encapsulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6159994A JP3056634B2 (en) | 1994-03-30 | 1994-03-30 | Epoxy resin composition for semiconductor encapsulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07268071A JPH07268071A (en) | 1995-10-17 |
| JP3056634B2 true JP3056634B2 (en) | 2000-06-26 |
Family
ID=13175792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6159994A Expired - Lifetime JP3056634B2 (en) | 1994-03-30 | 1994-03-30 | Epoxy resin composition for semiconductor encapsulation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3056634B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102227457B (en) * | 2008-11-07 | 2012-10-31 | 横滨橡胶株式会社 | One-pack type thermosetting epoxy resin composition |
-
1994
- 1994-03-30 JP JP6159994A patent/JP3056634B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07268071A (en) | 1995-10-17 |
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