JP2002194066A - Liquid epoxy-resin composition for encapsulating and electronic parts device - Google Patents
Liquid epoxy-resin composition for encapsulating and electronic parts deviceInfo
- Publication number
- JP2002194066A JP2002194066A JP2000398598A JP2000398598A JP2002194066A JP 2002194066 A JP2002194066 A JP 2002194066A JP 2000398598 A JP2000398598 A JP 2000398598A JP 2000398598 A JP2000398598 A JP 2000398598A JP 2002194066 A JP2002194066 A JP 2002194066A
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- Japan
- Prior art keywords
- epoxy resin
- resin composition
- liquid
- liquid sealing
- preferable
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子部品装置の封
止用に好適な液状封止用エポキシ樹脂組成物及びこれに
より封止された素子を備えた電子部品装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid sealing epoxy resin composition suitable for sealing an electronic component device, and an electronic component device provided with an element sealed by the epoxy resin composition.
【０００２】[0002]
【従来の技術】従来から、トランジスタ、ＩＣ等の電子
部品装置の素子封止の分野では生産性、コスト等の面か
ら樹脂封止が主流となり、エポキシ樹脂組成物が広く用
いられている。この理由としては、エポキシ樹脂が作業
性、成形性、電気特性、耐湿性、耐熱性、機械特性、イ
ンサート品との接着性等の諸特性にバランスがとれてい
るためである。ＣＯＢ（Chip on Board）、ＣＯＧ（Chi
p on Glass）等のベアチップ実装した半導体装置やＴＣ
Ｐ（Tape Carrier Package）においては、液状封止用エ
ポキシ樹脂組成物が封止材として多く用いられている。2. Description of the Related Art Conventionally, in the field of device sealing of electronic parts such as transistors and ICs, resin sealing has become the mainstream in terms of productivity and cost, and epoxy resin compositions have been widely used. The reason for this is that the epoxy resin is well balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products. COB (Chip on Board), COG (Chi
semiconductor device and TC mounted on bare chip such as p on Glass)
In P (Tape Carrier Package), a liquid sealing epoxy resin composition is often used as a sealing material.
【０００３】液状封止用エポキシ樹脂組成物の硬化に
は、高温で長時間の加熱が必要であり、近年、生産性の
向上を目的とした速硬化性の液状封止用エポキシ樹脂組
成物の需要が高まっている。また、最近では、液状封止
用エポキシ樹脂組成物の硬化後の評価に光学的自動検査
機を用いることが多いため、硬化後の表面は非鏡面が要
求されている。これは、光学的自動検査機においてハレ
ーションをおこさないためである。液状封止用エポキシ
樹脂組成物に、硬化剤として固形フェノールノボラック
樹脂を用いると、封止品の耐湿信頼性が良くなるという
長所がある反面、硬化後の外観が鏡面になりやすいとい
う短所がある。[0003] The curing of a liquid encapsulating epoxy resin composition requires heating at a high temperature for a long period of time. In recent years, a quick-curing liquid encapsulating epoxy resin composition for the purpose of improving productivity has been developed. Demand is growing. In addition, recently, an optical automatic inspection device is often used for evaluation of the epoxy resin composition for liquid encapsulation after curing, and therefore, a non-mirror surface is required for the surface after curing. This is to prevent halation in the optical automatic inspection machine. The use of a solid phenol novolak resin as a curing agent in a liquid sealing epoxy resin composition has the advantage of improving the moisture resistance reliability of the sealed product, but has the disadvantage that the appearance after curing tends to be a mirror surface. .
【０００４】[0004]
【発明が解決しようとする課題】本発明はかかる状況に
鑑みなされたもので、硬化物の表面が非鏡面になる液状
封止用エポキシ樹脂組成物及びこれにより封止された素
子を備えた電子部品装置を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides an epoxy resin composition for liquid sealing in which the surface of a cured product becomes non-mirror, and an electronic device provided with an element sealed thereby. A component device is provided.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記の課題
を解決するため鋭意検討を重ねた結果、硬化剤としてア
リル基含有フェノール樹脂を用い、かつ硬化物の表面の
反射率が１０％以下になるような液状封止用エポキシ樹
脂組成物により上記の目的を達成しうることを見い出
し、本発明を完成するに至った。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an allyl group-containing phenol resin is used as a curing agent, and the reflectance of the surface of the cured product is 10%. It has been found that the above object can be achieved by the liquid sealing epoxy resin composition as described below, and the present invention has been completed.
【０００６】すなわち、本発明は（１）（Ａ）エポキシ
樹脂及び（Ｂ）硬化剤を必須成分とし、（Ｂ）硬化剤が
アリル基含有フェノール樹脂を含有し、かつ硬化物の表
面の反射率が１０％以下である液状封止用エポキシ樹脂
組成物、（２）アリル基含有フェノール樹脂がアリル基
含有フェノールノボラック樹脂である上記（１）記載の
液状封止用エポキシ樹脂組成物、（３）（Ｃ）充填剤を
さらに含有する上記（１）又は（２）記載の液状封止用
エポキシ樹脂組成物、（４）（Ｄ）溶剤をさらに含有す
る上記（１）〜（３）のいずれかに記載の液状封止用エ
ポキシ樹脂組成物、（５）上記（１）〜（４）のいずれ
かに記載の液状封止用エポキシ樹脂組成物を用いたＴＣ
Ｐ用封止材、（６）上記（１）〜（４）のいずれかに記
載の液状封止用エポキシ樹脂組成物を用いて封止された
素子を備えた電子部品装置及び（７）上記（１）〜
（４）のいずれかに記載の液状封止用エポキシ樹脂組成
物を用いて封止された素子を備えたＴＣＰに関する。That is, the present invention comprises (1) (A) an epoxy resin and (B) a curing agent as essential components, (B) the curing agent contains an allyl group-containing phenolic resin, and the reflectance of the surface of the cured product is Is 10% or less, (2) the epoxy resin composition for liquid sealing according to the above (1), wherein the allyl group-containing phenol resin is an allyl group-containing phenol novolak resin, (3) (C) The epoxy resin composition for liquid encapsulation according to the above (1) or (2), further containing a filler, (4) any of the above (1) to (3) further containing a solvent (D). (5) TC using the liquid epoxy resin composition for liquid encapsulation according to any one of the above (1) to (4).
P sealing material, (6) an electronic component device including an element sealed with the liquid sealing epoxy resin composition according to any one of (1) to (4), and (7) the electronic component device described above. (1)-
(4) A TCP provided with an element sealed using the liquid sealing epoxy resin composition according to any of (4).
【０００７】[0007]
【発明の実施の形態】本発明において用いられる（Ａ）
エポキシ樹脂は、硬化可能な１分子中に２個以上のエポ
キシ基を有するエポキシ樹脂であれば特に制限はなく、
液状封止用エポキシ樹脂組成物に一般に使用されている
エポキシ樹脂を用いることができ、組成物が液状であれ
ば固形、液状のどちらか一方を用いても両者を併用して
も良い。たとえば、ビスフェノールＡ、ビスフェノール
Ｆ、ビスフェノールＡＤ、ビスフェノールＳ、ナフタレ
ンジオール、水添ビスフェノールＡ等とエピクロルヒド
リンの反応により得られるグリシジルエーテル型エポキ
シ樹脂、オルソクレゾールノボラック型エポキシ樹脂を
はじめとするフェノール類とアルデヒド類とを縮合又は
共縮合させて得られるノボラック樹脂をエポキシ化した
ノボラック型エポキシ樹脂、フタル酸、ダイマー酸等の
多塩基酸とエピクロルヒドリンの反応により得られるグ
リシジルエステル型エポキシ樹脂、ジアミノジフェニル
メタン、イソシアヌル酸等のポリアミンとエピクロルヒ
ドリンの反応により得られるグリシジルアミン型エポキ
シ樹脂、オレフィン結合を過酢酸等の過酸で酸化して得
られる線状脂肪族エポキシ樹脂、脂環族エポキシ樹脂な
どが挙げられ、これらを単独で用いても２種以上を組み
合わせて用いてもよい。なかでも、低粘度化の観点から
は液状エポキシ樹脂が好ましく、フェノール樹脂との反
応性の観点からはビスフェノール型液状エポキシ樹脂が
より好ましい。また、これらのエポキシ樹脂は、十分に
精製されたもので、イオン性不純物が少ないものが好ま
しい。例えば、遊離Ｎａイオン及び遊離Ｃｌイオンは５
００ｐｐｍ以下であることが好ましい。DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one curable molecule.
An epoxy resin generally used for a liquid sealing epoxy resin composition can be used. If the composition is liquid, either a solid or a liquid may be used, or both may be used in combination. For example, phenols and aldehydes such as glycidyl ether type epoxy resin and orthocresol novolak type epoxy resin obtained by reaction of epichlorohydrin with bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A, etc. Novolak-type epoxy resin obtained by condensing or co-condensing with novolak resin, glycidyl ester-type epoxy resin obtained by reaction of epichlorohydrin with polybasic acid such as phthalic acid and dimer acid, diaminodiphenylmethane, isocyanuric acid, etc. Glycidylamine type epoxy resin obtained by the reaction of polyamine with epichlorohydrin, linear aliphatic epoxy obtained by oxidizing olefin bond with peracid such as peracetic acid Butter, and the like alicyclic epoxy resins may be used in combination of two or more even with these alone. Among them, a liquid epoxy resin is preferable from the viewpoint of lowering the viscosity, and a bisphenol-type liquid epoxy resin is more preferable from the viewpoint of reactivity with the phenol resin. Further, it is preferable that these epoxy resins are sufficiently purified and have little ionic impurities. For example, free Na ions and free Cl ions are 5
It is preferably at most 00 ppm.
【０００８】本発明において用いられる（Ｂ）硬化剤と
しては、アリル基含有フェノール樹脂を含有していれば
特に制限はなく、エポキシ樹脂の硬化剤として一般に使
用されているものを用いることができる。たとえば、フ
ェノール樹脂、メラミン樹脂、アクリル樹脂、ユリア樹
脂、イソシアネート、脂肪族ポリアミン、ポリアミド樹
脂、芳香族ジアミン等のアミン化合物、酸無水物、ルイ
ス酸錯化合物などが挙げられ、これらを単独で用いても
２種以上を組み合わせて用いてもよい。なかでも、保存
安定性の観点からはフェノール樹脂が好ましく、接着性
の観点からは芳香族アミンが好ましい。また、組成物が
液状であれば固形硬化剤及び液状硬化剤のどちらか一方
を用いても両者を併用してもよいが、低粘度化の観点か
らは液状硬化剤が好ましい。The curing agent (B) used in the present invention is not particularly limited as long as it contains an allyl group-containing phenol resin, and those generally used as curing agents for epoxy resins can be used. For example, phenol resins, melamine resins, acrylic resins, urea resins, isocyanates, aliphatic polyamines, polyamide resins, amine compounds such as aromatic diamines, acid anhydrides, Lewis acid complex compounds, and the like. May be used in combination of two or more. Among them, a phenol resin is preferable from the viewpoint of storage stability, and an aromatic amine is preferable from the viewpoint of adhesiveness. If the composition is liquid, either a solid curing agent or a liquid curing agent may be used or both may be used in combination, but a liquid curing agent is preferred from the viewpoint of lowering the viscosity.
【０００９】本発明において硬化剤として用いられるア
リル基含有フェノール樹脂としては、アリル基を有する
ものであれば特に制限はないが、たとえば、下記一般式
（Ｉ）〜（Ｖ）で示される化合物等が挙げられ、これら
の１種を単独で用いても２種以上を組合わせて用いても
よい。The allyl group-containing phenolic resin used as a curing agent in the present invention is not particularly limited as long as it has an allyl group. Examples thereof include compounds represented by the following general formulas (I) to (V). These may be used alone or in combination of two or more.
【化１】 （ここで、式（Ｉ）〜（Ｖ）中のＲは水素原子、置換又
は非置換の炭素数１〜１０のアルキル基、置換又は非置
換の炭素数１〜１０のアルコキシ基、置換又は非置換の
炭素数１〜１０のアルキル基、置換又は非置換の炭素数
１〜１０のアリル基及び置換又は非置換の炭素数１〜１
２のアリール基から選ばれ、ｍ、ｎはそれぞれ独立に１
以上の整数を示す。）Embedded image (Where R in the formulas (I) to (V) is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted Substituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted allyl group having 1 to 10 carbon atoms and substituted or unsubstituted carbon group having 1 to 1 carbon atoms
And m and n are each independently 1
The following integers are shown. )
【００１０】なかでも、硬化物の表面が非鏡面になる観
点及び入手容易性の観点からは上記一般式（Ｉ）又は
（IV）で示されるフェノール樹脂が好ましく、硬化物表
面の非鏡面性と速硬化性の両立の観点からは上記一般式
（Ｉ）で示されるフェノール樹脂等のアリル基含有フェ
ノールノボラック樹脂がより好ましい。上記一般式
（Ｉ）で示されるフェノール樹脂としては、低粘度化の
観点から、Ｒが水素原子でｎが平均２〜３であるものが
より好ましい。また、同様に観点から、上記一般式
（Ｉ）で示されるフェノール樹脂の重量平均分子量は６
００以下が好ましく、５００未満がより好ましく、４５
０以下がさらに好ましく、粘度は、２５℃における粘度
が５〜８０Ｐａ・ｓであることが好ましく、１０〜５０
Ｐａ・ｓであることがより好ましく、１５〜４０Ｐａ・
ｓであることがさらに好ましく、水酸基当量は、１００
〜２００が好ましく、１２０〜１７０がより好ましく、
１３０〜１６０がさらに好ましい。上記一般式（IV）で
示されるフェノール樹脂としては、ｍ個の繰り返し単位
及びｎ個の繰り返し単位のランダム共重合体でもブロッ
ク共重合体でも交互共重合体でもかまわないが、硬化物
の表面が非鏡面になる観点及び低粘度化の観点から、Ｒ
が水素原子でｍ、ｎがそれぞれ平均１〜２であるものが
より好ましい。また、同様に観点から、上記一般式（I
V）で示されるフェノール樹脂の重量平均分子量は２０
０〜１２００が好ましく、３００〜１０００がより好ま
しく、４００〜６００がさらに好ましく、粘度は、６０
℃における粘度が０．５〜２０Ｐａ・ｓであることが好
ましく、１〜１０Ｐａ・ｓであることがより好ましく、
３〜６Ｐａ・ｓであることがさらに好ましく、水酸基当
量は、５０〜５００が好ましく、１００〜３５０がより
好ましく、１５０〜２５０がさらに好ましい。ここで、
重量平均分子量とは、ＧＰＣ測定によるポリスチレン換
算の重量平均分子量のことをいう。Among them, the phenolic resin represented by the above general formula (I) or (IV) is preferable from the viewpoint of the surface of the cured product becoming non-specular and the availability thereof, From the viewpoint of achieving a balance between fast curing properties, an allyl group-containing phenol novolak resin such as the phenol resin represented by the general formula (I) is more preferable. As the phenolic resin represented by the general formula (I), from the viewpoint of lowering the viscosity, those in which R is a hydrogen atom and n is an average of 2 to 3 are more preferable. Similarly, from the viewpoint, the phenol resin represented by the general formula (I) has a weight average molecular weight of 6
00 or less, more preferably less than 500, and 45 or less.
0 or less is more preferable, and the viscosity is preferably a viscosity at 25 ° C. of 5 to 80 Pa · s,
Pa · s, more preferably 15 to 40 Pa · s.
s, and the hydroxyl equivalent is preferably 100
~ 200 is preferable, 120 ~ 170 is more preferable,
130-160 is more preferred. The phenolic resin represented by the general formula (IV) may be a random copolymer, a block copolymer or an alternating copolymer of m repeating units and n repeating units, but the surface of the cured product is From the viewpoint of non-mirror surface and low viscosity, R
Is more preferably a hydrogen atom, and m and n each average 1 to 2. Similarly, from the viewpoint, the above general formula (I
The weight average molecular weight of the phenolic resin represented by V) is 20
0-1200 is preferable, 300-1000 is more preferable, 400-600 is more preferable, and the viscosity is 60
The viscosity at 0 ° C. is preferably 0.5 to 20 Pa · s, more preferably 1 to 10 Pa · s,
It is more preferably 3 to 6 Pa · s, and the hydroxyl equivalent is preferably 50 to 500, more preferably 100 to 350, and still more preferably 150 to 250. here,
The weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC.
【００１１】アリル基含有フェノール樹脂の配合量は、
その性能を発揮するために（Ｂ）硬化剤全量に対して３
０重量％以上が好ましく、４０重量％以上がより好まし
く、６０重量％以上がさらに好ましい。The compounding amount of the allyl group-containing phenol resin is as follows:
In order to exhibit its performance, (B) 3
0% by weight or more is preferable, 40% by weight or more is more preferable, and 60% by weight or more is further preferable.
【００１２】（Ａ）エポキシ樹脂と（Ｂ）硬化剤との当
量比は特に制限はないが、それぞれの未反応分を少なく
抑えるために、エポキシ樹脂に対して硬化剤を０．６〜
１．６当量の範囲に設定することが好ましく、０．７〜
１．４当量がより好ましく、０．８〜１．２当量がさら
に好ましい。０．６．〜１．６当量の範囲からはずれた
場合、硬化反応が不充分となり信頼性が低下する傾向が
ある。ここで、当量とは反応当量であり、たとえば、フ
ェノール樹脂の当量はエポキシ基１個に対しフェノール
性水酸基１個が反応するものとして計算され、芳香族ア
ミンの当量はエポキシ基１個に対しアミノ基の活性水素
１個が反応するものとして計算され、酸無水物の当量は
エポキシ基１個に対し酸無水物基１個が反応するものと
して計算される。The equivalent ratio of the epoxy resin (A) to the curing agent (B) is not particularly limited.
It is preferable to set the range of 1.6 equivalents,
1.4 equivalents are more preferred, and 0.8-1.2 equivalents are even more preferred. 0.6. When the amount is out of the range of from 1.6 to 1.6 equivalents, the curing reaction tends to be insufficient and the reliability tends to decrease. Here, the equivalent is a reaction equivalent. For example, the equivalent of a phenol resin is calculated as one epoxy group reacts with one phenolic hydroxyl group, and the equivalent of aromatic amine is one amino group per epoxy group. One active hydrogen of the group is calculated as reacting, and the equivalent of acid anhydride is calculated as one epoxy group reacting with one acid anhydride group.
【００１３】本発明の液状封止用エポキシ樹脂組成物に
は、必要に応じて硬化促進剤を用いることができる。硬
化促進剤としては液状封止用エポキシ樹脂組成物に一般
に使用されるもので特に制限はないが、たとえば、１，
８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、
１，５−ジアザ−ビシクロ（４，３，０）ノネン、５、
６−ジブチルアミノ−１，８−ジアザ−ビシクロ（５，
４，０）ウンデセン−７等のシクロアミジン化合物及び
これらの誘導体、これらのフェノール樹脂塩等の塩、又
はこれらの化合物に無水マレイン酸、１，４−ベンゾキ
ノン、２，５−トルキノン、１，４−ナフトキノン、
２，３−ジメチルベンゾキノン、２，６−ジメチルベン
ゾキノン、２，３−ジメトキシ−５−メチル−１，４−
ベンゾキノン、２，３−ジメトキシ−１，４−ベンゾキ
ノン、フェニル−１，４−ベンゾキノン等のキノン化合
物、ジアゾフェニルメタン、フェノール樹脂等のπ結合
をもつ化合物を付加してなる分子内分極を有する化合
物、トリエチレンジアミン、ベンジルジメチルアミン、
トリエタノールアミン、ジメチルアミノエタノール、ト
リス（ジメチルアミノメチル）フェノール等の三級アミ
ン化合物、２−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
イミダゾール等のイミダゾール化合物、トリブチルホス
フィン、メチルジフェニルホスフィン、トリフェニルホ
スフィン、ジフェニルホスフィン、フェニルホスフィン
等の有機ホスフィン化合物及びこれらの誘導体、又はこ
れらの化合物に上記キノン化合物、ジアゾフェニルメタ
ン、フェノール樹脂等のπ結合をもつ化合物を付加して
なる分子内分極を有する化合物等の有機リン化合物、ト
リフェニルホスフィントリフェニルボロン、テトラフェ
ニルホスホニウムテトラフェニルボレート、２−エチル
−４−メチルイミダゾールテトラフェニルボレート、Ｎ
−メチルモルホリンテトラフェニルボレート等のフェニ
ルボロン塩等及びこれらの誘導体などが挙げられ、これ
らの１種を単独で用いても２種以上を組合わせて用いて
もよい。硬化促進剤の配合量は、硬化促進効果が達成さ
れる量であれば特に制限されるものではないが、（Ａ）
エポキシ樹脂に対して０．１〜２０重量％が好ましく、
より好ましくは１〜１５重量％である。０．１重量％未
満では短時間での硬化性に劣る傾向があり、２０重量％
を超えると硬化速度が速すぎて制御が困難になったりポ
ットライフ、シェルライフ等の保存安定性が劣ったりす
る傾向がある。In the epoxy resin composition for liquid encapsulation of the present invention, a curing accelerator can be used if necessary. The curing accelerator is not particularly limited as it is generally used in a liquid sealing epoxy resin composition.
8-diaza-bicyclo (5,4,0) undecene-7,
1,5-diaza-bicyclo (4,3,0) nonene, 5,
6-dibutylamino-1,8-diaza-bicyclo (5,
(4,0) Cycloamidine compounds such as undecene-7 and derivatives thereof, salts thereof such as phenolic resin salts, and these compounds, or maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4 -Naphthoquinone,
2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-
Compounds having intramolecular polarization obtained by adding quinone compounds such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane and phenol resin. , Triethylenediamine, benzyldimethylamine,
Tertiary amine compounds such as triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-
Methylimidazole, 2-phenylimidazole, 2-
Imidazole compounds such as phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; and derivatives thereof; Compounds, diazophenylmethane, organic phosphorus compounds such as compounds having intramolecular polarization obtained by adding a compound having a π bond such as phenol resin, triphenylphosphine triphenylboron, tetraphenylphosphonium tetraphenylborate, 2-ethyl- 4-methylimidazole tetraphenyl borate, N
And phenylboron salts such as -methylmorpholine tetraphenylborate and derivatives thereof. These may be used alone or in combination of two or more. The amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved.
0.1 to 20% by weight based on the epoxy resin is preferable,
More preferably, it is 1 to 15% by weight. If it is less than 0.1% by weight, the curability in a short time tends to be inferior, and
If it exceeds 300, the curing speed tends to be too high to make the control difficult, and the storage stability such as pot life and shell life tends to be poor.
【００１４】本発明の液状封止用エポキシ樹脂組成物に
は、必要に応じて（Ｃ）充填剤を配合することができ
る。（Ｃ）充填剤としては、液状封止用エポキシ樹脂組
成物に一般に使用されるもので特に制限はないが、吸湿
性、線膨張係数低減、熱伝導性向上及び強度向上の観点
から無機充填剤が好ましい。たとえば、溶融シリカ、結
晶シリカ等のシリカ、炭酸カルシウム、タルク、クレ
ー、酸化アルミナ等のアルミナ、窒化珪素、炭化珪素、
窒化ホウ素、珪酸カルシウム、チタン酸カリウム、窒化
アルミ、ベリリア、ジルコニア、ジルコン、フォステラ
イト、ステアタイト、スピネル、ムライト、チタニア等
の粉体、又はこれらを球形化したビーズ、ガラス繊維な
どが挙げられる。さらに、難燃効果のある無機充填剤と
しては水酸化アルミニウム、水酸化マグネシウム、硼酸
亜鉛、モリブデン酸亜鉛等が挙げられる。これらの充填
剤は単独で用いても２種以上を組み合わせて用いてもよ
い。なかでも、粘度上昇の抑制及び硬化物物性の観点か
らはシリカが好ましく、溶融シリカがより好ましい。The liquid sealing epoxy resin composition of the present invention may optionally contain (C) a filler. (C) The filler is generally used in an epoxy resin composition for liquid encapsulation, and is not particularly limited. However, from the viewpoints of hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity, and improvement of strength, an inorganic filler is used. Is preferred. For example, fused silica, silica such as crystalline silica, calcium carbonate, talc, clay, alumina such as alumina oxide, silicon nitride, silicon carbide,
Examples include powders of boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, and the like, or spherical beads or glass fibers thereof. Further, examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate and the like. These fillers may be used alone or in combination of two or more. Among them, silica is preferable, and fused silica is more preferable, from the viewpoint of suppressing increase in viscosity and physical properties of a cured product.
【００１５】充填剤の形状は、流動性等の成形性の観点
から球形に近いことが好ましく、最密充填するように粒
度分布を広げた球形溶融シリカがより好ましい。（Ｃ）
充填剤の平均粒径は、特に球形シリカの場合、１〜２０
μｍの範囲が好ましく、２〜１０μｍの範囲がより好ま
しい。平均粒径が１μｍ未満では液状樹脂への分散性に
劣る傾向や液状封止用エポキシ樹脂組成物にチキソトロ
ピック性が付与されて流動特性に劣る傾向があり、２０
μｍを超えるとフィラ沈降を起こしやすくなる傾向や、
液状封止用エポキシ樹脂組成物の微細間隙への浸透性・
流動性が低下してボイド・未充填を招きやすくなる傾向
がある。また、これらの充填剤は、必要に応じて表面を
カップリング処理したものを用いてもよい。（Ｃ）充填
剤の配合量は、液状封止用エポキシ樹脂組成物の２０〜
９０重量％が好ましく、３０〜８５重量％がより好まし
く、５０〜８０重量％さらに好ましい。配合量が２０重
量％未満では熱膨張係数の低減効果が低くなり耐熱衝撃
性に劣る傾向があり、９０重量％を超えると液状封止用
エポキシ樹脂組成物の粘度が上昇し、流動性、浸透性及
びディスペンス性の低下を招く傾向がある。The shape of the filler is preferably close to spherical from the viewpoint of moldability such as fluidity, and more preferably spherical fused silica in which the particle size distribution is broadened so as to achieve the closest packing. (C)
The average particle size of the filler is 1 to 20 particularly in the case of spherical silica.
The range of μm is preferable, and the range of 2 to 10 μm is more preferable. If the average particle size is less than 1 μm, the dispersibility in the liquid resin tends to be poor, and the thixotropic property is imparted to the epoxy resin composition for liquid encapsulation, and the flow characteristics tend to be poor.
If it exceeds μm, the filler tends to settle,
Permeability of liquid sealing epoxy resin composition into fine gaps
There is a tendency that the fluidity is reduced and voids / unfilling are likely to occur. These fillers may be those whose surfaces have been subjected to a coupling treatment as required. (C) The compounding amount of the filler is 20 to 20 of the epoxy resin composition for liquid sealing.
90% by weight is preferable, 30 to 85% by weight is more preferable, and 50 to 80% by weight is further preferable. When the amount is less than 20% by weight, the effect of reducing the coefficient of thermal expansion is reduced and the thermal shock resistance tends to be inferior. When the amount exceeds 90% by weight, the viscosity of the epoxy resin composition for liquid encapsulation increases, resulting in fluidity and permeation. It tends to lead to a drop in dispensing and dispensing properties.
【００１６】本発明の液状封止用エポキシ樹脂組成物に
は、低粘度化のために必要に応じて（Ｄ）溶剤を配合す
ることができる。特に、固体のエポキシ樹脂及び硬化剤
を用いる場合には、液状の組成物を得るために、溶剤を
配合することが必要である。（Ｄ）溶剤としては、特に
制限はないが、たとえば、メチルアルコール、エチルア
ルコール、プロピルアルコール、ブチルアルコール等の
アルコール系溶剤、アセトン、メチルエチルケトン等の
ケトン系溶剤、エチレングリコールエチルエーテル、エ
チレングリコールメチルエーテル、エチレングリコール
ブチルエーテル、プロピレングリコールメチルエーテ
ル、ジプロピレングリコールメチルエーテル、プロピレ
ングリコールエチルエーテル、プロピレングリコールメ
チルエーテルアセテート等のグリコールエーテル系溶
剤、ブチロラクトン、バレロラクトン、カプロラクトン
等のラクトン系溶剤、ジメチルアセトアミド、ジメチル
ホルムアミド等のアミド系溶剤、トルエン、キシレンな
ど有機溶剤が挙げられ、これらの１種を単独で用いても
２種以上を組合わせて用いてもよい。なかでも、速硬化
性、成膜性等の成形性の観点からはグリコールエーテル
系溶剤及びラクトン系溶剤が好ましい。また、加熱硬化
時の急激な揮発による気泡形成を避ける観点からは沸点
が１００℃以上の溶剤が好ましい。（Ｄ）溶剤の配合
は、本発明の効果が得られる量であれば特に制限はない
が、液状封止用エポキシ樹脂組成物に対して、速硬化性
の観点から５〜３０重量％とすることが好ましく、１０
〜２０重量％がより好ましい。The liquid sealing epoxy resin composition of the present invention may optionally contain a solvent (D) for lowering the viscosity. In particular, when a solid epoxy resin and a curing agent are used, it is necessary to incorporate a solvent in order to obtain a liquid composition. (D) The solvent is not particularly restricted but includes, for example, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, ethylene glycol ethyl ether, ethylene glycol methyl ether Glycol ether solvents such as ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol methyl ether acetate; lactone solvents such as butyrolactone, valerolactone, and caprolactone; dimethylacetamide, dimethylformamide And organic solvents such as toluene and xylene. One of these alone may be used. It may be used also in combination of two or more thereof. Among them, glycol ether solvents and lactone solvents are preferred from the viewpoint of moldability such as rapid curability and film formability. From the viewpoint of avoiding the formation of bubbles due to rapid volatilization during heat curing, a solvent having a boiling point of 100 ° C. or higher is preferred. The mixing ratio of the solvent (D) is not particularly limited as long as the effect of the present invention can be obtained. However, the amount is 5 to 30% by weight with respect to the liquid sealing epoxy resin composition from the viewpoint of rapid curability. Preferably, 10
-20% by weight is more preferred.
【００１７】本発明の液状封止用エポキシ樹脂組成物に
は、その他の添加剤として、赤燐、リン酸エステル、メ
ラミン、メラミン誘導体、トリアジン環を有する化合
物、シアヌル酸誘導体、イソシアヌル酸誘導体等の窒素
含有化合物、シクロホスファゼン等の燐窒素含有化合
物、酸化亜鉛、酸化鉄、酸化モリブデン、フェロセン等
の金属化合物、三酸化アンチモン、四酸化アンチモン、
五酸化アンチモン等の酸化アンチモン、ブロム化エポキ
シ樹脂などの難燃剤、ハイドロタルサイト類、マグネシ
ウム、アルミニウム、チタン、ジルコニウム、ビスマス
等の元素の含水酸化物などのイオントラップ剤、高級脂
肪酸、高級脂肪酸金属塩、エステル系ワックス、ポリオ
レフィン系ワックス、ポリエチレン、酸化ポリエチレン
等の離型剤、シリコーンオイルやシリコーンゴム粉末等
の応力緩和剤、染料、カーボンブラック等の着色剤、希
釈剤、レベリング剤、消泡剤などを必要に応じて配合す
ることができる。The epoxy resin composition for liquid encapsulation of the present invention may further contain, as other additives, red phosphorus, phosphate esters, melamine, melamine derivatives, compounds having a triazine ring, cyanuric acid derivatives, isocyanuric acid derivatives and the like. Nitrogen-containing compounds, phosphorus-nitrogen-containing compounds such as cyclophosphazene, zinc oxide, iron oxide, molybdenum oxide, metal compounds such as ferrocene, antimony trioxide, antimony tetroxide,
Antimony oxides such as antimony pentoxide, flame retardants such as brominated epoxy resins, hydrotalcites, ion trapping agents such as hydrated oxides of elements such as magnesium, aluminum, titanium, zirconium and bismuth, higher fatty acids, higher fatty acid metals Release agents such as salts, ester waxes, polyolefin waxes, polyethylene and polyethylene oxide, stress relievers such as silicone oil and silicone rubber powder, dyes, coloring agents such as carbon black, diluents, leveling agents, defoamers And the like can be added as needed.
【００１８】本発明の液状封止用エポキシ樹脂組成物
は、成形後の硬化物の表面を非鏡面とする観点から、硬
化物の表面の反射率が１０％以下であることが必要であ
る。ここで、硬化物の表面の反射率とは、硬化物に入射
角４５℃〜７５℃で光照射した場合の光の反射率をい
い、入射角が４５℃〜６０℃での反射率が５％以下であ
ることが好ましく、３％以下であることが好ましく、２
％以下であることがさらに好ましい。硬化物の表面の反
射率の測定方法としては特に制限はないが、たとえば、
図１にその概略を示すように、デジタル変角光沢計を用
いて、本発明の液状封止用エポキシ樹脂組成物の硬化物
１に光源４から４５〜７５°の入射角６で白色光を照射
し、入射光２の光量に対する反射光３の光量を測定し、
白色板での測定値で校正して反射率を求める等の一般的
な手法が挙げられる。図１において、５は測定器を示
す。本発明においては、液状封止用エポキシ樹脂組成物
に配合する各種成分の組み合わせ及び配合量を調整する
ことによって、硬化物の表面の反射率が１０％以下であ
る液状封止用エポキシ樹脂組成物を得ることができる。
（Ｂ）硬化剤の選定とその配合量が特に重要である。The epoxy resin composition for liquid encapsulation of the present invention needs to have a reflectance of 10% or less on the surface of the cured product from the viewpoint of making the surface of the cured product non-specular after molding. Here, the reflectance of the surface of the cured product refers to the reflectance of light when the cured product is irradiated with light at an incident angle of 45 ° C to 75 ° C, and the reflectance at an incident angle of 45 ° C to 60 ° C is 5%. %, Preferably 3% or less, more preferably 2% or less.
% Is more preferable. The method for measuring the reflectance of the surface of the cured product is not particularly limited.
As schematically shown in FIG. 1, white light was applied to the cured product 1 of the liquid sealing epoxy resin composition of the present invention at an incident angle 6 of 45 to 75 ° from the light source 4 using a digital variable-angle gloss meter. Irradiate and measure the amount of reflected light 3 relative to the amount of incident light 2;
There is a general method of obtaining a reflectance by calibrating with a measured value on a white plate. In FIG. 1, reference numeral 5 denotes a measuring instrument. In the present invention, the epoxy resin composition for liquid encapsulation having a reflectance of 10% or less on the surface of the cured product is adjusted by adjusting the combination and the amount of various components to be added to the epoxy resin composition for liquid encapsulation. Can be obtained.
(B) The selection of the curing agent and the amount thereof are particularly important.
【００１９】本発明の液状封止用エポキシ樹脂組成物
は、上記各種成分を均一に分散混合できるのであれば、
いかなる手法を用いても調製できるが、一般的な手法と
して、所定の配合量の成分を秤量し、らいかい機、ミキ
シングロール、プラネタリミキサ等を用いて混合、混練
し、必要に応じて脱泡することによって得ることができ
る。The epoxy resin composition for liquid encapsulation of the present invention can be used as long as the above-mentioned various components can be uniformly dispersed and mixed.
It can be prepared by any method, but as a general method, weigh a specified amount of components, mix and knead using a mill, mixing roll, planetary mixer, etc., and degas if necessary Can be obtained.
【００２０】本発明で得られる液状封止用エポキシ樹脂
組成物により素子を封止して得られる電子部品装置とし
ては、リードフレーム、配線済みのテープキャリア、配
線板、ガラス、シリコンウエハ等の支持部材に、半導体
チップ、トランジスタ、ダイオード、サイリスタ等の能
動素子、コンデンサ、抵抗体、抵抗アレイ、コイル、ス
イッチ等の受動素子などの素子を搭載し、必要な部分を
本発明の液状封止用エポキシ樹脂組成物で封止して得ら
れる電子部品装置などが挙げられる。このような電子部
品装置としては、例えば、リードフレーム上に半導体素
子を固定し、ボンディングパッド等の素子の端子部とリ
ード部をワイヤボンディングやバンプで接続した後、本
発明の液状封止用エポキシ樹脂組成物を用いてディスペ
ンス方式等により封止してなる、ＰＬＣＣ（Plastic Le
aded Chip Carrier）、ＱＦＰ（Quad Flat Package）、
ＳＯＰ（Small Outline Package）、ＳＯＪ（Small Out
line J-leaded package）、ＴＳＯＰ（Thin Small Outl
ine Package）、ＴＱＦＰ（Thin Quad Flat Package）
等の一般的な樹脂封止型ＩＣ、テープキャリアにリード
ポンディングした半導体チップを、本発明の液状封止用
エポキシ樹脂組成物で封止したＴＣＰ（Tape Carrier P
ackage）、配線板やガラス上に形成した配線に、ワイヤ
ーボンディング、フリップチップボンディング、はんだ
等で接続した半導体チップを、本発明の液状封止用エポ
キシ樹脂組成物で封止したＣＯＢ（Chip On Board）、
ＣＯＧ（Chip On Glass）等のベアチップ実装した半導
体装置、配線板やガラス上に形成した配線に、ワイヤー
ボンディング、フリップチップボンディング、はんだ等
で接続した半導体チップ、トランジスタ、ダイオード、
サイリスタ等の能動素子及び／又はコンデンサ、抵抗
体、コイル等の受動素子を、本発明の液状封止用エポキ
シ樹脂組成物で封止したハイブリッドＩＣ、マルチチッ
プモジュール、マザーボード接続用の端子を形成したイ
ンターポーザ基板に半導体チップを搭載し、バンプまた
はワイヤボンディングにより半導体チップとインターポ
ーザ基板に形成された配線を接続した後、本発明の液状
封止用エポキシ樹脂組成物で半導体チップ搭載側を封止
したＢＧＡ（Ball Grid Array）、ＣＳＰ（Chip Size P
ackage）、ＭＣＰ（Multi Chip Package）などが挙げら
れる。また、プリント回路板にも本発明の液状封止用エ
ポキシ樹脂組成物は使用できる。なかでも、本発明の液
状封止用エポキシ樹脂組成物を使用したＴＣＰやＣＯ
Ｂ、ＣＯＧ等のベアチップ実装した半導体装置で優れた
特性を得ることができる。ＴＣＰは薄型、軽量で耐折り
曲げ実装性に優れ、ノート型パソコン等の液晶ドライ
バ、積層メモリモジュール等に用いられる。The electronic component device obtained by sealing the element with the epoxy resin composition for liquid sealing obtained in the present invention includes a support for a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer and the like. The components are mounted with active elements such as semiconductor chips, transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, resistor arrays, coils, switches and the like. An electronic component device obtained by sealing with a resin composition is exemplified. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, and a terminal portion of an element such as a bonding pad and a lead portion are connected by wire bonding or a bump. PLCC (Plastic Lec), which is sealed using a resin composition by a dispensing method or the like.
aded Chip Carrier), QFP (Quad Flat Package),
SOP (Small Outline Package), SOJ (Small Out
line J-leaded package), TSOP (Thin Small Outl)
ine Package), TQFP (Thin Quad Flat Package)
And the like. A general resin-encapsulated IC, such as a semiconductor chip lead-bonded to a tape carrier, is encapsulated with the epoxy resin composition for liquid encapsulation of the present invention.
COB (Chip On Board) in which a semiconductor chip connected to a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering or the like is sealed with the epoxy resin composition for liquid sealing of the present invention. ),
Semiconductor devices mounted on bare chips such as COG (Chip On Glass), wiring chips formed on wiring boards and glass, semiconductor chips connected by wire bonding, flip chip bonding, soldering, transistors, diodes,
A terminal for connecting a hybrid IC, a multi-chip module, and a motherboard in which an active element such as a thyristor and / or a passive element such as a capacitor, a resistor, and a coil are sealed with the epoxy resin composition for liquid sealing of the present invention. A BGA in which a semiconductor chip is mounted on an interposer substrate, and the semiconductor chip and the wiring formed on the interposer substrate are connected by bump or wire bonding, and then the semiconductor chip mounting side is sealed with the liquid sealing epoxy resin composition of the present invention. (Ball Grid Array), CSP (Chip Size P)
ackage), MCP (Multi Chip Package) and the like. Further, the epoxy resin composition for liquid sealing of the present invention can be used for a printed circuit board. In particular, TCP and CO using the epoxy resin composition for liquid encapsulation of the present invention.
Excellent characteristics can be obtained with a semiconductor device mounted on a bare chip such as B or COG. TCP is thin, lightweight, and excellent in bending resistance, and is used for a liquid crystal driver of a notebook computer, a stacked memory module, and the like.
【００２１】本発明の液状封止用エポキシ樹脂組成物を
用いて素子を封止する方法としては、ディスペンス方
式、注型方式、印刷方式等が挙げられる。Examples of the method for sealing the device using the epoxy resin composition for liquid sealing of the present invention include a dispense method, a casting method, a printing method and the like.
【００２２】[0022]
【実施例】次に実施例により本発明を説明するが、本発
明の範囲はこれらの実施例に限定されるものではない。Next, the present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples.
【００２３】実施例１及び比較例１ エポキシ樹脂としてエポキシ当量１６０のビスフェノー
ルＦ型液状エポキシ樹脂（東都化成株式会社製商品名Ｙ
ＤＦ−８１７０Ｃ）、ビスフェノールＡＤ型液状エポキ
シ樹脂（三井化学株式会社製商品名Ｒ−７１０）、ｏ−
クレゾールノボラック型エポキシ樹脂（東都化成株式会
社製商品名ＥＳＣＮ−１９５−６）、硬化剤として重量
平均分子量が４２６、水酸基当量が１４１、２５℃にお
ける粘度が２５Ｐａ・ｓで下記式（VI）で示されるアリ
ル基含有フェノール樹脂１、重量平均分子量が７１０、
水酸基当量が２１０、６０℃における粘度が４．４Ｐａ
・ｓで、下記式（VII）で示されモル比ｍ／ｎが１／１
のランダム共重合体であるアリル基含有フェノール樹脂
２、重量平均分子量が７５０、水酸基当量が１０５、軟
化点が８３℃のフェノールノボラック樹脂（明和化成株
式会社製商品名Ｈ−１００）、硬化促進剤として１，８
−ジアザビシクロ（５，４，０）ウンデセン−７のフェ
ノールノボラック樹脂塩（サンアプロ株式会社製商品名
ＳＡ−８４１）、充填剤として比表面積１ｍ２／ｇ、平
均粒径４μｍの球状溶融シリカ、溶剤としてプロピレン
グリコールモノメチルエーテルアセテートとγ−ブチロ
ラクトンとの重量比１／１の混合溶剤を、それぞれ表１
に示す重量部で配合し、三本ロールにて混練分散した
後、真空脱泡して、実施例１、２及び比較例１の液状封
止用エポキシ樹脂組成物を作製した。組成物の２５℃に
おける粘度はいずれも３Ｐａ・ｓであった。Example 1 and Comparative Example 1 As an epoxy resin, a bisphenol F type liquid epoxy resin having an epoxy equivalent of 160 (trade name Y manufactured by Toto Kasei Co., Ltd.)
DF-8170C), bisphenol AD type liquid epoxy resin (trade name: R-710, manufactured by Mitsui Chemicals, Inc.), o-
Cresol novolak type epoxy resin (trade name: ESCN-195-6, manufactured by Toto Kasei Co., Ltd.), having a weight average molecular weight of 426 as a curing agent, a hydroxyl equivalent of 141, and a viscosity at 25 ° C. of 25 Pa · s, represented by the following formula (VI): Allyl group-containing phenolic resin 1, having a weight average molecular weight of 710,
Hydroxyl equivalent is 210, viscosity at 60 ° C. is 4.4 Pa
In s, the molar ratio m / n represented by the following formula (VII) is 1/1
Allyl group-containing phenolic resin 2, a phenol novolak resin having a weight average molecular weight of 750, a hydroxyl equivalent of 105, and a softening point of 83 ° C. (trade name H-100, manufactured by Meiwa Kasei Co., Ltd.), a curing accelerator 1,8 as
Phenol novolak resin salt of diazabicyclo (5,4,0) undecene-7 (trade name: SA-841, manufactured by San Apro Co., Ltd.), spherical fused silica having a specific surface area of 1 m 2 / g and an average particle size of 4 μm as a filler, and a solvent Table 1 shows mixed solvents of propylene glycol monomethyl ether acetate and γ-butyrolactone at a weight ratio of 1/1.
, And kneaded and dispersed with a three-roll mill, followed by vacuum defoaming to produce the epoxy resin compositions for liquid sealing of Examples 1, 2 and Comparative Example 1. The viscosity of each of the compositions at 25 ° C. was 3 Pa · s.
【００２４】[0024]
【化２】 （ここで、ｍ及びｎは上記の重量平均分子量を示す１以
上の整数である。）Embedded image (Here, m and n are integers of 1 or more indicating the above-mentioned weight average molecular weight.)
【００２５】[0025]
【表１】 [Table 1]
【００２６】作製した実施例及び比較例の液状封止用エ
ポキシ樹脂組成物を用いて次の各試験を行なった。 （１）反射率 硬化物の表面の反射率を測定し、非鏡面か否かを評価し
た。ＴＣＰ（チップサイズ１５．６×１．９×０．６５
ｍｍ、デバイス孔１６．１×２．１ｍｍ、リードピッ
チ：６５〜１９５μｍ、ポリイミド製テープキャリア）
を、実施例１、２及び比較例１の液状封止用エポキシ樹
脂組成物を用いてディスペンス方式により１４０℃／１
５分の加熱条件で成形して作製し、液状封止用エポキシ
樹脂組成物（硬化物）の表面の反射率を、デジタル変角
光沢計（スガ試験器株式会社製）を用いて、図２に概略
図で示すように測定した。白色光源４を用いて、光源入
射角６を４５°、６０°又は７５°として測定した値
を、表面コーティングされたセラミック白色板で校正し
た。結果を表２に示す。 （２）速硬化性 実施例１及び比較例１の液状封止用エポキシ樹脂組成物
をディスペンス方式により１３０℃又は１４０℃で所定
時間加熱して３００μｍ厚のシート状に成形した硬化物
を、長さ７０ｍｍ、幅１０ｍｍの短冊状に切り取り試験
片とし、引張試験機（株式会社島津製作所製）を用い
て、ＪＩＳ−Ｋ−６９１１に準拠した３点支持型の曲げ
試験を行い、スパン距離２４ｍｍ、曲げ速度２ｍｍ／ｍ
ｉｎの条件で曲げ強度（σ、単位：ＭＰａ）及び曲げ弾
性率（Ｅ、単位：ＧＰａ）を求め、１４０℃／６０分の
加熱条件で成形した硬化物の値に対する百分率を算出し
て速硬化性を評価した。結果を表３に示す。The following tests were carried out using the prepared epoxy resin compositions for liquid encapsulation of Examples and Comparative Examples. (1) Reflectance The reflectance of the surface of the cured product was measured to evaluate whether the surface was non-mirror. TCP (chip size 15.6 × 1.9 × 0.65
mm, device hole 16.1 × 2.1 mm, lead pitch: 65 to 195 μm, polyimide tape carrier)
Using the epoxy resin compositions for liquid encapsulation of Examples 1 and 2 and Comparative Example 1 by a dispensing method at 140 ° C./1
It was molded under a heating condition of 5 minutes, and the surface reflectance of the epoxy resin composition for liquid encapsulation (cured product) was measured using a digital variable-angle gloss meter (manufactured by Suga Test Instruments Co., Ltd.). Was measured as shown in the schematic diagram. The value measured using the white light source 4 at a light source incident angle 6 of 45 °, 60 ° or 75 ° was calibrated with a surface-coated ceramic white plate. Table 2 shows the results. (2) Rapid curability A cured product obtained by heating the epoxy resin compositions for liquid encapsulation of Example 1 and Comparative Example 1 at 130 ° C. or 140 ° C. for a predetermined time by a dispense method to form a sheet having a thickness of 300 μm was obtained. The test piece was cut into a strip having a length of 70 mm and a width of 10 mm, and a three-point support type bending test based on JIS-K-6911 was performed using a tensile tester (manufactured by Shimadzu Corporation). Bending speed 2mm / m
The flexural strength (σ, unit: MPa) and flexural modulus (E, unit: GPa) were determined under the conditions of “in”, and the percentage of the value of the cured product molded under the heating conditions of 140 ° C./60 minutes was calculated to obtain a quick cure. The sex was evaluated. Table 3 shows the results.
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】次に、光学的自動検査機を用いて液状封止
用エポキシ樹脂組成物の硬化後の評価を行なったとこ
ろ、いずれの入射角でも硬化物表面の反射率が１０％以
下である実施例１及び２では、硬化物の表面が非鏡面で
あり、ハレーションを起こさず容易に評価できたのに対
して、反射率が４０％以上の比較例１では、硬化物の表
面が鏡面で、ハレーションを起こして評価が困難であっ
た。また、速硬化性の評価では、曲げ強度及び曲げ弾性
率は、ともに１４０℃／６０分で成形した硬化物に対す
る百分率が、成形温度１３０℃、１４０℃のいずれの場
合でも、実施例１は比較例１よりも高い。特に１４０℃
／１０分の値を比較すると、実施例１では曲げ強度、曲
げ弾性率ともに１００％であるのに対して、比較例１で
はそれぞれ９０．７％、９７．２％で著しく劣る。これ
らの結果から実施例１の液状封止用エポキシ樹脂組成物
が速硬化性であることが確認される。Next, the epoxy resin composition for liquid encapsulation was evaluated after curing using an automatic optical inspection machine. The reflectance of the cured product surface was 10% or less at any incident angle. In Examples 1 and 2, the surface of the cured product was non-specular and could be easily evaluated without causing halation. In Comparative Example 1 having a reflectance of 40% or more, the surface of the cured product was a mirror surface. Halation occurred and evaluation was difficult. Further, in the evaluation of the quick-curing property, the bending strength and the bending elastic modulus were both a percentage with respect to the cured product molded at 140 ° C./60 minutes, and the molding temperature was 130 ° C. or 140 ° C., and Example 1 was compared. Higher than in Example 1. Especially 140 ° C
Comparing the values of / 10 minutes, the flexural strength and the flexural modulus in Example 1 were both 100%, whereas those in Comparative Example 1 were significantly inferior at 90.7% and 97.2%, respectively. From these results, it is confirmed that the liquid sealing epoxy resin composition of Example 1 is quick-curing.
【００３０】[0030]
【発明の効果】本発明になる液状封止用エポキシ樹脂組
成物は、実施例で示したように、表面が非鏡面の硬化物
が得られるので光学的自動検査機においてハレーション
をおこさず評価が容易で、この液状封止用エポキシ樹脂
組成物を用いて素子を封止すれば半導体装置等の電子部
品装置の製造工程での管理等も簡便になり、その工業的
価値は大である。特に液状封止材が多く用いられるＣＯ
Ｂ、ＣＯＧ等のベアチップ実装した半導体装置やＴＣＰ
に有用である。The epoxy resin composition for liquid encapsulation according to the present invention, as shown in the examples, can obtain a cured product having a non-mirror surface, so that it can be evaluated without causing halation in an automatic optical inspection machine. If an element is encapsulated using the epoxy resin composition for liquid encapsulation, the management and the like in the production process of an electronic component device such as a semiconductor device can be simplified, and its industrial value is great. In particular, CO is often used as a liquid sealing material.
B, COG and other bare chip mounted semiconductor devices and TCP
Useful for
【図１】硬化物表面の反射率の測定方法を示す概略図FIG. 1 is a schematic diagram showing a method for measuring the reflectance of the surface of a cured product.
【図２】ＴＣＰにおいて液状封止用エポキシ樹脂組成物
の硬化物表面の反射率の測定方法を示す概略図FIG. 2 is a schematic diagram showing a method for measuring the reflectance of the surface of a cured product of a liquid sealing epoxy resin composition in TCP.
１：液状封止用エポキシ樹脂組成物の硬化物 ２：入射光 ３：反射光 ４：光源 ５：測定器 ６：入射角 ７：ソルダーレジスト ８：テープキャリア ９：Ｃｕリード １０：Ａｕバンプ １１：半導体チップ 1: Cured epoxy resin composition for liquid encapsulation 2: Incident light 3: Reflected light 4: Light source 5: Measuring instrument 6: Incident angle 7: Solder resist 8: Tape carrier 9: Cu lead 10: Au bump 11: Semiconductor chip
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｌ 23/31 (72)発明者 中村 泰章 茨城県結城市大字鹿窪1772−１ 日立化成 工業株式会社下館事業所内 Ｆターム(参考） 4J002 CC052 CD011 CD021 CD051 CD061 DE146 DE186 DE236 DF016 DJ006 DJ016 DJ046 DK006 FD016 FD207 GJ02 GQ05 HA01 HA05 4J036 AA01 AC01 AC05 AD01 AD08 AD21 AF08 AH07 DA01 DA02 FA02 FA05 FB08 JA07 4M109 AA01 BA03 BA05 EA02 EC11──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01L 23/31 (72) Inventor Yasumasa Nakamura 1772-1 Oshikakubo, Yuki-shi, Ibaraki Pref. Hitachi Chemical Co., Ltd. Shimodate Business In-house F-term (reference) 4J002 CC052 CD011 CD021 CD051 CD061 DE146 DE186 DE236 DF016 DJ006 DJ016 DJ046 DK006 FD016 FD207 GJ02 GQ05 HA01 HA05 4J036 AA01 AC01 AC05 AD01 AD08 AD21 AF08 AH07 DA01 DA02 FA02 FA05 BA03 EA08 EC07
Claims (7)
須成分とし、（Ｂ）硬化剤がアリル基含有フェノール樹
脂を含有し、かつ硬化物の表面の反射率が１０％以下で
ある液状封止用エポキシ樹脂組成物。An essential component is (A) an epoxy resin and (B) a curing agent, (B) the curing agent contains an allyl group-containing phenol resin, and the cured product has a surface reflectance of 10% or less. Epoxy resin composition for liquid sealing.
有フェノールノボラック樹脂である請求項１記載の液状
封止用エポキシ樹脂組成物。2. The epoxy resin composition for liquid sealing according to claim 1, wherein the allyl group-containing phenol resin is an allyl group-containing phenol novolak resin.
は請求項２記載の液状封止用エポキシ樹脂組成物。3. The epoxy resin composition for liquid sealing according to claim 1, further comprising (C) a filler.
のいずれかに記載の液状封止用エポキシ樹脂組成物。4. The method according to claim 1, further comprising (D) a solvent.
The epoxy resin composition for liquid sealing according to any one of the above.
用エポキシ樹脂組成物を用いたＴＣＰ用封止材。5. A sealing material for TCP using the epoxy resin composition for liquid sealing according to claim 1.
用エポキシ樹脂組成物を用いて封止された素子を備えた
電子部品装置。6. An electronic component device having an element sealed with the epoxy resin composition for liquid sealing according to claim 1.
用エポキシ樹脂組成物を用いて封止された素子を備えた
ＴＣＰ。7. A TCP comprising an element encapsulated with the epoxy resin composition for liquid encapsulation according to claim 1.
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|---|---|---|---|
| JP2000398598A JP4696359B2 (en) | 2000-12-27 | 2000-12-27 | Liquid sealing epoxy resin composition and electronic component device |
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|---|---|---|---|
| JP2000398598A JP4696359B2 (en) | 2000-12-27 | 2000-12-27 | Liquid sealing epoxy resin composition and electronic component device |
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|---|---|
| JP2002194066A true JP2002194066A (en) | 2002-07-10 |
| JP4696359B2 JP4696359B2 (en) | 2011-06-08 |
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ID=18863528
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| JP2000398598A Expired - Lifetime JP4696359B2 (en) | 2000-12-27 | 2000-12-27 | Liquid sealing epoxy resin composition and electronic component device |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004083761A (en) * | 2002-08-27 | 2004-03-18 | Matsushita Electric Works Ltd | Liquid-sealing material and semiconductor device |
| US8232355B2 (en) | 2005-11-25 | 2012-07-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic components and electronic component device |
| KR20150097435A (en) * | 2014-02-18 | 2015-08-26 | 주식회사 엘지화학 | Encapsulation film and organic electronic device comprising the same |
| WO2015126174A1 (en) * | 2014-02-18 | 2015-08-27 | 주식회사 엘지화학 | Encapsulation film and organic electronic device including same |
| WO2015147600A1 (en) * | 2014-03-27 | 2015-10-01 | 주식회사 엘지화학 | Sealing film and organic electronic device including same |
| US10103353B2 (en) | 2014-03-27 | 2018-10-16 | Lg Chem, Ltd. | Encapsulation film and organic electronic device comprising the same |
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| Publication number | Publication date |
|---|---|
| JP4696359B2 (en) | 2011-06-08 |
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