JPH08157694A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH08157694A JPH08157694A JP33172894A JP33172894A JPH08157694A JP H08157694 A JPH08157694 A JP H08157694A JP 33172894 A JP33172894 A JP 33172894A JP 33172894 A JP33172894 A JP 33172894A JP H08157694 A JPH08157694 A JP H08157694A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- resin composition
- amount
- inorganic
- 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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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、硬化物の透湿性が低
く、プレモールド型中空パッケージ用材料として好適な
エポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition which has a low moisture permeability of a cured product and is suitable as a material for premolded hollow packages.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】現在、
プラスチックは、量産性、低コスト、加工性、電気絶縁
性など多様な性能を有することから様々な分野で使用さ
れており、更に合成化学の発達と共に次々と新しいプラ
スチックが誕生している。また、プラスチックの欠点と
されてきた強度についてもプラスチック異種材料を組み
合わせた強化プラスチックが生まれたことでその強靱性
も向上してきている。今後もプラスチックは、建築材料
や輸送包装材料はもちろん、構造材料としても生産量の
大幅な伸びが予想されている。2. Description of the Related Art
Plastics are used in various fields because they have various performances such as mass productivity, low cost, processability, and electrical insulation properties, and new plastics are born one after another with the development of synthetic chemistry. Regarding strength, which has been regarded as a drawback of plastics, its toughness has also been improved by the production of reinforced plastics by combining different kinds of plastics. In the future, plastics are expected to grow significantly not only as building materials and transportation packaging materials but also as structural materials.
【０００３】各種プラスチックの中でも特にエポキシ樹
脂は、バランスのとれた硬化物物性を持っており、とり
わけ耐湿性や接着性に優れていることから、絶縁材料、
積層板、複合材料、接着剤、塗料、半導体封止材などの
広い用途に利用することができる。Among various plastics, the epoxy resin has a well-balanced cured physical property, and is particularly excellent in moisture resistance and adhesiveness.
It can be used for a wide range of applications such as laminated plates, composite materials, adhesives, paints, and semiconductor encapsulants.
【０００４】しかしながら、金属やセラミックは本質的
に非透湿であるのに対して、プラスチックは各種固有の
水分拡散係数を持っており、加湿条件に曝されるとこの
拡散係数に応じて吸水し、透湿していく。それ故、腕時
計、電卓等の精密機械や半導体パッケージ等の電子部
品、特に固体撮像素子（以下、ＣＣＤと略す）封止用中
空パッケージ等の防水性や気密性が要求される用途にプ
ラスチックを利用する場合はプラスチックの透湿性が問
題になることが多い。例えば直接水に接触しなくても高
温多湿の環境に長時間曝された場合、プラスチック製の
ＣＣＤ封止用中空パッケージは、徐々に吸水、透湿し、
更に気密性を保持した空間に飽和水蒸気圧から求められ
た飽和水蒸気量を越えた水分が存在すると、水分の凝集
により結露が発生し、その装置は使用不能となってしま
う。この点は、エポキシ樹脂の場合も同様である。However, while metals and ceramics are essentially impermeable to moisture, plastics have various inherent moisture diffusion coefficients, and when exposed to humidifying conditions, they absorb water according to this diffusion coefficient. , Breathing moisture. Therefore, plastics are used for precision machines such as wristwatches and calculators and electronic parts such as semiconductor packages, especially hollow packages for solid-state image sensor (hereinafter abbreviated as CCD) encapsulation requiring waterproofness and airtightness. When doing so, the moisture permeability of the plastic often becomes a problem. For example, when exposed to a hot and humid environment for a long time without direct contact with water, the plastic hollow package for CCD encapsulation gradually absorbs and permeates water,
Furthermore, if moisture in excess of the saturated vapor amount determined from the saturated vapor pressure is present in the airtight space, dew condensation occurs due to the aggregation of the moisture, which renders the device unusable. This point is the same in the case of an epoxy resin.
【０００５】従って、エポキシ樹脂、硬化剤、無機質充
填剤を主成分とするエポキシ樹脂組成物においては、従
来より透湿性の改善が課題となっており、このためエポ
キシ樹脂組成物中に無機系吸水剤を添加し、硬化物中を
透過してくる水分を無機系吸着剤に吸着させることによ
り、プレモールド型中空パッケージ内部への透湿を防止
する技術が提案されている。例えば、特開平６−４９３
３３号公報に示されているようにエポキシ樹脂組成物中
に吸水率の大きなシリカを含有させて透湿性を改善する
技術があり、また本出願人は、先に特願平６−２３６８
４号において水分拡散係数の小さな硬化物を得られるエ
ポキシ樹脂組成物に無機系吸水剤を併用して透湿性を改
善する技術を提案した。Therefore, in the epoxy resin composition containing the epoxy resin, the curing agent, and the inorganic filler as the main components, improvement of moisture permeability has been a problem from the past, and therefore, the inorganic water-absorbing agent is contained in the epoxy resin composition. There has been proposed a technique for preventing moisture permeation into the pre-mold type hollow package by adding an agent and adsorbing the moisture permeating through the cured product to the inorganic adsorbent. For example, JP-A-6-493
As disclosed in Japanese Patent Publication No. 33-33, there is a technique for improving moisture permeability by incorporating silica having a high water absorption rate into an epoxy resin composition, and the applicant of the present invention has previously filed Japanese Patent Application No. 6-2368.
No. 4 proposed a technique for improving moisture permeability by using an inorganic water-absorbing agent together with an epoxy resin composition capable of obtaining a cured product having a small water diffusion coefficient.
【０００６】しかしながら、無機系吸水剤はある温度以
上になると吸着した水分を放出する性質があり、本発明
者の検討によると、無機系吸水剤をそのままエポキシ樹
脂組成物に添加した場合、その後の加熱成形により半導
体装置を製造する際に無機系吸水剤が放出する水分によ
り硬化反応に悪影響を及ぼし、硬化物のガラス転移温度
の低下を招いてしまう場合があることが判明した。例え
ば、透湿信頼性試験を行なった場合に試験温度とガラス
転移温度の差が小さくなるために透湿量が大きくなり、
結果的に半導体装置の性能低下を招くことがある。However, the inorganic water-absorbing agent has a property of releasing adsorbed water at a temperature higher than a certain temperature. According to the study of the present inventors, when the inorganic water-absorbing agent is directly added to the epoxy resin composition, It has been found that the moisture released from the inorganic water-absorbing agent when the semiconductor device is manufactured by heat molding may adversely affect the curing reaction, which may lead to a decrease in the glass transition temperature of the cured product. For example, when a moisture permeability reliability test is performed, the amount of moisture permeability increases because the difference between the test temperature and the glass transition temperature decreases.
As a result, the performance of the semiconductor device may be degraded.
【０００７】また、無機系吸湿剤の性状は有機樹脂成分
のぬれ性に影響を与え、組成物の流動性を左右する。特
にその表面状態において、例えば比表面積が必要以上に
大きい場合、組成物の流動性が極端に悪化し、半導体封
止用としては不適となってしまう場合があることも判明
し、従ってこれらの問題点を解決することが望まれた。Further, the properties of the inorganic hygroscopic agent affect the wettability of the organic resin component and influence the fluidity of the composition. Especially in the surface state, for example, when the specific surface area is unnecessarily large, the fluidity of the composition is extremely deteriorated and it may be unsuitable for semiconductor encapsulation. It was hoped that the points would be resolved.
【０００８】本発明は上記要望に応えるためになされた
もので、成形時の硬化特性に優れていると共に、低透湿
性に優れた高品質の硬化物を与えるエポキシ樹脂組成物
を提供することを目的とする。The present invention has been made in order to meet the above-mentioned demands, and it is to provide an epoxy resin composition which is excellent in curing characteristics at the time of molding and gives a cured product of high quality excellent in low moisture permeability. To aim.
【０００９】[0009]
【課題を解決するための手段及び作用】本発明者らは、
上記目的を達成するため鋭意検討を重ねた結果、エポキ
シ樹脂、硬化剤、無機質充填剤を主成分とするエポキシ
樹脂組成物において、上記無機質充填剤の配合量をエポ
キシ樹脂と硬化剤との合計量１００重量部に対し２００
重量部以上とすること、更にこのエポキシ樹脂組成物に
無機系吸水剤を配合すること、この場合無機系吸水剤は
必ず再生処理を行い、吸着水分量が０．１重量％以下に
吸着水分が除去された状態でエポキシ樹脂組成物に添加
することで、硬化反応に悪影響もなく、成形時の硬化特
性に優れている上、低透湿性で高品質の硬化物を与え、
特にプレモールド型中空パッケージ用材料として好適な
エポキシ樹脂組成物が得られることを知見した。Means and Action for Solving the Problems The present inventors have
As a result of repeated intensive studies to achieve the above-mentioned object, an epoxy resin, a curing agent, in an epoxy resin composition containing an inorganic filler as a main component, the compounding amount of the inorganic filler is the total amount of the epoxy resin and the curing agent. 200 for 100 parts by weight
If the amount of adsorbed water is less than 0.1% by weight, the amount of adsorbed water should be 0.1% by weight or less. By adding to the epoxy resin composition in the removed state, there is no adverse effect on the curing reaction, excellent curing characteristics at the time of molding, low moisture permeability and giving a cured product of high quality,
In particular, it has been found that an epoxy resin composition suitable as a material for premolded hollow packages can be obtained.
【００１０】即ち、エポキシ樹脂組成物の構成成分とし
ては、エポキシ樹脂及び硬化剤を主とする有機樹脂成分
とともに無機質充填剤が不可欠であるが、無機質充填剤
は硬化物の膨張係数を下げて低応力化を図ることが主な
役割であるものの、基本的に吸水性がほぼゼロと考えら
れるため、その添加量が増えるにしたがって相対的に有
機成分は減ることになり、吸水率も低下させ得るもの
で、本発明者らの検討の結果、吸水率の点から無機質充
填剤の添加量はエポキシ樹脂及び硬化剤の合計量１００
重量部に対して２００重量部以上必要があることを見い
出した。That is, as the constituent component of the epoxy resin composition, the inorganic filler is indispensable together with the organic resin component mainly composed of the epoxy resin and the curing agent, but the inorganic filler lowers the expansion coefficient of the cured product and is low. Although the main role is to achieve stress, it is considered that water absorption is basically zero, so as the amount of addition increases, the organic components will decrease relatively, and the water absorption rate can also decrease. However, as a result of the study by the present inventors, from the viewpoint of water absorption, the addition amount of the inorganic filler is 100% of the total amount of the epoxy resin and the curing agent.
It has been found that more than 200 parts by weight is necessary with respect to parts by weight.
【００１１】加えて、単に拡散係数の小さなエポキシ樹
脂組成物を使用するだけではプレモールド型中空パッケ
ージ用材料としては不十分であり、本発明者らは、より
透湿性を低下させるため無機系吸水剤を添加することで
硬化物中を透過する水分を吸着させて、水分の透過スピ
ードを抑えるという手法を導入したが、この場合硬化特
性、硬化物の低透湿性の点から、無機系吸水剤は再生処
理、特に２００℃の温度で５時間以上処理するこによ
り、吸着水分量を０．１重量％未満にすること、更に組
成物の流動性や硬化物特性、低透湿性の点から、無機系
吸水剤としては、見かけ比重が０．５〜１．０ｇ／ｃｍ
3 、吸油量が１０〜５０ｍｌ／１００ｇ、比表面積が１
０〜１００ｍ2 ／ｇ、細孔容積が０．１０〜１．０ｍｌ
／ｇ、平均粒径が０．５〜１０μｍである球状の多孔質
シリカを使用し、これを温度２００℃以上、５時間以上
処理したものが有効であること、また添加量としては、
エポキシ樹脂と硬化剤との合計量１００重量部に対し１
０重量部以上が良好な結果を与えることを知見し、本発
明をなすに至ったものである。In addition, simply using an epoxy resin composition having a small diffusion coefficient is not sufficient as a material for a pre-mold type hollow package. Introducing a method of adsorbing moisture that permeates the cured product by adding an agent to suppress the moisture permeation speed.In this case, from the viewpoint of curing characteristics and low moisture permeability of the cured product, an inorganic water-absorbing agent is used. Is a regeneration treatment, in particular, a treatment at a temperature of 200 ° C. for 5 hours or more to reduce the amount of adsorbed moisture to less than 0.1% by weight, and in view of fluidity of the composition, cured product characteristics, and low moisture permeability, The inorganic water-absorbing agent has an apparent specific gravity of 0.5 to 1.0 g / cm.
3 , oil absorption 10-50ml / 100g, specific surface area 1
0-100 m 2 / g, pore volume 0.10-1.0 ml
/ G, a spherical porous silica having an average particle size of 0.5 to 10 μm is used, and it is effective to treat this at a temperature of 200 ° C. or higher for 5 hours or longer, and as an addition amount,
1 for every 100 parts by weight of epoxy resin and hardener
It was found that 0 parts by weight or more gives good results, and the present invention has been completed.
【００１２】このように、本発明では、水分透過の生じ
るエポキシ樹脂組成物において、無機質充填材を多量に
添加して硬化物の吸水率を減らすとともに、吸着水分量
の少ない無機系吸水剤を使用して硬化物の透過水分をト
ラップするもので、これによりかかるエポキシ樹脂組成
物で形成した中空パッケージの寿命を飛躍的に向上させ
ることができ、信頼性の高いプレモールド型中空パッケ
ージを得ることができるものである。As described above, in the present invention, in the epoxy resin composition in which water permeation occurs, a large amount of the inorganic filler is added to reduce the water absorption of the cured product, and the inorganic water absorbing agent having a small amount of adsorbed water is used. To trap the permeated water of the cured product, which can dramatically improve the life of the hollow package formed of such an epoxy resin composition, and to obtain a highly reliable premolded hollow package. It is possible.
【００１３】従って、本発明はエポキシ樹脂、硬化剤、
無機質充填剤を主成分とするエポキシ樹脂組成物におい
て、無機質充填剤をエポキシ樹脂と硬化剤との合計量１
００重量部に対して２００重量部以上配合すると共に、
見かけ比重が０．５〜１．０ｇ／ｍ3 、吸油量が１０〜
５０ｍｌ／１００ｇ、比表面積が１０〜１００ｍ2 ／
ｇ、細孔容積が０．１０〜１．０ｍｌ／ｇ、平均粒径が
０．５〜１０μｍである球状の多孔質シリカを２００℃
以上の温度で５時間以上処理することにより、吸着水分
量を０．１重量％未満に低減した無機系吸水剤をエポキ
シ樹脂と硬化剤との合計量１００重量部に対して１０重
量部以上添加したことを特徴とするエポキシ樹脂組成物
を提供する。Accordingly, the present invention provides an epoxy resin, a curing agent,
In an epoxy resin composition containing an inorganic filler as a main component, the total amount of the inorganic filler and the epoxy resin and the curing agent is 1
200 parts by weight or more with respect to 00 parts by weight,
Apparent specific gravity is 0.5 to 1.0 g / m 3 , oil absorption is 10
50 ml / 100 g, specific surface area 10-100 m 2 /
g, a pore volume of 0.10 to 1.0 ml / g, and a spherical porous silica having an average particle diameter of 0.5 to 10 μm at 200 ° C.
By treating at the above temperature for 5 hours or more, 10 parts by weight or more of an inorganic water absorbing agent whose adsorbed water content is reduced to less than 0.1% by weight is added to 100 parts by weight of the total amount of the epoxy resin and the curing agent. An epoxy resin composition characterized by the above is provided.
【００１４】以下、本発明につき更に詳しく説明する
と、本発明のエポキシ樹脂組成物は、エポキシ樹脂、硬
化剤、無機質充填剤を必須成分とする。The present invention will be described in more detail below. The epoxy resin composition of the present invention contains an epoxy resin, a curing agent and an inorganic filler as essential components.
【００１５】ここで、エポキシ樹脂としては、１分子中
にエポキシ基を少なくとも２個以上有するエポキシ樹脂
が使用され、従来半導体封止材用途に汎用されているビ
スフェノール型エポキシ樹脂、フェノールノボラック型
エポキシ樹脂、オルソクレゾールノボラック型エポキシ
樹脂、トリフェノールアルカン型エポキシ樹脂及びその
重合物、グリシジルエステル型エポキシ樹脂、脂環式エ
ポキシ樹脂、複素環型エポキシ樹脂、臭素化エポキシ樹
脂等のほか、信頼性試験中の吸湿後の半田熱衝撃におけ
る耐クラック性のレベルアップを考え、低吸水性のナフ
タレン型エポキシ樹脂やビフェニル型エポキシ樹脂、ジ
シクロペンタジエン−フェノール型エポキシ樹脂、アラ
ルキル−フェノール型エポキシ樹脂等が好適に用いられ
る。これらのエポキシ樹脂は、その１種を単独で又は２
種以上を併用して使用することができる。Here, as the epoxy resin, an epoxy resin having at least two epoxy groups in one molecule is used, and a bisphenol type epoxy resin or a phenol novolac type epoxy resin which has been generally used for semiconductor encapsulating materials has been used. , Orthocresol novolac type epoxy resin, triphenolalkane type epoxy resin and its polymer, glycidyl ester type epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, brominated epoxy resin, etc. Considering the improvement of crack resistance in solder thermal shock after moisture absorption, low water absorption naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-phenol type epoxy resin, aralkyl-phenol type epoxy resin, etc. are preferably used. To be These epoxy resins may be used alone or in combination of 2
One or more species can be used in combination.
【００１６】また、これらのエポキシ樹脂は軟化点が５
０〜１２０℃、特に７０〜１１０℃で、エポキシ当量が
１００〜４００を有するものが望ましい。軟化点が５０
℃未満のエポキシ樹脂を用いた場合、硬化物のガラス転
移温度が低下するばかりか、成形時にバリやボイドが発
生しやすい場合があり、また軟化点が１２０℃を越える
と粘度が高くなり過ぎて成形できなくなる場合がある。Further, these epoxy resins have a softening point of 5
Those having an epoxy equivalent of 100 to 400 at 0 to 120 ° C., particularly 70 to 110 ° C. are desirable. Softening point is 50
When an epoxy resin having a temperature of less than ℃ is used, not only the glass transition temperature of the cured product is lowered, but also burrs and voids are likely to occur during molding, and when the softening point exceeds 120 ° C., the viscosity becomes too high. It may not be possible to mold.
【００１７】これらのエポキシ樹脂は、半導体封止に用
いる場合、加水分解性塩素が１０００ｐｐｍ以下、特に
５００ｐｐｍ以下、ナトリウム、カリウムは１０ｐｐｍ
以下であることが好ましく、このようなエポキシ樹脂を
選択することで信頼性に優れたエポキシ樹脂組成物を得
ることができる。加水分解性塩素が１０００ｐｐｍを越
えたり、ナトリウム、カリウムが１０ｐｐｍを越える樹
脂を用いて半導体装置を封止し、長時間高温高湿下に半
導体装置を放置した場合、耐湿性が劣化する場合があ
る。When these epoxy resins are used for semiconductor encapsulation, hydrolyzable chlorine is 1000 ppm or less, particularly 500 ppm or less, and sodium and potassium are 10 ppm.
The following is preferable, and an epoxy resin composition having excellent reliability can be obtained by selecting such an epoxy resin. If the semiconductor device is sealed with a resin containing more than 1000 ppm of hydrolyzable chlorine or more than 10 ppm of sodium or potassium and left for a long time under high temperature and high humidity, the moisture resistance may deteriorate. .
【００１８】硬化剤としてはフェノール樹脂系が好適で
あり、従来の半導体封止材に使用されているフェノール
ノボラック樹脂等のほか、低吸水性のナフタレン型フェ
ノール樹脂、アラルキル−フェノール樹脂、ジシクロペ
ンタジエン−フェノール樹脂、テルペン型フェノール樹
脂等が挙げられ、これらの１種を単独で又は２種以上を
併用して用いることができる。なお、アミン系、アミド
系や酸無水物系は硬化物の耐性、耐熱性や保存安定性等
の点から好ましくない。As the curing agent, a phenol resin type is suitable, and in addition to the phenol novolac resin used in conventional semiconductor encapsulating materials, a low water absorption naphthalene type phenol resin, aralkyl-phenol resin, dicyclopentadiene. -Phenol resin, terpene type phenol resin and the like can be mentioned, and one of these can be used alone or two or more can be used in combination. In addition, amine-based, amide-based, and acid anhydride-based are not preferable from the viewpoints of resistance of cured products, heat resistance, storage stability, and the like.
【００１９】上記フェノール樹脂としては、軟化点が６
０〜１５０℃を有するものが好ましく、より好ましくは
７０〜１３０℃のものである。水酸基当量は９０〜２５
０のものが望ましい。このフェノール樹脂を半導体封止
用に用いる場合、ナトリウム、カリウムは１０ｐｐｍ以
下であることが好ましく、ナトリウム、カリウムが１０
ｐｐｍを越える樹脂で半導体装置を封止し、長時間高温
高湿下に半導体装置を放置した場合、耐湿性の劣化が促
進される場合がある。The above-mentioned phenol resin has a softening point of 6
Those having 0 to 150 ° C. are preferable, and those having 70 to 130 ° C. are more preferable. Hydroxyl equivalent is 90-25
0 is desirable. When this phenol resin is used for semiconductor encapsulation, sodium and potassium are preferably 10 ppm or less, and sodium and potassium are 10 ppm or less.
When a semiconductor device is sealed with a resin exceeding ppm and the semiconductor device is left under high temperature and high humidity for a long time, deterioration of moisture resistance may be accelerated.
【００２０】硬化剤の配合量は、エポキシ樹脂１００重
量部に対して２０〜９０重量部、好ましくは５０〜８０
重量部とすることができる。The amount of the curing agent compounded is 20 to 90 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the epoxy resin.
It can be by weight.
【００２１】また、本発明に使用される無機質充填剤
は、封止材の膨張係数を小さくし、半導体素子に加わる
応力を低下させることができるもので、具体的には破砕
状、球状の形状を持った溶融シリカ、結晶性シリカが主
に用いられ、この他にアルミナ、チッ化ケイ素、チッ化
アルミナなども使用可能である。なお、本発明では、硬
化物の低膨張化と成形性を両立させるためには無機質充
填剤として球状と破砕品のブレンド、あるいは球状品の
みを用いることが好ましい。また、無機質充填剤はあら
かじめシランカップリング剤で表面処理して使用するこ
とが好適である。更に、無機質充填剤としては、平均粒
径が５〜３０μｍのものが好ましく用いられる。The inorganic filler used in the present invention is capable of reducing the expansion coefficient of the encapsulant and reducing the stress applied to the semiconductor element. Specifically, it has a crushed or spherical shape. Fused silica and crystalline silica having the above are mainly used, and in addition to these, alumina, silicon nitride, alumina nitride and the like can also be used. In the present invention, in order to achieve both low expansion of the cured product and moldability, it is preferable to use a blend of spherical and crushed products or only spherical products as the inorganic filler. The inorganic filler is preferably surface-treated with a silane coupling agent before use. Further, as the inorganic filler, those having an average particle diameter of 5 to 30 μm are preferably used.
【００２２】無機質充填剤の配合量は、上記エポキシ樹
脂と全硬化剤の合計量１００重量部に対して２００重量
部以上、特に３００〜１０００重量部が好ましく、３０
０重量部以上になると水分の透過経路が長くなり、水分
拡散速度が低減されるため硬化物を低透湿化できる。な
お、２００重量部に満たないと膨張係数が大きくなって
半導体素子に加わる応力が増大し、素子特性の劣化を招
く場合がある。一方、１０００重量部を越えるとエポキ
シ樹脂組成物の粘度が高くなり、成形作業性が悪化する
場合が生じる。The compounding amount of the inorganic filler is 200 parts by weight or more, particularly preferably 300 to 1000 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the total curing agent, and 30
When it is 0 parts by weight or more, the moisture permeation path becomes long and the moisture diffusion rate is reduced, so that the moisture permeability of the cured product can be lowered. If the amount is less than 200 parts by weight, the expansion coefficient becomes large and the stress applied to the semiconductor element increases, which may lead to deterioration of element characteristics. On the other hand, when it exceeds 1000 parts by weight, the viscosity of the epoxy resin composition becomes high, which may deteriorate the molding workability.
【００２３】本発明のエポキシ樹脂組成物には、更に無
機系吸水剤を配合する。この場合、無機系吸水剤として
は、水分吸着能を有するものを種々選定して用いること
ができるが、見かけ比重が０．５〜１．０ｇ／ｃｍ3 、
特に好ましくは０．６〜０．８ｇ／ｃｍ3 、吸油量が１
０〜５０ｍｌ／１００ｇ、特に好ましくは２０〜４０ｍ
ｌ／１００ｇ、比表面積が１０〜１００ｍ2 ／ｇ、特に
好ましくは３０〜７０ｍ2 ／ｇ、細孔容積が０．１〜
１．０ｍｌ／ｇ、特に好ましくは０．３０〜０．４０ｍ
ｌ／ｇ、平均粒径が０．５〜１０μｍ、特に好ましくは
１〜３μｍである球状の多孔質シリカを使用するのが好
適である。The epoxy resin composition of the present invention further contains an inorganic water absorbing agent. In this case, as the inorganic water-absorbing agent, various ones having a water-adsorbing ability can be selected and used, but the apparent specific gravity is 0.5 to 1.0 g / cm 3 ,
Particularly preferably 0.6 to 0.8 g / cm 3 , the oil absorption is 1
0 to 50 ml / 100 g, particularly preferably 20 to 40 m
1/100 g, specific surface area 10 to 100 m 2 / g, particularly preferably 30 to 70 m 2 / g, pore volume 0.1 to
1.0 ml / g, particularly preferably 0.30 to 0.40 m
It is suitable to use spherical porous silica having a particle size of 1 / g and an average particle size of 0.5 to 10 μm, particularly preferably 1 to 3 μm.
【００２４】ここで、本発明においては、上記無機系吸
水剤としては吸着水分量が０．１重量％未満、好ましく
は０．０８重量％以下、更に好ましくは０．０５重量％
以下のものを使用する。吸着水分量が０．１重量％以上
では本発明の目的を達成し得ない。Here, in the present invention, the inorganic water absorbing agent has an adsorbed water content of less than 0.1% by weight, preferably 0.08% by weight or less, and more preferably 0.05% by weight.
Use the following: If the adsorbed water content is 0.1% by weight or more, the object of the present invention cannot be achieved.
【００２５】このような低吸着水分量とするため、本発
明では必ず無機系吸水剤の再生処理を行うもので、この
場合再生条件としては、再生温度２００℃以上、より好
ましくは２５０〜５００℃、再生時間５時間以上、より
好ましくは６〜１２時間の条件が推奨される。再生温度
２００℃未満または再生時間５時間未満の場合には吸着
水分量が０．１重量％以上となり、この無機系吸水剤を
使用したエポキシ樹脂組成物は加熱成形時に硬化不良を
起こし、プレモールド型中空パッケージ自体の性能を低
下させる原因となる。In order to obtain such a low adsorbed water content, in the present invention, the inorganic water absorbing agent is always regenerated. In this case, the regeneration condition is a regeneration temperature of 200 ° C. or higher, more preferably 250 to 500 ° C. It is recommended that the reproduction time is 5 hours or more, more preferably 6 to 12 hours. When the regeneration temperature is less than 200 ° C. or the regeneration time is less than 5 hours, the amount of adsorbed water becomes 0.1% by weight or more, and the epoxy resin composition using this inorganic water-absorbing agent causes curing failure during heat molding, resulting in pre-molding. This causes the performance of the hollow mold package itself to deteriorate.
【００２６】また更に、無機系吸水剤については、表面
を親水性の表面処理剤で処理したものを使用しても良
い。なお、通常無機充填剤の表面は疎水性の表面処理剤
で処理して、組成物の特性を向上させる手法がとられて
いるが、無機系吸水剤の場合は、逆に表面が透過水分を
はじく作用は好ましくないため、親水性の表面処理剤が
好適となる。Furthermore, as the inorganic water-absorbing agent, one whose surface is treated with a hydrophilic surface treating agent may be used. The surface of the inorganic filler is usually treated with a hydrophobic surface-treating agent to improve the characteristics of the composition.However, in the case of an inorganic water-absorbing agent, the surface conversely permeates moisture. Since the repelling action is not preferable, a hydrophilic surface treatment agent is suitable.
【００２７】上記親水性の表面処理剤としては、例えば
テトラエトキシシランの加水分解物や下記化合物が好ま
しい。As the hydrophilic surface treatment agent, for example, a hydrolyzate of tetraethoxysilane or the following compound is preferable.
【００２８】（ＣＨ3 Ｏ）3 Ｓｉ（ＣＨ2 ）3 ＯＨ Ｈ2 Ｎ（ＣＨ2 ）2 ＮＨ（ＣＨ2 ）3 Ｓｉ（ＯＣ
2 Ｈ5 ）3 Ｈ2 Ｎ（ＣＨ2 ）3 Ｓｉ（ＯＣＨ3 ）3 （ＣＨ3 Ｏ）Ｓｉ（ＣＨ3 ）2 ＯＨ(CH 3 O) 3 Si (CH 2 ) 3 OH H 2 N (CH 2 ) 2 NH (CH 2 ) 3 Si (OC
2 H 5) 3 H 2 N (CH 2) 3 Si (OCH 3) 3 (CH 3 O) Si (CH 3) 2 OH
【００２９】上記無機系吸水剤の配合量は、上記エポキ
シ樹脂と硬化剤の合計量１００重量部に対して１０重量
部以上であり、特に２０〜２００重量部が好ましい。１
０重量部に満たない場合、硬化物中を透過してくる水分
を十分にとらえる事が出来ず、プレモールド型中空パッ
ケージの内部に結露が発生して使用不能となる。この場
合、無機系吸水剤は、組成物全体に対して少なくとも１
重量％以上、好ましくは５重量％以上５０重量％以下と
なるように配合することが好ましく、使用量が１重量％
未満では硬化物の透湿性を十分に低下させることができ
なくなり、また５０重量％を越えるとエポキシ樹脂組成
物の流動性が低下する懸念がある。The blending amount of the inorganic water absorbing agent is 10 parts by weight or more, and particularly preferably 20 to 200 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. 1
If the amount is less than 0 parts by weight, the moisture that permeates through the cured product cannot be sufficiently captured, and dew condensation occurs inside the premolded hollow package, making it unusable. In this case, the inorganic water-absorbing agent is at least 1 with respect to the entire composition.
It is preferable that the compounding amount be 1% by weight or more, preferably 5% by weight or more and 50% by weight or less.
If it is less than 50% by weight, the moisture permeability of the cured product cannot be sufficiently lowered, and if it exceeds 50% by weight, the fluidity of the epoxy resin composition may be lowered.
【００３０】本発明のエポキシ樹脂組成物には、上述し
た必須成分に加え、従来公知の各種硬化促進剤を添加す
ることが好ましい。硬化促進剤としては、例えばイミダ
ゾール又はその誘導体、ホスフィン誘導体、３級アミン
又はその誘導体などが挙げられる。なお、硬化促進剤の
添加量は、本発明の硬化を妨げない範囲で通常量とする
ことができる。In addition to the above-mentioned essential components, it is preferable to add various conventionally known curing accelerators to the epoxy resin composition of the present invention. Examples of the curing accelerator include imidazole or its derivative, phosphine derivative, tertiary amine or its derivative, and the like. The addition amount of the curing accelerator can be a usual amount as long as the curing of the present invention is not hindered.
【００３１】本発明のエポキシ樹脂組成物は、低応力化
のためにシリコーン系の可撓性付与剤を添加することが
好ましい。可撓性付与剤としては、例えばシリコーンゴ
ムパウダー、シリコーンゲル、有機樹脂とシリコーンポ
リマーとのブロックポリマーなどが挙げられる。また、
このような可撓性付与剤を添加する代わりに二液タイプ
のシリコーンゴムやシリコーンゲルで無機質充填剤表面
を処理してもよい。なお、上記可撓性付与剤の使用量
は、組成物全体の０．５〜１０重量％、特に１〜５重量
％とすることが好ましく、使用量が０．５重量％未満で
は十分な耐衝撃性を与えない場合があり、１０重量％を
越えると機械的強度が不十分になる場合がある。The epoxy resin composition of the present invention preferably contains a silicone-based flexibility-imparting agent in order to reduce stress. Examples of the flexibility-imparting agent include silicone rubber powder, silicone gel, block polymers of organic resin and silicone polymer, and the like. Also,
Instead of adding such a flexibility-imparting agent, the surface of the inorganic filler may be treated with a two-pack type silicone rubber or silicone gel. The amount of the flexibility-imparting agent used is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the entire composition. It may not give impact properties, and if it exceeds 10% by weight, mechanical strength may become insufficient.
【００３２】また、本発明のエポキシ樹脂組成物には、
必要に応じてその他の任意成分を本発明の効果を妨げな
い範囲で配合することができる。このような任意成分と
しては、例えば従来公知の各種熱可塑性樹脂や、カルナ
バワックス、高級脂肪酸、合成ワックス類などの離型
剤、シランカップリング剤、難燃剤としての臭素化エポ
キシ樹脂、酸化アンチモン、リン化合物等が挙げられ
る。The epoxy resin composition of the present invention also comprises
If desired, other optional components may be blended within a range that does not impair the effects of the present invention. Examples of such optional components include various conventionally known thermoplastic resins, carnauba wax, higher fatty acids, release agents such as synthetic waxes, silane coupling agents, brominated epoxy resins as flame retardants, antimony oxide, Examples thereof include phosphorus compounds.
【００３３】なお、離型剤については、エポキシ樹脂組
成物との相溶性が良好なものを成形性に支障が生じない
限り最小限の量で配合することが好ましい。これは、例
えばＣＣＤなどのプレモールド型半導体装置では、構造
上エポキシ樹脂組成物を成形後、中空部に素子を搭載し
てからガラス蓋を接着するという工程が入るが、この場
合、仮にエポキシ樹脂と非相溶性の離型剤を多量に添加
すると、パッケージ接着面への離型剤のブリードにより
ガラス蓋の接着が著しく困難になり、このためパッケー
ジ接着面を水素炎バーナーであぶったり、やすりで粗面
化するなどの工程を入れざるを得なくなるためである。
それ故、離型剤としては、非相溶性のカルナバワックス
よりもステアリン酸アミド等の高級脂肪酸、ポリエチレ
ン系ワックス、モンタン系ワックス等の合成ワックス類
などが好適である。As the release agent, it is preferable to add a release agent having a good compatibility with the epoxy resin composition in the minimum amount as long as the moldability is not hindered. In a pre-mold type semiconductor device such as a CCD, for example, a step of mounting an element in the hollow portion and then adhering a glass lid after the epoxy resin composition is structurally formed is involved. If a large amount of a release agent that is incompatible with is added, the bleeding of the release agent on the package bonding surface makes it extremely difficult to bond the glass lid.For this reason, the package bonding surface can be burned with a hydrogen flame burner or ripped. This is because there is no choice but to add steps such as roughening.
Therefore, as the release agent, higher fatty acids such as stearic acid amide, synthetic waxes such as polyethylene wax and montan wax are more preferable than incompatible carnauba wax.
【００３４】また、離型剤を添加する際は、エポキシ樹
脂組成物の有機成分（各種樹脂等）に離型剤を添加し、
ニーダーなどでプレ混合し、十分分散させてから無機質
充填剤、無機系吸水剤を添加して混合することが好まし
く、このように添加すると離型効果及び撥水効果を向上
させることができる。When adding a release agent, the release agent is added to the organic component (various resins, etc.) of the epoxy resin composition,
It is preferable to pre-mix with a kneader or the like and sufficiently disperse it, and then add and mix the inorganic filler and the inorganic water-absorbing agent. By adding in this way, the releasing effect and the water-repellent effect can be improved.
【００３５】本発明のエポキシ樹脂組成物は、その製造
に際し、上述した成分の所定量を均一に攪拌、混合し、
予め７０〜９５℃に加熱してあるニーダー、ロール、エ
クストルーダーなどで混練、冷却し、粉砕するなどの方
法で得ることができる。なお、成分の配合順序に特に制
限はない。In producing the epoxy resin composition of the present invention, predetermined amounts of the above-mentioned components are uniformly stirred and mixed,
It can be obtained by kneading with a kneader, roll, extruder or the like which has been heated to 70 to 95 ° C. in advance, cooling, pulverizing, or the like. There is no particular limitation on the order of mixing the components.
【００３６】上述したように、本発明のエポキシ樹脂組
成物は、硬化物の透湿性が低く、プレモールド型の中空
パッケージ用材料に好適に使用できるものであるが、プ
レモールドを行なう場合は、従来より採用されている成
形法、例えばトランスファ成形、インジェクション成
形、注型法などを採用して行なうことができる。この場
合、エポキシ樹脂組成物の成形温度は１５０〜１８０
℃、ポストキュアーは１５０〜１８０℃で２〜１６時間
行なうことが好ましい。As described above, the epoxy resin composition of the present invention has a low moisture permeability of a cured product and can be suitably used as a pre-mold type hollow package material. It can be carried out by adopting conventionally used molding methods such as transfer molding, injection molding, and casting method. In this case, the molding temperature of the epoxy resin composition is 150 to 180
The post-curing is preferably performed at 150 to 180 ° C. for 2 to 16 hours.
【００３７】[0037]
【発明の効果】本発明のエポキシ樹脂組成物は、再生処
理を行い、吸着水分が除去された状態の無機系吸水剤を
添加したことにより、成形時の硬化特性と低透湿性に優
れた高品質の硬化物を与え、プレモールド型の中空パッ
ケージ用材料として好適な組成物である。The epoxy resin composition of the present invention is regenerated and added with an inorganic water-absorbing agent from which adsorbed water has been removed, so that the epoxy resin composition is excellent in curing characteristics during molding and low moisture permeability. It is a composition that gives a cured product of quality and is suitable as a material for a premolded hollow package.
【００３８】[0038]
【実施例】以下、実施例及び比較例を挙げて本発明を具
体的に説明するが、本発明は下記実施例に制限されるも
のではない。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００３９】［実施例、比較例］表１，２に示す成分に
加え、その有機成分１００重量部に対して離型剤として
ステアリン酸アミド１．５重量部を添加してニーダーで
十分に混練した後、γ−グリシドキシプロピルトリメト
キシシラン１．５重量部、三酸化アンチモン８．０重量
部、カーボンブラック２．０重量部、トリフェニルホス
フィン０．８重量部を加え、得られた配合物を熱二本ロ
ールで均一に溶融混練して、１３種類のエポキシ樹脂組
成物（実施例１〜７、比較例１〜６）を製造した。[Examples and Comparative Examples] In addition to the components shown in Tables 1 and 2, 1.5 parts by weight of stearic acid amide as a release agent was added to 100 parts by weight of the organic components, and kneading was sufficiently performed with a kneader. After that, 1.5 parts by weight of γ-glycidoxypropyltrimethoxysilane, 8.0 parts by weight of antimony trioxide, 2.0 parts by weight of carbon black, and 0.8 parts by weight of triphenylphosphine were added, and the resulting blend was obtained. The product was melt-kneaded uniformly with a hot two-roll mill to produce 13 kinds of epoxy resin compositions (Examples 1 to 7, Comparative Examples 1 to 6).
【００４０】ここで、無機系吸水剤としては下記のもの
を使用した。無機系吸水剤（１） 見かけ比重０．６９ｇ／ｍ3 、吸油量４０ｍｌ／１００
ｇ、比表面積３２．７ｍ2 ／ｇ、細孔容積０．３５ｍｌ
／ｇ、平均粒径２．８μｍの球状多孔質シリカ（商品
名：ＡＭＴ−シリカ＃３００Ｂ、水澤化学工業社製）を
熱風循環乾燥機内で２５０℃、１０時間の再生処理をし
たもの：吸着水分量０．６％（重量％以下同じ）。Here, the following were used as the inorganic water absorbing agent. Inorganic water absorbing agent (1) Apparent specific gravity 0.69 g / m 3 , oil absorption 40 ml / 100
g, specific surface area 32.7 m 2 / g, pore volume 0.35 ml
/ G, spherical porous silica having an average particle size of 2.8 μm (trade name: AMT-silica # 300B, manufactured by Mizusawa Chemical Co., Ltd.) in a hot air circulation dryer at 250 ° C. for 10 hours: Adsorbed moisture Amount of 0.6% (same as below by weight).
【００４１】無機系吸水剤（２） 同様に３００℃、６時間の再生処理をしたもの：吸着水
分量０．０５％。 Inorganic water-absorbing agent (2) which was regenerated at 300 ° C. for 6 hours in the same manner: 0.05% of adsorbed water content.
【００４２】無機系吸水剤（３） 同様に１００℃、２時間の再生処理をしたもの：吸着水
分量０．３％。The same as the inorganic water-absorbing agent (3) , which was regenerated at 100 ° C. for 2 hours: 0.3% of adsorbed water content.
【００４３】無機系吸水剤（４） 再生処理なし：吸着水分量２．６％。 Inorganic water absorbing agent (4) No regeneration treatment: Adsorbed water content 2.6%.
【００４４】無機系吸水剤（５） シランカップリング剤（ＣＨ3 Ｏ）Ｓｉ（ＣＨ3 ）2 Ｏ
Ｈを上記無機系吸水剤−１に対し１．０重量％添加して
処理を行なった表面処理無機系吸水剤。 Inorganic water absorbing agent (5) Silane coupling agent (CH 3 O) Si (CH 3 ) 2 O
A surface-treated inorganic water-absorbing agent which is obtained by adding 1.0% by weight of H to the above-mentioned inorganic water-absorbing agent-1.
【００４５】無機系吸水剤（６） 見かけ比重０．５０ｇ／ｍ3 、吸油量７０ｍｌ／１００
ｇ、比表面積４９７．７ｍ2 ／ｇ、細孔容積０．４１ｍ
ｌ／ｇ、平均粒径４．６μｍの球状多孔質シリカを熱風
循環乾燥機内で２５０℃、１０時間の再生処理をしたも
の：吸着水分量０．０８％。 Inorganic water absorbing agent (6) Apparent specific gravity 0.50 g / m 3 , oil absorption 70 ml / 100
g, specific surface area 497.7 m 2 / g, pore volume 0.41 m
Spherical porous silica of 1 / g and average particle diameter 4.6 μm was regenerated in a hot air circulation dryer at 250 ° C. for 10 hours: Adsorbed water content 0.08%.
【００４６】なお、表１，２に記載したエポキシ樹脂
（１）〜（３）、フェノール樹脂（１）〜（３）、臭素
化エポキシ樹脂、シリコーン変性エポキシ樹脂について
は以下に示す通りである。The epoxy resins (1) to (3), the phenol resins (1) to (3), the brominated epoxy resin, and the silicone-modified epoxy resin shown in Tables 1 and 2 are as shown below.
【００４７】[0047]
【化１】 Embedded image
【００４８】[0048]
【化２】 Embedded image
【００４９】次に、上記のエポキシ樹脂組成物について
以下の（イ）〜（ヘ）の諸特性を測定した。結果を表
１，２に示す。Next, the following properties (a) to (f) of the above epoxy resin composition were measured. The results are shown in Tables 1 and 2.
【００５０】（イ）スパイラルフロー ＥＭＭＩ規格に準じた金型を使用して、１７５℃、７０
ｋｇ／ｃｍ2 の条件で測定した。(A) Spiral flow Using a mold conforming to the EMMI standard, 175 ° C., 70
It was measured under the condition of kg / cm 2 .
【００５１】（ロ）成形硬度 １７５℃、７０ｋｇ／ｃｍ2 、成形時間２分の条件で成
形直後に成形品のバーコール硬度（Ｎｏ．９３５）を測
定した。(B) Molding hardness The Barcol hardness (No. 935) of the molded product was measured immediately after molding under the conditions of 175 ° C., 70 kg / cm 2 , and molding time of 2 minutes.
【００５２】（ハ）機械的強度（曲げ強度） ＪＩＳ Ｋ６９１１に準じて１７５℃、７０ｋｇ／ｃｍ
2 、成形時間２分の条件で１０×１００×４ｍｍの抗折
棒を成形し、１８０℃で４時間ポストキュアーしたもの
で測定した。(C) Mechanical strength (bending strength) According to JIS K6911, 175 ° C., 70 kg / cm
2. A bending bar of 10 × 100 × 4 mm was molded under the condition of molding time of 2 minutes, and post-cured at 180 ° C. for 4 hours for measurement.
【００５３】（ニ）ガラス転移温度、膨張係数 １７５℃、７０ｋｇ／ｃｍ2 、成形時間２分の条件で４
×４×１５ｍｍの試験片を成形し、１８０℃で４時間ポ
ストキュアーしたものを用い、ディラトメーターにより
毎分５℃で昇温させることにより測定した。(D) Glass transition temperature, expansion coefficient 175 ° C., 70 kg / cm 2 , molding time 2 minutes 4
It was measured by molding a test piece of × 4 × 15 mm, post-curing at 180 ° C. for 4 hours, and raising the temperature at 5 ° C./min with a dilatometer.
【００５４】（ホ）ＣＣＤ透湿信頼性 図１に示すようにエポキシ樹脂組成物１を中空箱型のプ
レモールドパッケージとしてリードフレーム２を介在さ
せて１７５℃、７０ｋｇ／ｃｍ2 、成形時間２分の条件
で成形した後、１８０℃で４時間ポストキュアーした。
次に、シリコーンチップ３を中空部に搭載した後、ボン
ディングワイヤー４を配線し、更に上記パッケージにエ
ポキシ樹脂接着剤６で透明なガラス蓋５を接着して測定
用試験体を得た。この気密封止されたパッケージを８５
℃、８５％ＲＨの雰囲気中に放置して５０時間毎に常温
下でガラス蓋の内側に結露が認められるか否かを測定
し、結露が生じ始めた試験時間を記録した。なお、結露
が生じない場合にはさらに試験を続行した。また、３０
０時間を満たずに結露の生じたものはＮＧと表現した。(E) CCD moisture permeability reliability As shown in FIG. 1, the epoxy resin composition 1 is used as a hollow box type premolded package with a lead frame 2 interposed at 175 ° C., 70 kg / cm 2 , molding time 2 minutes. After molding under the above conditions, post-curing was performed at 180 ° C. for 4 hours.
Next, after mounting the silicone chip 3 in the hollow portion, the bonding wire 4 was wired, and the transparent glass lid 5 was further adhered to the package with the epoxy resin adhesive 6 to obtain a measurement test body. This hermetically sealed package is
It was left to stand in an atmosphere of 85 ° C. and 85% RH, and every 50 hours, it was measured at room temperature whether or not dew condensation was observed inside the glass lid, and the test time when dew condensation started to occur was recorded. The test was continued if dew condensation did not occur. Also, 30
The case where dew condensation occurred within 0 hours was expressed as NG.
【００５５】[0055]
【表１】 [Table 1]
【００５６】[0056]
【表２】 [Table 2]
【００５７】実施例の結果から認められるように、無機
系吸水剤を添加するエポキシ樹脂組成物においては、添
加前に無機系吸水剤の吸着水分量をできるだけ除去して
おくと、硬化性が良好なためトランスファー成形により
プレモールド中空パッケージを成形する際に作業性が非
常に良くなり、その後半導体装置としての性能を向上し
た。また、無機系吸水剤として上記球状多孔質のシリカ
を使用する事で、流動性良いエポキシ樹脂組成物が得ら
れ、低透湿化したプレモールド型中空パッケージを作成
できた。As can be seen from the results of the examples, in the epoxy resin composition to which the inorganic water-absorbing agent is added, the curability is improved by removing the adsorbed water content of the inorganic water-absorbing agent as much as possible before the addition. Therefore, the workability when molding a pre-molded hollow package by transfer molding was greatly improved, and the performance as a semiconductor device was improved thereafter. Further, by using the spherical porous silica as the inorganic water-absorbing agent, an epoxy resin composition having good fluidity was obtained, and a pre-molded hollow package having low moisture permeability could be prepared.
【００５８】つまり、低吸水性のエポキシ樹脂及びフェ
ノール樹脂、そして溶融シリカを主成分として、再生処
理された球状多孔質シリカを添加すると、成形硬度が高
いためトランスファー成形直後の成形品やランナー部分
の金型離型性が良好であった。また、ＣＣＤ透湿信頼性
試験についてはガラス転移温度が試験温度の８５℃より
６０℃も高いため高い透湿信頼性が得られた（実施例
１，３及び６）。That is, when a regenerated spherical porous silica containing low-water-absorbing epoxy resin and phenol resin and fused silica as the main components is added, the molding hardness is high, so that the molded product or the runner portion immediately after the transfer molding is added. The mold releasability was good. In the CCD moisture permeability reliability test, a high moisture permeability reliability was obtained because the glass transition temperature was 60 ° C. higher than the test temperature of 85 ° C. (Examples 1, 3 and 6).
【００５９】またさらに、球状多孔質シリカを親水性の
シランカップリング剤で表面処理する事で、低透湿性し
たままさらにエポキシ樹脂組成物の流動性を向上できた
（実施例２）。Furthermore, by surface-treating the spherical porous silica with a hydrophilic silane coupling agent, the fluidity of the epoxy resin composition could be further improved while maintaining low moisture permeability (Example 2).
【００６０】しかも、エポキシ樹脂、フェノール樹脂に
従来より汎用されているものを使用しても、成形作業性
や透湿信頼性は良好であった（実施例４及び５）。Moreover, the molding workability and the moisture permeability reliability were good even when epoxy resins and phenol resins which were generally used conventionally were used (Examples 4 and 5).
【００６１】さらに、本発明の無機系吸水剤単独の添加
量、または無機系吸水剤と溶融シリカの両方の添加量を
エポキシ樹脂組成物の流動性を阻害しない範囲で増加さ
せる事で、さらに透湿信頼性を向上させ線膨張係数も低
減できた（実施例７，８及び９）。Further, by increasing the addition amount of the inorganic water-absorbing agent of the present invention alone or the addition amount of both the inorganic water-absorbing agent and the fused silica within a range that does not impair the fluidity of the epoxy resin composition, the transparency is further improved. It was possible to improve the wet reliability and reduce the linear expansion coefficient (Examples 7, 8 and 9).
【００６２】それに対して、本発明の再生条件に満たな
い再生処理をした場合、無機系吸水剤に残留する吸着水
分量が多くなり、成形時の加熱により水分が放出されて
硬化性が低下し、その影響で金型離型性が悪く、作業性
が悪化し、ガラス転移温度の低下により耐熱性が低下
し、浸透信頼性も低下した（比較例１）。On the other hand, when the regeneration treatment of the present invention is not performed, the amount of adsorbed moisture remaining in the inorganic water-absorbing agent becomes large, and the moisture is released by heating during molding to lower the curability. As a result, the mold releasability was poor, the workability was poor, the glass transition temperature was low, the heat resistance was low, and the penetration reliability was low (Comparative Example 1).
【００６３】さらに再生処理を行なわずそのままエポキ
シ樹脂組成物に添加すると、硬化性、耐熱性及び透湿信
頼性はさらに低下し、半導体装置として使用に耐えない
ものであった。その無機系吸水剤添加量を増やしても、
硬化性を低下させるばかりで透湿信頼性は改善されるど
ころかかえって低下した（比較例３及び４）。When it was added to the epoxy resin composition as it was without further regeneration treatment, the curability, heat resistance and moisture permeability reliability were further lowered, and it was unusable as a semiconductor device. Even if you increase the amount of inorganic water absorbing agent added,
The curability was not only lowered, but the moisture permeability reliability was not improved, but rather lowered (Comparative Examples 3 and 4).
【００６４】また、無機系吸水剤を添加しない場合、硬
化性及び耐熱性には問題ないが、十分な低透湿性は得ら
れなかった（比較例５及び６）。When the inorganic water-absorbing agent was not added, curability and heat resistance were satisfactory, but sufficient low moisture permeability was not obtained (Comparative Examples 5 and 6).
【００６５】さらに、比表面積及び吸油量の大きな無機
系吸水剤を使用した場合、有機樹脂分に対するぬれ性が
悪く、混練が不十分になった。また、流動性が極端に下
がり成形作業性が悪化し、スパイラルフロー以外の物理
特性は試験片が成形できず測定ができなかった（比較例
７）。Furthermore, when an inorganic water absorbing agent having a large specific surface area and a large oil absorption amount was used, the wettability with respect to the organic resin was poor and the kneading became insufficient. Further, the fluidity was extremely lowered, the molding workability was deteriorated, and the physical properties other than spiral flow could not be measured because the test piece could not be molded (Comparative Example 7).
【００６６】なお、本発明組成物（実施例１〜６）は、
離型剤であるステアリン酸アミドが硬化性エポキシ樹脂
とブレ混合されて分散状態が良好であり、硬化物の成型
時の離型剤が良好で撥水性にも富み、低透湿化されてい
るものであった。The compositions of the present invention (Examples 1 to 6) were
The release agent, stearic acid amide, is mixed well with the curable epoxy resin and the dispersion is good, and the release agent when molding the cured product is good, and it is also highly water repellent and has low moisture permeability. It was a thing.
【図１】ＣＣＤ透湿信頼性測定用の試験体の概略図であ
る。FIG. 1 is a schematic diagram of a test body for measuring the moisture permeability reliability of a CCD.
１ エポキシ樹脂 ２ リードフレーム ３ チップ ４ ボンディングワイヤー ５ ガラス蓋 ６ エポキシ系接着剤 1 Epoxy resin 2 Lead frame 3 Chip 4 Bonding wire 5 Glass lid 6 Epoxy adhesive
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池田 多春 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taharu Ikeda 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory
Claims (1)
主成分とするエポキシ樹脂組成物において、無機質充填
剤をエポキシ樹脂と硬化剤との合計量１００重量部に対
して２００重量部以上配合すると共に、見かけ比重が
０．５〜１．０ｇ／ｍ3 、吸油量が１０〜５０ｍｌ／１
００ｇ、比表面積が１０〜１００ｍ2 ／ｇ、細孔容積が
０．１０〜１．０ｍｌ／ｇ、平均粒径が０．５〜１０μ
ｍである球状の多孔質シリカを２００℃以上の温度で５
時間以上処理することにより、吸着水分量を０．１重量
％未満に低減した無機系吸水剤をエポキシ樹脂と硬化剤
との合計量１００重量部に対して１０重量部以上添加し
たことを特徴とするエポキシ樹脂組成物。1. An epoxy resin composition containing an epoxy resin, a curing agent and an inorganic filler as main components, the inorganic filler being blended in an amount of 200 parts by weight or more based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. Also, the apparent specific gravity is 0.5 to 1.0 g / m 3 , and the oil absorption is 10 to 50 ml / 1.
00 g, specific surface area 10 to 100 m 2 / g, pore volume 0.10 to 1.0 ml / g, average particle size 0.5 to 10 μm.
m spherical spherical silica at a temperature of 200 ° C or higher
An inorganic water-absorbing agent whose adsorbed water content is reduced to less than 0.1% by weight by treating for more than 10 hours is added in an amount of 10 parts by weight or more based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. Epoxy resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06331728A JP3119104B2 (en) | 1994-12-09 | 1994-12-09 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06331728A JP3119104B2 (en) | 1994-12-09 | 1994-12-09 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08157694A true JPH08157694A (en) | 1996-06-18 |
| JP3119104B2 JP3119104B2 (en) | 2000-12-18 |
Family
ID=18246939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06331728A Expired - Fee Related JP3119104B2 (en) | 1994-12-09 | 1994-12-09 | Epoxy resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP3119104B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001181574A (en) * | 1999-12-24 | 2001-07-03 | Kansai Paint Co Ltd | Coating composition and coated metal sheet prepared by using same |
| US6399677B2 (en) * | 1999-12-02 | 2002-06-04 | Shin-Etsu Chemical Co., Ltd. | Epoxy resin compositions and premolded semiconductor packages |
| JP2008156383A (en) * | 2006-12-20 | 2008-07-10 | Matsushita Electric Works Ltd | Liquid resin composition, semiconductor device and method for producing the same |
-
1994
- 1994-12-09 JP JP06331728A patent/JP3119104B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399677B2 (en) * | 1999-12-02 | 2002-06-04 | Shin-Etsu Chemical Co., Ltd. | Epoxy resin compositions and premolded semiconductor packages |
| US6569532B2 (en) | 1999-12-02 | 2003-05-27 | Sony Corporation | Epoxy resin compositions and premolded semiconductor packages |
| KR100678345B1 (en) * | 1999-12-02 | 2007-02-05 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Epoxy resin compositions and premolded semiconductor packages |
| JP2001181574A (en) * | 1999-12-24 | 2001-07-03 | Kansai Paint Co Ltd | Coating composition and coated metal sheet prepared by using same |
| JP2008156383A (en) * | 2006-12-20 | 2008-07-10 | Matsushita Electric Works Ltd | Liquid resin composition, semiconductor device and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3119104B2 (en) | 2000-12-18 |
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