JPH0820673A - Inorganic filler for resin and epoxy resin composition - Google Patents

Inorganic filler for resin and epoxy resin composition

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JPH0820673A
JPH0820673A JP17597794A JP17597794A JPH0820673A JP H0820673 A JPH0820673 A JP H0820673A JP 17597794 A JP17597794 A JP 17597794A JP 17597794 A JP17597794 A JP 17597794A JP H0820673 A JPH0820673 A JP H0820673A
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filler
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pts
inorganic
resin
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JP3033445B2 (en )
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Koji Futatsumori
Toshio Shiobara
Kazutoshi Tomiyoshi
浩二 二ッ森
利夫 塩原
和俊 富吉
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Shin Etsu Chem Co Ltd
信越化学工業株式会社
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Abstract

PURPOSE:To obtain an inorganic filler consisting of a specific composition, having a low viscosity at a room temperature or when melted at a high temperature even in the case where a large amount of the filler is compounded into an epoxy resin, etc., excellent in fluidity and little in aggregate generation when added to a resin. CONSTITUTION:This filler is obtained by compounding (A) 100 pts.wt., of a surface-treated filler obtained by treating 100 pts.wt. of an inorganic filler (e.g. crystalline silica and alumina) having an average particle diameter of 5-40mum with an alkoxy-containing silane (e.g. 3-glycidoxypropyltrimethoxysilane or phenyltrimethoxysilane) or its partially hydrated substance with (B) 1-40 pts.wt. of an inorganic filler which is not treated with the alkoxy-containing silane or its partially hydrated material and having an average diameter of <=4mum. Further, the amount of the alkoxy-containing silane used in the component A is preferably 0.1-0.6 pts.wt. based on 100 pts.wt. of the inorganic filler. The mixture of the component A with the component B is preferably passed through a 100-200 mesh sieve to remove aggregates.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明は、吸湿性低下などを目的としてエポキシ樹脂などに大量に配合しても、常温乃至高温溶融状態における粘度が低く、流動特性が良好であると共に、樹脂組成物中で凝集物を与えることが少ない樹脂用無機質充填剤及び該充填剤を用いたエポキシ樹脂組成物に関する。 The present invention relates also be blended in large quantities, such as the epoxy resin as the purpose of hygroscopicity reduction, low viscosity at room temperature to a high temperature molten state, with the flow characteristics are good, the resin composition epoxy resin composition agglomerates using a resin for inorganic fillers and the filler is small to give a medium related.

【0002】 [0002]

【従来の技術及び発明が解決しようとする課題】現在、 BACKGROUND OF invention is to provide a current,
半導体産業の中で樹脂封止型のダイオード、トランジスタ、IC、LSI、超LSIが主流となっており、この封止樹脂としてエポキシ樹脂は一般に他の熱硬化性樹脂に比べて成形性、接着性、電気特性、機械特性、耐湿性などに優れているため、エポキシ樹脂組成物で半導体装置を封止することが多く行われている。 Resin-sealed diode in the semiconductor industry, transistor, IC, LSI, and ultra LSI may become mainstream, epoxy resins are generally compared with other thermosetting resin moldability as the sealing resin, an adhesive , electrical properties, mechanical properties and excellent like moisture resistance, have been made many sealing the semiconductor device with the epoxy resin composition.

【0003】最近においては、これらの半導体装置は集積度が益々大きくなり、それに応じてチップ寸法も大きくなりつつある。 [0003] In recent years, these semiconductor devices integration becomes increasingly large, becoming larger chip size accordingly. 一方、これに対してパッケージ外観寸法は電子機器の小型化、軽量化の要求に伴い、薄型化が進んでいる。 On the other hand, the package Dimensions contrast miniaturization of electronic devices, with a demand for weight reduction, it is progressing thinner. 更に、半導体部品を回路基板へ取り付ける方法も、基板上の部品の高密度化や基板の薄型化のため、半導体部品の表面実装化が幅広く行われるようになってきた。 Furthermore, a method of attaching a semiconductor component to the circuit board, for high density and thickness of the substrate of the component on the board, has come to the surface mounting of semiconductor parts is carried out widely.

【0004】しかしながら、半導体装置を表面実装する場合、半導体装置全体を半田槽に浸漬するか又は半田が溶融するゾーンを通過させる方法が一般的であるが、その際の熱衝撃により封止樹脂層にクラックが発生したり、リードフレームやチップと封止樹脂との界面に剥離が生じたりする。 However, if surface mounting the semiconductor device, a method for passing a zone or solder is melted dipping the entire semiconductor device in a solder bath is generally, the sealing resin layer by thermal shock at that time or cracks occur, peeling at the interface between the lead frame and the chip and the sealing resin or occur. このようなクラックや剥離は、表面実装時の熱衝撃以前に半導体装置の封止樹脂層が吸湿していると更に顕著なものとなるが、実際の作業工程においては、封止樹脂層の吸湿は避けられず、このため実装後のエポキシ樹脂で封止した半導体装置の信頼性が大きく損なわれる場合がある。 Such cracks and peeling, but the sealing resin layer of the semiconductor device to thermal shock earlier during surface mounting becomes more more pronounced when are hygroscopic, in the actual working process, moisture in the sealing resin layer is inevitable, there is a case where the reliability of the semiconductor device encapsulated with the epoxy resin after this for implementation is significantly impaired.

【0005】このような状況から、封止樹脂層の吸湿を少なくして表面実装時のクラックや剥離の発生を防止するため、低吸湿性の封止樹脂が要求されてきており、このような低吸湿性の封止樹脂を得る方法の一つに無機質充填剤を多量に配合することが有効であることが知られている。 [0005] Under such circumstances, in order to prevent moisture absorption of less to cracking and peeling during surface mounting of the sealing resin layer has been low moisture absorption of the encapsulating resin is required, like this that a large amount of inorganic filler to one way of obtaining low moisture absorption of the encapsulating resin is known to be effective.

【0006】ところが、封止樹脂組成物に無機質充填剤を多量に配合すると、溶融粘度が高くなってしまい、流動特性が悪くなってしまうという問題があるが、上述した半導体装置をトランスファー成形する場合、樹脂組成物の溶融粘度はできる限り低くする必要がある。 [0006] However, when a large amount of inorganic filler in the sealing resin composition, becomes high melt viscosity, there is a problem that fluidity becomes poor, when transfer molding a semiconductor device described above , the melt viscosity of the resin composition should be as low as possible.

【0007】この場合、溶融粘度を低くするため、粒径の大きい充填剤と粒径の小さい充填剤とを併用する方法が知られており、また樹脂と無機質充填剤との界面を制御するため、無機質充填剤をシランカップリング剤で表面処理する方法が知られているが、これらの方法でもなお常温乃至高温溶融状態における粘度の低下が不十分であると共に、無機質充填剤の凝集物が多量に発生して硬化物の機械的強度が低下するという問題がある。 [0007] In this case, in order to lower the melt viscosity, a method using both the particle size of the larger filler and small particle size filler are known, and to control the interface between the resin and the inorganic filler , a method of surface treating the inorganic filler with a silane coupling agent is known, with a decrease in viscosity still at room temperature to a high temperature molten state by these methods is insufficient, aggregates of the inorganic filler is a large amount there is a problem of lowering the mechanical strength of the cured product occurs.

【0008】本発明は、上記事情に鑑みなされたもので、吸湿性を低下させる目的でエポキシ樹脂等に大量に配合した場合でも室温乃至高温溶融状態における粘度が低く、流動特性が良好であり、かつ樹脂に配合した場合、無機質充填剤の凝集物を与えることが少ない樹脂用無機質充填剤及び該充填剤を用いたエポキシ樹脂組成物を提供することを目的とする。 [0008] The present invention has been made in view of the above circumstances, even when large amounts blended in the epoxy resin or the like for the purpose of reducing the hygroscopicity low viscosity at room temperature to a high temperature molten state, has good flow properties, and when blended in resin, and an object thereof is to provide an epoxy resin composition using the resin for the inorganic filler be less to give aggregates of the inorganic filler and the filler.

【0009】 [0009]

【課題を解決するための手段及び作用】本発明者らは、 Means for Solving the Problems and effects of the present invention have found that,
上記目的を達成するため鋭意検討を重ねた結果、平均粒径5〜40μmの無機質充填剤100重量部をアルコキシ基含有シラン又はその部分加水分解物で処理した表面処理充填剤100重量部と、アルコキシ基含有シラン又はその部分加水分解物で表面処理されていない平均粒径4μm以下の無機質充填剤1〜40重量部とを混合してなる充填剤が有効であることを知見した。 Result of intensive investigations to achieve the above objects, an average particle size surface treatment filler 100 parts by weight of an inorganic filler 100 parts by weight was treated with an alkoxy group-containing silane or partial hydrolyzate thereof of 5 to 40 m, alkoxy It was found that filler formed by combining an group-containing silane or the average particle size 4μm or less of the inorganic filler 1 to 40 parts by weight which is not surface-treated with a partial hydrolyzate thereof is effective.

【0010】即ち、従来より平均粒径の異なる充填剤を併用することは公知であり、またアルコキシ基含有シラン又はその部分加水分解物で無機質充填剤の表面を処理することも公知であり、本発明者らは、これらを組み合わせて平均粒径の異なる充填剤を用いると共に、それぞれをアルコキシ基含有シラン又はその部分加水分解物で処理することを試みたが、流動性は良好であるものの、 [0010] That is, be used in combination with different filler average particle size than conventionally known, also known also treating the surface of the inorganic filler with an alkoxy group-containing silane or partial hydrolyzate thereof, the we, the use of different fillers having an average particle diameter in combination thereof, but each attempted to treatment with an alkoxy group-containing silane or partial hydrolyzate thereof, although fluidity is good,
充填剤の凝集物が多く、そのため硬化物の機械的強度が劣るものであるのに対し、平均粒径の異なる充填剤を併用する場合、粒径の大きい方のみをアルコキシ基含有シラン又はその部分加水分解物で処理し、粒径の小さい方をアルコキシ基含有シラン又はその部分加水分解物で表面処理せずにこれらを混合することで、意外にも樹脂に配合した場合に凝集物が少なく、かつ常温乃至高温溶融時における粘度が低く流動性が良好であることを見い出し、本発明をなすに至ったものである。 Many agglomerates of filler, while the one in which the mechanical strength of the order cured product is poor, when used in combination with different filler of average particle diameter, the larger only the alkoxy group-containing silane or a portion thereof having a particle size was treated with the hydrolyzate, the particle size of the smaller by mixing these without surface treatment with an alkoxy group-containing silane or partial hydrolyzate thereof, is less agglomerates when incorporated into surprisingly resin, and it found that fluidity low viscosity at room temperature to a high temperature melt is good, in which the present invention has been accomplished.

【0011】従って、本発明は、(A)平均粒径5〜4 Accordingly, the present invention, (A) an average particle size of 5 to 4
0μmの無機質充填剤100重量部をアルコキシ基含有シラン又はその部分加水分解物で処理した表面処理充填剤100重量部と、(B)アルコキシ基含有シラン又はその部分加水分解物で表面処理されていない平均粒径4 And surface treatment filler 100 parts by weight of the treated with an alkoxy group-containing silane or partial hydrolyzate thereof an inorganic filler 100 parts by weight of 0 .mu.m, have not been surface-treated with (B) an alkoxy group-containing silane or partial hydrolyzate thereof The average particle diameter of 4
μm以下の無機質充填剤1〜40重量部とを混合してなることを特徴とする樹脂用無機質充填剤、及びエポキシ樹脂と硬化剤と無機質充填剤とを含有してなるエポキシ樹脂組成物において、上記無機質充填剤として上記樹脂用無機質充填剤を使用したことを特徴とするエポキシ樹脂組成物を提供する。 Resin for inorganic filler, characterized in that μm formed by combining an following inorganic filler 1 to 40 parts by weight, and in the epoxy resin composition comprising an epoxy resin and a curing agent and an inorganic filler, to provide an epoxy resin composition characterized by using the above resin for the inorganic filler as the inorganic filler.

【0012】以下、本発明について更に詳しく説明すると、本発明の樹脂用無機質充填剤は、上述したように(A)アルコキシ基含有シラン又はその部分加水分解物で処理した平均粒径の大きい無機質充填剤と、(B)アルコキシ基含有シラン又はその部分加水分解物で表面処理されていない平均粒径の小さい無機質充填剤とを混合したものである。 [0012] Hereinafter, further the present invention will be described in detail, the resin for the inorganic filler of the present invention is greater inorganic fillers having an average particle size treated with as (A) an alkoxy group-containing silane or partial hydrolyzate thereof described above agent is obtained by mixing the (B) an alkoxy group-containing silane or less inorganic filler having an average particle size which is not surface-treated with a partial hydrolyzate thereof.

【0013】本発明においては、(A)成分の無機質充填剤の平均粒径は5〜40μm、好ましくは7〜30μ [0013] In the present invention, (A) an average particle size of the components of the inorganic filler is 5 to 40 m, preferably 7~30μ
mの範囲とする必要がある。 There is a need to be in the range of m. 平均粒径が5μmより小さいと(B)成分のより小さい平均粒径の無機質充填剤と併用した効果が発現せず、一方40μmより平均粒径が大きいと溶融時の流動性が悪くなる。 Average particle diameter of not exhibited the effect in combination with 5μm smaller component (B) of smaller average particle size of the inorganic filler, whereas the fluidity during melting with an average particle size of greater than 40μm deteriorate. 使用できる無機質充填剤の種類としては、従来公知の無機質充填剤を使用することができ、例えば破砕状や球状の溶融シリカ、結晶性シリカの他、アルミナ、窒化ケイ素、窒化アルミニウム等を挙げることができる。 The types of inorganic fillers which may be used, it is possible to use a conventionally known inorganic fillers, for example crushed or spherical fused silica, other crystalline silica, alumina, silicon nitride, and the like such as aluminum nitride it can. また、平均粒径、材質、 The average particle size, material,
形状の異なる2種以上の無機質充填剤を併用してもよく、硬化物の低膨張化と成形性とを両立させるためには球状品と破砕品との併用、あるいは球状品のみを用いることが推奨される。 May be used in combination of two or more kinds of inorganic fillers having different shapes, in order to achieve both a low expansion of the moldability of the cured product can be used only in combination with spherical products and crushed products, or spherical products recommended.

【0014】このような無機質充填剤を処理するアルコキシ基含有シランとしては、従来公知のものが使用可能であり、例えば3―グリシドキシプロピルトリメトキシシラン、3―アミノプロピルトリメトキシシラン、1, [0014] As such an alkoxy group-containing silane to handle inorganic filler is capable of conventionally known to use, for example, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 1,
3−ビス(γ−グリシドキシプロピル)−1,1,3, 1,3-bis (.gamma.-glycidoxypropyl) -1,1,3,
3−テトラメトキシ−1,3−ジシロキサン、1,3− 3-tetra-methoxy-1,3-disiloxane, 1,3
ジメチル−1,1,3,3−テトラメトキシ−1,3− Dimethyl-1,1,3,3-tetramethoxy-1,3
ジシロキサン、フェニルトリメトキシシラン、メチルトリエトキシシラン等を挙げることができ、これらの部分加水分解物を使用することもできる。 Disiloxane, phenyl trimethoxy silane, there may be mentioned methyl triethoxysilane, it is also possible to use these partial hydrolyzate.

【0015】アルコキシ基含有シラン又はその部分加水分解物の使用量は、無機質充填剤100部(重量部、以下同様)に対して0.1〜1部が好ましく、より好ましくは0.1〜0.6部の範囲である。 [0015] The amount of the alkoxy group-containing silane or partial hydrolyzate thereof, 100 parts of inorganic filler (parts by weight, hereinafter the same) preferably 0.1 to 1 parts per, more preferably 0.1 to 0 it is in the range of .6 parts. 0.1部より使用量が少ないと、樹脂組成物に配合した場合、樹脂と無機質充填剤との界面制御が十分にできない場合が生じ、一方1部より使用量が多いと、凝集物ができやすくなるおそれがある。 If less usage than 0.1 parts, when incorporated into the resin composition, the case where the interface control between the resin and the inorganic filler can not be sufficiently occurs, whereas many usage than 1 part, can agglomerate it may become easier.

【0016】(A)成分の表面処理充填剤を作成する方法としては、特に制限されないが、ヘンシェルミキサー等の公知の混合機に入れた無機質充填剤にスプレー等の散布手段でアルコキシ基含有シラン又はその部分加水分解物を散布し、その後無機質充填剤を混合して得ることができる。 [0016] As a method for creating a surface treatment filler of the component (A), although not particularly limited, an alkoxy group-containing silane with spraying means sprays such as inorganic fillers were placed in a known mixer such as a Henschel mixer or sprayed with a partial hydrolyzate thereof, it can then be mixed with inorganic filler. このままで(B)成分の無機質充填剤と混合してもよいが、より凝集物を少なくするために室温で数日間放置したり、あるいは熱処理したりした後、100 This remains in (B) may be mixed with the components of the inorganic filler, but the look and left for several days at room temperature in order to reduce a more aggregates, or after or heat treatment, 100
〜200メッシュの篩を通して凝集物を除くことが好ましい。 It is preferable to remove the agglomerates through a 200 mesh sieve.

【0017】一方、(B)成分の平均粒径が4μm以下、好ましくは0.2〜3μmの無機質充填剤としては、従来公知の無機質充填剤を使用でき、例えば破砕状や球状の溶融シリカ、結晶性シリカの他、アルミナ、窒化ケイ素、窒化アルミニウム等を挙げることができる。 Meanwhile, (B) the average particle size of component 4μm or less, preferably as the inorganic filler of 0.2 to 3 .mu.m, can be used conventionally known inorganic fillers, for example crushed or spherical fused silica, other crystalline silica, mention may be made of alumina, silicon nitride, aluminum nitride, or the like.
また、平均粒径、材質、形状の異なる2種以上の無機質充填剤を併用してもよい。 The average particle size, the material may be used in combination of two or more inorganic fillers having different shapes.

【0018】この(B)成分の無機質充填剤の使用量は、(A)成分の表面処理無機質充填剤100部に対して1〜40部、好ましくは3〜30部の範囲とする必要がある。 [0018] The amount of the component (B) of the inorganic filler, 1 to 40 parts, preferably should be in the range of 3 to 30 parts with respect to the surface treatment the inorganic filler 100 parts of component (A) . 使用量が1部より少ないと、樹脂と混合した場合の常温乃至高温溶融状態における粘度を十分に低くすることができず、一方40部を超えると経済的に不利になったり、凝集が起こりやすくなる。 The amount used is less than 1 part, it can not be sufficiently low viscosity at room temperature to a high temperature molten state when mixed with the resin, whereas may become economically disadvantageous if it exceeds 40 parts, easily occurs agglomeration Become.

【0019】(A)成分と(B)成分の充填剤の混合は、従来公知の混合装置を使用することができる。 [0019] Mixing of components (A) and (B) components of the filler may be used conventionally known mixing apparatus. 具体的にはヘンシェルミキサー、バーチカルミキサー、ボールミル、コンクリートミキサー等の混合機を挙げることができる。 Specifically may be mentioned a Henschel mixer, vertical mixer, a ball mill, a mixer such as a concrete mixer. なお、混合後100〜200メッシュの篩で凝集物を除いておくことが好ましい。 Incidentally, it is preferable to remove the agglomerates at 100 to 200 mesh sieve after mixing.

【0020】本発明の樹脂用無機質充填剤は、樹脂に多量配合した場合、常温乃至高温溶融時における粘度が低く、良好な流動性を保つと共に、樹脂に配合した場合の凝集物が可及的に少ないので、樹脂の機械的強度を低下させるおそれが可及的に少ない。 The resin for the inorganic filler of the present invention, when a large amount blended into the resin, a low viscosity at room temperature to a high temperature melt, with maintaining good flow properties, agglomerates of when incorporated into the resin as much as possible because small, the possibility of lowering the mechanical strength of the resin as much as possible less. このため、硬化性エポキシ樹脂、シリコーン樹脂、熱可塑性樹脂などの各種の樹脂の充填剤として有用であり、とりわけ半導体封止用エポキシ樹脂組成物の充填剤として極めて有用である。 Therefore, the curable epoxy resin are useful as fillers for various resins such as silicone resins, thermoplastic resins, especially very useful as fillers in the epoxy resin composition for semiconductor encapsulation.

【0021】以下、かかる樹脂用無機質充填剤を配合した本発明のエポキシ樹脂組成物について説明すると、本発明のエポキシ樹脂組成物は、エポキシ樹脂、硬化剤及び上記樹脂用無機質充填剤を主成分として配合したものである。 [0021] Hereinafter, to explain the epoxy resin composition of the present invention blended with the resin for the inorganic filler, the epoxy resin composition of the present invention, an epoxy resin, a curing agent and the resin for the inorganic filler as main components it is those that were formulated.

【0022】ここで、エポキシ樹脂としては、一分子中にエポキシ基を少なくとも2個有するエポキシ樹脂であればいずれのものも使用可能であり、具体的にはビスフェノールA型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、トリフェノールアルカン型エポキシ樹脂及びその重合物、ビフェニル型エポキシ樹脂、ジシクロペンタジエン―フェノールノボラック樹脂、フェノールアラルキル型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、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を用いることができる。 [0022] Here, as the epoxy resin, one if the molecule epoxy groups in an epoxy resin having at least two are any of the available ones, specifically bisphenol A type epoxy resin, phenol novolac type epoxy resins, triphenolalkane type epoxy resins and polymers thereof, biphenyl type epoxy resins, dicyclopentadiene - phenol novolak resin, phenol aralkyl type epoxy resins, naphthalene ring-containing epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and brominated epoxy resin. これらのエポキシ樹脂の中ではナフタレン環含有エポキシ樹脂やビフェニル型エポキシ樹脂が低吸湿、高接着性を得る点で好ましい。 Naphthalene ring-containing epoxy resins and biphenyl type epoxy resin is low hygroscopicity Among these epoxy resins, preferable from the viewpoint of obtaining a high adhesion property. なお、これらのエポキシ樹脂は、その使用にあたっては必ずしも1種類に限定されるものではなく、2種類又はそれ以上を混合して使用してもよい。 Incidentally, these epoxy resins are not necessarily limited to one kind when its use, may be used as a mixture of two or more.

【0023】また、硬化剤は特に制限されるものではなく、使用するエポキシ樹脂に応じて適宜選定することができ、例えばアミン系硬化剤、酸無水物系硬化剤、フェノールノボラック樹脂、クレゾールノボラック樹脂等のフェノールノボラック型硬化剤等が挙げられるが、中でもフェノールノボラック型硬化剤が好ましい。 Further, the curing agent is not particularly limited and may be appropriately selected depending on the epoxy resin used, for example, amine curing agents, acid anhydride curing agents, phenol novolak resin, cresol novolak resin Although phenol novolac type curing agent and the like. Among them, a phenol novolac type curing agent is preferred.

【0024】硬化剤の配合量は、エポキシ樹脂を硬化させ得る量であり、通常使用される量とすることができ、 [0024] The amount of the curing agent is an amount capable of curing the epoxy resin, it can be an amount that is normally used,
フェノールノボラック型硬化剤を用いた場合、エポキシ樹脂中のエポキシ基と硬化剤中のOH基との比がモル比で1:0.5〜1:1.5となるように配合することが好ましい。 When using a phenol novolac type hardener, 1 ratio of OH groups in the curing agent with the epoxy groups in the epoxy resin in a molar ratio: 0.5 is preferably blended such that 1.5 .

【0025】なお、本発明では、エポキシ樹脂と硬化剤との反応を促進させる目的で各種硬化促進剤、例えばイミダゾール類、三級アミン類、ホスフィン系化合物、シクロアミジン化合物などを配合することができる。 [0025] In the present invention, various curing accelerators for the purpose of promoting the reaction between the epoxy resin and the curing agent, for example imidazoles, tertiary amines, phosphine compounds, can be formulated and cycloamidine compound . 硬化促進剤の配合量は、特に制限はないが、通常全系に対して0.05〜1重量%程度とすることがよい。 The amount of curing accelerator is not particularly limited, it may be about 0.05 to 1% by weight with respect to the normal whole system.

【0026】また更に、本発明では硬化物の応力を低下させる目的で組成物中にシリコーン系ポリマーを配合してもよい。 [0026] Further, in the present invention may be blended silicone polymer in the composition for the purpose of reducing the stress of the cured product. シリコーン系ポリマーを配合すると、硬化物の熱衝撃テストにおけるパッケージクラックの発生を著しく少なくすることが可能である。 When blending the silicone-based polymer, it is possible to significantly reduce the occurrence of package cracks in the thermal shock test of the cured product. このシリコーン系ポリマーとしては、例えばエポキシ基、アミノ基、カルボキシル基、水酸基、ヒドロシリル基、ビニル基等を有するシリコーンオイル、シリコーンレジン、シリコーンゴム等やこれらシリコーンポリマーと有機重合体、例えば置換又は非置換のフェノールノボラック樹脂等の重合体を挙げることができる。 As the silicone polymer, for example an epoxy group, an amino group, a carboxyl group, a hydroxyl group, hydrosilyl group, silicone oil having a vinyl group and the like, silicone resin, silicone rubber, or the like, or silicone polymers and organic polymers, such as substituted or unsubstituted it can be mentioned polymers such phenolic novolak resin.

【0027】なお、シリコーン系ポリマーの添加量は特に限定されないが、通常エポキシ樹脂と硬化剤との合計量100部に対し、1〜50部とすることが好ましい。 [0027] The addition amount of the silicone-based polymer is not particularly limited, the total amount 100 parts of an ordinary epoxy resin and the curing agent, it is preferable that 1 to 50 parts.

【0028】更に、硬化物に可撓性や強靭性を付与する目的で、各種有機合成ゴム、メタクリル酸メチル―スチレン―ブタジエン共重合体、スチレン―エチレン―ブテン―スチレン共重合体等の熱可塑性樹脂を添加することができ、これによって硬化物に低応力を付与することができる。 Furthermore, for the purpose of imparting flexibility and toughness to the cured product, various organic synthetic rubbers, methyl methacrylate - styrene - butadiene copolymer, a styrene - ethylene - butene - thermoplastic such as styrene copolymers it can be added resin, whereby it is possible to impart low stress in the cured product.

【0029】本発明のエポキシ樹脂組成物には、上述した樹脂用無機質充填剤を配合するものであり、その配合量はエポキシ樹脂組成物全体に対し70〜94重量%、 [0029] The epoxy resin composition of the present invention is to blend the resin for inorganic filler described above, the amount thereof 70 to 94 wt% relative to the whole epoxy resin composition,
特に75〜92重量%の範囲とすることが好ましい。 Particularly preferably in the range of 75 to 92 wt%. 配合量が70重量%未満では、得られた硬化物の膨張係数が大きくなってしまうため応力特性が悪くなってしまう場合があり、一方94重量%を超えると、成形時の溶融粘度が高くなりすぎてボイド、未充填などが発生するおそれがある。 When the amount is less than 70 wt%, may stress characteristics for expansion coefficient increases the cured product obtained becomes poor, whereas when it exceeds 94 wt%, the higher the melt viscosity during molding too is void, there is a risk that such unfilled occurs.

【0030】本発明のエポキシ樹脂組成物には、更に必要により各種の添加剤を配合することができ、例えばカルナバワックス等のワックス類、ステアリン酸などの脂肪酸やその金属塩などの離型剤(中でも接着性、離型性の面からカルナバワックスが好適に用いられる)、有機ゴム系の可撓性付与剤、カーボンブラック、コバルトブルー、ベンガラ等の顔料、酸化アンチモン、ハロゲン化合物等の難燃化剤、γ―グリシドキシプロピルトリメトキシシラン等のシランカップリング剤、老化防止剤、その他の添加剤の1種又は2種以上を配合することができる。 [0030] The epoxy resin composition of the present invention may contain various additives necessary, for example, waxes such as carnauba wax, a release agent such as fatty acid or its metal salt such as stearic acid ( Among these adhesion, releasability of the carnauba wax is preferably used in view), an organic rubber-based flexible imparting agent include carbon black, cobalt blue, pigment red iron oxide, antimony oxide, flame retardant such as a halogen compound agents, .gamma.-glycidoxypropyltrimethoxysilane, etc. of the silane coupling agent, antioxidant, it is possible to formulate one or more kinds of other additives.

【0031】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撹拌、混合し予め70〜95℃に加熱してあるニーダー、ロール、エクストルーダー等で混練、冷却し、粉砕するなどの方法で得ることができるが、特にミキシングロール、押出機を用いた溶融混合法が好適に採用される。 The epoxy resin composition of the present invention, upon its manufacture, uniformly stirring predetermined amounts of the above components, a kneader which had been heated to the mixing in advance 70 to 95 ° C., roll, kneading by an extruder or the like, cooling and, can be obtained by methods such as grinding, especially a mixing roll, an extruder melt mixing method using a is preferably employed. ここで、各成分の配合順序に特に制限はない。 Here, there is no particular limitation on blending order of each component.

【0032】かくして得られる本発明のエポキシ樹脂組成物は、DIP型、フラットパック型、PLCC型、S [0032] Thus the epoxy resin composition of the present invention obtained is, DIP type, flat pack type, PLCC type, S
O型などの半導体パッケージに有効であり、この場合従来より採用されている成形法、例えばトランスファー成形、インジェクション成形、注型法等により行うことができる。 It is effective in the semiconductor package of O type such as can be done in this case molding method employed conventionally, for example transfer molding, injection molding, casting or the like. なお、本発明の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150〜185 Incidentally, the molding temperature of the epoxy resin composition of the present invention is 150 to 180 ° C., post-curing is 150 to 185
℃で2〜6時間行うことが好ましい。 It is preferably performed ℃ in 2 to 6 hours.

【0033】 [0033]

【発明の効果】本発明の樹脂用無機質充填剤は、樹脂に大量に配合した場合でも室温乃至高温溶融状態における粘度が低く、流動特性が良好であり、かつ無機質充填剤の凝集物の発生が可及的に少ない樹脂組成物を与えることができるものである。 Resin for the inorganic filler of the present invention exhibits a low viscosity at room temperature to a high temperature molten state even when a large amount blended into the resin, has good flow properties, and generation of aggregates of the inorganic filler those which can provide as much as possible small resin composition.

【0034】また、本発明のエポキシ樹脂組成物は、無機質充填剤を大量に配合し、吸湿性を可及的に低下させることができると共に、室温乃至高温溶融状態における粘度が低く、流動特性が良好であり、かつ組成物中の無機質充填剤の凝集物が可及的に少なく、このため半導体封止用として好適に使用できるものである。 [0034] The epoxy resin composition of the present invention, the inorganic filler in large quantities formulated, it is possible to reduce the hygroscopicity as much as possible, low viscosity at room temperature to a high temperature molten state, the flow characteristics it is good, and aggregates of the inorganic filler in the composition as much as possible reduced, in which the order can be suitably used for semiconductor encapsulation.

【0035】 [0035]

【実施例】以下、実施例と比較例を示し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 following is a description of the present invention by Examples and Comparative Examples, the present invention is not intended to be limited to the following Examples. なお、以下の例において部はいずれも重量部を示す。 All parts are both showing the parts in the following examples.

【0036】[実施例1〜3、比較例1〜3]表1に示す各種無機質充填剤及びγ−グリシドキシプロピルトリアルコキシシランを表1に示す量でヘンシェルミキサーを用いて混合して無機質充填剤混合物を調製した。 [0036] [Examples 1-3, Comparative Examples 1-3] Various inorganic fillers are shown in Table 1 and γ- glycidoxypropyl trialkoxysilane by mixing with a Henschel mixer in the amounts shown in Table 1 Inorganic the filler mixture was prepared.

【0037】なお、表中の処理方法及びフィラー凝集物の測定方法を次に示す。 [0037] Incidentally, the following method of measuring the processing method and filler agglomerates in the table. <処理方法> (A):表1中Aで示した充填剤のみを5分間混合した後、スプレーにてγ−グリシドキシプロピルトリアルコキシシランを用いてシランカップリング処理し、その後10分間混合し、室温で1日放置後に100メッシュ篩処理を行った。 <Processing method> (A): After mixing the only filler 5 minutes indicated in Table 1 A, and silane coupling treatment using γ- glycidoxypropyltrialkoxysilane a spray, subsequently mixed for 10 minutes and it was subjected to 100-mesh sieve treatment after left for one day at room temperature. その後、表1の比率でBで示した充填剤を加えて20分間混合した後に100メッシュ篩で篩分けを行った。 This was followed by sieving with a 100-mesh sieve after mixed with a filler shown in B in a ratio of Table 1 20 min. (A+B):全ての充填剤を5分間混合した後に、スプレーにてシランカップリング処理し、その後10分間混合し、室温で1日放置後に100メッシュ篩で篩分け処理を行った。 (A + B): all filler After mixing for 5 minutes, and silane coupling treatment by a spray, then mixed for 10 minutes, was sieved at 100 mesh sieve after standing at room temperature for 1 day. <フィラー凝集物測定方法>得られた無機質充填剤混合物100gをアセトン300gに溶解したものを200 200 The <filler agglomerates measuring method> The resulting inorganic filler mixture 100g which was dissolved in acetone 300g
メッシュ篩にアセトンで洗浄しながら通したときの篩上の重量を計り、この重量を全体の重量に対する%で表した。 Weighed on the sieve when the through washing with acetone mesh sieve to represent the weight in% of the total weight.

【0038】次に、エポキシ当量198、軟化点60℃ Next, epoxy equivalent 198, softening point 60 ° C.
のエポキシ化クレゾールノボラック樹脂51部、エポキシ当量280の臭素化エポキシ化フェノールノボラック樹脂6部、フェノール当量110、軟化点90℃のフェノールノボラック樹脂33部、下記式(a)で示される化合物60部と下記式(b)で示される化合物40部との反応生成物10部、トリフェニルホスフィン0.65 51 parts of an epoxy cresol novolac resin, 6 parts of a brominated epoxy phenolic novolac resin having an epoxy equivalent of 280, phenol equivalent 110, phenol novolak resin 33 parts of a softening point 90 ° C., and compound 60 parts represented by the following formula (a) the reaction product 10 parts of the compound 40 parts represented by the following formula (b), triphenylphosphine 0.65
部、三酸化アンチモン10部、カルナバワックス1.2 Parts, 10 parts of antimony trioxide, carnauba wax 1.2
部、γ―グリシドキシプロピルトリメトキシシラン1. Parts, .gamma.-glycidoxypropyltrimethoxysilane 1.
0部、カーボン1部及び上記方法で得られた無機質充填剤混合物400部を配合し、80℃のミキシングロールで5分間溶融混合した後、シート状にして取り出し、これを冷却粉砕して組成物を得た。 0 parts by blending inorganic filler mixture 400 parts of the obtained carbon 1 part of the above method, after the melt mixed for 5 minutes with a mixing roll 80 ° C., taken out into a sheet, the composition of which is cooled milled It was obtained.

【0039】 [0039]

【化1】 [Formula 1]

【0040】得られた組成物について、下記に示す(イ)〜(ニ)の諸試験を行った。 [0040] The resulting composition was subjected to various tests shown in the following (a) to (d). 結果を表1に併記する。 The results are shown in Table 1. (イ)組成物中の凝集物 組成物の粉体100gをアセトン300gに溶解したものを200メッシュ篩にアセトンで洗浄しながら通したときの篩上の重量を計り、凝集物とした。 (B) a powder 100g aggregates composition in the composition weighed on the sieve when the through washing with acetone that was dissolved in acetone 300g in 200 mesh sieve, and the aggregates. (ロ)溶融粘度 島津製作所製高化式フローテスターを用いて175℃、 (B) 175 ° C. using a melt viscosity Shimadzu high reduction type flow tester,
10kg荷重における粘度を測定した。 Viscosity was measured at 10kg load. (ハ)スパイラルフロー EMMI規格に準じた金型を使用して175℃、70k (C) 175 ° C. using a mold in accordance with the spiral flow EMMI standards, 70k
gf/cm 2の条件で測定した。 It was measured under the conditions of gf / cm 2. (ニ)曲げ強度 JIS―K6911に準じて、175℃、70kgf/ (D) in accordance with bending strength JIS-K6911, 175 ℃, 70kgf /
cm 2 、成形時間2分の条件で10×4×100mmの抗折棒を成形し、室温で測定した。 cm 2, by forming a transverse bar 10 × 4 × 100 mm under the conditions of 2 minutes molding time was measured at room temperature.

【0041】 [0041]

【表1】 [Table 1]

【0042】表1から、同じ2種のシリカを用いた実施例1と比較例1とを比較してみると、2種のシリカの両方をアルコキシ基含有シランで処理した場合(比較例1)は、凝集物が多く、その結果曲げ強度が低くなるのに対し、2種のシリカのうち粒径の大きい方のみをアルコキシ基含有シランで処理した場合(実施例1)は、凝集物が少なく、溶融粘度が低く、曲げ強度も高いことが認められる。 [0042] Table 1, A comparison with Comparative Example 1 and Example 1 using the same two silica, if both of the two silica treated with an alkoxy group-containing silane (Comparative Example 1) , many aggregates, whereas the result the bending strength is low, if the two inner particle diameter of the silica larger only treated with an alkoxy group-containing silane (example 1), the aggregate is small , low melt viscosity, flexural strength is observed to be high. また、粒径の小さなシリカを配合しないと(比較例2、3)、溶融粘度が非常に高く、流動性が悪い(スパイラルフローが低い)ことが認められる。 Moreover, not blended with small silica particle size (Comparative Examples 2 and 3), the melt viscosity is very high, it is recognized that poor flowability (spiral flow is low).

───────────────────────────────────────────────────── フロントページの続き (72)発明者 塩原 利夫 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 ────────────────────────────────────────────────── ─── of the front page continued (72) inventor Shiobara Gunma Prefecture Toshio Usui District Matsuida Oaza people viewed the first address 10 Shin-Etsu Chemical Co., Ltd. silicone electronic materials technology within the Institute

Claims (2)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 (A)平均粒径5〜40μmの無機質充填剤100重量部をアルコキシ基含有シラン又はその部分加水分解物で処理した表面処理充填剤100重量部と、(B)アルコキシ基含有シラン又はその部分加水分解物で表面処理されていない平均粒径4μm以下の無機質充填剤1〜40重量部とを混合してなることを特徴とする樹脂用無機質充填剤。 And 1. A (A) an average particle size of surface treated filler 100 parts by weight of an inorganic filler 100 parts by weight was treated with an alkoxy group-containing silane or partial hydrolyzate thereof in 5 to 40 m, (B) an alkoxy group-containing resin for inorganic filler, characterized in that formed by combining an average particle size 4μm or less of the inorganic filler 1 to 40 parts by weight which is not surface-treated with a silane or partial hydrolyzate thereof.
  2. 【請求項2】 エポキシ樹脂と硬化剤と無機質充填剤とを含有してなるエポキシ樹脂組成物において、上記無機質充填剤として請求項1記載の樹脂用無機質充填剤を使用したことを特徴とするエポキシ樹脂組成物。 2. A comprising an epoxy resin and a curing agent and an inorganic filler epoxy resin composition, characterized by using a resin for inorganic filler according to claim 1, wherein as said inorganic filler Epoxy resin composition.
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JP2002322243A (en) * 2001-04-26 2002-11-08 Sumitomo Bakelite Co Ltd Method of production for epoxy resin composition and semiconductor device
KR100697938B1 (en) * 2003-03-25 2007-03-20 스미토모 베이클라이트 가부시키가이샤 Resin composition for sealing semiconductor and semiconductor device using the same
KR100697937B1 (en) * 2003-03-11 2007-03-20 스미토모 베이클라이트 가부시키가이샤 Resin composition for encapsulating semiconductor chip and semiconductor device therewith
US7291684B2 (en) 2003-03-11 2007-11-06 Sumitomo Bakelite Co., Ltd. Resin composition for encapsulating semiconductor chip and semiconductor device therewith
US7431990B2 (en) 2004-05-27 2008-10-07 Sumitomo Bakelite Co Resin composition for encapsulating semiconductor chip and semiconductor device therewith
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US7655295B2 (en) * 2005-06-14 2010-02-02 Siemens Energy, Inc. Mix of grafted and non-grafted particles in a resin
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