JPH06100313A - Surface treated silica, its production and filler for resin composition for sealing semiconductor - Google Patents

Surface treated silica, its production and filler for resin composition for sealing semiconductor

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Publication number
JPH06100313A
JPH06100313A JP27385092A JP27385092A JPH06100313A JP H06100313 A JPH06100313 A JP H06100313A JP 27385092 A JP27385092 A JP 27385092A JP 27385092 A JP27385092 A JP 27385092A JP H06100313 A JPH06100313 A JP H06100313A
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silica
coupling agent
silane coupling
surface
treated silica
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JP27385092A
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JP2671727B2 (en )
Inventor
Takayuki Aoki
Koji Futatsumori
Shigeki Ino
Toshio Shiobara
Miyuki Wakao
浩二 二ツ森
茂樹 井野
利夫 塩原
幸 若尾
貴之 青木
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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 efficiently produce surface treated silica suitable for a filler of composite material and to provide a cured composition having low stress, excellent moisture-resistant reliability, impact-resistant reliability, heat-resistant reliability by blending the surface treated silica with a resin composition.
CONSTITUTION: Silica is blended with a silane coupling agent containing one or more functional groups while stirring and the surface of silica particles is coated with the silane coupling agent. The silica particles coated with the silane coupling agent are blended with an organic compound containing one or more functional groups capable of being reacted with the functional groups while stirring and further the silica is covered with the organic compound to produce surface treated silica.
COPYRIGHT: (C)1994,JPO&Japio

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、半導体装置封止用樹脂組成物などの複合材料に機械的強度を付与する成分として好適に使用し得る表面処理シリカ並びにその製造方法及びこの表面処理シリカからなる半導体封止樹脂組成物用充填剤に関する。 The present invention relates to a surface-treated silica and its preparation and the surface-treated silica can be suitably used as a component to impart mechanical strength to the composite material such as a semiconductor device encapsulating resin composition comprising a semiconductor encapsulating resin composition for fillers.

【0002】 [0002]

【従来の技術及び発明が解決しようとする課題】従来、 BACKGROUND OF invention is to provide a conventional,
トランジスタ、IC、LSI等の半導体素子は、通常セラミックパッケージやプラスチックパッケージ等により封止され、半導体装置化されている。 Transistor, IC, semiconductor devices such as LSI, normally sealed by a ceramic package or a plastic package or the like, and is a semiconductor device of. 上記セラミックパッケージは、構成材料そのものが耐熱性を有し、また、 The ceramic package, the material itself has heat resistance, also,
耐浸透性にも優れているため、温度、湿度に対して強く、しかも中空パッケージのため機械的強度も高く、信頼性の高い封止が可能である。 Because of its excellent in penetration resistance, temperature, resistant to moisture, yet the mechanical strength for hollow packages is high, it is possible to reliable sealing.

【0003】しかしながら、セラミックパッケージの構成材料は比較的高価なものであり、量産性に劣るという問題があるため、最近では、プラスチックパッケージを用いた樹脂封止が主流となっている。 However, the material of the ceramic package is a relatively expensive, due to a problem of poor productivity, in recent years, resin sealing using a plastic package has become mainstream. この樹脂封止には、その特性が優れることから、エポキシ樹脂組成物が主として使用されている。 This resin sealing, since its characteristics are excellent, epoxy resin compositions have been used mainly. しかし、半導体分野の技術革新によって半導体装置の集積度が向上すると共に、素子サイズの大型化、配線の微細化が進み、また、パッケージが小型化、薄型化する傾向にあり、これに伴って封止材料に対して従来以上の信頼性(低応力、耐湿信頼性、 However, the integration of the semiconductor device is improved by innovations semiconductor field, enlargement of the device size, miniaturization of wiring advances, also the package size reduction, there is a tendency to thin, along with this seal higher than conventional reliability against stop material (low stress, moisture resistance reliability,
耐衝撃信頼性、耐熱信頼性、耐クラック性)の向上が要望されている。 Impact reliability, heat resistance reliability, improvement in crack resistance) has been desired. この要望に対応するため、封止樹脂をゴム変性することによって熱応力を低減させたり、無機質充填剤を増量することなどが検討されてきたが、複合材料に充分な信頼性を与えるものは少なく、このため、上述した素子サイズの大型化に対応するために上記信頼性を向上し得る技術の開発が強く望まれている。 To accommodate this need, or to reduce thermal stress by a rubber-modified sealing resin, such as by increasing the inorganic filler has been studied, less is intended to provide sufficient reliability for the composite material , Thus, development of a technology capable of improving the reliability is strongly demanded in order to cope with enlargement of the device size as described above.

【0004】本発明は上記事情に鑑みなされたもので、 [0004] The present invention has been made in view of the above circumstances,
半導体装置封止用樹脂組成物等の複合材料に配合する無機質充填剤として好適に使用し得る表面シリカ及びこの表面処理シリカを得るための製造方法を提供することを目的とする。 And to provide a manufacturing method for obtaining the surface silica and the surface-treated silica can be suitably used as the inorganic filler to be blended into composite materials such as a semiconductor device sealing resin composition.

【0005】 [0005]

【課題を解決するための手段及び作用】本発明者は上記目的を達成するため鋭意検討を行った結果、官能基を1 Means and operation for solving the problems] The present inventors have result of extensive investigations to achieve the above objects, a functional group 1
個以上有するシランカップリング剤とシリカを混合撹拌してシリカ粒子の表面を上記シランカップリング剤で被覆し、該シランカップリング剤で被覆されたシリカ粒子を上記官能基と反応可能な官能基を1個以上有する有機化合物と混合撹拌して更に上記有機化合物で上記シリカ粒子を被覆することにより、所望の特性を有するシリカを得ることができ、また、この表面処理シリカを半導体封止用エポキシ樹脂組成物等の複合材料に無機質充填剤として配合した場合、無機質充填剤であるシリカと樹脂マトリックスの親和力が強化されるため、低応力でしかも耐衝撃信頼性、耐湿信頼性、耐クラック性に優れた硬化物を得ることができ、特に半導体封止用樹脂組成物の充填剤として非常に有用であることを知見し、本発明をなすに至った。 The surface of the silica particles coated with the silane coupling agent of a silane coupling agent and silica having FOB stirred together, the silica particles coated with the silane coupling agent a functional group capable of reacting with the functional group by covering the silica particles in addition the organic compound was mixed and stirred with an organic compound having 1 or more, it is possible to obtain silica having the desired characteristics, a semiconductor encapsulating epoxy resin the surface-treated silica when incorporated into a composite material such compositions as inorganic filler, because the affinity of the silica and the resin matrix is ​​a mineral filler is enhanced, yet the impact reliability at low stress, humidity resistance reliability, the crack resistance superior the cured product can be obtained with, in particular, to findings to be very useful as fillers in the resin composition for semiconductor encapsulation, the present invention has been accomplished.

【0006】以下、本発明を更に詳しく説明すると、本発明の表面処理シリカは、官能基を1個以上有するシランカップリング剤でシリカ粒子の表面を被覆し、更に上記官能基と反応可能な官能基を1個以上有する有機化合物で被覆してなるものである。 [0006] Hereinafter, when describing the present invention in more detail, the surface-treated silica of the present invention, the surface of the silica particles coated with functional groups with one or more with silane coupling agent, further capable of reacting with the functional group functionality those formed by coating an organic compound having one or more groups.

【0007】ここで、上記表面処理されるシリカの種類、形状は特に限定されるものではなく、具体的には溶融シリカ、結晶シリカ等が挙げられる。 [0007] Here, the kind of silica being the surface treatment, the shape is not particularly limited, and specifically fused silica, crystalline silica and the like. また、その粒径も制限はないが、半導体封止用樹脂組成物の充填剤として用いる場合は平均粒径が5〜70μmのものが好ましい。 Further, it is also not limited the particle size, the average particle size when used as a filler for semiconductor sealing resin composition is preferably from 5 to 70 m.

【0008】上記シリカのカップリングに用いられる官能基を1個以上有するシランカップリング剤としては公知のものが使用でき、例示するとγ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、N−β−(アミノエチル)γ−アミノプロピルトリメトキシシラン、N [0008] As the silane coupling agent having at least one functional group used for coupling the silica can be used known ones, To illustrate .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropyl methyl diethoxy silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) .gamma.-aminopropyltrimethoxysilane, N
−β−(アミノエチル)γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、ビニルシリエトキシシラン、トリメトキシシリルプロピルナジック酸無水物等が挙げられる。 -.beta.-(aminoethyl) .gamma.-aminopropyl methyl diethoxy silane, .gamma.-aminopropyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-chloropropyl trimethoxy silane, vinyl silicon silane, tri methoxysilylpropyl nadic anhydride, and the like.

【0009】一方、上記シランカップリング剤の官能基と反応可能な官能基を1個以上有する有機化合物としては下記に示す官能基を有するものが挙げられるが、官能基はこれらに限定されるものではない。 On the other hand, those examples of the organic compound having a functional group capable of reacting with functional groups of the silane coupling agent 1 or more but include those having a functional group shown below, functional groups that are limited to is not.

【0010】 [0010]

【化1】 [Formula 1]

【0011】このような官能基を1個以上有する有機化合物としては、下記に示すものが例示され、これらの1 [0011] As the organic compound having such a functional group 1 or more, it is exemplified those illustrated below, these 1
種を単独で又は2種以上を組み合わせて用いることができる。 It can be used alone or in combination of two or more species.

【0012】 [0012]

【化2】 ## STR2 ##

【0013】本発明の表面処理シリカを得るには、まず、官能基を1個以上有する上記シランカップリング剤とシリカを混合して撹拌し、シリカ粒子の表面を上記シランカップリング剤で被覆する。 To obtain a surface-treated silica of [0013] the present invention, first, stirring a mixture of the silane coupling agent and silica having one or more functional groups, to coat the surface of the silica particles by the silane coupling agent . この場合、シランカップリングの配合量はシリカ100部(重量部、以下同じ)に対して0.01〜10部、特に0.1〜2部とすることが好ましい。 In this case, the amount of the silane coupling 100 parts silica (parts by weight, hereinafter the same) 0.01 to 10 parts per, it is preferable to particularly 0.1 to 2 parts.

【0014】シリカとシランカップリング剤を混合撹拌する場合、シランカップリング剤とシリカ表面に存在するシラノール基の結合を強固なものにするため、シランカップリング剤と混合撹拌する前に、適当な温度で長時間熱成、または高温で熱処理することが好ましい。 [0014] When mixing stirring silica and silane coupling agent, for bonding of silanol groups present on the silane coupling agent and the silica surface made firm, prior to mixing and stirring with a silane coupling agent, a suitable it is preferred to heat treatment prolonged NetsuNaru or at elevated temperature, a temperature. この場合、熱成温度は20〜50℃で10〜50時間、熱処理の場合は50〜200℃で1〜8時間行うことが好ましい。 In this case, 10 to 50 hours at NetsuNaru temperature 20 to 50 ° C., in the case of heat treatment preferably carried out 1-8 hours at 50 to 200 ° C..

【0015】上記の被覆処理については無溶媒系で行う方法(乾式処理)と溶媒中で行う方法(湿式処理)、無溶媒系で処理した後に溶媒中で処理する方法などが挙げられるが、水、アルコール、トルエン等の溶媒中で行うことが最も好ましい。 [0015] The above coating treatment method carried out in a solvent method carried out without solvent system (dry processing) (wet treatment), but a method of treating in a solvent after treatment with solvent-free systems including, water , alcohol, and most preferably carried out in a solvent such as toluene. なお、乾式処理は、ヘンシェル等の高速撹拌装置を用いて表面処理を行い、湿式処理はフラスコ等の容器に溶剤とシリカを入れて撹拌しながらカップリング剤を添加して表面処理を行う。 Incidentally, the dry process, surface treatment was performed using a high-speed stirrer such as a Henschel, a wet process for surface treatment by adding a coupling agent while stirred in the solvent and silica in a container of the flask, and the like. また、この被覆処理はシリカを70〜130℃に保ち、撹拌機で撹拌しながらシランカップリング剤を添加し、更に温度70 Also, the coating process keeps silica in 70 to 130 ° C., was added a silane coupling agent while stirring at a stirrer, temperature further 70
〜130℃で1〜5時間撹拌するなどの方法を採用することができる。 130 can be adopted a method such as stirring 1-5 hours at ° C.. この場合ジアザビシクロウンデセン等の触媒を用いることが好ましい。 It is preferred in this case using a catalyst such as diazabicycloundecene.

【0016】このようにして表面がシランカップリング剤で被覆されたシリカ粒子の表面を更に上記シランカップリング剤の官能基と反応可能な官能基を1個以上有する有機化合物で被覆するには、好ましくは温度25〜1 [0016] coated with an organic compound having this way one or more further functional groups capable of reacting with functional groups of the silane coupling agent surface of the silica particles coated with a silane coupling agent surface is preferably at a temperature 25 to 1
20℃に保ちながら上記有機化合物を添加し、1〜10 Adding the organic compound while maintaining the 20 ° C., 1 to 10
時間撹拌を継続する方法を採用することができる。 It is possible to employ a method to continue time stirring. この場合も上記シランカップリング剤との混合と同様にジアザビシクロウンデセン等の触媒を用いることが好ましい。 Again it is preferred to use a catalyst of diazabicycloundecene or the like similarly to the mixing of the silane coupling agent.

【0017】上記シランカップリング剤と上記有機化合物との割合は、上記シランカップリング剤の当量をA、 The ratio between the silane coupling agent and the organic compound, the equivalent of the silane coupling agent A,
上記有機化合物の当量をBとすると、0.01≦B/A When B equivalent of the organic compound, 0.01 ≦ B / A
≦2、特に0.04≦B/A≦1.2とすることが好ましい。 ≦ 2, and particularly preferably to 0.04 ≦ B / A ≦ 1.2. この値が0.01未満では未反応で残存する上記シランカップリング剤の官能基が多いため上記有機化合物の効果が発揮されない場合があり、また、2を超えると未反応の上記有機化合物が残留するため、この表面処理シリカを複合材料中に配合した場合、樹脂成分に悪影響を及ぼしてしまう場合がある。 This value is less than 0.01 may effect of the organic compound for the functional group of the silane coupling agent is more remaining in unreacted not exhibited, also, the organic compound unreacted exceeds 2 residual to, when formulated with the surface-treated silica in the composite material, in some cases adversely affect the resin component.

【0018】上記のようにシランカップリング剤及び有機化合物で処理した反応生成物から有機溶媒を減圧下で留去した後、これを乾燥させることにより、目的とする表面処理シリカを得ることができる。 [0018] After distilling off the organic solvent under reduced pressure from the reaction product treated with a silane coupling agent and an organic compound as described above, by drying this, it is possible to obtain a surface-treated silica for the purpose .

【0019】本発明の表面処理シリカを従来公知の成形材料、封止材料等の各種樹脂組成物に配合し、この組成物を硬化させた場合、低応力でしかも耐衝撃信頼性、耐湿信頼性、耐熱信頼性、耐クラック性に優れた硬化物を与えることができる。 The surface-treated silica conventionally known molding materials of the present invention, by blending various resin materials such as sealing materials, when cured the composition, yet impact reliability at low stress, moisture resistance reliability it can provide heat resistance reliability, excellent cured crack resistance. 従って本発明の表面処理シリカは半導体封止用樹脂組成物の充填剤として好適に使用される。 Thus surface-treated silica of the present invention is suitably used as a filler for semiconductor sealing resin composition. この場合、樹脂100部に対して表面処理シリカの配合量は100〜450部とすることが好ましい。 In this case, the amount of surface-treated silica with respect to 100 parts of the resin is preferably set to 100 to 450 parts.

【0020】なお、本発明の表面処理シリカを複合材料の充填剤として用いる場合、組成物のその他の成分は従来公知の複合材料成分と同様の配合とすることができる。 [0020] In the case of using the surface-treated silica of the present invention as a filler of the composite material, the other components of the composition may be a blend similar to conventional composite components.

【0021】 [0021]

【実施例】以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, Examples and Comparative Examples, the present invention will be described in detail, the present invention is not intended to be limited to the following examples.

【0022】[実施例1]リフラックスコンデンサー、 [0022] [Example 1] reflux condenser,
撹拌機及び滴下ロートを具備した内容積5リットルの四口フラスコ内にシリカ(平均粒径30μm)3kgと溶媒としてトルエン2kgを入れ、2時間共沸脱水した後、撹拌機で撹拌しながら112℃の温度で滴下ロートにてエポキシ基含有シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン,信越化学工業株式会社製,KBM403)15gを20分間で滴下し、更に同温度で3時間撹拌した後、撹拌を継続しながら同温度でパラアミノフェノール7gを添加し、更に同温度で3時間撹拌を継続した。 Stirrer and silica content volume of 5 liter four-necked flask equipped with a dropping funnel was placed toluene 2kg as (average particle size 30 [mu] m) 3 kg and a solvent, after 2 hours azeotropic dehydration, agitation 112 ° C. with stirrer epoxy group-containing silane coupling agent at a dropping funnel at a temperature (.gamma.-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., KBM403) 15 g was added dropwise at 20 minutes and stirred for 3 hours at the same temperature after, it was added while continuing para-aminophenol 7g at the same temperature and stirring was continued for an additional 3 hours of stirring at the same temperature. このようにして得られた反応物から溶媒を減圧下で留去した後、150℃で4時間乾燥させ、表面処理シリカ3kgを得た。 After distilling off the solvent under reduced pressure from the reaction product obtained in this way was dried for 4 hours at 0.99 ° C., to obtain a surface-treated silica 3 kg.

【0023】この表面処理シリカ(無機質充填剤)と他の封止樹脂成分を表1に示す配合割合で扮体混合し、ブスコニーダを用いて溶融混練し、エポキシ樹脂組成物を製造した。 [0023] The other of the sealing resin component The surface-treated silica (inorganic filler) were mixed dressed body at the mixing ratio shown in Table 1 was melt-kneaded using a Busukonida was producing an epoxy resin composition. このエポキシ樹脂組成物を用いて、ガラス転移温度用試験片(直径4mm、長さ15mmの試験片)、直径70mmの円盤、信頼性評価用半導体チップをそれぞれ175℃、70kg/cm 2 、成形時間2分の条件でトランスファー成形し、180℃で4時間硬化して、各種信頼性評価試験用成形物を得、耐熱信頼性、 Using this epoxy resin composition, the glass transition temperature for test pieces (diameter 4 mm, length 15mm of the test piece), a disc of diameter 70 mm, 175 ° C. The reliability evaluation semiconductor chip, respectively, 70 kg / cm 2, molding time and transfer molding under the conditions of 2 minutes, and cured for 4 hours at 180 ° C., to obtain a variety of reliability evaluation test moldings, heat resistance reliability,
耐熱衝撃性及び耐クラック性を以下の信頼性評価試験方法により評価した。 The thermal shock resistance and crack resistance were evaluated by the following reliability evaluation test method. 結果を表2に示す。 The results are shown in Table 2.

【0024】(信頼性評価試験方法) 耐熱信頼性試験片をTMA法(熱機械分析法)によって毎分5℃ずつ温度を上昇させることにより、ガラス転移温度を測定した。 [0024] By increasing the temperature per minute 5 ° C. by (reliability evaluation test method) heat resistance reliability test piece TMA method (thermal mechanical analysis method), the glass transition temperature was measured. 耐熱衝撃性各試料を恒温槽で180℃に加熱した後、インパクトテスターで熱時の破壊試験を行い、試料が破壊されまでの全吸収エネルギーにより評価した。 After heating the thermal shock resistance of each sample to 180 ° C. in a thermostat, performs destructive testing during heat impact tester, the sample was evaluated by the total absorption energy up destroyed. 耐クラック性各試料を121℃、100%RHの雰囲気中に100時間放置し、吸湿させた後、温度240℃の半田浴に30 Crack resistance Each sample 121 ° C., allowed to stand for 100 hours in an atmosphere of RH 100%, After moisture absorption, in a solder bath at a temperature 240 ° C. 30
秒間浸漬する試験を行い、発生したパッケージクラックの数により評価した。 Perform seconds immersion test was evaluated by the number of generated package cracks.

【0025】[実施例2]ヘンシェルミキサーにシリカ(平均粒径30μm)3kgとアミノ基含有シランカップリング剤(N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン,信越化学工業株式会社製,KB [0025] [Example 2] Henschel mixer to silica (average particle size 30 [mu] m) 3 kg and an amino group-containing silane coupling agent (N-beta (aminoethyl) .gamma.-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., KB
M603)15gを入れて15分間混合した後、120 M603) were mixed for 15 minutes to put 15 g, 120
℃で4時間熱処理した。 It was heat-treated for 4 hours at ℃. これを実施例1で用いたものと同様の四口フラスコに移し、溶媒としてトルエン1kg This was transferred to a similar four-necked flask as that used in Example 1, toluene 1kg as solvent
とメチルイソブチルケトン1kgを入れ、撹拌機で撹拌しながら112℃の温度で下記式で示す有機化合物YX And placed methyl isobutyl ketone 1 kg, the organic compound shown by the stirring 112 ° C. at a stirrer temperature by the following formula YX
4000H(油化シェルエポキシ社製)を22.4g添加し、更に同温度で3時間撹拌を継続した。 Was added 4000H (manufactured by Yuka Shell Epoxy Co.) 22.4 g, it was further continued for 3 hours at the same temperature. このようにして得られた反応物から溶媒を減圧下で留去した後、1 After distilling off the solvent under reduced pressure In this manner the reaction product obtained by, 1
20℃で4時間乾燥させ、表面処理シリカ3kgを得た。 Dried 4 hours at 20 ° C., to obtain a surface-treated silica 3 kg.

【0026】 [0026]

【化3】 [Formula 3]

【0027】このようにして得られた表面処理シリカと他の封止成分を表1に示す配合割合で実施例1と同様の方法により混合してエポキシ樹脂組成物を製造し、実施例1と同様の試験片を作製して同様の信頼性評価試験を行った。 [0027] The thus surface-treated silica and other sealing components obtained by mixing in the same manner as in Example 1 at a mixing ratio shown in Table 1 to produce an epoxy resin composition, as in Example 1 It was subjected to the same reliability evaluation test was prepared in the same manner as the test piece. 結果を表2に併記する。 The results are shown in Table 2.

【0028】[実施例3]ヘンシェルミキサーにシリカ(平均粒径30μm)3kgとエポキシ基含有シランカップリング剤(KBM403)15gを入れて15分間混合した後、下記式で示すジアミンBAPPHG(2, [0028] [Example 3] After mixing a Henschel mixer to silica (average particle size 30 [mu] m) 3 kg and an epoxy group-containing silane coupling agent (KBM403) Put 15 g 15 min, diamine BAPPHG (2 represented by the following formula,
2−ビス[4−(4−アミノフェノキシp−フェニル] 2- bis [4- (4-aminophenoxy p- phenyl]
プロパン)を26.2g入れ、更に15分間混合した。 Put 26.2g propane) and mixed further for 15 minutes.
このようにして得られたものを120℃で4時間乾燥させ、表面シリカ3kgを得た。 Thus those obtained by drying for 4 hours at 120 ° C., to obtain a surface silica 3 kg.

【0029】 [0029]

【化4】 [Of 4]

【0030】このようにして得られた表面処理シリカと他の封止成分を表1に示す配合割合で実施例1と同様にして混合し、実施例1と同様の試験片を作製して同様の信頼性評価試験を行った。 [0030] The thus to surface treated silica obtained by the other sealing components were mixed in the same manner as in Example 1 at a mixing ratio shown in Table 1, similarly to prepare a similar test piece of Example 1 It was carried out of the reliability evaluation test. 結果を表2に併記する。 The results are shown in Table 2.

【0031】[実施例4]実施例1で用いたものと同様の四口フラスコにシリカ(平均粒径30μm)3kgとキシレン2kgを入れ、撹拌機で撹拌しながら120℃ [0031] [Example 4] silica same four-necked flask as used in Example 1 (average particle size 30 [mu] m) placed 3kg and xylene 2 kg, stirring 120 ° C. with stirrer
の温度で滴下ロートにて下記式で示す酸無水物含有シランカップリング剤15gを20分間で滴下し、更に同温度で3時間撹拌した後、撹拌を継続しながら実施例3で用いたジアミンを18.9g添加し、更に150℃で6 After an acid anhydride-containing silane coupling agent 15g represented by the following formula at a dropping funnel at a temperature dropwise over 20 minutes and stirred for 3 hours at the same temperature, the diamine used in Example 3 with stirring continued 18.9g was added, 6 a further 0.99 ° C.
時間乾燥させ、表面処理シリカ3kgを得た。 Dried time, to obtain a surface-treated silica 3 kg.

【0032】 [0032]

【化5】 [Of 5]

【0033】このようにして得られた表面処理シリカと他の封止成分を表1に示す配合割合で実施例1と同様にして混合することによりエポキシ樹脂組成物を製造し、 [0033] to produce an epoxy resin composition by mixing the thus surface-treated silica obtained by the other sealing component in the same manner as in Example 1 at a mixing ratio shown in Table 1,
実施例1と同様の試験片を作製して同様の信頼性評価試験を行った。 It was subjected to the same reliability evaluation test was prepared in the same manner as the test piece of Example 1. 結果を表2に併記する。 The results are shown in Table 2.

【0034】[比較例1]無処理シリカと他の封止樹脂成分を表1に示す配合割合で実施例1と同様にして混合してエポキシ樹脂組成物を製造し、実施例1と同様の信頼性評価試験を行った。 [0034] Comparative Example 1] untreated silica and other sealing resin component to produce the epoxy resin composition was mixed in the same manner as in Example 1 at a mixing ratio shown in Table 1, as in Example 1 It was subjected to reliability evaluation test.

【0035】[比較例2]実施例1で用いたものと同様の四口フラスコにシリカ3kgとトルエン2kgを入れ、2時間共沸脱水した後、撹拌機で撹拌しながら11 [0035] [Comparative Example 2] Put silica 3kg and toluene 2kg similar four-necked flask as that used in Example 1, after 2 hours azeotropic dehydration with stirring at a stirrer 11
2℃の温度で滴下ロートにてエポキシ基含有シランカップリング剤(信越化学工業株式会社製,KBM403) 2 ℃ temperature in the epoxy group-containing silane coupling agent at a dropping funnel (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)
15gを20分間で滴下し、更に同温度で3時間撹拌した。 It was added dropwise 15g in 20 minutes, and stirred for 3 hours at the same temperature.

【0036】このようにして得られた表面処理シリカと他の封止成分を表1に示す配合割合で実施例1と同様にして混合してエポキシ樹脂組成物を製造し、実施例1と同様の試験片を作製して同様の信頼性評価試験を行った。 [0036] Thus the surface treated silica obtained by the other sealing components are mixed in the same manner as in Example 1 at a mixing ratio shown in Table 1 to produce an epoxy resin composition, similarly to Example 1 It was subjected to the same reliability evaluation tests to prepare a test piece. 結果を表2に併記する。 The results are shown in Table 2.

【0037】 [0037]

【表1】 [Table 1] *単位は全て重量部 * All units are parts by weight

【0038】 [0038]

【表2】 [Table 2]

【0039】 [0039]

【発明の効果】本発明によれば、複合材料の充填剤として好適な表面処理シリカを簡単に効率よく製造することができ、この表面処理シリカを樹脂組成物に配合した場合、低応力、耐湿信頼性、耐衝撃信頼性、耐熱信頼性に優れた硬化物を与える。 According to the present invention, if it is possible to manufacture easily and efficiently suitable surface treated silica as a filler of the composite material, the surface-treated silica was incorporated into the resin composition, low stress, moisture reliability, impact reliability, a cured product excellent in heat resistance reliability give. 従って、本発明のシリカは半導体封止用樹脂組成物の充填剤として有用である。 Therefore, the silica of the present invention are useful as fillers in the resin composition for semiconductor encapsulation.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 青木 貴之 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−ン電子材料 技術研究所内 (72)発明者 井野 茂樹 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−ン電子材料 技術研究所内 (72)発明者 若尾 幸 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−ン電子材料 技術研究所内 ────────────────────────────────────────────────── ─── of the front page continued (72) inventor Takayuki Aoki Gunma Prefecture Usui District Matsuida Oaza people viewed the first address 10 Shin-Etsu Chemical Co., Ltd. silicon - down electronic materials technology in the Laboratory (72) inventor Shigeki Ino Gunma Prefecture Usui District Matsuida Oaza people viewed the first address 10 Shin-Etsu Chemical Co., Ltd. silicon - down electronic materials technology in the Laboratory (72) inventor Miyuki Wakao Gunma Prefecture Usui District Matsuida Oaza people viewed the first address 10 Shin-Etsu Chemical Co., Ltd. silicon - down electronic materials in the Institute of technology

Claims (3)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 官能基を1個以上有するシランカップリング剤でシリカ粒子の表面を被覆し、更に上記官能基と反応可能な官能基を1個以上有する有機化合物で被覆してなることを特徴とする表面処理シリカ。 1. A wherein the functional groups covering the surface of the silica particles with one or more with silane coupling agent, formed by further coated with an organic compound having functional groups capable of reacting one or more of the above functional groups and surface treated silica.
  2. 【請求項2】 官能基を1個以上有するシランカップリング剤とシリカを混合撹拌してシリカ粒子の表面を上記シランカップリング剤で被覆し、該シランカップリング剤で被覆されたシリカ粒子を上記官能基と反応可能な官能基を1個以上有する有機化合物と混合撹拌して更に上記有機化合物で上記シリカ粒子を被覆することを特徴とする表面処理シリカの製造方法。 2. A functional group were mixed and stirred one or more with silane coupling agent and silica surface of the silica particles coated with the silane coupling agent, the silica particles coated with the silane coupling agent a method for producing a surface-treated silica comprising coating the silica particles with further the organic compound was mixed and stirred with an organic compound having a functional group capable of reacting with the functional groups 1 or more.
  3. 【請求項3】 請求項1記載の表面処理シリカからなる半導体封止用樹脂組成物用充填剤。 3. A process according to claim 1 resin composition for semiconductor encapsulation filler consisting of surface-treated silica described.
JP27385092A 1992-09-17 1992-09-17 Surface treated silica and its manufacturing method and a semiconductor sealing resin composition for fillers Expired - Fee Related JP2671727B2 (en)

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JPH06157551A (en) * 1992-11-27 1994-06-03 Shin Etsu Chem Co Ltd Silicone-modified acid anhydride and its production
EP0679700A2 (en) * 1994-04-28 1995-11-02 Toyo Ink Manufacturing Co., Ltd. Aqueous coating composition
WO1999055789A1 (en) * 1998-04-24 1999-11-04 Catalysts & Chemicals Industries Co., Ltd. Coating liquid for forming silica-based film having low dielectric constant and substrate having film of low dielectric constant coated thereon
JP2002114891A (en) * 2000-10-05 2002-04-16 Sumitomo Bakelite Co Ltd Epoxy resin composition, prepreg using the same and copper-clad laminate
JP2006290712A (en) * 2005-04-15 2006-10-26 Tayca Corp Hydrophobic positive charged silica fine powder, manufacturing method of the same and toner for electrostatic latent image development in which the same is added as external additive
WO2007074824A1 (en) * 2005-12-28 2007-07-05 Nissan Motor Co., Ltd. Metal oxide derivative, resin composition, and process for production of resin composition
JP2007176752A (en) * 2005-12-28 2007-07-12 Nissan Motor Co Ltd Production method of particulate metal oxide derivative
JP2008518067A (en) * 2004-10-25 2008-05-29 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッドCiba Specialty Chemicals Holding Inc. Functionalized nanoparticles
JP2008521958A (en) * 2004-11-25 2008-06-26 サントル・ナシヨナル・ド・ラ・ルシエルシユ・シヤンテイフイク A method of dispersing functional molecules on the carrier surface, the carrier produced by this method
WO2009028503A1 (en) * 2007-08-27 2009-03-05 Nof Corporation Thermoplastic resin composition
US7645828B2 (en) 2005-04-01 2010-01-12 Kawamura Institute Of Chemical Research Monodisperse silica spheres containing polyamine and process for producing the same
US8879275B2 (en) 2012-02-21 2014-11-04 International Business Machines Corporation Anti-corrosion conformal coating comprising modified porous silica fillers for metal conductors electrically connecting an electronic component

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157551A (en) * 1992-11-27 1994-06-03 Shin Etsu Chem Co Ltd Silicone-modified acid anhydride and its production
EP0679700A2 (en) * 1994-04-28 1995-11-02 Toyo Ink Manufacturing Co., Ltd. Aqueous coating composition
EP0679700A3 (en) * 1994-04-28 1996-02-21 Toyo Ink Mfg Co Aqueous coating composition.
WO1999055789A1 (en) * 1998-04-24 1999-11-04 Catalysts & Chemicals Industries Co., Ltd. Coating liquid for forming silica-based film having low dielectric constant and substrate having film of low dielectric constant coated thereon
JP2002114891A (en) * 2000-10-05 2002-04-16 Sumitomo Bakelite Co Ltd Epoxy resin composition, prepreg using the same and copper-clad laminate
JP4529268B2 (en) * 2000-10-05 2010-08-25 住友ベークライト株式会社 Epoxy resin composition, prepreg and copper-clad laminate using the same
JP2008518067A (en) * 2004-10-25 2008-05-29 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッドCiba Specialty Chemicals Holding Inc. Functionalized nanoparticles
US8877954B2 (en) 2004-10-25 2014-11-04 Basf Se Functionalized nanoparticles
JP2008521958A (en) * 2004-11-25 2008-06-26 サントル・ナシヨナル・ド・ラ・ルシエルシユ・シヤンテイフイク A method of dispersing functional molecules on the carrier surface, the carrier produced by this method
US7645828B2 (en) 2005-04-01 2010-01-12 Kawamura Institute Of Chemical Research Monodisperse silica spheres containing polyamine and process for producing the same
JP2006290712A (en) * 2005-04-15 2006-10-26 Tayca Corp Hydrophobic positive charged silica fine powder, manufacturing method of the same and toner for electrostatic latent image development in which the same is added as external additive
JP4743845B2 (en) * 2005-04-15 2011-08-10 テイカ株式会社 Hydrophobic positively chargeable silica fine powder, its preparation and an electrostatic latent image developing toner prepared by adding it as an external additive
WO2007074824A1 (en) * 2005-12-28 2007-07-05 Nissan Motor Co., Ltd. Metal oxide derivative, resin composition, and process for production of resin composition
JP2007176752A (en) * 2005-12-28 2007-07-12 Nissan Motor Co Ltd Production method of particulate metal oxide derivative
JP2007177137A (en) * 2005-12-28 2007-07-12 Mitsubishi Chemicals Corp Metal oxide derivative, resin composition and manufacturing method of resin composition
US8575268B2 (en) 2007-08-27 2013-11-05 Nof Corporation Thermoplastic resin composition
WO2009028503A1 (en) * 2007-08-27 2009-03-05 Nof Corporation Thermoplastic resin composition
US8879275B2 (en) 2012-02-21 2014-11-04 International Business Machines Corporation Anti-corrosion conformal coating comprising modified porous silica fillers for metal conductors electrically connecting an electronic component

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