JP2005170771A - Finely basic silica powder, method for producing the same, and resin composition - Google Patents
Finely basic silica powder, method for producing the same, and resin composition Download PDFInfo
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本発明は、輸送、分級等の粉体操作が容易で、樹脂に混合された際に、凝集を抑制し、均一に分散され、粘度上昇が防止されるシリカ粉体及びその製造方法に関する。また、本発明は該シリカ粉体と有機樹脂からなり、耐吸湿性、耐はんだクラック性に優れ、低膨張性の樹脂組成物に関する。 The present invention relates to a silica powder that can be easily handled by powders such as transportation and classification, suppresses aggregation and is uniformly dispersed when mixed with a resin, and a method for producing the same. The present invention also relates to a resin composition comprising the silica powder and an organic resin, excellent in moisture absorption resistance and solder crack resistance, and having low expansion.
半導体装置などの電子部品の封止方法として、セラミックスや、熱硬化性樹脂を用いる方法が、従来より行われている。なかでも、エポキシ樹脂系封止材による封止が、経済性及び性能のバランスより好ましく広く行われている。 As a method for sealing electronic components such as semiconductor devices, a method using ceramics or a thermosetting resin has been conventionally performed. Among these, sealing with an epoxy resin-based sealing material is preferably performed more widely than the balance between economy and performance.
近年の半導体装置の高機能化、高集積化等に伴い、従来の主流であったボンディングワイヤーを用いる方法に変わって、バンプ（突起電極）により半導体素子と基板を電気的に接続する方法、いわゆるフリップチップを用いた表面実装が増加している。このフリップチップ実装方式の半導体装置では、ヒートサイクル試験でバンプの接合部等にクラック等の欠陥が発生する場合がある。その為これを防止するために、半導体素子と基板の隙間及びバンプの周囲等を液状のエポキシ樹脂系封止材で充填し硬化することにより改良する方法（アンダーフィル）が行われている。 A method of electrically connecting a semiconductor element and a substrate by bumps (projection electrodes) instead of a conventional method using a bonding wire in accordance with recent high performance and high integration of a semiconductor device, so-called Surface mounting using flip chips is increasing. In this flip chip mounting type semiconductor device, a defect such as a crack may occur in a joint portion of a bump or the like in a heat cycle test. Therefore, in order to prevent this, a method (underfill) has been performed in which the gap between the semiconductor element and the substrate, the periphery of the bump, and the like are filled with a liquid epoxy resin sealing material and cured.
フリップチップ実装方式等の半導体装置を封止する封止材は、耐湿信頼性、耐電気腐食性、耐ヒートサイクル性等の特性が要求されるが、その為に、封止材中にシリカ等の無機充填材を配合することにより吸湿率を低下させるとともに熱膨張率を低下させることにより耐湿信頼性や耐ヒートサイクル性を向上させる方法が行われている。 A sealing material for sealing a semiconductor device such as a flip chip mounting method requires characteristics such as moisture resistance reliability, electric corrosion resistance, and heat cycle resistance. For this purpose, silica or the like is included in the sealing material. A method of improving moisture resistance reliability and heat cycle resistance by reducing the moisture absorption rate by blending the inorganic filler and reducing the coefficient of thermal expansion has been performed.
シリカ等の無機充填材の配合量を増加させる程、封止材の吸湿率の低下と熱膨張係数の低下が可能となり、耐湿信頼性や耐ヒートサイクル性を向上できるが、一方無機充填材の配合量を増加させる程、封止材の粘度が増加し、流動性が著しく低下する傾向があり問題となる。特に、フリップチップ実装においては、数十μｍ程度の半導体素子と基板の隙間に封止材を充填する必要があるため、封止材には高い浸入充填性が要求される。よって、このような封止材には、無機充填材の充填率を高くしてもなるべく粘度が高くならずに、高い侵入充填性を得る為に、無機充填材として球状で比表面積の小さい無機粒子が要求されている。 Increasing the blending amount of inorganic fillers such as silica can reduce the moisture absorption rate and thermal expansion coefficient of the sealing material, and improve moisture resistance reliability and heat cycle resistance. As the blending amount is increased, the viscosity of the sealing material increases and the fluidity tends to be remarkably lowered, which is a problem. In particular, in flip-chip mounting, since it is necessary to fill a sealing material in a gap between a semiconductor element of about several tens of μm and a substrate, the sealing material is required to have a high penetration filling property. Therefore, in order to obtain a high intrusion filling property without increasing the viscosity as much as possible even if the filling rate of the inorganic filler is increased, such a sealing material is an inorganic material having a spherical shape and a small specific surface area. Particles are required.
係る観点から、下記特許文献１には、シリカ粒子を火炎中で溶融する方法が開示されている。下記特許文献２には、酸素を含む雰囲気内においてバーナにより化学炎を形成し、この化学炎中に金属粉末を粉塵雲を形成しうる量投入して燃焼させて、酸化物超微粒子を合成する製造方法の開示がある。また、下記特許文献３には、酸化物を構成する金属粉末をキャリアガスとともに反応容器内へ供給する第１工程と、該反応容器内で発火させて火炎を形成し、該金属粉末を燃焼させ酸化物の粉末を合成する第２工程とからなる酸化物粉末の製造方法において、第１工程は、小粒径の金属酸化物と上記金属粉末との混合物を供給し、第２工程は、上記金属酸化物を核として上記金属粉末の燃焼により合成される酸化物により粒成長させることを特徴とする酸化物粉末の製造方法の開示がある。 From this point of view, Patent Document 1 below discloses a method of melting silica particles in a flame. In Patent Document 2 below, a chemical flame is formed by a burner in an atmosphere containing oxygen, and an amount of metal powder that can form a dust cloud is introduced into the chemical flame and burned to synthesize ultrafine oxide particles. There is a disclosure of a manufacturing method. Patent Document 3 listed below includes a first step of supplying a metal powder constituting an oxide into a reaction vessel together with a carrier gas, and igniting in the reaction vessel to form a flame and combusting the metal powder. In the method for producing an oxide powder comprising the second step of synthesizing the oxide powder, the first step supplies a mixture of the metal oxide having a small particle size and the metal powder, and the second step includes the above step. There is a disclosure of a method for producing an oxide powder, characterized in that a metal oxide is used as a nucleus to cause grain growth with an oxide synthesized by combustion of the metal powder.
一方、シリカ粒子を表面処理して封止材用充填材に使用する試みがなされており、例えば、下記特許文献４や下記特許文献５には、無機質充填剤粒子表面をシランカップリング剤（アルコキシ基を２個以上含むものが好適）で表面処理し、成形性に優れた半導体封止用エポキシ樹脂組成物を製造することが開示されている。 On the other hand, attempts have been made to surface-treat silica particles and use them as fillers for sealing materials. For example, in Patent Document 4 and Patent Document 5 below, the surface of inorganic filler particles is treated with a silane coupling agent (alkoxy). It is disclosed that an epoxy resin composition for semiconductor encapsulation having excellent moldability is produced by surface treatment with a compound containing two or more groups.
しかしながら、上記の技術では、樹脂中で無機質充填剤粒子が凝集しやすく、不均一で、粘度が高く、その結果、流動性が低く、更なる成形性向上を図ることができないという問題があった。 However, the above technique has a problem that the inorganic filler particles easily aggregate in the resin, are non-uniform, have a high viscosity, and as a result, have low fluidity and cannot be further improved in moldability. .
無機粒子含有樹脂複合材料において、無機粒子とマトリックスポリマーとの間を強固な結合で結ぶことは重要である。粒子の表面を改質してマトリックスと結合を強くする方法として、シランカップリング剤で処理するのは一般的である。しかし、金属を燃焼して得られる金属酸化物粉体であるアドマファイン（商標名）のような微粒子の場合は処理によって凝集が起こりやすく、樹脂中に分散しにくくなり、コンパンドの成形時の粘度が高くなる問題点がある。例えば、エポキシシラン処理シリカをエポキシ樹脂に配合する場合は粘度が非常に高くなることがその典型である。 In the inorganic particle-containing resin composite material, it is important to connect the inorganic particles and the matrix polymer with a strong bond. Treatment with a silane coupling agent is a common method for modifying the particle surface to strengthen the bond with the matrix. However, in the case of fine particles such as Admafine (trade name), which is a metal oxide powder obtained by burning metal, it is easy to agglomerate by processing, it is difficult to disperse in the resin, and the viscosity at the time of molding the compound There is a problem that becomes high. For example, when epoxy silane-treated silica is blended with an epoxy resin, the viscosity is typically very high.
このように、コンパンドの粘度を下げ、流動性を上げることは、無機フィラーを大量に配合しなければならない半導体ＥＭＣ（Ｅｐｏｘｉ Ｍｏｌｄｉｎｇ ｃｏｍｐａｕｎｄ）射止剤等のアプリケーションにおいて特に重要である。 Thus, reducing the viscosity of the compound and increasing the fluidity are particularly important in applications such as semiconductor EMC (Epoxy Molding compound) shot-stopping agent in which a large amount of inorganic filler must be blended.
上記従来技術の問題点に鑑み、本発明は、輸送、分級等の粉体操作が容易で、樹脂に混合された際に、凝集を抑制し、均一に分散され、粘度上昇が防止されるシリカ粉体及びその製造方法を提供することを目的とする。又、本発明は、耐吸湿性、耐はんだクラック性に優れ、低膨張性の樹脂組成物を提供することを目的とする。 In view of the above-mentioned problems of the prior art, the present invention is a silica that can be easily handled in powders such as transportation and classification, suppresses agglomeration and is uniformly dispersed, and prevents an increase in viscosity when mixed with a resin. An object is to provide a powder and a method for producing the same. Another object of the present invention is to provide a resin composition having excellent moisture absorption resistance and solder crack resistance and low expansion.
上記課題を解決するため、第１に本発明は、シリカ粉体の表面が塩基性物質又は塩基性混合物で処理された微塩基性シリカ粉体の発明であって、該シリカ粉体又は微塩基性シリカ粉体は所定値以上の粒径の粗粒がカットされていることを特徴とする。この塩基性シリカ粉体は、適当な親水性を有し、優れた流動性、分散性を有する。この塩基性シリカ粉体をエポキシ樹脂組成物等に配合した場合、組成物の粘度が低く、硬化後の物性も優れている。 In order to solve the above problems, first, the present invention is an invention of a finely basic silica powder in which the surface of the silica powder is treated with a basic substance or a basic mixture, the silica powder or the fine base The silica powder is characterized in that coarse particles having a particle size of a predetermined value or more are cut. This basic silica powder has appropriate hydrophilicity and excellent fluidity and dispersibility. When this basic silica powder is blended in an epoxy resin composition or the like, the viscosity of the composition is low and the physical properties after curing are also excellent.
このように、シリカ粉体を少量の塩基性物質又は塩基性混合物で処理するとともに、粗粒カットを行うことによって、粉体自身の流動性が飛躍的に向上され、輸送、分級等の操作が容易になる。しかも、製造装置への付着が極めて少なく、連続生産が可能になった。本発明の塩基性シリカ粉体は微塩基性であるため、例えば、エポキシ樹脂中に配合されるシランカップリング剤を効率良く吸着、固着し、低粘度、高流動性の樹脂コンパウンドが得られる。又、シランカップリング剤を固着することによって、フィラー表面と樹脂の密着性が良く、耐はんだリフロー性、低吸湿性等の優れた物性が得られる。 In this way, the silica powder is treated with a small amount of a basic substance or a basic mixture, and by performing coarse grain cutting, the fluidity of the powder itself is dramatically improved, and operations such as transportation and classification can be performed. It becomes easy. In addition, there is very little adhesion to manufacturing equipment, and continuous production has become possible. Since the basic silica powder of the present invention is slightly basic, for example, a silane coupling agent blended in an epoxy resin can be efficiently adsorbed and fixed to obtain a low viscosity, high fluidity resin compound. Further, by adhering the silane coupling agent, the adhesion between the filler surface and the resin is good, and excellent physical properties such as solder reflow resistance and low moisture absorption are obtained.
本発明において、塩基性物質又は塩基性混合物としては、１atmの時の沸点が１５０℃以下であるものがガス状で処理できるので好ましい。但し、沸点が１５０℃を越えるものでもシリカ粉体との混合処理を行うことが出来る。 In the present invention, as the basic substance or the basic mixture, those having a boiling point of 150 ° C. or less at 1 atm are preferable because they can be treated in a gaseous state. However, even those having a boiling point exceeding 150 ° C. can be mixed with the silica powder.
塩基性物質又は塩基性混合物としては、アンモニア、有機アミン、シラザン類、窒素を含む環状化合物又はその溶液、アミン系シランカップリング剤又はその溶液等が挙げられる。これら塩基性物質の中で、シラザン類が好ましく例示され、特に、へキサメチルジシラザン（ＨＭＤＳ）が好ましい。 Examples of the basic substance or basic mixture include ammonia, organic amines, silazanes, nitrogen-containing cyclic compounds or solutions thereof, amine-based silane coupling agents or solutions thereof, and the like. Of these basic substances, silazanes are preferably exemplified, and hexamethyldisilazane (HMDS) is particularly preferred.
シリカ粉体をシラザン類で処理した場合において、処理されたシリカ粉体の抽出水のＰＨ値が、用いられる純水のＰＨと比べて少なくとも０．１以上高いことが好ましい。これにより、シリカ粉体が適量に塩基性化されたことが確認できる。ここで、粉体抽出水のＰＨ測定方法は次の通りである。粉体を３．５ｇ秤量しプラスチック製容器に入れる。７０ｍｌの脱イオン水を入れて、振動機で３０分間振動させる。遠心分離機で固液分離させて、上澄みの水のＰＨを測定する。 In the case where the silica powder is treated with silazanes, the pH value of the extracted silica powder extracted from the treated silica powder is preferably at least 0.1 higher than the pH of the pure water used. This confirms that the silica powder has been basified to an appropriate amount. Here, the pH measurement method of the powder extracted water is as follows. Weigh 3.5 g of powder and place in a plastic container. Add 70 ml of deionized water and vibrate with a vibrator for 30 minutes. The pH of the supernatant water is measured after solid-liquid separation with a centrifuge.
本発明において、シリカ粉体の製造方法は限定されない。例えば、金属シリコンを燃焼して得られるシリカ粉体、シリカ破砕物を溶融して得られる溶融シリカ粉体、シリカ破砕物等が例示される。 In the present invention, the method for producing the silica powder is not limited. Examples thereof include silica powder obtained by burning metal silicon, fused silica powder obtained by melting silica crushed material, silica crushed material, and the like.
金属シリコンを燃焼して得られる球状シリカ粉体とは、シリコン金属粉末、シリコンとアルミニウム、マグネシウム、ジルコニウム、チタン等の合金粉末、その他ムライト組成に調合したアルミニウム粉末とシリコン粉末、スピネル組成に調合したマグネシウム粉末とアルミニウム粉末、コージェライト組成に調合したアルミニウム粉末、マグネシウム粉末、シリコン粉末等の金属粉末混合物を、キャリアガスとともに酸素を含む雰囲気中で化学炎を形成し、この化学炎中に目的とするシリカ（ＳｉＯ２）を主成分とする金属酸化物の超微粒子を得るものである。本発明では、金属シリコンを燃焼して得るシリカを主成分とする金属酸化物粉体が好ましい。また、前記金属を燃焼してうるシリカ粉体は、平均粒子径が０．０１μｍ以上の真球状粒子であるものが好ましく、平均粒子径が０．０１μｍから２０μｍの真球状粒子であるものがより好ましく、平均粒子径が０．２μｍから２０μｍの真球状粒子であるものがより好ましい。 Spherical silica powder obtained by burning metallic silicon is silicon metal powder, silicon and aluminum, magnesium, zirconium, titanium and other alloy powders, and other aluminum powder and silicon powder prepared in mullite composition, and spinel composition. Metal powder mixture of magnesium powder and aluminum powder, aluminum powder prepared in cordierite composition, magnesium powder, silicon powder, etc., forms a chemical flame in an atmosphere containing oxygen together with a carrier gas, and this chemical flame is aimed at Metal oxide ultrafine particles mainly composed of silica (SiO 2 ) are obtained. In the present invention, a metal oxide powder mainly composed of silica obtained by burning metal silicon is preferable. The silica powder obtained by burning the metal is preferably a true spherical particle having an average particle diameter of 0.01 μm or more, more preferably a true spherical particle having an average particle diameter of 0.01 μm to 20 μm. Preferably, the particles are true spherical particles having an average particle size of 0.2 μm to 20 μm.
又、溶融シリコンは、シリカ粒子等を火炎中で溶融する方法で製造され、その製造方法は、例えば上記特許文献１等に開示されている。 Moreover, the molten silicon is manufactured by a method of melting silica particles or the like in a flame, and the manufacturing method is disclosed in, for example, Patent Document 1 described above.
本発明で言うシラザン類は分子中にＳｉ−Ｎ結合を有する珪素化合物で、オルガノシラザンと称することもあり、例えば、ヘキサメチルジシラザン、ヘキサフェニルジシラザン、ジメチルアミノトリメチルシラン、トリシラザン、シクロトリシラザン、１，１，３，３，５，５−ヘキサメテルシクロトリシラザン、などのシラサン類から選択される化合物又はその組み合わせである。この中で、ヘキサメチルジシラザン（ＨＭＤＳ）がシリカの凝集を抑制し、酸性であるシリカを塩基性に傾け、有機物に対する親和性を向上させ、シランカップリング剤などの付着の均一性を向上させて、エポキシ樹脂に対する安定性を向上させるなどの点で好ましい。 Silazanes referred to in the present invention are silicon compounds having a Si—N bond in the molecule, and are sometimes referred to as organosilazanes. For example, hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane. , 1,1,3,3,5,5-hexametacyclotrisilazane, etc. or a combination thereof. Among them, hexamethyldisilazane (HMDS) suppresses the aggregation of silica, tilts acidic silica to basic, improves affinity for organic substances, and improves the uniformity of adhesion of silane coupling agents and the like. In view of improving the stability to the epoxy resin, it is preferable.
塩基性物質であるアミン系シランカップリング剤は下記一般式
（Ｒ１）ｎ（Ｒ２）ｍ（Ｒ３）ｌＳｉ
で表すもので、ｎ＋ｍ＋ｌは４である。Ｒ１は一級、二級及び三級アミンの置換基でＳｉ原子とＣ−Ｓｉ結合で結合されている。Ｒ２は炭化水素基でＳｉ原子とＣ−Ｓｉ結合で結合されている。Ｒ３は加水分解可能な置換基で、Ｓｉ原子とＳｉ−ＯＲ（Ｒは炭化水素基）、Ｓｉ−ＯＣＯＲ（Ｒは炭化水素基）、Ｓｉ−ＮＨＣＯＲ（Ｒは炭化水素基）、Ｓｉ−ＮＲ１Ｒ２（Ｒ１、Ｒ２は炭化水素基又は水素）などの結合で結合されている。具体的にはＮ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、などがあげられる。
The amine-based silane coupling agent, which is a basic substance, has the following general formula (R 1 ) n (R 2 ) m (R 3 ) l Si
N + m + 1 is 4. R 1 is a primary, secondary and tertiary amine substituent and is bonded to the Si atom by a C—Si bond. R 2 is a hydrocarbon group and is bonded to the Si atom by a C—Si bond. R 3 is a hydrolyzable substituent, Si atom and Si-OR (R is a hydrocarbon group), Si-OCOR (R is a hydrocarbon group), Si-NHCOR (R is a hydrocarbon group), Si-NR 1 R 2 (R 1 and R 2 are hydrocarbon groups or hydrogen) and the like. Specific examples include N-phenyl-γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.
塩基性物質又は塩基性混合物のシリカ粉体に対する処理量は粉体表面積１ｍ２当り０．０５から５μモル、好ましくは０．０５から１μモルがよい。０．０５μモル未満の場合は、処理効果が不十分で、５μモルを超える場合は粉体表面が疎水性となりハンドリング性が逆に悪くなる。又、表面が疎水性であるため、エポキシ樹脂などに対する密着性も悪くなる。更に粉体表面の水酸基がなくなるため、更なるシランカップリング剤などの処理が不可能となる。シリカ、アルミナの場合はＩＲスペクトル上３７４０ｃｍ−１付近の水酸基の吸収ピークが完全に消失しない程度の処理は最も望ましい。 The processing amount of the basic substance or basic mixture with respect to the silica powder is 0.05 to 5 μmol, preferably 0.05 to 1 μmol per 1 m 2 of the powder surface area. When the amount is less than 0.05 μmol, the treatment effect is insufficient. When the amount exceeds 5 μmol, the powder surface becomes hydrophobic and handling properties are adversely affected. Further, since the surface is hydrophobic, adhesion to an epoxy resin or the like is also deteriorated. Furthermore, since there are no hydroxyl groups on the powder surface, further treatment with a silane coupling agent or the like becomes impossible. In the case of silica and alumina, the treatment is most desirable so that the absorption peak of the hydroxyl group in the vicinity of 3740 cm −1 in the IR spectrum is not completely lost.
本発明の微塩基性シリカ粉体は、エポキシシラン、アミノシラン、アクリルシラン、チオールシラン等のシランカップリング剤で処理することが好ましい。 The slightly basic silica powder of the present invention is preferably treated with a silane coupling agent such as epoxy silane, amino silane, acrylic silane, or thiol silane.
本発明で言うシランカップリング剤とは、アミノ基、グリシジル基、メルカプト基、ウレイド基、ヒドロシ基、アルコキシ基、メルカプト基から選択される活性基を有する化合物またはその組み合わせである。具体的には、シランカップリング剤として、γ−グリシドキシプロピルトリエトキシシラン、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等のエポキシシラン、アミノプロピルトリエトキシシラン、ウレイドプロピルトリエトキシシラン、Ｎ−フェニルアミノプロピルトリメトキシシラン等のアミノシラン、フェニルトリメトキシシラン、メチルトリメトキシシラン、オクタデシルトリメトキシシラン等の疎水性シラン化合物やメルカプトシラン等が例示される。 The silane coupling agent referred to in the present invention is a compound having an active group selected from an amino group, a glycidyl group, a mercapto group, a ureido group, a hydroxyl group, an alkoxy group, and a mercapto group, or a combination thereof. Specifically, epoxy silanes such as γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxy as silane coupling agents. Examples thereof include aminosilanes such as silane and N-phenylaminopropyltrimethoxysilane, hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, and octadecyltrimethoxysilane, mercaptosilane, and the like.
本発明においては、粗粒カットはシリカ粉体自体に行ってもよく、又は塩基性物質で処理された塩基性シリカ粉体を粗粒カットしてもよい。 In the present invention, the coarse particle cutting may be performed on the silica powder itself, or the basic silica powder treated with a basic substance may be coarsely cut.
又、シリカ粉体の最大粒子径以上の粒径を持つ金属粒子等の導電性粒子が除去されていることが好ましい。 Further, it is preferable that conductive particles such as metal particles having a particle size larger than the maximum particle size of the silica powder are removed.
本発明においては、粗粒カットされたシリカ粉体又は微塩基性シリカ粉体は、単一の粒径分布を有するものであっても良く、または異なる粒径分布を有する複数の粉体の混合物であっても良い。 In the present invention, the coarsely cut silica powder or the slightly basic silica powder may have a single particle size distribution, or a mixture of a plurality of powders having different particle size distributions. It may be.
フィラーを樹脂に高充填させるために、粒径の異なるものを適当に配合することが有効である。具体的には大きいフィラーが最密充填した時の隙間に小さいフィラーを順次充填していく考え方が一般的で、例えばＨｏｒｓｉｅｌｄモデルがその一例である。又、実際の粉体を最密充填なるように配合するための計算法も知られている。しかし、未処理の粉体、或いは従来知られている方法で処理された粉体に対して、上記最密充填しても未だ十分な低粘度が達成できない。本発明の方法で処理したシリカ粉体は、塩基性物質を併用することによって、従来のカップリング剤処理よりはるかに処理が均一で、樹脂に対する親和性も格段に高い。従って、本発明のフィラーを樹脂に配合すると、粘度が非常に低くなり、上記最密充填の方法で異なる粒径の粉体を最密充填になるように配合すると従来のフィラー技術では達成できない低粘度樹脂組成物が得られる。 In order to fill the resin with a high amount of filler, it is effective to appropriately mix those having different particle diameters. Specifically, a general idea is that small fillers are sequentially filled in gaps when large fillers are closely packed, for example, the Horsield model. In addition, a calculation method for blending actual powder so as to be closely packed is also known. However, it is still impossible to achieve a sufficiently low viscosity even with the closest packing of untreated powder or powder treated by a conventionally known method. The silica powder treated by the method of the present invention is treated more uniformly than the conventional coupling agent treatment by using a basic substance in combination, and the affinity for the resin is remarkably high. Therefore, when the filler of the present invention is blended with a resin, the viscosity becomes very low, and when the powders of different particle sizes are blended so as to be close packed by the above close packing method, low viscosity cannot be achieved by the conventional filler technology. A viscous resin composition is obtained.
本発明における平均粒径と粗粒カットの具体例は以下のようなものである。
（１）平均粒径０．０１μから３０μ、最大粒径７５μの粒径分布を有する球状シリカ粒子の少なくとも一種類以上のシリカ粒子非混合粉又は混合粉。
（２）平均粒径０．０１μから２０μ、最大粒径４５μの粒径分布を有する球状シリカ粒子の少なくとも一種類以上のシリカ粒子非混合粉又は混合粉。
（３）平均粒径０．０１μから１０μ、最大粒径２０μの粒径分布を有する球状シリカ粒子の少なくとも一種類以上のシリカ粒子非混合粉又は混合粉。
（４）平均粒径０．０１μから５μ、最大粒径１０μの粒径分布を有する球状シリカ粒子の少なくとも一種類以上のシリカ粒子非混合粉又は混合粉。
（５）平均粒径０．０１μから３μ、最大粒径５μの粒径分布を有する球状シリカ粒子の少なくとも一種類以上のシリカ粒子非混合粉又は混合粉。
（６）平均粒径０．０１μから１．５μ、最大粒径３μの粒径分布を有する球状シリカ粒子の少なくとも一種類以上のシリカ粒子非混合粉又は混合粉。
上記のように、粗粒カットされていることが、諸物性を発揮させる上で好ましい。
Specific examples of the average particle diameter and coarse grain cut in the present invention are as follows.
(1) At least one kind of silica particle non-mixed powder or mixed powder of spherical silica particles having a particle size distribution with an average particle size of 0.01 to 30 μ and a maximum particle size of 75 μ.
(2) At least one kind of silica particle non-mixed powder or mixed powder of spherical silica particles having a particle size distribution with an average particle size of 0.01 μm to 20 μm and a maximum particle size of 45 μm.
(3) At least one kind of silica particle non-mixed powder or mixed powder of spherical silica particles having a particle size distribution with an average particle size of 0.01 to 10 μm and a maximum particle size of 20 μm.
(4) At least one kind of silica particle non-mixed powder or mixed powder of spherical silica particles having a particle size distribution with an average particle size of 0.01 to 5 μm and a maximum particle size of 10 μm.
(5) At least one kind of silica particle non-mixed powder or mixed powder of spherical silica particles having a particle size distribution with an average particle size of 0.01 to 3 μ and a maximum particle size of 5 μ.
(6) At least one kind of spherical silica particles having a particle size distribution with an average particle size of 0.01 μm to 1.5 μm and a maximum particle size of 3 μm, or non-mixed powder or mixed powder.
As described above, it is preferable that coarse grains are cut in order to exhibit various physical properties.
第２に、本発明は、シリカ粉体の表面を塩基性物質又は塩基性混合物で処理する微塩基性シリカ粉体の製造方法であって、該シリカ粉体又は微塩基性シリカ粉体は所定値以上の粒径の粗粒をカットする工程を含むことを特徴とする。 Second, the present invention relates to a method for producing a fine basic silica powder in which the surface of the silica powder is treated with a basic substance or a basic mixture, wherein the silica powder or the fine basic silica powder is a predetermined one. Including a step of cutting coarse particles having a particle size equal to or greater than the value.
塩基性物質又は塩基性混合物でシリカ粉体を処理することにより、シリカ表面を酸性から塩基性に変換し、ＨＭＤＳ等のシラザン類以外のシランカップリング剤の吸着、固着を促進する。また、シリカのエポキシ樹脂等の有機樹脂に対する活性を抑制しエポキシ樹脂等との反応による粘性増加を抑制する。これにより、エポキシ樹脂等の充填時に低粘度かつ高流動性を実現することが可能となる。特に、シリカ粉体をＨＭＤＳで処理した場合は、処理作業が容易である上に、シリカが微塩基性になると同時に、シリカ表面の一部がトリメチル化されるため、粉体の凝集がなくなり、樹脂への濡れ性も向上され、好適である。又、粗粒カットすることで、有機樹脂等の諸物性を発揮させる上で好ましい。 By treating the silica powder with a basic substance or a basic mixture, the silica surface is converted from acidic to basic, and adsorption and fixation of silane coupling agents other than silazanes such as HMDS are promoted. Moreover, the activity with respect to organic resins, such as an epoxy resin of a silica, is suppressed and the viscosity increase by reaction with an epoxy resin etc. is suppressed. This makes it possible to achieve low viscosity and high fluidity when filled with epoxy resin or the like. In particular, when the silica powder is treated with HMDS, the processing operation is easy and the silica becomes slightly basic, and at the same time, a part of the silica surface is trimethylated, so that the aggregation of the powder is eliminated. The wettability to the resin is also improved, which is preferable. In addition, it is preferable to exhibit various physical properties such as organic resin by cutting coarse particles.
塩基性物質又は塩基性混合物の処理に関して、シリカ粉体を予め処理してもよいが、樹脂などと混合してコンパウンドを造る工程中で行うこともできる。例えば、シリカ粉体をヘンシェルミキサーに投入して、塩基性物質又は塩基性混合物と混合して処理した後に直ちに樹脂、添加剤、硬化剤、触媒、カップリング剤などを投入してプレミキシングして、ロール、押し出し機などでコンパウンドを作ることが出来る。 With respect to the treatment of the basic substance or the basic mixture, the silica powder may be treated in advance, but it can also be carried out in the process of making a compound by mixing with a resin or the like. For example, silica powder is put into a Henschel mixer, mixed with a basic substance or a basic mixture, processed, and then immediately mixed with resin, additive, curing agent, catalyst, coupling agent, etc. You can make a compound with a roll, an extruder, etc.
第３に、本発明は、有機樹脂組成物の発明であり、塩基性物質又は塩基性混合物で表面処理された上記シリカ粉体を、有機樹脂に配合したことを特徴とする。塩基性シリカ粉体を添加することで、特に有機樹脂の耐熱性を高め、低熱膨張とし、低吸湿性とすることができる。 Thirdly, the present invention is an invention of an organic resin composition, characterized in that the silica powder surface-treated with a basic substance or a basic mixture is blended in an organic resin. By adding basic silica powder, the heat resistance of the organic resin can be particularly enhanced, the thermal expansion can be reduced, and the moisture absorption can be reduced.
本発明で使用される樹脂としては特に限定されず、エポキシ樹脂、ポリウレタン、不飽和ポリエステル、フェノール樹脂、尿素樹脂、ポリイミド、ポリアミドイミド、メラミン樹脂、光硬化樹脂、シリコーンなどの熱硬化性樹脂、ＬＣＰ、ＰＰＳ、ＰＥＳ、ＰＥＥＫ、ＰＣ、ＡＢＳ、ＰＭＭＡ、ポリオレフィン、ナイロン、ＰＰＯ、ＰＯＭ、等の熱可塑性樹脂、不飽和ポリエステル塗料又はワニス、アクリル塗料又はワニス、エポキシ塗料又はワニス、ポリイミド、ポリアミドイミド塗料又はワニス、フェノール樹脂塗料などの塗膜又は織物含浸用ワニス等が例示される。 The resin used in the present invention is not particularly limited, and is a thermosetting resin such as epoxy resin, polyurethane, unsaturated polyester, phenol resin, urea resin, polyimide, polyamideimide, melamine resin, photocuring resin, silicone, and LCP. , PPS, PES, PEEK, PC, ABS, PMMA, polyolefin, nylon, PPO, POM, etc., thermoplastic resin, unsaturated polyester paint or varnish, acrylic paint or varnish, epoxy paint or varnish, polyimide, polyamideimide paint or Examples thereof include coating films such as varnishes and phenolic resin paints, varnishes for impregnating fabrics, and the like.
これらの中で、半導体装置や液晶装置の封止材用樹脂として用いられる１分子中にエポキシ基を２個以上有するエポキシ樹脂が特に好ましい。即ち、第４に、本発明は、エポキシ樹脂組成物の発明であり、少なくとも（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）触媒に、（Ｄ）無機充填材として上記微塩基性シリカ粉体を全エポキシ樹脂組成物中に７０重量％以上含むことを特徴とする。ここで、（Ｄ）無機充填材として上記の塩基性シリカ粉体を全エポキシ樹脂組成物中に７０重量％以上、好ましくは８５〜９５重量％含む。 Among these, an epoxy resin having two or more epoxy groups in one molecule used as a resin for a sealing material of a semiconductor device or a liquid crystal device is particularly preferable. That is, fourthly, the present invention is an invention of an epoxy resin composition, and includes at least (A) an epoxy resin, (B) a curing agent, (C) a catalyst, and (D) the above slightly basic silica as an inorganic filler. 70% by weight or more of powder is included in the total epoxy resin composition. Here, (D) 70 wt% or more, preferably 85 to 95 wt% of the above basic silica powder is contained in the total epoxy resin composition as an inorganic filler.
同様に、少なくとも（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）触媒に、（Ｄ）無機充填材として上記微塩基性シリカ粉体を含むことを特徴とする封止用液状エポキシ樹脂組成物である。 Similarly, at least (A) an epoxy resin, (B) a curing agent, (C) a catalyst, and (D) the above-mentioned slightly basic silica powder as an inorganic filler, the liquid epoxy resin composition for sealing It is a thing.
更に、織物クロス含浸用ワニス又はフィルム形成用ワニスに、上記微塩基性シリカ粉体を配合したことを特徴とする樹脂組成物である。 Furthermore, the resin composition is characterized in that the fine basic silica powder is blended in a woven cloth impregnating varnish or a film forming varnish.
本発明に用いるエポキシ樹脂としては特に限定されず、１分子中にエポキシ基を２個以上有するモノマー、オリゴマー、及びポリマー全般が用いられる。例えば、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、ビスフェノール型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、トリアジン核含有エポキシ樹脂等が例示される。これらは単独でも混合して用いてもよい。無機充填材はエポキシ樹脂組成物中に高充填されることが好ましいため、エポキシ樹脂組成物の流動性を良好に維持するには低粘度樹脂が好ましい。 The epoxy resin used in the present invention is not particularly limited, and monomers, oligomers, and polymers generally having two or more epoxy groups in one molecule are used. For example, biphenyl type epoxy resin, stilbene type epoxy resin, bisphenol type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin, triazine core containing An epoxy resin etc. are illustrated. These may be used alone or in combination. Since the inorganic filler is preferably highly filled in the epoxy resin composition, a low-viscosity resin is preferable in order to maintain good fluidity of the epoxy resin composition.
本発明では、上記エポキシ樹脂組成物にフェノール樹脂を加えて半導体封止用エポキシ樹脂組成物とすることが出来る。用いるフェノール樹脂としては特に限定されず、１分子中にフェノール性水酸基を２個以上有するモノマー、オリゴマー、及びポリマー全般を言う。例えば、ジシクロペンタジエン変性フェノール樹脂、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂等が例示される。これらは単独でも混合して用いてもよい。無機充填材はエポキシ樹脂組成物中に高充填されるのが好ましいため、エポキシ樹脂組成物の流動性を良好に維持するには低粘度樹脂が好ましい。エポキシ樹脂のエポキシ基数とフェノール樹脂のフェノール性水酸基数との当量比としては、エポキシ基数／フェノール性水酸基数＝０．８〜１．２の範囲が好ましい。 In this invention, a phenol resin can be added to the said epoxy resin composition, and it can be set as the epoxy resin composition for semiconductor sealing. It does not specifically limit as a phenol resin to be used, The monomer, oligomer, and polymer in general which have two or more phenolic hydroxyl groups in 1 molecule are said. For example, dicyclopentadiene modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, terpene modified phenol resin, triphenolmethane type resin and the like are exemplified. These may be used alone or in combination. Since the inorganic filler is preferably highly filled in the epoxy resin composition, a low-viscosity resin is preferred in order to maintain good fluidity of the epoxy resin composition. The equivalent ratio of the number of epoxy groups of the epoxy resin to the number of phenolic hydroxyl groups of the phenol resin is preferably in the range of epoxy group number / phenolic hydroxyl group number = 0.8 to 1.2.
本発明に用いる硬化剤としては特に限定されず、エポキシ基とフェノール性水酸基との硬化反応を促進させるものであればよく、一般に封止材料に使用されているものを広く使用することができる。例えば、１，８−ジアザビシクロ（５，４，０）ウンデセン−７、２−メチルイミダゾール、トリフェニルホスフィン等が例示される。これらは単独でも混合して用いてもよい。 It does not specifically limit as a hardening | curing agent used for this invention, What is necessary is just to accelerate the hardening reaction of an epoxy group and a phenolic hydroxyl group, and what is generally used for the sealing material can be used widely. For example, 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, triphenylphosphine and the like are exemplified. These may be used alone or in combination.
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｄ）成分の他、必要に応じて、カーボンブラック、ベンガラ等の着色剤、天然ワックス、合成ワックス等の離型剤、シリコーンオイル、イオン捕捉剤、難燃剤、ゴム等の低応力添加剤等の種々の添加剤等を適宜配合しても差し支えない。 In addition to the components (A) to (D), the epoxy resin composition of the present invention includes, if necessary, colorants such as carbon black and bengara, mold release agents such as natural wax and synthetic wax, silicone oil, and ion trapping. Various additives such as additives, flame retardants, and low stress additives such as rubber may be appropriately blended.
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｄ）成分、及びその他の添加剤等をミキサー等を用いて充分に均一に常温混合した後、熱ロール又はニーダー等で溶融混練し、冷却後粉砕して得られる。本発明のエポキシ樹脂組成物を用いて、半導体素子等の電子部品を封止し、半導体装置を製造するには、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の成形方法で成形硬化すればよい。 The epoxy resin composition of the present invention is obtained by mixing the components (A) to (D) and other additives sufficiently uniformly at room temperature using a mixer or the like, then melt-kneading with a hot roll or a kneader, and cooling. Obtained by post-grinding. In order to seal an electronic component such as a semiconductor element and manufacture a semiconductor device using the epoxy resin composition of the present invention, it may be molded and cured by a molding method such as a transfer mold, a compression mold, or an injection mold.
本発明のエポキシ樹脂組成物は、半導体装置や液晶表示装置の封止材料として特に有用である。 The epoxy resin composition of the present invention is particularly useful as a sealing material for semiconductor devices and liquid crystal display devices.
本発明の微塩基性シリカ粉体は、（１）保存による凝集が発生しない、（２）ミクロオーダー以上の粗粒を気流分級、篩分級で容易に除去できる、（３）エポキシ樹脂と混合する際、シランカップリング剤を効率良く吸着、固着する、（４）エポキシ樹脂コンパウンドの粘度が低く、高流動性を示す、（５）硬化物の耐はんだリフロー性等の物性が優れている、という効果を奏する。 The finely basic silica powder of the present invention is (1) no aggregation due to storage, (2) coarse particles of micro order or more can be easily removed by airflow classification and sieve classification, and (3) mixed with an epoxy resin. At this time, the silane coupling agent is efficiently adsorbed and fixed, (4) the epoxy resin compound has low viscosity and high fluidity, and (5) the cured product has excellent physical properties such as solder reflow resistance. There is an effect.
又、本発明の微塩基性シリカ粉体は、エポキシ樹脂に配合した際、従来の表面処理粉末や未処理粉末より低粘度である。これにより、得られたエポキシ樹脂組成物は高流動性で、かつ金属酸化物粉末の高充填を可能とする。金属酸化物粉末の高充填により、耐湿性、硬性、熱膨張、重合収縮等が改善され、封止材料として優れたものとなる。 Further, the finely basic silica powder of the present invention has a lower viscosity than conventional surface-treated powder and untreated powder when blended in an epoxy resin. Thereby, the obtained epoxy resin composition has high fluidity and enables high filling of the metal oxide powder. Due to the high filling of the metal oxide powder, moisture resistance, hardness, thermal expansion, polymerization shrinkage and the like are improved, and it becomes an excellent sealing material.
以下、実施例と比較例を用いて本発明を説明する。 Hereinafter, the present invention will be described using examples and comparative examples.
［比較例１］
平均粒径が０．２μ、比表面積が１６ｍ２/ｇの球状シリカ（（株）アドマテックス製、SO-C1）を篩で１０５μ以上の粗大粒子を除去して、比較例サンプル１を作製した。
[Comparative Example 1]
Coarse silica (SO-C1 manufactured by Admatechs Co., Ltd.) having an average particle diameter of 0.2 μ and a specific surface area of 16 m 2 / g was removed with a sieve to remove coarse particles of 105 μ or more, and Comparative Sample 1 was produced. .
［実施例１］
比較例１の比較例サンプル１を１００重量部混粉機に投入し、粉体を攪拌しながら、０．２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で７５μ以上の粗大粒子を除去して、実施例サンプル１を作製した。
[Example 1]
Comparative Example Sample 1 of Comparative Example 1 was charged into a 100 parts by weight powder mixer, and 0.2 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse powder of 75 μm or more was removed from the treated powder with a sieve to prepare Example Sample 1.
［実施例２］
比較例１の比較例サンプル１を１００重量部混粉機に投入し、粉体を攪拌しながら、０．２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で４５μ以上の粗大粒子を除去して、実施例サンプル２を作製した。
[Example 2]
Comparative Example Sample 1 of Comparative Example 1 was charged into a 100 parts by weight powder mixer, and 0.2 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse particles of 45 μ or more were removed from the treated powder with a sieve to prepare Example Sample 2.
［実施例３］
比較例１の比較例サンプル１を１００重量部混粉機に投入し、粉体を攪拌しながら、０．２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で20μ以上の粗大粒子を除去して、実施例サンプル３を作製した。
[Example 3]
Comparative Example Sample 1 of Comparative Example 1 was charged into a 100 parts by weight powder mixer, and 0.2 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse particles of 20 μ or more were removed from the treated powder with a sieve to prepare Example Sample 3.
［実施例４］
比較例１の比較例サンプル１を１００重量部混粉機に投入し、粉体を攪拌しながら、０．２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を気流分級で１０μ以上の粗大粒子を除去して、実施例サンプル４を作製した。
[Example 4]
Comparative Example Sample 1 of Comparative Example 1 was charged into a 100 parts by weight powder mixer, and 0.2 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. Example powder 4 was prepared by removing coarse particles of 10 μm or more from the treated powder by airflow classification.
［実施例５］
比較例１の比較例サンプル１を１００重量部混粉機に投入し、粉体を攪拌しながら、０．２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を気流分級で５μ以上の粗大粒子を除去して、実施例サンプル５を作製した。
[Example 5]
Comparative Example Sample 1 of Comparative Example 1 was charged into a 100 parts by weight powder mixer, and 0.2 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. Example powder 5 was prepared by removing coarse particles of 5 μ or more from the treated powder by airflow classification.
［実施例６］
比較例１の比較例サンプル１を１００重量部混粉機に投入し、粉体を攪拌しながら、０．２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を気流分級で３μ以上の粗大粒子を除去して、実施例サンプル６を作製した。
[Example 6]
Comparative Example Sample 1 of Comparative Example 1 was charged into a 100 parts by weight powder mixer, and 0.2 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. Example powder 6 was prepared by removing coarse particles of 3 μm or more from the treated powder by airflow classification.
［比較例２］
平均粒径が０．５μ、比表面積が６．７ｍ２/ｇの球状シリカ（（株）アドマテックス製、SO-C2）を篩で１０５μ以上の粗大粒子を除去して、比較例サンプル２を作製した。
[Comparative Example 2]
Coarse silica (SO-C2 manufactured by Admatechs Co., Ltd.) having an average particle diameter of 0.5 μ and a specific surface area of 6.7 m 2 / g is removed with a sieve to remove coarse particles of 105 μ or more, and Comparative Sample 2 is obtained. Produced.
［実施例７］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で７５μ以上の粗大粒子を除去して、実施例サンプル７を作製した。
[Example 7]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.1 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse particles of 75 μ or more were removed from the treated powder with a sieve to prepare Example Sample 7.
［実施例８］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で４５μ以上の粗大粒子を除去して、実施例サンプル８を作製した。
[Example 8]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.1 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse particles of 45 μ or more were removed from the treated powder with a sieve to prepare Example Sample 8.
［実施例９］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル９を作製した。
[Example 9]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.1 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 9.
［実施例１０］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を気流分級で１０μ以上の粗大粒子を除去して、実施例サンプル１０を作製した。
[Example 10]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.1 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. Example powder 10 was produced by removing coarse particles of 10 μm or more from the treated powder by air classification.
［実施例１１］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を気流分級で５μ以上の粗大粒子を除去して、実施例サンプル１１を作製した。
[Example 11]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.1 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. Example powder 11 was prepared by removing coarse particles of 5 μ or more from the treated powder by airflow classification.
［実施例１２］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を気流分級で３μ以上の粗大粒子を除去して、実施例サンプル１１を作製した。
[Example 12]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.1 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. Example powder 11 was prepared by removing coarse particles of 3 μm or more from the treated powder by airflow classification.
［実施例１３］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．０１重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル１３を作製した。
[Example 13]
Comparative Example Sample 2 of Comparative Example 2 was charged into a 100 parts by weight powder mixer, and 0.01 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 13.
［実施例１４］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．３重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル１３を作製した。
[Example 14]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and 0.3 parts by weight of hexamethyldisilazane was sprayed while the powder was stirred to process the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 13.
［実施例１５］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のアンモニアを噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル１５を作製した。
[Example 15]
Comparative Example Sample 2 of Comparative Example 2 was charged into a 100 parts by weight powder mixer and the powder was treated by spraying 0.1 part by weight of ammonia while stirring the powder. Example particles 15 were produced by removing coarse particles of 20 μm or more from the treated powder with a sieve.
［実施例１６］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、０．１重量部のエチレンジアミンを噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル１６を作製した。
[Example 16]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and the powder was treated by spraying 0.1 part by weight of ethylenediamine while stirring the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 16.
［実施例１７］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、１重量部のKBM903の１０％メチルエチルケトン溶液を噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル１７を作製した。
[Example 17]
Comparative Example Sample 2 of Comparative Example 2 was put into a 100 parts by weight powder mixer, and the powder was treated by spraying 1 part by weight of a 10% methyl ethyl ketone solution of KBM903 while stirring the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 17.
［実施例１８］
比較例２の比較例サンプル２を１００重量部混粉機に投入し、粉体を攪拌しながら、１重量部のイミダゾールの１０％メチルエチルケトン溶液を噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル１８を作製した。
[Example 18]
Comparative Example Sample 2 of Comparative Example 2 was charged into a 100 parts by weight powder mixer, and the powder was treated by spraying 1 part by weight of a 10% methyl ethyl ketone solution of imidazole while stirring the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 18.
［比較例３］
平均粒径が６μ、比表面積が４．８m２/ｇの溶融球状シリカを篩で１０５μ以上の粗大粒子を除去して、比較例サンプル３を作製した。
[Comparative Example 3]
Comparative sample 3 was prepared by removing coarse particles having a mean particle size of 6 μ and a specific surface area of 4.8 m 2 / g using a sieve and removing particles of 105 μ or more with a sieve.
［実施例１９］
比較例３の比較例サンプル３を篩で７５μ以上の粗大粒子を除去して、実施例サンプル１９を作製した。
[Example 19]
Example Sample 19 was produced by removing coarse particles of 75 μm or more from Comparative Example 3 of Comparative Example 3 with a sieve.
［実施例２０］
比較例３の比較例サンプル３を１００重量部混粉機に投入し、粉体を攪拌しながら、０．０６重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で７５μ以上の粗大粒子を除去して、実施例サンプル２０を作製した。
[Example 20]
Comparative Example Sample 3 of Comparative Example 3 was charged into a 100 parts by weight powder mixer, and 0.06 parts by weight of hexamethyldisilazane was sprayed while stirring the powder to process the powder. The coarse particles of 75 μ or more were removed from the treated powder with a sieve to prepare Example Sample 20.
［実施例２１］
比較例３の比較例サンプル３を１００重量部混粉機に投入し、粉体を攪拌しながら、０．０６重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で４５μ以上の粗大粒子を除去して、実施例サンプル２１を作製した。
[Example 21]
Comparative Example Sample 3 of Comparative Example 3 was charged into a 100 parts by weight powder mixer, and 0.06 parts by weight of hexamethyldisilazane was sprayed while stirring the powder to process the powder. Example particles 21 were prepared by removing coarse particles of 45 μm or more from the treated powder with a sieve.
［実施例２２］
比較例３の比較例サンプル３を１００重量部混粉機に投入し、粉体を攪拌しながら、０．０６重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で２０μ以上の粗大粒子を除去して、実施例サンプル２２を作製した。
[Example 22]
Comparative Example Sample 3 of Comparative Example 3 was charged into a 100 parts by weight powder mixer, and 0.06 parts by weight of hexamethyldisilazane was sprayed while stirring the powder to process the powder. The coarse powder of 20 μm or more was removed from the treated powder with a sieve to prepare Example Sample 22.
［比較例４］
平均粒径が２５μ、比表面積が１．８ｍ２/ｇの溶融球状シリカを篩で１０５μ以上の粗大粒子を除去して、比較例サンプル４を作製した。
[Comparative Example 4]
Comparative sample 4 was prepared by removing fused particles of 105 μm or more from fused spherical silica having an average particle size of 25 μm and a specific surface area of 1.8 m 2 / g with a sieve.
［実施例２３］
比較例４の比較例サンプル４を篩で７５μ以上の粗大粒子を除去して、実施例サンプル２３を作製した。
[Example 23]
The comparative sample 4 of the comparative example 4 removed the coarse particle of 75 micrometers or more with the sieve, and the Example sample 23 was produced.
［実施例２４］
比較例３の比較例サンプル３を１００重量部混粉機に投入し、粉体を攪拌しながら、０．０２重量部のヘキサメチルジシラザンを噴霧して粉体を処理した。処理後の粉体を篩で７５μ以上の粗大粒子を除去して、実施例サンプル２４を作製した。
[Example 24]
Comparative Example Sample 3 of Comparative Example 3 was put into a 100 parts by weight powder mixer, and 0.02 parts by weight of hexamethyldisilazane was sprayed while stirring the powder to process the powder. The coarse particles of 75 μ or more were removed from the treated powder with a sieve to prepare Example Sample 24.
上記実施例及び比較例の諸物性、塩基性物質処理、粒径カットを表１に一覧にした。 Table 1 lists various physical properties, basic substance treatments, and particle size cuts of the above Examples and Comparative Examples.
［処理粉体の評価-１］
アドマファインSO-C2をレファレンスとして用いた。軟化点７０℃のクレゾールノボラック型エポキシ樹脂２０重量部、軟化点８０℃のフェノールノボラック樹脂２０重量部、トリフェニルフォスフィン０．２重量、KBM403、０．４重量部とアドマファインSO-C2、６０重量部を混合した後、東洋精機製R60型ラボブラストミルに入れて、回転数１００rpm、温度１００℃の条件下で、１５分間混合し、最低トルクを測定する。
[Evaluation of treated powder-1]
Admafine SO-C2 was used as a reference. 20 parts by weight of a cresol novolac type epoxy resin having a softening point of 70 ° C., 20 parts by weight of a phenol novolac resin having a softening point of 80 ° C., 0.2 weight by weight of triphenylphosphine, KBM403, 0.4 parts by weight and Admafine SO-C2, 60 After mixing the parts by weight, the mixture is placed in a R60 type lab blast mill manufactured by Toyo Seiki, and mixed for 15 minutes under the conditions of a rotation speed of 100 rpm and a temperature of 100 ° C., and the minimum torque is measured.
軟化点７０℃のクレゾールノボラック型エポキシ樹脂20重量部、軟化点８０℃のフェノールノボラック樹脂２０重量部、トリフェニルフォスフィン０．２重量、KBM403、０．４重量部と試験粉体６０重量部を混合した後、東洋精機製R60型ラボブラストミルに入れて、回転数１００rpm、温度１００℃の条件下で、１５分間混合し、最低トルクを測定する。SO-C2に対する相対最低トルクは下式であらわす。
相対最低トルク＝（試験粉体サンプルの最低トルク／SO-C2の最低トルク）×100
測定結果を表２にまとめた。
20 parts by weight of a cresol novolac type epoxy resin having a softening point of 70 ° C., 20 parts by weight of a phenol novolac resin having a softening point of 80 ° C., 0.2 part by weight of triphenylphosphine, 0.4 part by weight of KBM403, and 60 parts by weight of a test powder. After mixing, the mixture is placed in a Toyo Seiki R60 type lab blast mill and mixed for 15 minutes under the conditions of a rotation speed of 100 rpm and a temperature of 100 ° C., and the minimum torque is measured. The relative minimum torque for SO-C2 is expressed by the following equation.
Relative minimum torque = (Minimum torque of test powder sample / Minimum torque of SO-C2) x 100
The measurement results are summarized in Table 2.
［樹脂組成物の硬化物断面のＳＥＭ観察］
上記各サンプルを表３のように混合して用いて得られた実施例２５〜３７、比較例６〜８の樹脂組成物をプレス成型して、１８０℃、５時間で硬化させた。硬化物を破断し、断面のＳＥＭ観察を行い、フィラー界面と樹脂マトリックスの密着性を評価した。結果は表３にまとめた。
[SEM observation of cross section of cured product of resin composition]
The resin compositions of Examples 25 to 37 and Comparative Examples 6 to 8 obtained by mixing the above samples as shown in Table 3 were press-molded and cured at 180 ° C. for 5 hours. The cured product was broken, and the cross-sectional SEM observation was performed to evaluate the adhesion between the filler interface and the resin matrix. The results are summarized in Table 3.
又、実施例２５〜３７、比較例６〜８で得られた樹脂組成物１７０ｇをメチルエチルケトンで溶かして、超音波で分散させた。最大粒径に応じて篩を通してオン品中の導電性粒子を含む着色粒子の数を数えた。結果は表３にまとめた。 Further, 170 g of the resin compositions obtained in Examples 25 to 37 and Comparative Examples 6 to 8 were dissolved in methyl ethyl ketone and dispersed by ultrasonic waves. The number of colored particles including conductive particles in the on-product was counted through a sieve according to the maximum particle size. The results are summarized in Table 3.
［処理粉体の評価方法-２］
［実施例３８］
平均粒径が２μ、比表面積が２ｍ２／g、最大粒径２０μの球状シリカ（アドマファインSE6200）を４０重量部、平均粒径が０．５μ、比表面積が５．５ｍ２／g、最大粒径２０μの球状シリカ（アドマファインSE2200）を１６重量部、平均粒径が０．２μ、比表面積が１６ｍ２／g、最大粒径２０μの球状シリカ（アドマファインSE1200）を４重量部、をミキサーに投入して、粉体を攪拌しながら、０．０２重量部のヘキサメチルシラザンを噴霧して粉体を処理した後、ミキサーにZX-1059（エポキシ樹脂）を４０重量部、KBM403(エポキシシランカップリング剤)を０．３重量部、2PHZ(硬化触媒)を３重量部投入して混合した。得られた樹脂組成物を三本ロールで分散させて、液状エポキシ硬化物を得た。この樹脂組成物を３０℃、シェアレート23S-1で粘度を測定したところ、９６００cpsという値を得た。
[Processed powder evaluation method-2]
[Example 38]
40 parts by weight of spherical silica (Admafine SE6200) with an average particle size of 2μ, specific surface area of 2m 2 / g, maximum particle size of 20μ, average particle size of 0.5μ, specific surface area of 5.5m 2 / g, maximum 16 parts by weight of spherical silica (Admafine SE2200) having a particle size of 20 μ, 4 parts by weight of spherical silica (Admafine SE1200) having an average particle size of 0.2 μ, a specific surface area of 16 m 2 / g and a maximum particle size of 20 μ, The mixture was put into a mixer and the powder was treated by spraying 0.02 part by weight of hexamethylsilazane while stirring the powder, and then 40 parts by weight of ZX-1059 (epoxy resin) and KBM403 (epoxy) (Silane coupling agent) and 0.3 parts by weight of 2PHZ (curing catalyst) were added and mixed. The obtained resin composition was dispersed with three rolls to obtain a liquid epoxy cured product. When the viscosity of this resin composition was measured at 30 ° C. and a shear rate of 23S-1, a value of 9600 cps was obtained.
［比較例９］
平均粒径が２μ、比表面積が２ｍ２／g、の球状シリカ（アドマファインSE6000）を４０重量部、平均粒径が０．５μ、比表面積が５．５ｍ２／gの球状シリカ（アドマファインSO-E2）を１６重量部、平均粒径が０．２μ、比表面積が１６ｍ２／gの球状シリカ（アドマファインSO-E1）を４重量部、ZX-1059（エポキシ樹脂）を４０重量部、KBM403(エポキシシランカップリング剤)を０．３重量部、2PHZ(硬化触媒)を３重量部投入して混合した。得られた樹脂組成物を三本ロールで分散させて、液状エポキシ硬化物を得た。この樹脂組成物を３０℃、シェアレート23S-1で粘度を測定したところ、３１０００cpsという値を得た。
[Comparative Example 9]
40 parts by weight of spherical silica (Admafine SE6000) having an average particle diameter of 2 μm and a specific surface area of 2 m 2 / g, spherical silica having an average particle diameter of 0.5 μm and a specific surface area of 5.5 m 2 / g (Admafine) 16 parts by weight of SO-E2), 4 parts by weight of spherical silica (Admafine SO-E1) having an average particle size of 0.2 μm and a specific surface area of 16 m 2 / g, and 40 parts by weight of ZX-1059 (epoxy resin) KBM403 (epoxysilane coupling agent) 0.3 parts by weight and 2PHZ (curing catalyst) 3 parts by weight were added and mixed. The obtained resin composition was dispersed with three rolls to obtain a liquid epoxy cured product. When the viscosity of this resin composition was measured at 30 ° C. and a shear rate of 23S-1, a value of 31000 cps was obtained.
［処理粉体の評価方法-３］
軟化点７０℃のクレゾールノボラック型エポキシ樹脂20重量部、軟化点８０℃のフェノールノボラック樹脂２０重量部、トリフェニルフォスフィン０．２重量、と試験粉体、６０重量部、メチルエチルケトン１００重量部を混合して分散機で粉体を分散してワニスを作製した。ワニスを塗布して溶媒を蒸発した後、１９０℃、５時間塗布膜を硬化させた。膜の破断面のＳＥＭ観察を行った。結果を表４にまとめた。
[Processed powder evaluation method-3]
20 parts by weight of a cresol novolac type epoxy resin having a softening point of 70 ° C., 20 parts by weight of a phenol novolac resin having a softening point of 80 ° C., 0.2 weight of triphenylphosphine, 60 parts by weight of test powder, and 100 parts by weight of methyl ethyl ketone are mixed. Then, the powder was dispersed with a disperser to prepare a varnish. After applying the varnish and evaporating the solvent, the coating film was cured at 190 ° C. for 5 hours. SEM observation of the fracture surface of the film was performed. The results are summarized in Table 4.
［エポキシ樹脂封止材での評価］
表５に示すように、エポキシ樹脂：EOCN1020-65（日本化薬製、エポキシ当量２００）、フェノール硬化剤：DL-92（明和化成製、フェノール当量１１０）、カルナバワックス（日興ファインプロダクツ製）、KBM403(信越化学製エポキシシランカップリング剤)、トリフェニルフォスフィン（北興化学製 TPPと略す）からなるシリカ充填材を実施例４１〜４３および比較例１２を調製した。これらをヘンシェルミキサー（三井鉱山株式会社製、型式FM20C/I、回転数２４００rpm）により１０分プリブレンドした。これらを、３０ｍｍφの二軸押出機を用いて溶融混練温度１１０℃、平均滞留時間５分で溶融混練後、冷却・粉砕して半導体封止用エポキシ樹脂組成物を製造した。
[Evaluation with epoxy resin encapsulant]
As shown in Table 5, epoxy resin: EOCN1020-65 (manufactured by Nippon Kayaku, epoxy equivalent 200), phenol curing agent: DL-92 (manufactured by Meiwa Kasei, phenol equivalent 110), carnauba wax (manufactured by Nikko Fine Products), Examples 41 to 43 and Comparative Example 12 were prepared using a silica filler composed of KBM403 (epoxy silane coupling agent manufactured by Shin-Etsu Chemical) and triphenylphosphine (abbreviated as TPP manufactured by Hokuko Chemical). These were pre-blended for 10 minutes using a Henschel mixer (Mitsui Mining Co., Ltd., model FM20C / I, rotational speed 2400 rpm). These were melt kneaded using a 30 mmφ twin screw extruder at a melt kneading temperature of 110 ° C. and an average residence time of 5 minutes, and then cooled and ground to produce an epoxy resin composition for semiconductor encapsulation.
これらの物性を以下のように評価した。
≪溶融粘度≫ 高化式フローテスターを用い、９８Ｎの加圧下、直径１ｍｍのノズルを用い、温度１７５℃で粘度を測定した。
≪曲げ強度≫ 曲げ強度は、ＪＩＳ Ｋ６９１１に従って、１７５℃、６．９ＭＰａ、成形時間２分の条件で１０×４×１００ｍｍの抗折棒を成形し、１８０℃で４時間ポストキュアーしたものの室温での曲げ強度を測定した。
≪吸水率≫ １７５℃、６．９ＭＰａ、成形時間２分の条件で直径５０×３ｍｍの円盤を成形し、１８０℃で４時間ポストキュアーしたものを８５℃／８５％ＲＨの恒温恒湿器に１６８時間放置し、吸水率を測定した。
These physical properties were evaluated as follows.
<< Melting Viscosity >> Using a Koka flow tester, the viscosity was measured at a temperature of 175 ° C. under a pressure of 98 N using a nozzle having a diameter of 1 mm.
«Bending strength» The bending strength was 1050 ° C, 6.9 MPa, molding time 2 minutes in accordance with JIS K6911, and 10 × 4 × 100 mm bending rod was molded and post-cured at 180 ° C for 4 hours at room temperature. The bending strength of was measured.
«Water absorption rate» A disk with a diameter of 50 x 3 mm was molded under the conditions of 175 ° C, 6.9 MPa, molding time of 2 minutes, and post-cured at 180 ° C for 4 hours into a constant temperature and humidity chamber of 85 ° C / 85% RH After standing for 168 hours, the water absorption was measured.
表５の結果より、本発明のエポキシ樹脂組成物は、溶融粘度が低く、曲げ強度に優れ、吸水率が低いことが分る。 From the results in Table 5, it can be seen that the epoxy resin composition of the present invention has low melt viscosity, excellent bending strength, and low water absorption.
又、本発明の微塩基性シリカ粉体は、エポキシ樹脂等に配合して、半導体装置や液晶表示装置の封止材料等に用いることが出来る。 Further, the slightly basic silica powder of the present invention can be blended in an epoxy resin or the like and used as a sealing material for a semiconductor device or a liquid crystal display device.
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| PCT/JP2004/000851 WO2005080270A1 (en) | 2003-12-15 | 2004-01-29 | Fine basic silica powder, process for producing the same and resin composition |
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| WO2005080270A1 (en) | 2005-09-01 |
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