JP4004270B2 - High thermal conductive inorganic powder and resin composition - Google Patents
High thermal conductive inorganic powder and resin composition Download PDFInfo
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- JP4004270B2 JP4004270B2 JP2001339067A JP2001339067A JP4004270B2 JP 4004270 B2 JP4004270 B2 JP 4004270B2 JP 2001339067 A JP2001339067 A JP 2001339067A JP 2001339067 A JP2001339067 A JP 2001339067A JP 4004270 B2 JP4004270 B2 JP 4004270B2
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00439—Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00465—Heat conducting materials
Description
【０００１】
【発明の属する技術分野】
本発明は、高熱伝導性無機粉末および樹脂組成物に関する。詳しくは、層厚が限られたところに使用される接着剤や、アンダーフィル等の半導体封止材等を製造するのに好適な高熱伝導性無機粉末と、それを樹脂に充填した樹脂組成物に関するものである。
【０００２】
【従来の技術】
電子機器の小型化、高機能化に伴い、電子部品の各所で用いられる樹脂組成物に充填される絶縁性無機粉末の微細化も進んでいる。例えば、半導体の実装方法の一つであるフリップチップ実装では、チップ保護に用いる封止材料（アンダーフィル材）を数１０μｍ程度の基板とチップの隙間へ浸透させる為、液状エポキシ樹脂に微細な無機粉末を充填したアンダーフィル材が用いられている。
【０００３】
しかしながら、無機粉末の充填量が多くなると、狭ギャップへ浸透しにくく、生産性が非常に悪くなるといった問題がある。これを解決するには樹脂組成物の粘度を下げる必要があり、低粘度ほど浸透性が向上する。こういった低粘度化はアンダーフィル材に限らず他用途の樹脂においても共通した課題であり、粘度に最も影響するのが充填される無機粉末の物性であると考えられている。特開２００１−２００１３９号公報には、アンダーフィル材用の無機充填材が開示され、２μｍ以下の粒子径をもつ粉末が無機粉末全体の５０％以上がよいとされている。しかし、微粉が多くなると、樹脂組成物の粘度が容易に高粘度化するので、高充填化が困難となる。
【０００４】
更に最近では、絶縁性の他に放熱性が求められる用途が出現し、充填材および樹脂の両面からの検討が進められている。従来、高熱伝導性無機粉末としては、窒化アルミニウム、酸化アルミニウム、結晶シリカ等が知られているが、その形状が破砕形状やカットエッジを有さない形状（丸味状）であるのでこれもまた樹脂組成物の粘度を容易に高め高充填させることができず、結果として満足する放熱性が得られない。また、これら粉末は樹脂との混合時に使用するニーダ、ロールや、成型時に用いる金型を激しく摩耗させてしまう為、生産性を悪化させてしまう。
【０００５】
【発明が解決しようとする課題】
本発明は、上記に鑑みてなされたものであり、その目的は樹脂に高充填しても容易に高粘度化せず、しかも放熱性に優れた樹脂組成物を調製することのできる、高熱伝導性無機粉末と、それを樹脂に充填した樹脂組成物を提供することである。
【０００６】
【課題を解決するための手段】
すなわち、本発明は以下のとおりである。
（請求項１）平均粒子径が1〜２０μｍ、最大粒径が４５μｍ以下の無機粉末からなり、粒度域３〜４０μｍの構成粒子である無機粉末Ｘの真円度が０．８０以上の球状でしかも熱伝導率１０Ｗ／ｍＫ以上であり、粒度域０．１〜１．５μｍの構成粒子である無機粉末Ｙの真円度が０．３０以上０．８０未満の球状又は非球状でしかも熱伝導率が無機粉末Ｘと同等以下であり、Ｘ／Ｙの質量比が１〜３０であり、かつ無機粉末Ｘが酸化アルミニウム粉末であり、無機粉末Ｙが結晶シリカ粉末、溶融（非晶質）シリカ粉末、酸化アルミニウム粉末のいずれか一方又は組み合わせであることを特徴とする高熱伝導性無機粉末。
（請求項２）シランカップリング剤、チタネート系カップリング剤及びアルミネート系カップリング剤から選ばれた１種又は２種以上の表面処理剤Ａにて表面処理が施されていることを特徴とする請求項１記載の高熱伝導性無機粉末。
（請求項３）ポリカルボン酸系界面活性剤及び／又はポリアクリル酸系界面活性剤の表面処理剤Ｂにて表面処理が施されてなることを特徴とする請求項１又は２記載の高熱伝導性無機粉末。
（請求項４）表面処理剤Ａと表面処理剤Ｂの質量比（Ｂ／Ａ）が１〜３０であることを特徴とする請求項３記載の高熱伝導性無機粉末。
（請求項５）請求項１、２、３又は４記載の高熱伝導性無機粉末が充填されてなることを特徴とする樹脂組成物。
【０００７】
【発明の実施の形態】
以下、更に詳しく本発明について説明する。
【０００８】
本発明の高熱伝導性無機粉末は、平均粒子径が1〜２０μｍであり、かつ最大粒径が４５μm以下であることが第１条件である。平均粒径が１μm未満であると、熱伝導率が著しく低下してしまい、２０μｍよりも大きいと混合機や金型等を激しく摩耗させてしまうので生産性が低下する。また、最大粒径が４５μmよりも大きいと、樹脂組成物の粘度が容易に高まるだけでなく、粗大粒子が狭ギャップに詰まってしまい、樹脂組成物の浸透を妨げてしまい用途に制約を受ける。ここで、最大粒径とは、水篩法で篩上に残る残量が０．５質量％未満の粒径を意味する。
【０００９】
本発明の高熱伝導性無機粉末は、粒度域によって真円度の異なる２種以上の粉末が混合されたと同じような粒度構成を有している。もっとも、そのように混合されたものであってもよい。すなわち、本発明の高熱伝導性無機粉末は、無機粉末Ｘと無機粉末Ｙとを含み、粒度域３〜４０μｍの構成粒子である無機粉末Ｘの真円度が０．８０以上の球状でしかも熱伝導率１０Ｗ／ｍＫ以上であり、粒度域０．１〜１．５μｍの構成粒子である無機粉末Ｙの真円度が０．３０以上０．８０未満の球状又は非球状でしかも熱伝導率が無機粉末Ｘと同等以下であることが第２条件となる。
【００１０】
本発明において、無機粉末Ｘを粒度域３〜４０μｍ、無機粉末Ｙを粒度域０．１〜１．５μｍに選定した理由は、多くの実験の結果、これらの粒度域の粉末を制御することによって樹脂組成物の粘度、熱伝導率ともに最も良好になることを見いだしたことによる。また、無機粉末Ｘの真円度が０．８０未満であると、この無機粉末が樹脂組成物の粘性に最も大きな影響を与えていることから、樹脂組成物が容易に高粘度化されて高充填が困難となる。更に、その熱伝導率が１０Ｗ／ｍＫ未満であると十分に高い放熱特性を樹脂組成物に付与することができない。一方、無機粉末Ｙは樹脂組成物の熱伝導率に大きく影響しないが、無機粉末Ｘ同士間に入り込んで熱パスを助長する効果がある。従って、真円度が０．３０未満であると無機粉末Ｘ同士間への進入が困難となり、０．８以上では無機粉末Ｘとの接触点が減ってしまい、熱パス助長効果も低下してしまう。また、その熱伝導率が無機粉末Ｘのそれを超えても、樹脂組成物の熱伝導率は無機粉末Ｘに大きく影響されているので、熱伝導率はそれほど向上せず、無機粉末Ｙとして、無機粉末Ｘよりも熱伝導率の大きなものを用いてもよいが、わざわざ比較的高価な熱伝導率の大きな粉体を用いることの意義が小さい。
【００１１】
ここで、真円度は、走査型電子顕微鏡（日本電子社製「ＪＸＡ−８６００Ｍ型」）と画像解析装置（日本アビオニクス社製）を用いて測定することができる。すなわち、粉末のＳＥＭ写真から粒子の投影面積（Ａ）と周囲長（ＰＭ）を測定する。周囲長（ＰＭ）に対応する真円の面積を（Ｂ）とすると、その粒子の真円度はＡ／Ｂとして表される。そこで、試料粒子の周囲長（ＰＭ）と同一の周囲長を持つ真円を想定すると、ＰＭ＝２πｒ、Ｂ＝πｒ2であるから、Ｂ＝π×（ＰＭ／２π）2となり、この粒子の真円度は、真円度＝Ａ／Ｂ＝Ａ×４π／（ＰＭ）2として算出することができる。そこで、本発明においては、任意１００個の粒子について測定し、その平均値でもって粉末の真円度とする。
【００１２】
無機粉末Ｘは、化学的安定性、熱伝導性の点から酸化アルミニウム粉末が最適である。一方、無機粉末Ｙは、結晶シリカ粉末、溶融（非晶質）シリカ粉末、酸化アルミニウム粉末のいずれか一方又は組み合わせであることが最適である。
【００１３】
本発明の高熱伝導性無機粉末は、無機粉末Ｘと無機粉末Ｙの割合が、Ｘ／Ｙの質量比で１〜３０であることが第３条件である。無機粉末Ｙは、無機粉末Ｘによる樹脂組成物の低粘度を助長し、樹脂への高充填を可能にする。Ｘ／Ｙ比が1未満であると微粉域の割合が少なすぎて樹脂組成物が容易に高粘度化し、また３０超となると熱伝導性付与効果が著しく低下する。本発明の高熱伝導性無機粉末は、無機粉末Ｘと無機粉末Ｙの合計が６０％以上（１００％を含む）で構成されていることが好ましく、その合計が１００％未満である場合の残部は、真円度０．８０以上でしかも１．５〜３μｍの球状無機粉末で構成されていることが好ましい。
【００１４】
次に、他の本発明について説明する。これらの発明は、樹脂組成物の熱伝導性を更に向上させることができる高熱伝導性無機粉末であり、上記本発明の高熱伝導性無機粉末（以下、「高熱伝導性無機粉末基材」ともいう。）の改良に関するものである。
【００１５】
その１は、高熱伝導性無機粉末基材をシラン系カップリング剤、チタネート系カップリング剤及びアルミネート系カップリング剤から選ばれた一種又は二種以上の表面処理剤Ａにて表面処理された高熱伝導性無機粉末（以下、「高熱伝導性無機粉末Ａ」ともいう。）である。これを用いることによって、樹脂との密着性が更に高められ、高熱伝導性無機粉末Ａと樹脂間での界面熱抵抗が低下し、更なる高熱伝導性を付与することができる。表面処理剤Ａとしては、高熱伝導性無機粉末基材との反応性の点からシラン系カップリング剤が好ましい。
【００１６】
シランカップリング剤としては、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、β（３，４エポキシシンクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシリメトキシプロピルメチルジエトキシシラン、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−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプト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等であり、これらを一種または二種以上が用いられる。
【００１７】
表面処理剤Ａによる高熱伝導性無機粉末基材の表面処理方法は、流体ノズルを用いた噴霧方式、せん断力のある攪拌、ボールミル、ミキサー等の乾式法、水系または有機溶剤系等の湿式法を採用することができる。せん断力は、高熱伝導性無機粉末基材の破壊が起こらない程度にして行うことに注意が必要である。
【００１８】
乾式法における系内温度ないしは湿式法における処理後の乾燥温度は、表面処理剤Ａの種類に応じ熱分解しない領域で適宜決定される。例えば、γ−アミノプロピルトリエトキシシランである場合の温度は、８０〜１５０℃が望ましい。
【００１９】
その２は、アンダーフィル材のように樹脂組成物が低粘度である場合、高熱伝導性無機粉末が沈降して樹脂組成物の熱伝導性が損なわれないようにするため、ポリカルボン酸系界面活性剤、ポリアクリル酸系界面活性剤界面活性剤から選ばれた一種または二種以上の表面処理剤Ｂによって、高熱伝導性無機粉末基材又は高熱伝導性無機粉末Ａを表面処理した高熱伝導性無機粉末（以下、両者を総称して「高熱伝導性無機粉末Ｂ」ともいう。また、前者による処理粉を「高熱伝導性無機粉末ｂ１」、後者による処理粉を「高熱伝導性無機粉末ｂ２」ともいう。）である。
【００２０】
表面処理剤Ｂによる、高熱伝導性無機粉末基材ないしは高熱伝導性無機粉末Ａの表面処理は、表面処理剤Ａの処理方法に準じて行われるが、表面処理剤Ａの場合と同様に、表面処理剤Ｂの熱分解が起こらない温度で処理しなければならないことに注意が要る。
【００２１】
本発明においては、表面処理剤Ａと表面処理剤Ｂとによる処理は、どちらか一方でもよく両方であってもよい。両方の処理によって、樹脂との密着性向上と高熱伝導性無機粉末の沈降防止を同時に低減することができ、樹脂組成物の放熱性を向上させることができる。
【００２２】
また、表面処理剤Ａと表面処理剤Ｂによる両方の処理の場合、その処理は別々に行っても良く、また同時に行っても効果がある。従って、表面処理剤Ａと表面処理剤Ｂはあらかじめ混合された表面処理剤組成物であることが取り扱いの点で望ましく、その混合割合は、表面処理剤Ｂ／表面処理剤Ａの質量比で１〜３０であることが好ましい。該比が、１未満であると、過剰な表面処理剤Ａによって樹脂組成物の粘度上昇、表面処理剤Ｂの不足による十分な沈降防止効果が得られない。一方、該比が３０超となると、過剰な表面処理剤Ｂによって、高熱伝導性無機粉末の表面処理剤Ａ表面の吸着サイトが埋められ、表面処理剤Ａの未反応が増加し、樹脂との密着性が十分に向上しない。
【００２３】
本発明の樹脂組成物は、上記した本発明の高熱伝導性無機粉末、すなわち高熱伝導性無機粉末基材、高熱伝導性無機粉末Ａ、高熱伝導性無機粉末Ｂ（すなわち高熱伝導性無機粉末ｂ１、高伝導性無機粉末ｂ２）のいずれか単独または二種以上が充填されてなるものである。充填量は、用途によって異なり、５０〜９５質量％が一般的である。
【００２４】
樹脂としては、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル、フッ素樹脂、ポリイミド、ポリアミドイミド、ポリエーテルイミド等のポリアミド、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のポリエステル、ポリフェニレンエーテル、ポリフェニレンスルフィド、全芳香族ポリエステル、ポリスルホン、液晶ポリマー、ポリエーテルスルホン、ポリカーボネート、マレイミド変性樹脂、ＡＢＳ樹脂、ＡＡＳ（アクリロニトリル−アクリルゴム・スチレン）樹脂、ＡＥＳ（アクリロニトリル・エチレン・プロピレン・ジエンゴム−スチレン）樹脂等が使用される。
【００２５】
樹脂組成物がアンダーフィル材のように液状樹脂組成物である場合、樹脂には液状エポキシ樹脂が用いられる。液状エポキシ樹脂としては、一分子中にエポキシ基を二個以上有するエポキシ樹脂であればいかなるものでも使用可能である。その具体例をあげれば、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、フェノール類とアルデヒド類のノボラック樹脂をエポキシ化したもの、ビスフェノールＡ、ビスフェノールＦ及びビスフェノールＳなどのグリシジルエーテル、フタル酸やダイマー酸などの多塩基酸とエポクロルヒドリンとの反応により得られるグリシジルエステル酸エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、アルキル変性多官能エポキシ樹脂、β−ナフトールノボラック型エオキシ樹脂、１，６−ジヒドロキシナフタレン型エポキシ樹脂、２，７−ジヒドロキシナフタレン型エポキシ樹脂、ビスヒドロキシビフェニル型エポキシ樹脂、更には難燃性を付与するために臭素などのハロゲンを導入したエポキシ樹脂等である。この中でも常温で液状のエポキシ樹脂が好適に用いられるが、特にビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂などが挙げられ、これらを一種または２種類以上が使用される。
【００２６】
液状エポキシ樹脂の硬化剤については、液状エポキシ樹脂と反応して硬化させるものであれば特に限定されず、例えば、フェノール、クレゾール、キシレノール、レゾルシノール、クロロフェノール、ｔ−ブチルフェノール、ノニルフェノール、イソプロピルフェノール、オクチルフェノール等の群から選ばれた１種又は２種以上の混合物をホルムアルデヒド、パラホルムアルデヒド又はパラキシレンとともに酸化触媒下で反応させて得られるノボラック型樹脂、ポリパラヒドロキシスチレン樹脂、ビスフェノールＡやビスフェノールＳ等のビスフェノール化合物、ピロガロールやフロログルシノール等の３官能フェノール類、無水マレイン酸、無水フタル酸や無水ピロメリット酸等の酸無水物、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族アミン等を挙げることができる。
【００２７】
本発明の樹脂組成物には、次の成分を必要に応じて配合することができる。すなわち、低応力化剤として、シリコーンゴム、ポリサルファイドゴム、アクリル系ゴム、ブタジエン系ゴム、スチレン系ブロックコポリマーや飽和型エラストマー等のゴム状物質、各種熱可塑性樹脂、シリコーン樹脂等の樹脂状物質、更にはエポキシ樹脂、フェノール樹脂の一部又は全部をアミノシリコーン、エポキシシリコーン、アルコキシシリコーンなどで変性した樹脂など、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メトキシシラン、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など、表面処理剤として、Ｚｒキレート、チタネートカップリング剤、アルミニウム系カップリング剤など、難燃助剤として、Ｓｂ2Ｏ3、Ｓｂ2Ｏ4、Ｓｂ2Ｏ5など、難燃剤として、ハロゲン化エポキシ樹脂やリン化合物など、着色剤として、カーボンブラック、酸化鉄、染料、顔料などである。
【００２８】
本発明の樹脂組成物には、エポキシ樹脂と硬化剤との反応を促進させるために硬化促進剤を配合することができる。その硬化促進剤としては、１，８−ジアザビシクロ（５，４，０）ウンデセン−７，トリフェニルホスフィン、ベンジルジメチルアミン、２−メチルイミダゾール等がある。
【００２９】
本発明の樹脂組成物は、上記各材料の所定量を撹拌、溶解、混合、分散させることにより製造することができる。これらの混合物の混合、撹拌、分散等の装置は特に限定されないが、撹拌、加熱装置を備えたライカイ機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。またこれらの装置を適宜組み合わせて使用してもよい。
【００３０】
本発明の樹脂組成物をアンダーフィル材として用いるとき、半導体チップと基板との間隙にそれを浸透させて封止する際の温度は６０〜１２０℃とすることが好ましい。
【００３１】
【実施例】
以下、実施例、比較例をあげて更に具体的に本発明を説明する。
【００３２】
実施例１〜７ 比較例１〜６
表１に示す無機粉末１〜１３を準備し、これを表２に示すような配合で混合し、高熱伝導性無機粉末基材イ〜ホ（実施例１〜５）と、チ〜ワ（比較例１〜６）を調整した。それらの粉末特性を表４に示す。また、高熱伝導性無機粉末ヘ（実施例６）および高熱伝導性無機粉末ト（実施例７）は、高熱伝導性無機粉末基材イを以下に従って表面処理し、本発明の高熱伝導性無機粉末Ａおよび高熱伝導性無機粉末ｂ１としたものである。
【００３３】
ボール径２０ｍｍ、ボール充填率５０体積％の１０リットル容器内に、高熱伝導性無機粉末基材イを１ｋｇ、表３に示す表面処理剤Ａ又は表面処理剤Ｂを投入し、常温、常圧の条件下にて１回／秒の速度で１時間運転し、１２０℃にて１時間乾燥させ、高熱伝導性無機粉末ヘおよびトを得た。
【００３４】
表５に示される割合で各材料を混合し、これに高熱伝導性無機粉末イ〜ワを無機粉末換算で７５質量％の割合で混合し、樹脂組成物を製造した。これの粘度、熱伝導率、摩耗量を以下に従って測定した。それらの結果を表６に示す。
【００３５】
（１）粘度
Ｅ型粘度計型（東京計器社製「ＥＨＤ粘度計」）を用い、温度４０℃、１０ｒｐｍの回転数による粘度測定を行った。
【００３６】
（２）熱伝導率
直径２８ｍｍ、厚さ３ｍｍの円盤状サイズ穴を設けた金型に樹脂組成物を流し込み、脱気後１５０℃×２０分で成型した。熱伝導率測定装置（アグネ社製「ＡＲＣ−ＴＣ−１型」）を用い、室温において温度傾斜法で測定した。
【００３７】
（３）摩耗量
厚み６ｍｍ、孔径３ｍｍのアルミニウム製ディスクの孔に樹脂組成物を３００ｍｍ3通過させた後のディスクの質量減少量を摩耗量として評価した。
【００３８】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
表１〜６から明らかなように、本発明の高熱伝導性無機粉末を用いた樹脂組成物は、粘度、熱伝導性、摩耗性の全てにおいて、比較例よりも優れていることが分かる。
【００４５】
実施例８、９
表面処理剤Ａおよび表面処理剤Ｂからなる表面処理剤組成物を用いて試験を行った。すなわち、高熱伝導性無機粉末基材イ、表面処理剤Ａ：シランカップリング剤（商品名：信越化学工業製ＫＢＭ−４０３）、表面処理剤Ｂ：ポリカルボン酸系界面活性剤（商品名：日本油脂株式会社製マリアニムＡＫＭ−０５３１）を用いて試験を行った。
【００４６】
表面処理方法は、ボール径２０ｍｍ、ボール充填率５０体積％の１０リットル容器内に高熱伝導性無機粉末基材イを１ｋｇ、表面処理剤組成物を表面処理Ａの質量換算で０．３６ｇになるよう投入し、常温、常圧の条件下にて１回／秒の速度で１時間運転した後、１２０℃にて１時間乾燥させ、高熱伝導性無機粉末ｂ２とした。その結果を表７に示す。
【００４７】
【表７】
表７からも明らかなように、表面処理剤Ａと表面処理剤Ｂの混合物からなる表面処理剤組成物であっても十分に高く樹脂組成物の熱伝導率が向上することが分かる。
【００４９】
【発明の効果】
本発明によれば、樹脂に高充填しても容易に高粘度化せず、しかも放熱性に優れた樹脂組成物を調製することのできる、高熱伝導性無機粉末と、それを樹脂に充填した樹脂組成物とが提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention is related to the highly thermally conductive inorganic powder and a resin composition. For more information, and the adhesive used at the layer thickness is limited, and a suitable highly thermally conductive inorganic powder to manufacture semiconductor encapsulation such as underfill, a resin composition which was filled in a resin it is those related to.
[0002]
[Prior art]
Along with miniaturization and higher functionality of electronic devices, miniaturization of insulating inorganic powders filled in resin compositions used in various parts of electronic components is also progressing. For example, in flip chip mounting, which is one of semiconductor mounting methods, a sealing material (underfill material) used for chip protection penetrates into the gap between a substrate of about several tens of micrometers and the chip, so that a fine inorganic substance is added to the liquid epoxy resin. An underfill material filled with powder is used.
[0003]
However, when the filling amount of the inorganic powder is increased, there is a problem that it is difficult to penetrate into the narrow gap and the productivity is extremely deteriorated. In order to solve this, it is necessary to lower the viscosity of the resin composition, and the lower the viscosity, the better the permeability. Such lowering of viscosity is a problem common not only to underfill materials but also to resins for other uses, and it is considered that the physical properties of the inorganic powder to be filled have the most influence on the viscosity. Japanese Patent Laid-Open No. 2001-200199 discloses an inorganic filler for an underfill material, and it is said that a powder having a particle size of 2 μm or less should be 50% or more of the entire inorganic powder. However, when the amount of fine powder increases, the viscosity of the resin composition is easily increased, so that it is difficult to increase the filling.
[0004]
More recently, applications that require heat dissipation in addition to insulation have emerged, and studies are being made from both the filler and resin aspects. Conventionally, aluminum nitride, aluminum oxide, crystalline silica, and the like are known as high thermal conductive inorganic powders, but this is also a resin because it has a crushed shape or a shape without a cut edge (round shape). The viscosity of the composition cannot be easily increased and highly filled, and as a result, satisfactory heat dissipation cannot be obtained. In addition, these powders severely wear the kneader and roll used when mixing with the resin, and the mold used during molding, which deteriorates productivity.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above, and an object thereof is to provide a high thermal conductivity capable of preparing a resin composition that does not easily increase in viscosity even when highly charged into a resin and has excellent heat dissipation. and sex inorganic powder, it is to provide a resin sets Narubutsu filled in a resin.
[0006]
[Means for Solving the Problems]
That is, the present invention is as follows.
(Claim 1) The inorganic powder X, which is composed of inorganic powder having an average particle size of 1 to 20 μm and a maximum particle size of 45 μm or less, is spherical with a roundness of 0.80 or more. In addition, the inorganic powder Y, which is a constituent particle having a thermal conductivity of 10 W / mK or more and a particle size range of 0.1 to 1.5 μm, is spherical or non-spherical with a roundness of 0.30 or more and less than 0.80 and is also thermally conductive the rate is equal to or lower than the inorganic powder X, Ri weight ratio 1 to 30 der of X / Y, and the inorganic powder X is aluminum oxide powder, inorganic powder Y is crystalline silica powder, fused (amorphous) A highly thermally conductive inorganic powder characterized by being one or a combination of silica powder and aluminum oxide powder.
(Claim 2) The surface treatment is performed with one or more surface treatment agents A selected from silane coupling agents, titanate coupling agents and aluminate coupling agents. The highly heat-conductive inorganic powder according to claim 1 .
(Claim 3) The high thermal conductivity according to claim 1 or 2, wherein the surface treatment is performed with a surface treatment agent B of a polycarboxylic acid surfactant and / or a polyacrylic acid surfactant. Inorganic powder.
(Claim 4) The high thermal conductive inorganic powder according to claim 3, wherein the mass ratio (B / A ) of the surface treatment agent A and the surface treatment agent B is 1 to 30.
(Claim 5) A resin composition comprising the highly heat-conductive inorganic powder according to claim 1, 2, 3 or 4.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0008]
The first condition of the highly heat-conductive inorganic powder of the present invention is that the average particle size is 1 to 20 μm and the maximum particle size is 45 μm or less. When the average particle size is less than 1 μm, the thermal conductivity is remarkably lowered. When the average particle size is more than 20 μm, the mixer, the mold, and the like are severely worn, and the productivity is lowered. On the other hand, when the maximum particle size is larger than 45 μm, not only the viscosity of the resin composition is easily increased, but also the coarse particles are clogged in a narrow gap, which impedes the penetration of the resin composition and is restricted in use. Here, the maximum particle size means a particle size in which the remaining amount remaining on the sieve by the water sieving method is less than 0.5% by mass.
[0009]
The highly thermally conductive inorganic powder of the present invention has a particle size configuration similar to that obtained by mixing two or more powders having different roundness depending on the particle size range. However, it may be a mixture of such materials. That is, the highly heat-conductive inorganic powder of the present invention includes the inorganic powder X and the inorganic powder Y, and the inorganic powder X, which is a constituent particle having a particle size range of 3 to 40 μm, has a spherical shape with a roundness of 0.80 or more and heat. The inorganic powder Y, which is a constituent particle having a conductivity of 10 W / mK or more and a particle size range of 0.1 to 1.5 μm, is spherical or non-spherical with a roundness of 0.30 or more and less than 0.80, and has a thermal conductivity. The second condition is equal to or less than that of the inorganic powder X.
[0010]
In the present invention, the reason why the inorganic powder X is selected to have a particle size range of 3 to 40 μm and the inorganic powder Y is selected to have a particle size range of 0.1 to 1.5 μm is that as a result of many experiments, by controlling the powder in these particle size ranges. This is because it has been found that the viscosity and thermal conductivity of the resin composition are the best. Further, if the roundness of the inorganic powder X is less than 0.80, the inorganic powder has the greatest influence on the viscosity of the resin composition, so that the resin composition is easily increased in viscosity and increased in viscosity. Filling becomes difficult. Furthermore, if the thermal conductivity is less than 10 W / mK, sufficiently high heat dissipation characteristics cannot be imparted to the resin composition. On the other hand, the inorganic powder Y does not greatly affect the thermal conductivity of the resin composition, but has an effect of entering between the inorganic powders X and promoting the heat path. Therefore, when the roundness is less than 0.30, it becomes difficult to enter between the inorganic powders X. When the roundness is 0.8 or more, the number of contact points with the inorganic powder X decreases, and the heat path promoting effect also decreases. End up. Moreover, even if the thermal conductivity exceeds that of the inorganic powder X, the thermal conductivity of the resin composition is greatly influenced by the inorganic powder X, so the thermal conductivity does not improve so much, and as the inorganic powder Y, A material having a higher thermal conductivity than that of the inorganic powder X may be used, but the significance of using a relatively expensive powder having a higher thermal conductivity is small.
[0011]
Here, the roundness can be measured using a scanning electron microscope (“JXA-8600M type” manufactured by JEOL Ltd.) and an image analysis device (manufactured by Nippon Avionics Co., Ltd.). That is, the projected area (A) and the perimeter (PM) of the particles are measured from the SEM photograph of the powder. When the area of a perfect circle corresponding to the perimeter (PM) is (B), the roundness of the particle is expressed as A / B. Therefore, assuming a perfect circle having the same circumference as that of the sample particle (PM), PM = 2πr and B = πr 2 , so that B = π × (PM / 2π) 2 , The roundness can be calculated as roundness = A / B = A × 4π / (PM) 2 . Therefore, in the present invention, an arbitrary 100 particles are measured, and the roundness of the powder is determined by the average value.
[0012]
The inorganic powder X is optimally aluminum oxide powder from the viewpoint of chemical stability and thermal conductivity. On the other hand, inorganic powders Y is crystal silica powder, fused (amorphous) silica powder, it is optimally one or a combination of aluminum oxide powder.
[0013]
The third condition of the high thermal conductivity inorganic powder of the present invention is that the ratio of the inorganic powder X and the inorganic powder Y is 1 to 30 in terms of a mass ratio of X / Y. The inorganic powder Y promotes the low viscosity of the resin composition by the inorganic powder X and enables high filling of the resin. When the X / Y ratio is less than 1, the proportion of the fine powder region is too small, and the resin composition easily increases in viscosity, and when it exceeds 30, the effect of imparting thermal conductivity is significantly reduced. The high thermal conductivity inorganic powder of the present invention is preferably composed of 60% or more (including 100%) of the inorganic powder X and inorganic powder Y, and the balance when the total is less than 100% is Further, it is preferably composed of spherical inorganic powder having a roundness of 0.80 or more and 1.5 to 3 μm.
[0014]
Next, another embodiment of the present invention will be described. These inventions are high thermal conductive inorganic powders that can further improve the thermal conductivity of the resin composition, and are also referred to as the high thermal conductive inorganic powders of the present invention (hereinafter referred to as “high thermal conductive inorganic powder base materials”). )).
[0015]
In No. 1, a high thermal conductive inorganic powder base material was surface-treated with one or more surface treatment agents A selected from silane coupling agents, titanate coupling agents and aluminate coupling agents. It is a high thermal conductive inorganic powder (hereinafter also referred to as “high thermal conductive inorganic powder A”). By using this, the adhesiveness with the resin is further enhanced, the interfacial thermal resistance between the high thermal conductive inorganic powder A and the resin is lowered, and further high thermal conductivity can be imparted. As the surface treatment agent A, a silane coupling agent is preferable from the viewpoint of reactivity with the high thermal conductive inorganic powder base material.
[0016]
As silane coupling agents, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β (3,4 epoxy epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-glycylmethoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltri Examples thereof include ethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like, and one or more of these are used.
[0017]
The surface treatment method of the highly heat conductive inorganic powder base material with the surface treatment agent A is a spray method using a fluid nozzle, a shearing stirring, a dry method such as a ball mill or a mixer, or a wet method such as an aqueous or organic solvent. Can be adopted. It should be noted that the shearing force is set so that the high thermal conductive inorganic powder base material is not broken.
[0018]
The system temperature in the dry method or the drying temperature after the treatment in the wet method is appropriately determined in the region where thermal decomposition does not occur depending on the type of the surface treatment agent A. For example, the temperature in the case of γ-aminopropyltriethoxysilane is desirably 80 to 150 ° C.
[0019]
The second is that when the resin composition has a low viscosity, such as an underfill material, the highly heat-conductive inorganic powder settles so that the thermal conductivity of the resin composition is not impaired. High thermal conductivity obtained by surface-treating a highly thermally conductive inorganic powder substrate or highly thermally conductive inorganic powder A with one or more surface treatment agents B selected from an surfactant and a polyacrylic acid surfactant. Inorganic powder (hereinafter, both are collectively referred to as “highly thermally conductive inorganic powder B”. The former treated powder is “highly thermally conductive inorganic powder b1”, and the latter treated powder is “highly thermally conductive inorganic powder b2”. It is also called.)
[0020]
The surface treatment of the high thermal conductivity inorganic powder base material or the high thermal conductivity inorganic powder A with the surface treatment agent B is performed in accordance with the treatment method of the surface treatment agent A. It should be noted that the treatment must be performed at a temperature at which thermal decomposition of the treatment agent B does not occur.
[0021]
In the present invention, the treatment with the surface treatment agent A and the surface treatment agent B may be either one or both. By both treatments, the adhesion with the resin and the prevention of sedimentation of the high thermal conductive inorganic powder can be reduced at the same time, and the heat dissipation of the resin composition can be improved.
[0022]
Further, in the case of both treatments with the surface treatment agent A and the surface treatment agent B, the treatments may be performed separately or at the same time. Accordingly, the surface treatment agent A and the surface treatment agent B are desirably a surface treatment agent composition mixed in advance from the viewpoint of handling, and the mixing ratio is 1 in terms of the mass ratio of the surface treatment agent B / the surface treatment agent A. It is preferably ~ 30. When the ratio is less than 1, an excessive surface treatment agent A cannot provide a sufficient sedimentation preventing effect due to an increase in the viscosity of the resin composition and a shortage of the surface treatment agent B. On the other hand, when the ratio exceeds 30, the adsorption site on the surface of the surface treatment agent A of the high thermal conductive inorganic powder is filled with the excess surface treatment agent B, and the unreacted surface treatment agent A increases, Adhesion does not improve sufficiently.
[0023]
The resin composition of the present invention comprises the above-described highly thermally conductive inorganic powder of the present invention, that is, a highly thermally conductive inorganic powder substrate, a highly thermally conductive inorganic powder A, and a highly thermally conductive inorganic powder B (that is, highly thermally conductive inorganic powder b1, Any one or two or more of highly conductive inorganic powders b2) are filled. The filling amount varies depending on the application, and is generally 50 to 95% by mass.
[0024]
Examples of the resin include epoxy resin, silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyamide such as polyimide, polyamideimide, and polyetherimide, polyester such as polybutylene terephthalate and polyethylene terephthalate, and polyphenylene ether. , Polyphenylene sulfide, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS resin, AAS (acrylonitrile-acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber / styrene) Resin or the like is used.
[0025]
When the resin composition is a liquid resin composition such as an underfill material, a liquid epoxy resin is used as the resin. As the liquid epoxy resin, any epoxy resin having two or more epoxy groups in one molecule can be used. Specific examples include phenol novolac type epoxy resins, orthocresol novolak type epoxy resins, epoxidized phenol and aldehyde novolak resins, glycidyl ethers such as bisphenol A, bisphenol F and bisphenol S, phthalic acid, Glycidyl ester acid epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, alkyl-modified polyfunctional epoxy resin obtained by reaction of polybasic acid such as dimer acid and epochlorohydrin, β-naphthol novolak-type epoxy resin, 1,6-dihydroxynaphthalene-type epoxy resin, 2,7-dihydroxynaphthalene-type epoxy resin, bishydroxybiphenyl-type epoxy resin, and halo such as bromine to impart flame retardancy Is introduced epoxy resin or the like down. Of these, epoxy resins that are liquid at room temperature are preferably used, and in particular, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, alicyclic epoxy resins, and the like, and these are one or two types. The above is used.
[0026]
The curing agent for the liquid epoxy resin is not particularly limited as long as it is cured by reacting with the liquid epoxy resin. For example, phenol, cresol, xylenol, resorcinol, chlorophenol, t-butylphenol, nonylphenol, isopropylphenol, octylphenol Such as novolak-type resin, polyparahydroxystyrene resin, bisphenol A, bisphenol S, and the like obtained by reacting a mixture of one or two or more selected from the group such as formaldehyde, paraformaldehyde or paraxylene under an oxidation catalyst Bisphenol compounds, trifunctional phenols such as pyrogallol and phloroglucinol, acid anhydrides such as maleic anhydride, phthalic anhydride and pyromellitic anhydride, metaphenylenediamine, diaminodiphenyl Methane, and aromatic amines such as diaminodiphenyl sulfone.
[0027]
The resin composition of the present invention may contain the following components as necessary. That is, as a low stress agent, silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, rubbery substances such as styrene block copolymers and saturated elastomers, various thermoplastic resins, resinous substances such as silicone resins, Is an epoxy resin, a resin obtained by modifying a part or all of a phenol resin with aminosilicone, epoxysilicone, alkoxysilicone, or the like. As a silane coupling agent, γ-glycidoxypropyltrimethoxysilane, β- (3,4- Epoxy cyclohexyl) Epoxy silanes such as ethyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, aminosilanes such as N-phenylaminopropyltrimethoxysilane, phenyltrimethoxysilane, methyltri Hydrophobic silane compounds such as methoxysilane and octadecyltrimethoxysilane, mercaptosilane and the like, surface treatment agents such as Zr chelates, titanate coupling agents and aluminum coupling agents, and flame retardant aids such as Sb 2 O 3 and Sb Examples of the flame retardant include 2 O 4 and Sb 2 O 5 , halogenated epoxy resins and phosphorus compounds, and examples of the colorant include carbon black, iron oxide, dye, and pigment.
[0028]
In the resin composition of the present invention, a curing accelerator can be blended to accelerate the reaction between the epoxy resin and the curing agent. Examples of the curing accelerator include 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like.
[0029]
The resin composition of the present invention can be produced by stirring, dissolving, mixing, and dispersing predetermined amounts of each of the above materials. A device for mixing, stirring, and dispersing these mixtures is not particularly limited, and a lykai machine equipped with a stirring and heating device, a three-roll, a ball mill, a planetary mixer, and the like can be used. Moreover, you may use combining these apparatuses suitably.
[0030]
When using the resin composition of this invention as an underfill material, it is preferable that the temperature at the time of making it infiltrate into the gap | interval of a semiconductor chip and a board | substrate and sealing is 60-120 degreeC.
[0031]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
[0032]
Examples 1-7 Comparative Examples 1-6
Inorganic powders 1 to 13 shown in Table 1 were prepared and mixed in a formulation as shown in Table 2. High heat conductive inorganic powder base materials A to E (Examples 1 to 5) and C to W (Comparison) Examples 1 to 6) were prepared. Their powder properties are shown in Table 4. In addition, the high heat conductive inorganic powder (Example 6) and the high heat conductive inorganic powder (Example 7) were obtained by surface-treating the high heat conductive inorganic powder substrate A according to the following, and the high heat conductive inorganic powder of the present invention. A and highly heat-conductive inorganic powder b1.
[0033]
In a 10 liter container having a ball diameter of 20 mm and a ball filling rate of 50% by volume, 1 kg of a high thermal conductive inorganic powder base material A and surface treatment agent A or surface treatment agent B shown in Table 3 are charged at room temperature and normal pressure. It was operated for 1 hour at a rate of 1 time / second under the conditions, and dried at 120 ° C. for 1 hour to obtain highly thermally conductive inorganic powders and powders.
[0034]
Each material was mixed in the ratio shown in Table 5, and high heat conductive inorganic powders I to W were mixed in this ratio at a ratio of 75% by mass in terms of inorganic powder to produce a resin composition. The viscosity, thermal conductivity, and wear amount of this were measured according to the following. The results are shown in Table 6.
[0035]
(1) Viscosity Using an E-type viscometer (“EHD Viscometer” manufactured by Tokyo Keiki Co., Ltd.), the viscosity was measured at a temperature of 40 ° C. and a rotation speed of 10 rpm.
[0036]
(2) The resin composition was poured into a mold provided with a disk-shaped hole having a thermal conductivity diameter of 28 mm and a thickness of 3 mm, and molded at 150 ° C. for 20 minutes after degassing. Using a thermal conductivity measuring device ("ARC-TC-1 type" manufactured by Agne Corporation), the temperature gradient was measured at room temperature.
[0037]
(3) Amount of wear The amount of decrease in the mass of the disc after passing 300 mm 3 of the resin composition through the hole of an aluminum disc having a thickness of 6 mm and a hole diameter of 3 mm was evaluated as the amount of wear.
[0038]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
As is clear from Tables 1 to 6, it can be seen that the resin composition using the highly heat-conductive inorganic powder of the present invention is superior to the comparative example in all of viscosity, heat conductivity, and wear.
[0045]
Examples 8 and 9
A test was conducted using a surface treatment agent composition comprising surface treatment agent A and surface treatment agent B. That is, high thermal conductive inorganic powder substrate (i), surface treatment agent A: silane coupling agent (trade name: KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), surface treatment agent B: polycarboxylic acid surfactant (trade name: Japan) The test was conducted using Marianim AKM-053) manufactured by Yushi Co., Ltd.
[0046]
In the surface treatment method, 1 kg of the high thermal conductive inorganic powder base material a is placed in a 10 liter container having a ball diameter of 20 mm and a ball filling rate of 50% by volume, and the surface treatment agent composition is 0.36 g in terms of mass of the surface treatment A. After being operated for 1 hour at a rate of 1 time / second under normal temperature and normal pressure conditions, it was dried at 120 ° C. for 1 hour to obtain highly heat-conductive inorganic powder b2. The results are shown in Table 7.
[0047]
[Table 7]
As is clear from Table 7, it can be seen that even a surface treatment agent composition comprising a mixture of surface treatment agent A and surface treatment agent B is sufficiently high to improve the thermal conductivity of the resin composition.
[0049]
【The invention's effect】
According to the present invention, a highly thermally conductive inorganic powder capable of preparing a resin composition that does not easily increase in viscosity even when highly filled into a resin and is excellent in heat dissipation, and filled with the resin are provided. A resin composition is provided.
Claims (5)
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| JP4501526B2 (en) * | 2004-05-14 | 2010-07-14 | 住友化学株式会社 | High thermal conductive resin composition |
| JP4634891B2 (en) * | 2005-08-18 | 2011-02-16 | 信越化学工業株式会社 | Thermally conductive silicone grease composition and cured product thereof |
| JP5012127B2 (en) * | 2007-03-24 | 2012-08-29 | 三菱マテリアル株式会社 | Manufacturing method of cement and concrete admixture |
| JP2009235402A (en) * | 2008-03-05 | 2009-10-15 | Hitachi Chem Co Ltd | Adhesive film |
| JP5503915B2 (en) * | 2009-07-30 | 2014-05-28 | 住友化学株式会社 | Liquid crystal polyester composition and electronic circuit board using the same |
| TWI522423B (en) | 2010-08-31 | 2016-02-21 | 道康寧東麗股份有限公司 | Polysiloxane composition and cured product thereof |
| CN103250243B (en) * | 2010-12-16 | 2016-04-27 | 三菱电机株式会社 | Semiconductor device |
| JP5767863B2 (en) * | 2011-06-01 | 2015-08-26 | 電気化学工業株式会社 | Spherical alumina powder, method for producing the same, and composition using the same |
| JP5755977B2 (en) * | 2011-09-08 | 2015-07-29 | 電気化学工業株式会社 | High thermal conductive resin composition |
| JP5921723B2 (en) | 2013-01-11 | 2016-05-24 | 三菱電機株式会社 | Semiconductor device |
| CN105659711A (en) * | 2013-10-17 | 2016-06-08 | 住友电木株式会社 | Epoxy-resin composition, carrier material with resin layer, metal-based circuit board, and electronic device |
| US10202530B2 (en) | 2014-08-27 | 2019-02-12 | Jnc Corporation | Composition for heat-dissipation members, heat-dissipation member, electronic device, and method of producing heat dissipating member |
| WO2017034003A1 (en) * | 2015-08-26 | 2017-03-02 | デンカ株式会社 | Thermally conductive resin composition |
| CN108713042A (en) * | 2016-03-02 | 2018-10-26 | 捷恩智株式会社 | The manufacturing method of Low thermal expansion member composition, Low thermal expansion member, e-machine and Low thermal expansion member |
| MY189227A (en) | 2016-05-16 | 2022-01-31 | Martinswerk Gmbh | Alumina products and uses thereof in polymer compositions with high thermal conductivity |
| JP2020122037A (en) * | 2019-01-29 | 2020-08-13 | 東洋インキＳｃホールディングス株式会社 | Pigment dispersion and inkjet ink |
| KR20230107646A (en) * | 2020-11-16 | 2023-07-17 | 스미또모 베이크라이트 가부시키가이샤 | Resin composition for semiconductor encapsulation and semiconductor device |
| CN115838583A (en) * | 2022-12-26 | 2023-03-24 | 广州市白云化工实业有限公司 | Anti-settling high-fluidity flame-retardant double-component organic silicon pouring sealant and preparation method thereof |
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