JP2020164592A - エポキシ樹脂組成物及びその硬化物 - Google Patents
エポキシ樹脂組成物及びその硬化物 Download PDFInfo
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- JP2020164592A JP2020164592A JP2019064453A JP2019064453A JP2020164592A JP 2020164592 A JP2020164592 A JP 2020164592A JP 2019064453 A JP2019064453 A JP 2019064453A JP 2019064453 A JP2019064453 A JP 2019064453A JP 2020164592 A JP2020164592 A JP 2020164592A
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- epoxy resin
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- thermal conductivity
- graphite particles
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Abstract
Description
このような中、特許文献1には、従来のアルミニウムブロック製ヒートシンクに代わる膨張黒鉛製のヒートシンクにおいて、切削加工時の膨張黒鉛の飛散や、その加工性・強度の課題に対して、熱硬化性樹脂として特にフェノール樹脂の粉体を用いてそれと膨張黒鉛のチップとの樹脂組成物をヒートシンクへ応用した例が示されている。ここでは、使用している汎用のフェノール樹脂粉体は溶融粘度が高いため、成形性と熱伝導性の両立に課題があった。また、熱伝導性を担う黒鉛粒子を高充填することが難しく、熱伝導率向上の面でも課題があった。
また、特許文献2には、エポキシ樹脂と高熱伝導性フィラーを用いた樹脂組成物が例示されているが、黒鉛粒子を用いた詳細な検討例は示されていない。
さらに、特許文献3には、ベース樹脂として熱可塑性樹脂を用いた黒鉛粒子を含む熱伝導性組成物が開示されており、熱伝導性に優れることが示されている。しかしながら、この特許文献3の主要樹脂であるポリフェニレンスルフィド樹脂に代表される熱可塑性樹脂は、高分子量ポリマーであることから溶融粘度が高く、ここでも成形性と熱伝導性の両立に課題があった。
エポキシ樹脂としては、分子中にエポキシ基を2個以上有する通常のエポキシ樹脂をすべて使用できる。例を挙げれば、ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール、4,4' −ビフェノール、3,3',5,5’−テトラメチル−4,4’−ジヒドロキシビフェニル、レゾルシン、ナフタレンジオール類等の2価のフェノール類のエポキシ化物、トリス−(4−ヒドロキシフェニル)メタン、1,1,2,2−テトラキス(4−ヒドロキシフェニル)エタン、フェノールノボラック、o−クレゾールノボラック等の3価以上のフェノール類のエポキシ化物、ジシクロペンタジエンとフェノール類から得られる共縮合樹脂のエポキシ化物、クレゾール類とホルムアルデヒドとアルコキシ基置換ナフタレン類から得られる共縮合樹脂のエポキシ化物、フェノール類とパラキシリレンジクロライド等から得られるフェノールアラルキル樹脂のエポキシ化物、フェノール類とビスクロロメチルビフェニル等から得られるビフェニルアラルキル型フェノール樹脂のエポキシ化物、ナフトール類とパラキシリレンジクロライド等から合成されるナフトールアラルキル樹脂類のエポキシ化物等がある。これらのエポキシ樹脂は、1種又は2種以上を混合して用いることができる。
エポキシ樹脂A:4,4’−ジヒドロキシジフェニルエーテルのグルシジルエーテル化物(YSLV−80DE 日鉄ケミカル&マテリアル製、エポキシ当量163g/eq.、150℃での溶融粘度0.008Pa・s)
エポキシ樹脂B:ビスフェノールA型エポキシ樹脂(YD−128 日鉄ケミカル&マテリアル株式会社製、エポキシ当量190g/eq.、150℃での溶融粘度0.02Pa・s)
エポキシ樹脂C:ビスフェノールF型エポキシ樹脂(YDF−170 日鉄ケミカル&マテリアル株式会社製、エポキシ当量170g/eq.、150℃での溶融粘度0.002Pa・s)
エポキシ樹脂D:フェノールノボラックのグルシジルエーテル化物(YDPN−6300 日鉄ケミカル&マテリアル株式会社製、エポキシ当量174g/eq.、150℃での溶融粘度0.03Pa・s)
エポキシ樹脂E:ビスフェノールA型エポキシ樹脂(YD−011 日鉄ケミカル&マテリアル株式会社製、エポキシ当量475g/eq.、150℃での溶融粘度1.8Pa・s)
硬化剤A:フェノールノボラックBRG−555(アイカ工業製、OH当量105g/eq.)
硬化剤B:4,4’−ジヒドロキシジフェニルエーテル(東京化成工業製試薬、OH当量101g/eq.)
黒鉛粒子:平均粒子径20μm、熱伝導率200W/m・K
硬化促進剤:トリフェニルホスフィン(東京化成工業製試薬)
上記で示した原料を用いて、表1に示す配合量で混練してエポキシ樹脂組成物を調整した。表中の数値は配合における重量部を示す。エポキシ樹脂と硬化剤の配合比率は全て、エポキシ樹脂/硬化剤の官能基が当量比で1.0とした。
1)エポキシ当量
エポキシ樹脂A〜Eのそれぞれについて、溶剤としてメチルエチルケトンを使用し、臭素化テトラエチルアンモニウム酢酸溶液を加え、電位差滴定装置にて0.1mol/L過塩素酸−酢酸溶液を用いて測定した。
BROOKFIELD製、CAP2000H型回転粘度計を用いて、エポキシ樹脂A〜Eのそれぞれについて、150℃にて測定した。
規格(EMMI−1−66)に準拠したスパイラルフロー測定用金型でエポキシ樹脂組成物をスパイラルフローの注入圧力(150Kgf/cm2)、硬化温度170℃、硬化時間3分の条件で成形して流動長を調べた。
エポキシ樹脂組成物を150Kgf/cm2の圧力で成形し、170℃、3分の条件で硬化させ成形物(硬化物)を得た。成形物の表面状態を目視により、〇、△、×の3段階で評価した。
〇:凹凸がなく光沢あり、△:所々に凹凸があるものの光沢あり、×:凹凸があり光沢なし
熱機械的分析装置(TMA測定装置、セイコーインスツル製)を用い、上記成形物(硬化物)を圧縮モードにおいて、200ml/分の窒素気流下、昇温速度10℃/分で200℃まで昇温、スキャンすることにより求めた。
示差走査熱量分析装置(DSC測定装置、セイコーインスツル製)を用い、50ml/分の窒素気流下、昇温速度10℃/分で220℃まで昇温、スキャンし、上記成形物(硬化物)の結晶の融点に基づく吸熱ピークにより求めた。
上記成形物(硬化物)の熱伝導率は、NETZSCH製LFA447型熱伝導率計を用いて非定常熱線法により測定した。
Claims (6)
- エポキシ樹脂、硬化剤及び黒鉛粒子を必須成分として含むエポキシ樹脂組成物において、エポキシ樹脂は、その150℃での溶融粘度が0.001〜1.0Pa・sであり、黒鉛粒子の含有率が60〜95重量%であることを特徴とするエポキシ樹脂組成物。
- 請求項1〜3のいずれか一項に記載のエポキシ樹脂組成物を硬化させたものであることを特徴とするエポキシ樹脂硬化物。
- 前記エポキシ樹脂硬化物が、LED用放熱部材に用いられることを特徴とする請求項4に記載のエポキシ樹脂硬化物。
- 前記LED用放熱部材が、LED用ヒートシンクであることを特徴とする請求項5に記載のエポキシ樹脂硬化物。
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JP2004281261A (ja) * | 2003-03-17 | 2004-10-07 | Nippon Steel Chem Co Ltd | 燃料電池用セパレータ及びその製造方法 |
JP2005285552A (ja) * | 2004-03-30 | 2005-10-13 | Nippon Steel Chem Co Ltd | 燃料電池セパレータ用組成物および燃料電池セパレータの製造方法 |
JP2015061924A (ja) * | 2014-12-02 | 2015-04-02 | 日立化成株式会社 | 熱伝導シート、熱伝導シートの製造方法、及び熱伝導シートを用いた放熱装置 |
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