JP2004311577A - Thermally conductive composite sheet and method of manufacturing the same - Google Patents
Thermally conductive composite sheet and method of manufacturing the same Download PDFInfo
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- JP2004311577A JP2004311577A JP2003100416A JP2003100416A JP2004311577A JP 2004311577 A JP2004311577 A JP 2004311577A JP 2003100416 A JP2003100416 A JP 2003100416A JP 2003100416 A JP2003100416 A JP 2003100416A JP 2004311577 A JP2004311577 A JP 2004311577A
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47C—CHAIRS; SOFAS; BEDS
- A47C9/00—Stools for specified purposes
- A47C9/02—Office stools not provided for in main groups A47C1/00, A47C3/00 or A47C7/00; Workshop stools
- A47C9/027—Stools for work at ground level
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47C—CHAIRS; SOFAS; BEDS
- A47C3/00—Chairs characterised by structural features; Chairs or stools with rotatable or vertically-adjustable seats
- A47C3/20—Chairs or stools with vertically-adjustable seats
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47C—CHAIRS; SOFAS; BEDS
- A47C7/00—Parts, details, or accessories of chairs or stools
- A47C7/62—Accessories for chairs
Landscapes
- Laminated Bodies (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cooling Or The Like Of Electrical Apparatus (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、発熱性電子部品等の放熱シートとして用いられる熱伝導性複合シートおよびその製造方法に関する。
【０００２】
【従来技術】
テレビ、コンピュータ、通信装置等の電子機器の小型化により、これらに搭載される回路の集積度が増大している。そして、この集積回路に実装される電子部品、特にＣＰＵ等のＩＣパッケージは発熱によって性能が低下するため、放熱対策として、金属板等からなりＩＣパッケージ等の熱を伝導して外部に放出するヒートシンクが用いられている。
【０００３】
さらに、ＩＣパッケージとヒートシンクの間の熱伝導効率を高めるべく、両者の間に熱伝導性の良いグリース、シリコーンゴムシート等を介装することが従来から行われている。ところが、熱伝導性グリースは部品の汚染やオイルのブリード（分離）の他、粘度が上昇して被着面と強固に密着し、リワーク（電子部品の修理、交換等のためヒートシンク等の熱伝導性部材を取り外すこと）時に電子部品がヒートシンクと一緒に外れる等の欠点があった。また、熱伝導性シリコーンゴムシートの場合、硬度を高くするとリワーク性は向上するが、電子部品との追随性が低下して界面熱抵抗が大となり放熱性能が劣化し、一方で硬度が低いと電子機器へのマウントが難しくなる欠点があった。
【０００４】
このようなことから、熱軟化性の樹脂シートにより、電子部品との追随性を向上させて放熱性能を高める技術が報告されている（例えば、特許文献１参照）。又、シートの厚み方向だけでなく、面方向への熱伝導性を向上させて放熱性能をさらに高める方策として、面方向への熱伝導性が良いグラファイトシートを用いた技術が報告されている（例えば、特許文献２参照）。
【０００５】
【特許文献１】
特開２００２−３２９９８９号公報
【特許文献２】
特公平３−５１３０２号公報
【０００６】
【発明が解決しようとする課題】
しかしながら、上記特許文献１記載の技術の場合、樹脂シート表面が熱軟化性のため、リワーク性が不充分である。又、特許文献２記載の技術の場合、面方向の熱伝導性は改善されるものの、グラファイト層にゴム成分を塗工し、このゴム層によって電子部品への密着を付与しているため、塗工工程に非常に手間がかかり、さらにリワーク性も充分とはいえない。
【０００７】
一方、上記した各種の問題、つまり、シートの面方向の熱伝導性や電子部品とのリワーク性を同時に改善しようとして複数のシートを徒に積層すると、シートの厚み方向の熱伝導性が大幅に低下して放熱性能も劣化する。従って、単純に従来の放熱シートを組み合わせただけでは、放熱性能とリワーク性をともに満足するものは得られない。
【０００８】
本発明者らは、上記課題を解決するために種々検討した結果、リワーク性を確保するため外層の少なくとも一方にシリコーンゴム層を設け、内層には対象物との追随性を向上させる熱軟化性の中間層を設ける３層構造により、熱伝導性とリワーク性をともに向上させることに成功した。又、本発明者らは、この中間層として熱伝導性充填剤を含有しない材料を用いると放熱性能が極端に低下することも見出した。従って、本発明は上記の課題を解決するためになされたものであり、熱伝導性とリワーク性をともに向上させることができる熱伝導性複合シートおよびその製造方法の提供を目的とする。
【０００９】
【課題を解決するための手段】
上記した目的を達成するために、本発明によれば、（ａ）熱伝導性充填剤を含有するシリコーンゴムからなる熱伝導性シリコーンゴム層と、（ｂ）シリコーン樹脂及び熱伝導性充填剤を含有し、粘着性を有する熱軟化性熱伝導層と、（ｃ）面方向への熱伝導率が２０〜５００Ｗ／（ｍ・Ｋ）の熱伝導層とをこの順で積層した構造を有することを特徴とする熱伝導性複合シートが提供される。
このようにすると、外層側にリワーク性の優れた熱伝導性シリコーンゴム層が存在し、その熱は熱軟化性熱伝導層を介して反対側の熱伝導層から効率よく放熱されるので、熱伝導性、放熱性、及びリワーク性をともに満足できる。
【００１０】
前記熱伝導層の表面に、さらに（ｄ）シリコーン樹脂および熱伝導性充填剤を含有し、粘着性を有する第２の熱軟化性熱伝導層を設けてもよい。
このようにすると、熱軟化により第２の熱軟化性熱伝導層がヒートシンク等と密着するので、熱伝導層からヒートシンク等へ効率よく熱伝導し、放熱性がさらに向上する。
【００１１】
又、本発明によれば、（ａ）熱伝導性充填剤を含有するシリコーンゴムからなる熱伝導性シリコーンゴム層と、（ｂ）シリコーン樹脂及び熱伝導性充填剤を含有し、粘着性を有する熱軟化性熱伝導層と、（ｅ） 熱伝導性充填剤を含有するシリコーンゴムからなり前記熱伝導性シリコーンゴム層より硬度が低い第２の熱伝導性シリコーンゴム層とをこの順で積層した構造を有することを特徴とする熱伝導性複合シートが提供される。
このようにすると、表裏の外層側にいずれもリワーク性の優れた熱伝導性シリコーンゴム層が存在するので、リワーク性が大幅に向上する。又、一方の外層側の熱は熱軟化性熱伝導層を介して反対側の外層から放熱されるので、熱伝導性にも優れる。
【００１２】
さらに、本発明によれば、前記熱伝導性シリコーンゴム層、前記熱軟化性熱伝導層、及び前記熱伝導層又は前記第２の熱伝導性シリコーンゴム層をこの順に積層した状態で、室温圧着又は熱圧着することを特徴とする熱伝導性複合シートの製造方法が提供される。
【００１３】
【発明の実施の形態】
以下、本発明に係る熱伝導性複合シートおよびその製造方法の実施の形態について説明する。
【００１４】
１．第１の実施形態
［熱伝導性シリコーンゴム層］
この層は、本発明に係る熱伝導性複合シートの外層側にあって放熱対象物（電子部品等）に接触し、その熱を伝導するものであり、リワーク性を付与するとともに、形状安定性を高めてシート製造時の生産性を確保するべく、所定硬度を有する。又、熱伝導性を付与すべく、熱伝導性シリコーンゴム層には、熱伝導性充填剤が含有されている。シリコーンゴムとしては特にその種類は制限されないが、例えば、（Ａ）１分子中に２個以上のアルケニル基を有するオルガノポリシロキサン、（Ｂ）１分子中に、珪素原子に結合した水素原子を２個以上有するポリオルガノハイドロジェンシロキサン、（Ｃ）白金系触媒を含むシリコーンゴム、を使用することができる。又、熱伝導性充填剤としては、銅、銀、アルミニウム等の金属の粉末、アルミナ、シリカ、酸化マグネシウム、酸化亜鉛等の金属酸化物の粉末、窒化アルミニウム、窒化ケイ素、窒化ホウ素等の金属窒化物の粉末、人工ダイヤモンド粉末、を使用することができる。熱伝導性充填剤の含有割合は、例えば、熱伝導性シリコーンゴム層全体に対し、７０〜９７重量％とすることができ、好ましくは８５〜９５重量％とすることができる。熱伝導性充填剤の含有量が少ないと、熱伝導性シリコーンゴム層の熱伝導性が低下し、含有量が多いと、均一な熱伝導性シリコーンゴムが得られないからである。
【００１５】
熱伝導性シリコーンゴム層の硬度は、シート生産時の取り扱い性、形状保持性を確保すべく、好ましくはアスカーＣ硬度で１０〜６０、より好ましくはアスカーＣ硬度で２０〜５０とする。ここでアスカーＣ硬度とは、ＳＲＩＳ ０１０１（日本ゴム協会規格）及びＪＩＳ−Ｓ ６０５０に基づき、スプリング式硬さ試験機アスカーＣ型を使用して測定した硬さである。熱伝導性シリコーンゴム層のアスカーＣ硬度が１０未満であると、シートが軟らかくなり過ぎて形状保持が困難となり、補強性が不十分となって生産性が低下する。逆に大きすぎると、電子部品等との密着性が低下し、追随性が悪くなって放熱性能の低下を招く。又、ＪＩＳ−Ｋ６２５３に規定されるデュロメータタイプＡ硬度を指標とした場合、好ましくは３０〜１００、より好ましくは４０〜９０とする。なお、一般に、アスカーＣ硬度は、デュロメータタイプＡ硬度では測定が困難な柔らかい材料の硬度を測定する指標である。
【００１６】
熱伝導性シリコーンゴム層に用いることができる、市販されている熱伝導性シリコーンゴムシートとしては、ＴＣ−５０ＴＨＳ（アスカーＣ硬度２０、信越化学工業株式会社製；商品名）、ＴＣ−５０ＴＸＳ（アスカーＣ硬度４０、信越化学工業株式会社製；商品名）、ＴＣ−２０ＢＧ（デュロメータタイプＡ硬度８５、信越化学工業株式会社製；商品名）、ＴＣ−４５ＢＧ（デュロメータタイプＡ硬度８５、信越化学工業株式会社製；商品名）、ＴＣ−３０ＥＧ（デュロメータタイプＡ硬度９０、信越化学工業株式会社製；商品名）、ＴＣ−４５ＥＧ（デュロメータタイプＡ硬度９０、信越化学工業株式会社製；商品名）が挙げられる。
【００１７】
［熱軟化性熱伝導層］
この層は、シリコーン樹脂マトリックス中に熱伝導性充填剤が分散されて構成されるものである。また、この層は、本発明に係る熱伝導性複合シートの中間層をなし、その粘着性により外層同士をつなぎ合わせる機能を有するとともに、熱伝導性充填剤により良好な熱伝導性を確保してシート全体の熱伝導性も向上させるものである。シリコーン樹脂は、粘着性を有し熱軟化性のものであれば特にその種類は制限されないが、例えば以下の式で表される、Ｄ体（２官能性構造単位）及びＴ体（３官能性構造単位）を所定組成で含むものを挙げることができる。
Ｄ１ ｍＴｐＤ２ ｍ
ここで、Ｄ１はジメチルシロキサン単位（すなわち、（ＣＨ３）２ＳｉＯ）を、Ｔはフェニルシロキサン単位（すなわち、（Ｃ６Ｈ５）２ＳｉＯ３／２）を、Ｄ２はメチルビニルシロキサン単位（すなわち、（ＣＨ３）（ＣＨ２＝ＣＨ）ＳｉＯ）を示す。又、（ｍ＋ｎ）／ｐ＝０．２５〜４．０（モル比）、（ｍ＋ｎ）／ｍ＝１．０〜４．０の関係にある。上記式で表される組成物であれば粘着性が発現される。
【００１８】
ここで、熱軟化性とは、熱により低粘度化、熱軟化または融解することをいい、熱軟化性熱伝導層が流動化して被着面に追随・密着することにより、界面熱抵抗を低減する。そして、通常４０〜１００℃、特に４０〜９０℃の温度範囲において、低粘度化、熱軟化、又は融解して表面が流動化するものを「熱軟化性」を有するものとすることができる。
【００１９】
シリコーン樹脂に分散させる熱伝導性充填剤としては、上記した熱伝導性シリコーンゴム層に用いたものと同様のものを用いることができる。又、熱伝導性充填剤の含有割合は例えば、熱軟化性熱伝導性層全体に対し、７０〜９７重量％とすることができ、好ましくは８５〜９５重量％とすることができる。熱伝導性充填剤の含有量を規定した理由は、上記熱伝導性シリコーンゴム層の場合と同様である。
【００２０】
熱軟化性熱伝導層に用いることができる、市販されている熱軟化性熱伝導性シートとしては、ＰＣＳ−ＴＣ−１０、ＰＣＳ−ＴＣ−１１、ＰＣＳ−ＴＣ−２０（いずれも信越化学工業株式会社製；商品名）が挙げられる。
【００２１】
［熱伝導層］
この層は、シートの反対側の外層にあってヒートシンク等の放熱部材等に接触し、中間層を介して伝導された熱を放熱する機能を有するとともに、面方向の熱伝導性が高いために放熱性能が高くなっている。そして、熱伝導層の面方向の熱伝導性率を２０〜５００Ｗ／（ｍ・Ｋ）とすることで、面方向へ熱が伝導され易くなる。熱伝導性が２０Ｗ／（ｍ・Ｋ）未満であると、面方向の熱伝導性が充分でなく、５００Ｗ／（ｍ・Ｋ）を超えても熱伝導性の効果が飽和する。熱伝導層としては、グラファイトシート、アルミホイル等が使用できる。
【００２２】
熱伝導層に用いることができる、市販されているグラファイトシートとしては、ＭＡＣＦＯＩＬ（ジャパンマテックス株式会社製；商品名）、ＰＧＳグラファイトシート（松下電器産業株式会社製；商品名）が挙げられ、アルミホイルとしては例えば日本軽金属株式会社製のものが挙げられる。
【００２３】
そして、上記熱伝導性シリコーンゴム層と、熱軟化性熱伝導層と、熱伝導層とをこの順で積層することにより、第１の実施形態に係る熱伝導性複合シートが構成される。このような構成により、離型性の良好な熱伝導性シリコーンゴム層が最外層として電子部品等の放熱対象物と接触するので、いわゆるリワーク性を向上させることができる。そして、面方向の熱伝導性に優れた熱伝導層が反対側の外層に位置するので、熱伝導層から外部への放熱が促進される。さらに、中間層となる熱軟化性熱伝導層により、熱伝導性シリコーンゴム層からの熱を熱伝導層へ効率よく伝導させることができるので、放熱特性が大幅に向上する。又、熱軟化性熱伝導層が熱軟化することによって、外層の熱伝導性シリコーンゴム層も放熱対象物と密着し、放熱対象物の熱を伝導しやすくなる。
【００２４】
２．第２の実施形態
この熱伝導性複合シートは、上記熱伝導層の表面に、さらに第２の熱軟化性熱伝導層を設けたものである。第２の熱軟化性熱伝導層は、上記熱軟化性熱伝導層と同様、シリコーン樹脂マトリックス中に熱伝導性充填剤が分散されて構成されるものである。第２の熱軟化性熱伝導層に用いるシリコーン樹脂、熱伝導性充填剤、及びその含有割合は、上記熱軟化性熱伝導層について説明した中から選択することができ、又、上記熱軟化性熱伝導層と同一の樹脂や熱伝導性充填剤を用いてもよく、他の種類の樹脂等を用いてもよい。
【００２５】
第２の熱軟化性熱伝導層が外層に位置することにより、この層の表面が流動化し被着面（ヒートシンク等）に追随、密着するので、被着面との間に空隙が生じず界面熱抵抗が低減し、熱伝導層の熱をヒートシンク等に効率良く伝導させることができ、放熱特性が大幅に向上する。
【００２６】
３．第３の実施形態
この熱伝導性複合シートは、上記第１の実施形態に係る熱伝導性複合シートの熱伝導層に代えて、第２の熱伝導性シリコーンゴム層を設けたものである。第２の熱伝導性シリコーンゴム層に用いるシリコーンゴム、熱伝導性充填剤、及びその含有割合は、上記熱伝導性シリコーンゴム層について説明した中から選択することができ、又、上記熱伝導性シリコーンゴム層と同一のシリコーンゴムや熱伝導性充填剤を用いてもよく、他の種類の樹脂等を用いてもよい。
【００２７】
第２の熱伝導性シリコーンゴム層は、上記熱伝導性シリコーンゴム層より硬度を低くする。この理由は、上記熱伝導性シリコーンゴム層が形状安定性を高めるべく比較的高い硬度を有するので、第２の熱伝導性シリコーンゴム層の硬度を高くする必要がなく、その分被着面（電子部品又はヒートシンク等）との密着性、追随性を向上させて放熱特性を改善させるためである。
【００２８】
なお、第３の実施形態に係る熱伝導性複合シートの場合、対象との追随性の良好な第２の熱伝導性シリコーンゴム層側を放熱対象物（電子部品等）に接触させ、やや硬質な熱伝導性シリコーンゴム層側を外部（ヒートシンク等）に接触させるのが好ましい。
【００２９】
第２の熱伝導性シリコーンゴム層が外層に位置することにより、この層の表面が被着面（電子部品又はヒートシンク等）に追随、密着し易くなるので、被着面との間に空隙が生じず界面熱抵抗が低減し、その結果として放熱特性が向上する。又、粘着性の熱軟化性の樹脂である中間層が外層に表出しないので、シートの取り扱い性、リワーク性も良好となる。
【００３０】
次に、本発明に係る熱伝導性複合シートの製造方法について説明する。本発明の製造方法は、熱伝導性シリコーンゴム層、熱軟化性熱伝導層、及び熱伝導層又は第２の熱伝導性シリコーンゴム層を、室温圧着又は熱圧着することにより熱伝導性複合シートを製造するものである。
【００３１】
室温圧着の場合は、例えばテープ状の熱伝導性シリコーンゴムシートとグラファイトシートの間に、離型処理したポリマーフィルムが表面に貼着されたテープ状の熱軟化性熱伝導性シートを供給し、ポリマーフィルムを剥がした後、熱伝導性シリコーンゴムシート、グラファイトシート、及び熱軟化性熱伝導性シートがこの順で積層されたものを室温の双ロール間に通して圧着する。熱圧着の場合は、上記双ロールを熱軟化性熱伝導性シートの熱軟化温度以上（例えば８０〜１２０℃）に加熱して同様に圧着する。なお、圧着はロール法の他、ヒートプレス等を用いてもよい。又、上記第２の実施形態に係る熱伝導性複合シートを製造する場合は、グラファイトシートの外側に上記と同様のテープ状の熱軟化性熱伝導性シートを供給し、全体を圧着すればよい。
【００３２】
次に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
【００３３】
【実施例】
１．各材料の準備
以下のシート及び粘着剤を準備した。
［熱伝導性シリコーンゴムシート］
ａ−１；ＴＣ−５０ＴＸＳ（商品名；信越化学工業株式会社製、厚さ５００μｍ、アスカーＣ硬度４０）
ａ−２；ＴＣ−５０ＴＨＳ（商品名；信越化学工業株式会社製、厚さ５００μｍ、アスカーＣ硬度２０）
ａ−３；ＴＣ−４５ＢＧ（商品名；信越化学工業株式会社製、厚さ４５０μｍ、デュロメータＡ硬度８５）
ａ−４；ＴＣ−４５ＥＧ（商品名；信越化学工業株式会社製、厚さ４５０μｍ、デュロメータＡ硬度９０）
［熱軟化性熱伝導性シート］
ｂ−１；ＰＣＳ−ＴＣ−２０−Ｇ−１０（商品名；信越化学工業株式会社製、厚さ１００μｍ）
ｂ−２；ＰＣＳ−ＴＣ−１１−Ｇ−１３（商品名；信越化学工業株式会社製、厚さ１３０μｍ）
［熱伝導性シート］
ｃ−１；ＭＡＣＦＯＩＬ（商品名；ジャパンマテックス株式会社製、厚さ１３０μｍ、面方向の熱伝導率１５０Ｗ／（ｍ・Ｋ））
ｃ−２；アルミホイル（日本軽金属株式会社製、厚さ５０μｍ、面方向の熱伝導率２３７Ｗ／（ｍ・Ｋ））
［熱軟化性熱伝導性シート］
ｄ−１；ＰＣＳ−ＴＣ−２０−Ｇ−２０（商品名；信越化学工業株式会社製、厚さ２００μｍ）
［熱伝導性シリコーンゴムシート］
ｅ−１；ＴＣ−２０ＢＧ（商品名；信越化学工業株式会社製、厚さ２００μｍ、デュロメータＡ硬度８５）
［シリコーン粘着剤］
ｂ−３；ＫＲ−１０１−１０（商品名；信越化学工業株式会社製）
【００３４】
２．熱伝導性複合シートの製造
上記熱伝導性シリコーンゴムシート、熱軟化性熱伝導性シート、熱伝導性シートを適宜組合せ、室温の双ロール間に通して圧着して熱伝導性複合シートを製造した。熱圧着の場合は、上記双ロールを１００℃に加熱して同様に圧着した。なお、一部の試料については、熱軟化性熱伝導性シートを用いる代わりにシリコーン粘着剤を用い、このシリコーン粘着剤を上記熱伝導性シリコーンゴムシート又は熱伝導性シートに塗布した後、上記双ロールを用いて同様に圧着した。
【００３５】
３．評価
得られた各熱伝導性複合シートを５×５ｃｍに切り出し、この試験片について下記特性を評価した。
シート厚み
マイクロメーター（株式会社ミツトヨ製、型式；Ｍ８２０−２５ＶＡ）を用いて測定した。
熱抵抗
トランジスタ（富士電機株式会社製；商品名２ＳＤ９２３）とヒートシンク（株式会社オーエス製；商品名ＦＢＡ−１５０−ＰＳ）の間に各試験片を介装し、圧縮加重３４５ｋＰａで荷重した。ヒートシンクは予め恒温水槽の中に入れ６５℃に保温しておき、実験開始とともに恒温槽から取出して試験片を取り付けた。次に、トランジスタに１０Ｖ、３Ａの電力を供給し、５分経過後のトランジスタの温度Ｔ１と、ヒートシンクに埋め込んだ熱電対の温度Ｔ２を測定し、次式からサンプルの熱抵抗ＲＳ（℃／Ｗ）を算出した。
ＲＳ＝（Ｔ１−Ｔ２）／３０
（３）リワーク性
二枚の標準アルミニウムプレートの間に各試験片を挟み、圧縮加重４９０ｋＰａで荷重した後、１５０℃のオーブン中に９６時間放置した。放置後、アルミニウムプレートを引き離す方向へ手で力を加え、アルミニウムプレートと試験片との間の剥がれやすさを判定した。
評価Ａ：容易に剥がれる
評価Ｂ：若干の力を加えると剥がれる
評価Ｃ：剥がれにくい
評価Ｄ：非常に剥がれにくく、層間剥離を起こしやすい
【００３６】
得られた熱伝導性複合シートの構成、及び評価結果を表１に示す。なお、表１において、第１層、第２層の順に各シート（又は粘着剤）が積層され、又、第１層側をトランジスタに接触させ、反対側の外層をヒートシンク側に接触させた。
【００３７】
【表１】
表１から明らかなように、各実施例はいずれも、熱抵抗が低くて（０．５℃／Ｗ以下）放熱性能に優れるとともに、リワーク性にも優れたものとなっている。なお、実施例３、４は、高硬度のシリコーンゴムを熱伝導性シリコーンゴムシートとして外層側に設けたため、若干熱抵抗が高くなったが実用上は問題がなく、さらにリワーク性が大幅に向上した。又、面方向の熱伝導性に優れた熱伝導層を外層側に設けた実施例１、２、５〜７、９の場合、熱抵抗が約０．３℃／Ｗ以下と極めて低いものとなった。
【００３９】
一方、中間層としてシリコーン粘着剤を用いた比較例１〜３の場合、この中間層の熱伝導性が低下したため、いずれも熱抵抗が０．５℃／Ｗを超えた。又、２層構造とした比較例４、５の場合、外層が外部と密着して層間剥離を起こした。外層側に粘着性の熱軟化性熱伝導層を設けた比較例６の場合、シート表面の粘着性が高くなったためにリワーク性が悪化した。
【００４０】
【発明の効果】
以上の説明で明らかなように、本発明の熱伝導性複合シートは、熱伝導性とリワーク性に共に優れており、発熱性電子部品等の放熱、冷却のために用いられる放熱構造体用として好適なものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a heat conductive composite sheet used as a heat dissipation sheet for heat-generating electronic components and the like, and a method for producing the same.
[0002]
[Prior art]
2. Description of the Related Art As electronic devices such as televisions, computers, and communication devices have become smaller, the degree of integration of circuits mounted thereon has increased. Since the performance of electronic components mounted on this integrated circuit, especially IC packages such as CPUs, deteriorates due to heat generation, a heat sink made of a metal plate or the like, which conducts heat of the IC package or the like and discharges the heat to the outside, is used as a heat dissipation measure. Is used.
[0003]
Further, in order to increase the heat conduction efficiency between the IC package and the heat sink, it has been conventionally performed to interpose grease, a silicone rubber sheet, or the like having good heat conductivity between the two. However, thermal conductive grease, in addition to contamination of parts and bleeding (separation) of oil, increases in viscosity and firmly adheres to the surface to be adhered, and rework (heat conduction for heat sink etc. for repair or replacement of electronic parts etc.) However, there is a drawback that the electronic component comes off together with the heat sink when the conductive member is removed. In the case of a heat-conductive silicone rubber sheet, increasing the hardness improves reworkability, but reduces the ability to follow electronic components, increases interfacial thermal resistance, and degrades heat dissipation performance. There is a drawback that mounting on electronic devices becomes difficult.
[0004]
For this reason, a technique has been reported in which a heat-softening resin sheet is used to improve the ability to follow electronic components to enhance heat dissipation performance (for example, see Patent Document 1). In addition, as a measure for improving the thermal conductivity not only in the thickness direction of the sheet but also in the plane direction to further enhance the heat radiation performance, a technique using a graphite sheet having good thermal conductivity in the plane direction has been reported ( For example, see Patent Document 2).
[0005]
[Patent Document 1]
JP 2002-329989 A [Patent Document 2]
Japanese Patent Publication No. 3-51302
[Problems to be solved by the invention]
However, in the case of the technique described in Patent Document 1, reworkability is insufficient because the surface of the resin sheet is thermally softened. Further, in the case of the technology described in Patent Document 2, although the thermal conductivity in the surface direction is improved, a rubber component is applied to the graphite layer, and the rubber layer provides adhesion to electronic components. The construction process is very time-consuming and reworkability is not sufficient.
[0007]
On the other hand, when the above-mentioned various problems, that is, the thermal conductivity in the surface direction of the sheet and the reworkability with the electronic component are simultaneously laminated to improve the thermal conductivity in the thickness direction of the sheet, the thermal conductivity in the thickness direction of the sheet greatly increases. As a result, the heat radiation performance deteriorates. Therefore, simply combining conventional heat radiation sheets does not provide a material that satisfies both heat radiation performance and reworkability.
[0008]
The present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, provided a silicone rubber layer on at least one of the outer layers to ensure reworkability, and a heat-softening property for improving the followability with the object in the inner layer. With the three-layer structure in which the intermediate layer is provided, both the thermal conductivity and the reworkability were successfully improved. The present inventors have also found that when a material that does not contain a thermally conductive filler is used as the intermediate layer, the heat radiation performance is extremely reduced. Accordingly, the present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a thermally conductive composite sheet capable of improving both thermal conductivity and reworkability, and a method for producing the same.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, according to the present invention, (a) a heat conductive silicone rubber layer comprising a silicone rubber containing a heat conductive filler, and (b) a silicone resin and a heat conductive filler are provided. A heat-softening heat conductive layer containing and having adhesiveness, and a heat conductive layer having a heat conductivity in the direction of the plane of (c) of 20 to 500 W / (m · K) are laminated in this order. A heat conductive composite sheet is provided.
In this case, the heat conductive silicone rubber layer having excellent reworkability exists on the outer layer side, and the heat is efficiently radiated from the heat conductive layer on the opposite side via the heat softening heat conductive layer. Both conductivity, heat dissipation, and reworkability can be satisfied.
[0010]
On the surface of the heat conductive layer, a second heat softening heat conductive layer containing (d) a silicone resin and a heat conductive filler and having tackiness may be provided.
With this configuration, the second heat-softening heat conductive layer is in close contact with the heat sink or the like due to the heat softening, so that the heat is efficiently conducted from the heat conductive layer to the heat sink or the like, and the heat dissipation is further improved.
[0011]
Further, according to the present invention, (a) a thermally conductive silicone rubber layer made of a silicone rubber containing a thermally conductive filler, and (b) a silicone resin and a thermally conductive filler are contained, and the composition has an adhesive property. A heat-softening heat-conductive layer and (e) a second heat-conductive silicone rubber layer made of a silicone rubber containing a heat-conductive filler and having a lower hardness than the heat-conductive silicone rubber layer were laminated in this order. A heat conductive composite sheet having a structure is provided.
In this case, since the thermally conductive silicone rubber layer having excellent reworkability is present on both the front and back outer layers, the reworkability is greatly improved. In addition, heat on one outer layer side is radiated from the outer layer on the other side via the heat-softening heat conductive layer, so that heat conductivity is also excellent.
[0012]
Further, according to the present invention, the heat conductive silicone rubber layer, the heat softening heat conductive layer, and the heat conductive layer or the second heat conductive silicone rubber layer are laminated in this order, and are pressed at room temperature. Alternatively, a method for producing a thermally conductive composite sheet, which is characterized by performing thermocompression bonding, is provided.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of a heat conductive composite sheet and a method for manufacturing the same according to the present invention will be described.
[0014]
1. First Embodiment [Thermal Conductive Silicone Rubber Layer]
This layer is located on the outer layer side of the heat conductive composite sheet according to the present invention, and is in contact with a heat-dissipating object (such as an electronic component) and conducts its heat. And has a predetermined hardness in order to increase productivity and secure productivity during sheet production. Further, in order to impart thermal conductivity, the thermally conductive silicone rubber layer contains a thermally conductive filler. The type of the silicone rubber is not particularly limited, and examples thereof include (A) an organopolysiloxane having two or more alkenyl groups in one molecule, and (B) two hydrogen atoms bonded to a silicon atom in one molecule. Or more polyorganohydrogensiloxanes, and (C) a silicone rubber containing a platinum-based catalyst. Examples of the thermally conductive filler include powders of metals such as copper, silver, and aluminum; powders of metal oxides such as alumina, silica, magnesium oxide, and zinc oxide; and metal nitrides such as aluminum nitride, silicon nitride, and boron nitride. Product powder and artificial diamond powder. The content ratio of the thermally conductive filler can be, for example, 70 to 97% by weight, and preferably 85 to 95% by weight, based on the entire thermally conductive silicone rubber layer. When the content of the heat conductive filler is small, the heat conductivity of the heat conductive silicone rubber layer is reduced, and when the content is large, a uniform heat conductive silicone rubber cannot be obtained.
[0015]
The hardness of the thermally conductive silicone rubber layer is preferably 10 to 60 as Asker C hardness, more preferably 20 to 50 as Asker C hardness, in order to ensure handleability and shape retention during sheet production. Here, the Asker C hardness is a hardness measured by using a spring type hardness tester Asker C type based on SRIS 0101 (Standard of the Japan Rubber Association) and JIS-S6050. If the Asker C hardness of the thermally conductive silicone rubber layer is less than 10, the sheet becomes too soft to hold the shape, and the reinforcing property becomes insufficient, and the productivity decreases. On the other hand, if it is too large, the adhesion to electronic components and the like will be reduced, and the followability will be reduced, leading to a reduction in heat radiation performance. When the durometer type A hardness specified in JIS-K6253 is used as an index, it is preferably 30 to 100, more preferably 40 to 90. In general, Asker C hardness is an index for measuring the hardness of a soft material that is difficult to measure with a durometer type A hardness.
[0016]
Commercially available thermally conductive silicone rubber sheets that can be used for the thermally conductive silicone rubber layer include TC-50THS (Asker C hardness 20, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name) and TC-50TXS (Asker C hardness 40, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name; TC-20BG (durometer type A hardness 85, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name); TC-45BG (durometer type A hardness 85, Shin-Etsu Chemical Co., Ltd.) TC-30EG (durometer type A hardness 90, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name), and TC-45EG (durometer type A hardness 90, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name). Can be
[0017]
[Thermal softening heat conductive layer]
This layer is formed by dispersing a thermally conductive filler in a silicone resin matrix. In addition, this layer constitutes an intermediate layer of the heat conductive composite sheet according to the present invention, and has a function of joining outer layers by its adhesiveness, and secures good heat conductivity by the heat conductive filler. It also improves the thermal conductivity of the entire sheet. The type of the silicone resin is not particularly limited as long as it is tacky and heat-softening. For example, D-form (bifunctional structural unit) and T-form (trifunctional Structural unit) having a predetermined composition.
D 1 m T p D 2 m
Here, D 1 is a dimethylsiloxane unit (ie, (CH 3 ) 2 SiO), T is a phenylsiloxane unit (ie, (C 6 H 5 ) 2 SiO 3/2 ), and D 2 is a methylvinylsiloxane unit. (That is, (CH 3 ) (CH 2 ＣＨCH) SiO). In addition, (m + n) /p=0.25 to 4.0 (molar ratio) and (m + n) /m=1.0 to 4.0. The composition represented by the above formula exhibits tackiness.
[0018]
Here, the term “thermal softening” means that the viscosity is reduced, thermally softened or melted by heat, and the thermal softening heat conductive layer is fluidized and follows and adheres to the adherend surface, thereby reducing interfacial thermal resistance. I do. In a temperature range of usually 40 to 100 ° C., particularly 40 to 90 ° C., a material whose surface is fluidized by low viscosity, heat softening, or melting can have “heat softening property”.
[0019]
As the thermally conductive filler to be dispersed in the silicone resin, the same materials as those used in the above thermally conductive silicone rubber layer can be used. Further, the content ratio of the heat conductive filler can be, for example, 70 to 97% by weight, and preferably 85 to 95% by weight, based on the entire heat softening heat conductive layer. The reason for defining the content of the heat conductive filler is the same as in the case of the heat conductive silicone rubber layer.
[0020]
Examples of commercially available heat-softening heat conductive sheets that can be used for the heat-softening heat conductive layer include PCS-TC-10, PCS-TC-11, and PCS-TC-20 (all of which are Shin-Etsu Chemical Co., Ltd.). Made by company; trade name).
[0021]
[Heat conduction layer]
This layer, which is located on the outer layer on the opposite side of the sheet and has a function of contacting a heat radiating member such as a heat sink and radiating heat conducted through the intermediate layer, and has a high thermal conductivity in a plane direction. Heat dissipation performance is high. By setting the thermal conductivity in the plane direction of the heat conductive layer to 20 to 500 W / (m · K), heat is easily conducted in the plane direction. If the thermal conductivity is less than 20 W / (m · K), the thermal conductivity in the plane direction is not sufficient, and even if it exceeds 500 W / (m · K), the effect of the thermal conductivity is saturated. As the heat conductive layer, a graphite sheet, aluminum foil, or the like can be used.
[0022]
Examples of commercially available graphite sheets that can be used for the heat conductive layer include MACFOIL (manufactured by Japan Matex Co., Ltd .; trade name) and PGS graphite sheet (manufactured by Matsushita Electric Industrial Co., Ltd .; trade name). Examples thereof include those manufactured by Nippon Light Metal Co., Ltd.
[0023]
Then, the heat conductive silicone rubber layer, the heat softening heat conductive layer, and the heat conductive layer are laminated in this order to form the heat conductive composite sheet according to the first embodiment. With such a configuration, the so-called reworking property can be improved because the thermally conductive silicone rubber layer having good releasability comes into contact with an object to be radiated such as an electronic component as the outermost layer. Since the heat conductive layer having excellent heat conductivity in the plane direction is located on the outer layer on the opposite side, heat radiation from the heat conductive layer to the outside is promoted. Furthermore, the heat from the heat-conductive silicone rubber layer can be efficiently transmitted to the heat-conductive layer by the heat-softening heat-conductive layer serving as the intermediate layer, so that the heat radiation characteristics are greatly improved. In addition, when the heat-softening heat conductive layer thermally softens, the heat conductive silicone rubber layer of the outer layer also comes into close contact with the heat radiating object and easily conducts the heat of the heat radiating object.
[0024]
2. Second Embodiment This heat conductive composite sheet is obtained by further providing a second heat softening heat conductive layer on the surface of the heat conductive layer. The second heat-softening heat-conductive layer is formed by dispersing a heat-conductive filler in a silicone resin matrix, similarly to the heat-softening heat-conductive layer. The silicone resin used for the second heat-softening heat conductive layer, the heat conductive filler, and the content thereof can be selected from those described for the heat softening heat conductive layer. The same resin or heat conductive filler as the heat conductive layer may be used, or another type of resin or the like may be used.
[0025]
When the second heat-softening heat conductive layer is located on the outer layer, the surface of this layer is fluidized and follows the adhered surface (such as a heat sink) and adheres closely. The thermal resistance is reduced, the heat of the heat conductive layer can be efficiently conducted to a heat sink or the like, and the heat radiation characteristics are greatly improved.
[0026]
3. Third Embodiment This heat conductive composite sheet is provided with a second heat conductive silicone rubber layer instead of the heat conductive layer of the heat conductive composite sheet according to the first embodiment. The silicone rubber, the thermally conductive filler, and the content thereof used in the second thermally conductive silicone rubber layer can be selected from those described for the thermally conductive silicone rubber layer. The same silicone rubber or heat conductive filler as the silicone rubber layer may be used, or another type of resin or the like may be used.
[0027]
The second thermally conductive silicone rubber layer has a lower hardness than the above thermally conductive silicone rubber layer. The reason is that the heat conductive silicone rubber layer has a relatively high hardness in order to enhance the shape stability, so that it is not necessary to increase the hardness of the second heat conductive silicone rubber layer. This is for improving the adhesiveness and followability with an electronic component or a heat sink to improve the heat radiation characteristics.
[0028]
In the case of the heat conductive composite sheet according to the third embodiment, the side of the second heat conductive silicone rubber layer having good followability with the object is brought into contact with the heat radiating object (such as an electronic component), and is slightly hard. It is preferable to bring the heat-conductive silicone rubber layer side into contact with the outside (such as a heat sink).
[0029]
When the second thermally conductive silicone rubber layer is located on the outer layer, the surface of this layer follows the adhered surface (such as an electronic component or a heat sink) and easily adheres to the outer surface. This does not occur, and the interface thermal resistance is reduced, resulting in improved heat dissipation characteristics. In addition, since the intermediate layer, which is an adhesive heat-softening resin, does not appear in the outer layer, the sheet can be easily handled and reworked.
[0030]
Next, a method for producing the heat conductive composite sheet according to the present invention will be described. The production method of the present invention includes a heat conductive composite sheet formed by pressing a heat conductive silicone rubber layer, a heat softening heat conductive layer, and a heat conductive layer or a second heat conductive silicone rubber layer at room temperature or thermocompression. Is to manufacture.
[0031]
In the case of room temperature pressure bonding, for example, between a tape-like heat-conductive silicone rubber sheet and a graphite sheet, a tape-like heat-softening heat-conductive sheet having a release-treated polymer film adhered to the surface is supplied, After peeling off the polymer film, a laminate of a thermally conductive silicone rubber sheet, a graphite sheet, and a thermally softened thermally conductive sheet in this order is passed between twin rolls at room temperature and pressed. In the case of thermocompression bonding, the twin rolls are heated to a temperature equal to or higher than the heat softening temperature of the thermosoftening heat conductive sheet (for example, 80 to 120 ° C.) and similarly press bonded. The press bonding may be performed by a heat press or the like in addition to the roll method. When manufacturing the heat conductive composite sheet according to the second embodiment, a tape-like heat softening heat conductive sheet similar to the above may be supplied to the outside of the graphite sheet, and the whole may be pressed. .
[0032]
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
[0033]
【Example】
1. Preparation of Each Material The following sheet and adhesive were prepared.
[Thermal conductive silicone rubber sheet]
a-1; TC-50TXS (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 500 μm, Asker C hardness 40)
a-2; TC-50THS (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 500 μm, Asker C hardness 20)
a-3; TC-45BG (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 450 μm, durometer A hardness 85)
a-4; TC-45EG (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 450 μm, durometer A hardness 90)
[Thermo-softening heat conductive sheet]
b-1; PCS-TC-20-G-10 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 100 μm)
b-2; PCS-TC-11-G-13 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 130 μm)
[Thermal conductive sheet]
c-1; MACFOIL (trade name; manufactured by Japan Matex Co., Ltd., thickness: 130 μm, thermal conductivity in the plane direction: 150 W / (m · K))
c-2; aluminum foil (manufactured by Nippon Light Metal Co., Ltd., thickness 50 μm, thermal conductivity in plane direction 237 W / (m · K))
[Thermo-softening heat conductive sheet]
d-1; PCS-TC-20-G-20 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 200 μm)
[Thermal conductive silicone rubber sheet]
e-1; TC-20BG (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., thickness 200 μm, durometer A hardness 85)
[Silicone adhesive]
b-3; KR-101-10 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.)
[0034]
2. Manufacture of heat conductive composite sheet The above heat conductive silicone rubber sheet, heat softening heat conductive sheet, and heat conductive sheet were appropriately combined, passed between twin rolls at room temperature, and pressed to produce a heat conductive composite sheet. . In the case of thermocompression bonding, the twin rolls were heated to 100 ° C. and pressed similarly. For some of the samples, a silicone pressure-sensitive adhesive was used instead of the heat-softening heat-conductive sheet, and after applying the silicone pressure-sensitive adhesive to the heat-conductive silicone rubber sheet or the heat-conductive sheet, Bonding was similarly performed using a roll.
[0035]
3. Evaluation Each of the obtained heat conductive composite sheets was cut into a size of 5 × 5 cm, and the test pieces were evaluated for the following characteristics.
It was measured using a sheet thickness micrometer (manufactured by Mitutoyo Corporation, model number: M820-25VA).
Each test piece was interposed between a heat resistance transistor (manufactured by Fuji Electric Co., Ltd .; product name 2SD923) and a heat sink (manufactured by OS Co., Ltd .; product name: FBA-150-PS), and a load was applied with a compression load of 345 kPa. The heat sink was placed in a constant temperature water bath in advance and kept at 65 ° C., and was taken out of the constant temperature bath and a test piece was attached when the experiment was started. Next, power of 10 V and 3 A is supplied to the transistor, the temperature T 1 of the transistor after 5 minutes and the temperature T 2 of the thermocouple embedded in the heat sink are measured, and the thermal resistance R S ( ° C / W) was calculated.
R S = (T 1 −T 2 ) / 30
(3) Reworkability Each test piece was sandwiched between two standard aluminum plates, loaded with a compression load of 490 kPa, and then left in an oven at 150 ° C. for 96 hours. After the standing, a force was manually applied in a direction in which the aluminum plate was pulled apart, and the ease of peeling between the aluminum plate and the test piece was determined.
Evaluation A: Easily peeled off Evaluation B: Peeling off when a slight force is applied C: Hardly peeled off Evaluation D: Very hard to peel off and easily cause delamination
Table 1 shows the structure of the obtained heat conductive composite sheet and the evaluation results. In Table 1, each sheet (or adhesive) was laminated in the order of the first layer and the second layer, and the first layer was brought into contact with the transistor, and the outer layer on the opposite side was brought into contact with the heat sink.
[0037]
[Table 1]
As is clear from Table 1, each of the examples has a low thermal resistance (0.5 ° C./W or less), excellent heat dissipation performance, and excellent reworkability. In Examples 3 and 4, since a high-hardness silicone rubber was provided on the outer layer side as a heat-conductive silicone rubber sheet, the heat resistance was slightly increased, but there was no problem in practical use, and the reworkability was greatly improved. did. Further, in the case of Examples 1, 2, 5 to 7, and 9 in which a heat conductive layer having excellent heat conductivity in the plane direction was provided on the outer layer side, the heat resistance was extremely low, about 0.3 ° C./W or less. became.
[0039]
On the other hand, in the case of Comparative Examples 1 to 3 in which a silicone pressure-sensitive adhesive was used as the intermediate layer, the thermal resistance of the intermediate layer was lowered, and the thermal resistance exceeded 0.5 ° C./W in all cases. In the case of Comparative Examples 4 and 5 having a two-layer structure, the outer layer came into close contact with the outside and delamination occurred. In the case of Comparative Example 6 in which an adhesive thermosoftening heat conductive layer was provided on the outer layer side, the reworkability was deteriorated due to the increased adhesiveness of the sheet surface.
[0040]
【The invention's effect】
As is clear from the above description, the heat conductive composite sheet of the present invention is excellent in both heat conductivity and reworkability, and is used for heat dissipation structures used for heat dissipation and cooling of heat-generating electronic components and the like. It is suitable.
Claims (4)
（ｂ）シリコーン樹脂及び熱伝導性充填剤を含有し、粘着性を有する熱軟化性熱伝導層と、
（ｃ）面方向への熱伝導率が２０〜５００Ｗ／（ｍ・Ｋ）の熱伝導層と
をこの順で積層した構造を有することを特徴とする熱伝導性複合シート。(A) a thermally conductive silicone rubber layer comprising a silicone rubber containing a thermally conductive filler;
(B) a heat-softening heat-conductive layer containing a silicone resin and a heat-conductive filler and having tackiness;
(C) A heat conductive composite sheet having a structure in which a heat conductivity layer having a heat conductivity in the plane direction of 20 to 500 W / (m · K) is laminated in this order.
（ｄ）シリコーン樹脂および熱伝導性充填剤を含有し、粘着性を有する第２の熱軟化性熱伝導層
が設けられたことを特徴とする請求項１記載の熱伝導性複合シート。The heat conductive layer further comprises (d) a second heat softening heat conductive layer containing a silicone resin and a heat conductive filler and having an adhesive property, on a surface of the heat conductive layer. Heat conductive composite sheet.
（ｂ）シリコーン樹脂及び熱伝導性充填剤を含有し、粘着性を有する熱軟化性熱伝導層と、
（ｅ） 熱伝導性充填剤を含有するシリコーンゴムからなり前記熱伝導性シリコーンゴム層より硬度が低い第２の熱伝導性シリコーンゴム層と
をこの順で積層した構造を有することを特徴とする熱伝導性複合シート。(A) a thermally conductive silicone rubber layer comprising a silicone rubber containing a thermally conductive filler;
(B) a heat-softening heat-conductive layer containing a silicone resin and a heat-conductive filler and having tackiness;
(E) having a structure in which a second thermally conductive silicone rubber layer made of silicone rubber containing a thermally conductive filler and having a lower hardness than the thermally conductive silicone rubber layer is laminated in this order. Thermal conductive composite sheet.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003100416A JP2004311577A (en) | 2003-04-03 | 2003-04-03 | Thermally conductive composite sheet and method of manufacturing the same |
| CN2004100300290A CN100407415C (en) | 2003-04-03 | 2004-03-17 | Heat conduction composite chip and its mfg. method |
| TW093109250A TW200502288A (en) | 2003-04-03 | 2004-04-02 | Thermal conductive multilayer and method for preparing the same |
| KR1020040022783A KR20040086802A (en) | 2003-04-03 | 2004-04-02 | Thermal-Conductive Composite Sheets and Process for Preparing the Same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003100416A JP2004311577A (en) | 2003-04-03 | 2003-04-03 | Thermally conductive composite sheet and method of manufacturing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2004311577A true JP2004311577A (en) | 2004-11-04 |
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ID=33464559
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003100416A Pending JP2004311577A (en) | 2003-04-03 | 2003-04-03 | Thermally conductive composite sheet and method of manufacturing the same |
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|---|---|
| JP (1) | JP2004311577A (en) |
| KR (1) | KR20040086802A (en) |
| CN (1) | CN100407415C (en) |
| TW (1) | TW200502288A (en) |
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| WO2006126582A1 (en) * | 2005-05-24 | 2006-11-30 | Nitto Denko Corporation | Thermally conductive composite sheet and method for manufacturing electronic component assembly using same |
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| JP2010219290A (en) * | 2009-03-17 | 2010-09-30 | Shin-Etsu Chemical Co Ltd | Thermally conductive composite sheet and method of manufacturing the same |
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2003
- 2003-04-03 JP JP2003100416A patent/JP2004311577A/en active Pending
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2004
- 2004-03-17 CN CN2004100300290A patent/CN100407415C/en not_active Expired - Fee Related
- 2004-04-02 KR KR1020040022783A patent/KR20040086802A/en not_active Application Discontinuation
- 2004-04-02 TW TW093109250A patent/TW200502288A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200502288A (en) | 2005-01-16 |
| CN1536653A (en) | 2004-10-13 |
| KR20040086802A (en) | 2004-10-12 |
| CN100407415C (en) | 2008-07-30 |
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