JP6674590B1 - 熱伝導性シート、これを用いた実装方法及びこれを用いた接合方法 - Google Patents
熱伝導性シート、これを用いた実装方法及びこれを用いた接合方法 Download PDFInfo
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- JP6674590B1 JP6674590B1 JP2019551486A JP2019551486A JP6674590B1 JP 6674590 B1 JP6674590 B1 JP 6674590B1 JP 2019551486 A JP2019551486 A JP 2019551486A JP 2019551486 A JP2019551486 A JP 2019551486A JP 6674590 B1 JP6674590 B1 JP 6674590B1
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- Prior art keywords
- heat conductive
- uncured composition
- conductive sheet
- sheet
- reaction catalyst
- Prior art date
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
-
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Abstract
Description
(1)硬化反応触媒を含有した熱伝導性シートの少なくとも一主面に、熱伝導性未硬化組成物を接合し、この状態で電気・電子部品に組み込み、しかる後、硬化反応触媒を含有した熱伝導性シート内の反応触媒により、未硬化組成物を硬化させる。
(2)硬化反応触媒を含有した熱伝導性シートの少なくとも一主面に、熱伝導性未硬化組成物を接合した電気・電子部品を圧着し、しかる後、硬化反応触媒を含有した熱伝導性シート内の反応触媒により、未硬化組成物を硬化させる。
(3)硬化反応触媒を含有した熱伝導性シートを接合した電気・電子部品を、熱伝導性未硬化組成物に圧着し、しかる後、硬化反応触媒を含有した熱伝導性シート内の反応触媒により、熱伝導性未硬化組成物を硬化させる。
(A)ベースポリマー成分:1分子中に平均2個以上かつ分子鎖両末端のケイ素原子に結合したアルケニル基を含有する直鎖状オルガノポリシロキサン:100重量部
(B)架橋成分:1分子中に平均2個以上のケイ素原子に結合した水素原子を含有するオルガノハイドロジェンポリシロキサンが、前記A成分中のケイ素原子結合アルケニル基1モルに対して、1モル未満の量
(C)熱伝導性粒子:A成分100重量部に対して100〜3000重量部
硬化触媒を含有した熱伝導性シリコーンシートは、下記コンパウンドが好ましい。
(D)ベースポリマー:付加反応硬化型又は過酸化物硬化型シリコーンゴム或いはシリコーンゲル100重量部
(E)白金系金属触媒:D成分に対して重量単位で1〜3500ppm(硬化有効量の10〜35000倍)。
(F)熱伝導性粒子:D成分100重量部に対して100〜3000重量部
(1)ベースポリマー成分(A成分)
ベースポリマー成分は、一分子中にケイ素原子に結合したアルケニル基を2個以上含有するオルガノポリシロキサンであり、アルケニル基を2個含有するオルガノポリシロキサンは本発明の未硬化組成物における主剤(ベースポリマー成分)である。このオルガノポリシロキサンは、アルケニル基として、ビニル基、アリル基等の炭素原子数2〜8、特に2〜6の、ケイ素原子に結合したアルケニル基を一分子中に2個有する。粘度は25℃で10〜1000000mPa・s、特に100〜100000mPa・sであることが作業性、硬化性などから望ましい。
l,mは、一般的には0<l+m≦10000を満足する0又は正の整数であり、好ましくは5≦l+m≦2000、より好ましくは10≦l+m≦1200で、かつ0<l/(l+m)≦0.2、好ましくは、0.0011≦l/(l+m)≦0.1を満足する整数である。
本発明のB成分のオルガノハイドロジェンポリシロキサンは架橋剤として作用するものであり、この成分中のSiH基とA成分中のアルケニル基とが付加反応(ヒドロシリル化)することにより硬化物を形成するものである。かかるオルガノハイドロジェンポリシロキサンは、一分子中にケイ素原子に結合した水素原子(即ち、SiH基)を2個以上有するものであればいずれのものでもよく、このオルガノハイドロジェンポリシロキサンの分子構造は、直鎖状、環状、分岐状、三次元網状構造のいずれであってもよいが、一分子中のケイ素原子の数(即ち、重合度)は2〜1000、特に2〜300程度のものを使用することができる。
E成分の触媒成分はヒドロシリル化反応に用いられる触媒を用いることができる。例えば白金黒、塩化第2白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類やビニルシロキサンとの錯体、白金ビスアセトアセテート等の白金系触媒、パラジウム系触媒、ロジウム系触媒などの白金族金属触媒が挙げられる。D成分に対して重量単位で1〜3500ppm(硬化有効量の10〜35000倍)添加するのが好ましい。
C及びF成分の熱伝導性粒子は、マトリックス成分であるA成分100重量部に対して100〜3000重量部添加するのが好ましい。これにより熱伝導率を高く保つことができる。熱伝導粒子としては、アルミナ,酸化亜鉛,酸化マグネシウム、窒化アルミ、窒化ホウ素、水酸化アルミ、石英及びシリカから選ばれる少なくとも一つであることが好ましい。形状は球状,鱗片状,多面体状等様々なものを使用できる。アルミナを使用する場合は、純度99.5重量%以上のα−アルミナが好ましい。熱伝導性粒子の比表面積は0.06〜10m2/gの範囲が好ましい。比表面積はBET比表面積であり、測定方法はJIS R1626にしたがう。平均粒子径を用いる場合は、0.1〜100μmの範囲が好ましい。粒子径の測定はレーザー回折光散乱法により、メディアン径を測定する。この測定器としては、例えば堀場製作所製社製のレーザー回折/散乱式粒子分布測定装置LA−950S2がある。
適用される熱硬化型シリコーンゴム或いはゲルは、ジメチルシリコーンゴム或いはゲル、メチルビニルシリコーンゴム或いはゲル、メチルフェニルビニルシリコーンゴム或いはゲル、フロロシリコーンゴム或いはゲル等に適用できる。一般にシリコーンゴム或いはゲルには、必要に応じ種々の充填剤、添加剤が使用されているが、これらも特に制限なく、シリカゲル、アエロジル#200(商品名)に代表される補強性シリカ、セライトに代表されるけい藻土、また、必要に応じ、加工助剤や難燃付与剤、耐熱性向上剤、可塑性、顔料等の添加剤を使用してもよい。また、シリコーンゴム或いはゲルの硬化系は付加反応硬化型、過酸化物硬化型どちらも使用でき、また、硬化していなくてもよい。
本発明の組成物には、必要に応じて前記以外の成分を配合することができる。例えばベンガラ、酸化チタン、酸化セリウムなどの耐熱向上剤、難燃助剤、フィラーの表面処理等の目的でアルキルトリアルコキシシランなどを添加してもよい。フィラー表面処理などの目的で添加する材料として、アルコキシ基含有シリコーンを添加しても良い。シランカップリング剤等の接着プロモーターを添加しても良い。着色、調色の目的で有機或いは無機顔料を添加しても良い。
(1)図3Aは自動実装機7をシリコーンシート1の表面まで移動した状態を示す説明図である。硬化シート1の下面には未硬化シート2が接合されている。硬化シート1と未硬化組成物2の積層体はキャリアテープ(図示省略)の上に配列され、1枚ずつ左側に送られる。右側の離れた位置には、配線基板10の上にCPUが搭載された電子部品11が配置されている。
(2)図3Bは自動実装機先端部7のエアーを矢印8の方向に吸引し、硬化シート1を吸着した状態を示す説明図である。硬化シート1の下には未硬化組成物2が接合されている。
(3)図3Cは硬化シート1を吸着した状態でCPUを搭載する電子部品11の上方まで移動した状態を示す説明図である。
(4)図3Dは硬化シート1を電子部品11上に設置し、エアーを矢印9に示すように開放し、電子部品11上に硬化シート1と未硬化組成物2を実装した状態を示す説明図である。
(5)図3Eは自動実装機先端部7を上に移動し、1サイクルを終了した状態を示す説明図である。
(実施例1〜8、比較例1〜2)
(1)触媒含有シートの配合物1〜9の作成
表1〜2に示すように配合物1〜9を作成した。配合物1〜9に使用した各材料の内容は次のとおりである。
ベースポリマー:シリコーンポリマー、東レ・ダウコーニングシリコーン社製、商品名"SE1185U"
ベースポリマー:シリコーンポリマー、ブルースターシリコーン社製、商品名"BS 621V350"
過酸化物硬化剤:シリコーン硬化剤、東レ・ダウコーニングシリコーン社製、商品名" RC-4"
架橋剤:シリコーン架橋剤、ブルースターシリコーン社製、商品名"BS FLD 626V30H2.5"
架橋剤:シリコーン架橋剤、東レ・ダウコーニングシリコーン社製、商品名"SH-1107"
硬化遅延剤:日信化学工業社製、商品名"オルフィンB"
硬化遅延剤:エチニルシクロヘキサノール
付加反応触媒:白金系触媒、東レ・ダウコーニングシリコーン社製、商品名"SRX-212"
熱伝導性フィラー:アルミナ平均粒子径38μm、昭和電工社製、商品名"AS-10"
表3に示すように配合物10〜12を作成した。配合物10〜12に使用した各材料の内容は次のとおりである。
ベースポリマー:シリコーンポリマー、ブルースターシリコーン社製、商品名"BS 621V350"
架橋剤:シリコーン架橋剤、ブルースターシリコーン社製、商品名"BS FLD 626V30H2.5"
熱伝導性フィラー:アルミナ平均粒子径38μm、昭和電工社製、商品名"AS-10"
付加反応触媒:白金系触媒、東レ・ダウコーニングシリコーン社製、商品名"SRX-212"
表4〜5に示すように、触媒含有シートと未硬化組成物を接合し、未硬化組成物の硬化が進むことによりグリース状の組成物の表面から付着、転写しなくなるまでの時間を調べた。各条件と評価は次のとおりである。
触媒含有シートの厚み:0.5mm
未硬化組成物の塗布厚み:2.0mm
タッキネスチェッカー(東洋精機株式会社製)を用いて測定した。接触子を接触荷重5N、接触時間3秒で対象物に押しつけ、引き剥がした際の応力をロードセル方式で検出した。
<熱伝導率の測定>
熱伝導性シートの熱伝導率は、ホットディスク(ISO/CD 22007-2準拠)により測定した。この熱伝導率測定装置31は図11Aに示すように、ポリイミドフィルム製センサ32を2個の試料33a,33bで挟み、センサ32に定電力をかけ、一定発熱させてセンサ32の温度上昇値から熱特性を解析する。センサ32は先端34が直径7mmであり、図11Bに示すように、電極の2重スパイラル構造となっており、下部に印加電流用電極35と抵抗値用電極(温度測定用電極)36が配置されている。熱伝導率は以下の式(数1)で算出する。
(1)実施例1と比較例1から、触媒含有シートに触媒を含まないと、未硬化組成物は硬化しない。
(2)実施例1〜4から、触媒シートの性状は、未硬化ゴム、付加硬化、ゲル、過酸化物加硫ゴム、付加硬化ゴムいずれでも良い。
(3)実施例5〜7から、未硬化組成物の硬化速度は触媒シートの触媒量で調整できる。
(4)実施例5、8、9から、未硬化組成物の硬化後の性状は未硬化組成物の配合で調整できる。
(5)比較例2から、触媒シートに架橋剤、未硬化組成物に触媒を入れても、架橋剤は浸透せず硬化しない。但し、未硬化組成物から触媒が浸透し触媒シートが硬化する。
2 未硬化組成物
3a,3b,4a,4b 保護フィルム
5 発熱性電子部品
6 ヒートシンク
7 自動実装機先端部
8,9 自動実装機先端部のエアー方向
10 配線基板
11 電子部品の発熱部
12 ディスペンサー
13a−13c 未硬化組成物
14,15,21 電気・電子部品
16 トレイ
17,23 棒状の未硬化組成物
18 チューブ
19 ボビン
20 リボン状の未硬化組成物
22 キャビティー(凹部)
24 金属プレート
25 熱伝導性シリコーンゴム硬化シート
26 ディスペンスされた未硬化組成物
31 熱伝導率測定装置
32 ポリイミドフィルム製センサ
33a,33b 試料
34 センサ先端
35 印加電流用電極
36 抵抗値用電極(温度測定用電極)
Claims (17)
- 熱伝導性シートであって、
硬化反応触媒を含有した熱伝導性シートの少なくとも一主面に、硬化反応触媒を含有しない熱伝導性未硬化組成物が接合されており、
前記硬化反応触媒を含有した熱伝導性シートは、前記熱伝導性未硬化組成物を硬化させるため必要な量の硬化反応触媒を含み、
前記熱伝導性未硬化組成物は、
(A)ベースポリマー成分:1分子中に平均2個以上かつ分子鎖両末端のケイ素原子に結合したアルケニル基を含有する直鎖状オルガノポリシロキサン:100重量部
(B)架橋成分:1分子中に平均2個以上のケイ素原子に結合した水素原子を含有するオルガノハイドロジェンポリシロキサンが、前記A成分中のケイ素原子結合アルケニル基1モルに対して、1モル未満の量
(C)熱伝導性粒子:A成分100重量部に対して100〜3000重量部
のコンパウンドであることを特徴とする熱伝導性シート。 - 前記未硬化組成物を硬化するための前記硬化反応触媒量は1〜3500ppmである請求項1に記載の熱伝導性シート。
- 前記硬化反応触媒は白金族金属触媒である請求項1又は2に記載の熱伝導性シート。
- 前記硬化反応触媒を含有した熱伝導性シートは、シリコーンゴムシート、シリコーンゲルシート、天然ゴムシート、合成ゴムシート及びパラフィンシートから選ばれる少なくとも一つのシートである請求項1〜3のいずれに記載の熱伝導性シート。
- 前記硬化反応触媒を含有した熱伝導性シート及び前記未硬化組成物には熱伝導性フィラーが混合されており、全体として熱伝導率が0.5W/mK以上である請求項1〜4のいずれかに記載の熱伝導性シート。
- 前記硬化反応触媒を含有した熱伝導性シートの厚みは0.1〜1.5mmの範囲である請求項1〜5のいずれかに記載の熱伝導性シート。
- 前記熱伝導性未硬化組成物は、付加反応または縮合反応で硬化する請求項1〜6のいずれかに記載の熱伝導性シート。
- 前記熱伝導性未硬化組成物は、硬化後粘着性を有する請求項1〜7のいずれかに記載の熱伝導性シート。
- 前記熱伝導性未硬化組成物は、未硬化のシリコーンゴム、未硬化のシリコーンゲル、未硬化のシリコーングリース、未硬化のシリコーンオイル、及び未硬化の接着シリコーンゴムから選ばれる少なくとも一つである請求項1〜8のいずれかに記載の熱伝導性シート。
- 前記熱伝導性未硬化組成物は、パテシート、リボン、又はディスペンサー、シリンジ及びチューブから選ばれる少なくとも一つの容器から押し出された状態である請求項1〜9のいずれかに記載の熱伝導性硬化シート。
- 請求項1〜10のいずれかに記載の熱伝導性硬化シートを用いた実装方法であって、
硬化反応触媒を含有した熱伝導性シートの少なくとも一主面に、
(A)ベースポリマー成分:1分子中に平均2個以上かつ分子鎖両末端のケイ素原子に結合したアルケニル基を含有する直鎖状オルガノポリシロキサン:100重量部
(B)架橋成分:1分子中に平均2個以上のケイ素原子に結合した水素原子を含有するオルガノハイドロジェンポリシロキサンが、前記A成分中のケイ素原子結合アルケニル基1モルに対して、1モル未満の量
(C)熱伝導性粒子:A成分100重量部に対して100〜3000重量部
のコンパウンドであり、硬化反応触媒を含有しない熱伝導性未硬化組成物を接合し、
前記硬化反応触媒を含有した熱伝導性シートの硬化反応触媒の拡散により、前記熱伝導性未硬化組成物を硬化させることを特徴とする熱伝導性シートを用いた実装方法。 - 前記硬化反応触媒を含有した熱伝導性シートの少なくとも一主面に、硬化反応触媒を含有しない熱伝導性未硬化組成物を接合した状態で電気・電子部品に組み込む請求項11に記載の熱伝導性シートを用いた実装方法。
- 前記硬化反応触媒を含有した熱伝導性シートの少なくとも一主面に、硬化反応触媒を含有しない熱伝導性未硬化組成物を接合した電気・電子部品を圧着する請求項11に記載の熱伝導性シートを用いた実装方法。
- 前記硬化反応触媒を含有した熱伝導性シートに電気・電子部品を接合しておき、この状態で、前記熱伝導性シートの少なくとも一主面に熱伝導性未硬化組成物に圧着する請求項11に記載の熱伝導性シートを用いた実装方法。
- 前記熱伝導性未硬化組成物を硬化させる時間が、25℃の室温で4〜48時間である請求項11〜14のいずれかに記載の熱伝導性シートを用いた実装方法。
- 前記熱伝導性未硬化組成物は、パテシート、リボン、ディスペンサーに収納、シリンジに収納及びチューブに収納された状態で実装工程に供給される請求項11〜15のいずれかに記載の熱伝導性シートを用いた実装方法。
- 請求項1〜10のいずれかに記載の熱伝導性硬化シートを用いた接合方法であって、
未硬化組成物の硬化後の粘着性により、前記未硬化組成物と前記未硬化組成物に接触する物体を接合することを特徴とする熱伝導性硬化シートを用いた接合方法。
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WO2019216190A1 (ja) | 2019-11-14 |
CN111093991B (zh) | 2023-04-14 |
EP3643498A4 (en) | 2020-12-16 |
US20200176350A1 (en) | 2020-06-04 |
US11450589B2 (en) | 2022-09-20 |
JPWO2019216190A1 (ja) | 2020-05-28 |
EP3643498B1 (en) | 2021-06-02 |
CN111093991A (zh) | 2020-05-01 |
EP3643498A1 (en) | 2020-04-29 |
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