TWI821405B - 導熱性聚矽氧橡膠組成物與其片材及其製造方法 - Google Patents

導熱性聚矽氧橡膠組成物與其片材及其製造方法 Download PDF

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TWI821405B
TWI821405B TW108134049A TW108134049A TWI821405B TW I821405 B TWI821405 B TW I821405B TW 108134049 A TW108134049 A TW 108134049A TW 108134049 A TW108134049 A TW 108134049A TW I821405 B TWI821405 B TW I821405B
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thermally conductive
sheet
polysiloxane
conductive polysiloxane
mass
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小川敏樹
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日商富士高分子工業股份有限公司
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Abstract

一種導熱性聚矽氧組成物，其以聚矽氧為基質成分，且包含導熱填充劑，基質成分包含具有乙烯基之聚矽氧基礎聚合物與不具有乙烯基之聚矽氧油，導熱填充劑包含氮化鋁粒子，且包含作為硬化成分之過氧化物。本發明之導熱性聚矽氧片材1係將導熱性聚矽氧組成物（3、4）塗佈於玻璃布2之上漿片材之至少一面，使厚度為0.1～1 mm。藉此而提供柔軟且具有強度、導熱性亦高之導熱性聚矽氧橡膠組成物與其片材及其製造方法。

Description

導熱性聚矽氧橡膠組成物與其片材及其製造方法
本發明係關於一種導熱性聚矽氧橡膠組成物與其片材及其製造方法。
電腦(CPU)、電晶體、發光二極體(LED)等半導體於使用中發熱，由於該熱而存在電子零件之性能降低之現象。因此，於發熱之電子零件上安裝散熱體。由於散熱器大多為金屬，因此為了使CPU與散熱部之密接良好，採用插入片狀或凝膠狀之導熱性組成物而提高密接度之方法。此種導熱性組成物為了提高最終目標之散熱材料之導熱率，必須大量含有導熱性無機粉體，但若單純地增加導熱性無機粉體之摻合，則於彈性體狀之散熱材料之情形時，存在硬度變得過高，無法將電子零件與散熱器之間隔設定為規定薄度之問題，以及無法按照期待填充電子零件與散熱器之間隙等問題。又，於彈性體或凝膠狀散熱材料之情形時，存在壓縮永久變形變大，長期可靠性亦降低之傾向。進而，亦存在由於高溫熱歷程而使硬度上升之問題。
為了解決該等問題，自先前便提出了各種方法。本申請人於專利文獻1中提出了藉由烷基矽烷化合物對小粒子之氧化鋁進行表面處理之方法。又，還有使用0.1~5μm之無定形氧化鋁與5~50μm之球狀氧化鋁之提案(專利文獻2)等。進而於專利文獻3中提出了使用玻璃布之導熱性片材。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本再表2009-136542號公報
[專利文獻2]日本特開平2-41362號公報
[專利文獻3]日本特開2015-233104號公報
但是，先前技術之導熱性聚矽氧橡膠存在熱阻值高之問題。
本發明為了解決上述習知之問題，提供熱阻值低之導熱性聚矽氧橡膠組成物與其片材及其製備方法。
本發明之導熱性聚矽氧組成物以聚矽氧為基質成分，且包含導熱填充劑，其特徵在於：上述基質成分包含具有乙烯基之聚矽氧基礎聚合物與不具有乙烯基之聚矽氧油，上述導熱填充劑包含氮化鋁粒子，且包含作為硬化成分之過氧化物。
本發明之導熱性聚矽氧片材係將上述導熱性聚矽氧組成物塗佈於玻璃布之上漿片材之至少一面上而成者，其特徵在於：上述導熱性聚矽氧片材之厚度為0.1~1mm。
本發明之導熱性聚矽氧片材之製造方法之特徵在於：於上述導熱性聚矽氧組成物中加入稀釋液而製成塗佈液，使上述塗佈液含浸於玻璃布中，於乾燥後進行加熱硬化，藉此製成上漿片材，於上述玻璃布之上漿片材之至少一面塗佈上述塗佈液，於乾燥後進行加熱硬化。
本發明藉由使基質成分包含具有乙烯基之聚矽氧基礎聚合物與不具有乙烯基之聚矽氧油，上述導熱填充劑包含氮化鋁粒子，且包含作為硬化成分之過氧化物，可提供熱阻值較低之導熱性聚矽氧橡膠組成物與其片材及其製造方法。
1:導熱性聚矽氧片材
2:玻璃布之上漿片材層
3、4:導熱性聚矽氧塗佈層
10:熱阻測定裝置
11:電晶體
12:散熱片
13:壓板
14:電晶體之溫度感測器
15:散熱片之溫度感測器
16:M3螺釘
圖1係本發明之一實施方式之導熱性聚矽氧片材之示意性剖面圖。
圖2A係表示熱阻測定方法之示意性俯視圖，圖2B係圖2A之I-I線之示意性剖視圖。
於本發明中，由於下述理由而較佳為並不使用鉑系觸媒。
(1)本發明品於溶解於溶劑中之狀態下進行塗佈，但剩餘之材料從成本方面考慮用於下一次生產中。然而，若為鉑系觸媒(加成反應系)，則壽命比過氧化物硬化系短地進行硬化，因此難以用於下一次之生產中。
(2)若為鉑系觸媒(加成反應系)，則僅於具有乙烯基之部位進行反應。因此，硬化並不充分。過氧化物硬化係於乙烯基與甲基之部位進行反應，因此充分地進行硬化。
本發明人研究了是否能夠藉由添加具有乙烯基之聚矽氧基礎聚合物與不具有乙烯基之聚矽氧油而改善熱阻值之問題。此處，所謂聚矽氧膠係表示聚矽氧油(流體)與聚矽氧橡膠(固體)之中間性狀。本發明之具有乙烯基之聚矽氧基礎聚合物係指具有乙烯基之聚矽氧膠與聚矽氧油。
於本發明之基質成分中，具有乙烯基之聚矽氧基礎聚合物之反 應性高，與不具有乙烯基者相比而言強度變高。不具有乙烯基之聚矽氧油雖然反應性低，但表現出柔軟性。因此，具有乙烯基之聚矽氧膠與聚矽氧油，以及不具有乙烯基之聚矽氧油能夠獲得強度與柔軟性之平衡。
又，為了進行高導熱化，習知填充大量氧化鋁，但如果填充大量氧化鋁，則成為強度降低，柔軟性亦降低之傾向。因此，填充氮化鋁粒子，可實現高導熱化，並且可良好地保持強度與柔軟性。
於本發明中，利用過氧化物硬化劑，藉由自由基反應硬化作用而進行硬化。過氧化物硬化劑較佳為相對於基質成分100質量份而言為0.01~10質量份，更佳為0.1~8質量份。作為過氧化物硬化劑，較佳為如過氧化苯甲醯、雙(對甲基苯甲醯)過氧化物之醯基系過氧化物；如二-第三丁基過氧化物、2,5-二甲基-2,5-二(過氧化第三丁基)己烷、過氧化第三丁基異丙苯、過氧化二異丙苯基之烷基系過氧化物；以及如過氧苯甲酸第三丁酯之酯系有機過氧化物。
於將基質成分設為100質量份時，具有乙烯基之聚矽氧基礎聚合物(聚矽氧膠)較佳為50~90質量份，更佳為55~85質量份，進而較佳為60~80質量份。
於將基質成分設為100質量份時，不具有乙烯基之聚矽氧油較佳為5~20質量份，更佳為7~17質量份，進而較佳為10~15質量份。又，於本發明之組成物中亦可含有兩封端之乙烯基聚矽氧油。於將基質成分設為100質量份時，兩封端之乙烯基聚矽氧油較佳為5~25質量份，更佳為10~23質量份，進而較佳為12~22質量份。
不具有乙烯基之油若為被稱為二甲基聚矽氧油者，則基本上可為任意者，此外還有苯基甲基聚矽氧油，氟聚矽氧油等。
基質成分較佳為於1分子中具有至少2個矽原子鍵結烯基之聚矽氧烷。作為烯基，可例示：乙烯基、烯丙基、丙烯基等，作為烯基以外之有機 基，可列舉：由甲基、乙基、丙基、丁基、戊基、己基、辛基、癸基、十二烷基等所例示之烷基；由苯基、甲苯基等所例示之芳基；β-苯基乙基等芳烷基；由3,3,3-三氟丙基、3-氯丙基等所例示之經鹵素取代之烷基等。又，亦可於分子鏈末端等具有少量之經基。聚矽氧烷之分子結構可為直鏈狀、含有支鏈之直鏈狀、環狀、網狀之任一種，亦可併用兩種以上之二有機聚矽氧烷。聚矽氧烷之分子量並無特別限定，可使用黏度低之液狀者至黏度高之生橡膠狀者，但是為了進行硬化而成為橡膠狀彈性體，較佳為於25℃之黏度為100mPa‧s以上，更佳為藉由凝膠滲透層析法(GPC)之聚苯乙烯換算之數量均分子量為200,000~700,000之範圍之生橡膠狀。
較佳為相對於基質成分100質量份而加入導熱填充劑600~2000質量份，更佳為700~1900質量份，進而較佳為800~1800質量份。又，於將導熱填充劑設為100質量份時，氮化鋁粒子較佳為10~100質量份，更佳為15~90質量份，進而較佳為20~80質量份。
作為導熱填充劑，較佳為進而含有氧化鋁粒子。於將導熱填充劑設為100質量份時，氧化鋁粒子較佳為20~100質量份，更佳為25~90質量份，進而較佳為30~80質量份。氧化鋁粒子較佳為將平均粒徑為10μm以上且20μm以下之粒子(A)與平均粒徑為0.01μm以上且未達10μm之粒子(B)加以混合而使用。A：B之混合比例以質量比計而言較佳為90：10~10：90。
導熱填充劑之平均粒徑較佳為0.01~20μm，更佳為0.1~15μm。藉此可使與基質樹脂之混合性及加工性良好。再者，平均粒徑係於利用雷射繞射光散射法之粒度分佈測定中，基於體積基準之累積粒度分佈之D50(中值粒徑)。作為該測定器，例如有堀場製作所公司製造之雷射繞射/散射式粒子分佈測定裝置LA-950S2。
較佳為於導熱性聚矽氧組成物中不含補強性二氧化矽。若含有 補強性二氧化矽，則存在硬度上升，接觸熱阻變高之缺點。
於本發明之組成物中，可視需要摻合上述以外之成分。例如，能夠以鐵丹等無機顏料、填料之表面處理等為目的而添加烷基三烷氧基矽烷、流動性調整劑、黏著賦予劑、阻燃劑等。作為以填料之表面處理等為目的而添加之材料，亦可添加含有烷氧基之聚矽氧。
本發明之導熱性聚矽氧片材係將上述導熱性聚矽氧組成物塗佈於玻璃布之上漿片材之至少一面上而形成者。較佳為塗佈於兩面上。導熱性聚矽氧片材之厚度為0.1~1mm。於厚度未達0.1mm時，製造困難，若超過1mm，則塗佈困難。玻璃布較佳為使用質量為25~54g/m2，密度為經紗、緯紗均為56~60根/25mm，平織組織之梭織物。
本發明之導熱性聚矽氧片材之一例之塊體之導熱率較佳為1W/m‧k以上，更佳為3.3W/m‧k以上。此處，所謂塊體係指溶解於溶劑中之前的加入了聚矽氧基礎聚合物、填料、其他添加劑之狀態。
至於本發明之導熱性聚矽氧片材之製造方法，首先，於上述導熱性聚矽氧組成物中加入稀釋液而製成塗佈液。該塗佈液係對藉由如下方式而製成之組成物，添加過氧化物硬化成分與稀釋溶劑而製成者，即，上述組成物係加入基質樹脂成分、導熱填充劑、視需要加入之阻燃劑、顏料並將其混合均勻而製成者。稀釋溶劑若為可塗佈之程度，則適量即可。於塗佈時，黏度較佳為3,000~10,000cps。
其次，使上述塗佈液含浸於玻璃布中，進行乾燥、加熱硬化而製成上漿片材。該上漿片材成為填縫玻璃布片材。
其次，於上述玻璃布之上漿片材之至少一面塗佈上述塗佈液，於乾燥後進行加熱硬化，而獲得導熱性聚矽氧片材。塗佈較佳為刮刀塗布。其原因在於刮刀塗布能夠較薄地塗佈。硬化條件較佳為溫度為150~180℃，硬化時間為3~ 10分鐘。
以下使用圖式對本發明加以說明。圖1係本發明之一實施方式之導熱性聚矽氧片材之示意性剖面圖。該導熱性聚矽氧片材1係於使玻璃纖維布含浸塗佈液，進行乾燥、加熱硬化而成之上漿片材層2之兩面塗佈含有導熱性聚矽氧組成物之塗佈液，於乾燥後進行加熱硬化而成者。3、4為導熱性聚矽氧塗佈層。
圖2A係表示熱阻測定方法之示意性俯視圖，圖2B係該I-I線之示意性剖視圖。該熱阻測定方法係以ASTM D5470為基準，藉由熱阻測定裝置10測得導熱性聚矽氧片材1之熱阻值。於電晶體11與散熱片12之間夾入衝壓成菱形(TO-3型)之導熱性聚矽氧片材1，以規定之轉矩進行螺固，對電晶體11施加恒定功率使其發熱，根據電晶體11與散熱片12之溫度差而測定熱阻值。13為壓板，14為電晶體之溫度感測器，15為散熱片之溫度感測器，16為M3螺釘。轉矩之一例為3kg‧cm(0.29Nm)、5kg‧cm(0.49Nm)、7kg‧cm(0.69Nm)。
[實施例]
以下，使用實施例進行說明。本發明並不限定於實施例。
<熱阻測定方法>
使用圖2A~B所示之裝置進行測定。
熱阻值係藉由以下之式而算出。
Rt=(Tc-Tf)/P0
其中，Rt：熱阻值(K‧cm2/W)
Tc：電晶體溫度(℃)
Tf：散熱片之溫度(℃)
P0：恆定功率(W)
測定裝置如下所述。
電晶體：2SC2245(TO-3型)
散熱片：40CH104L-90-K
(實施例1)
(1)原料
(A)基質成分
(A-1)具有乙烯基之聚矽氧膠：Elkem Japan公司製造，於兩末端及側鏈上具有乙烯基之膠，80g
(A-2)兩封端之乙烯基聚矽氧油：Elkem Japan公司製造，黏度為350mm2/s(溫度為25℃)
(A-3)不具有乙烯基之聚矽氧油：由東麗道康寧公司製造，黏度為300cs(溫度為25℃)
(B)導熱填充劑
(B-1)氮化鋁(平均粒徑為10μm)：東洋鋁公司製造
(B-2)氧化鋁(平均粒徑為12μm)：日本輕金屬公司製造
(B-3)氧化鋁(平均粒徑為2μm)：昭和電工公司製造
(B-4)氧化鋁(平均粒徑為0.3μm)：住友化學公司製造
(C)顏料
旭化成瓦克公司製造、「Brown 105A」
(D)過氧化物硬化成分
雙-4-甲基苯甲醯過氧化物
用混練機均勻地混練以上之各原料，製成導熱性聚矽氧組成物。
(2)塗佈液1
於上述原料組成物100g中加入3g作為過氧化物硬化成分之雙-4-甲基苯甲醯過氧化物之50%漿料液與適量之作為稀釋材料之溶劑二甲苯，製成塗佈液1。
(3)塗佈液2
於上述原料組成物100g中加入0.8g作為過氧化物硬化成分之雙-4-甲基苯甲醯過氧化物之50%漿料液與適量之作為稀釋材料之溶劑二甲苯，製成塗佈液2。
(4)塗佈加工
首先，使塗佈液1含浸於厚度約35μm之玻璃布(質量為25g/m2，密度為經紗、緯紗均為56根/25mm，平織組織之梭織物)中，進行乾燥，加熱硬化而製成上漿片材。
其次，藉由刮刀塗佈機將塗佈液2塗佈於上漿片材之單面上，進行乾燥後放入至加熱器中，進行180℃之加熱硬化3分鐘。繼而，藉由刮刀塗佈器於上漿片材之另一面上塗佈塗佈液2，並進行乾燥。其後，放入至加熱器中，進行180℃之加熱硬化3分鐘。如此地進行而製造總厚度為0.2mm與0.33mm之導熱性聚矽氧片材。
(比較例1~3)
除了不添加上述(A-3)之不具有乙烯基之聚矽氧油以外，與實施例1同樣地實施。將各成分之添加量彙總示於表1中，將熱阻值彙總示於表2中。
Figure 108134049-A0305-02-0010-1
Figure 108134049-A0305-02-0011-2
根據表1~2可知：本發明之實施例品之熱阻值可以獲得低於比較例1~3之值。
[產業上之可利用性]
本發明之導熱性聚矽氧組成物及片材可應用於介於電子零件之發熱部與散熱片之間的散熱構件等。
1:導熱性聚矽氧片材
2:玻璃布之上漿片材層
3、4:導熱性聚矽氧塗佈層

Claims (10)

  1. 一種導熱性聚矽氧組成物，其以聚矽氧聚合物為基質成分，包含導熱填充劑，其特徵在於：上述基質成分包含於兩末端及側鏈上具有乙烯基之聚矽氧基礎聚合物、不具有乙烯基之聚矽氧油與具有兩封端乙烯基之聚矽氧油，上述於兩末端及側鏈上具有乙烯基之聚矽氧基礎聚合物係表示聚矽氧油(流體)與聚矽氧橡膠(固體)之中間性狀之聚矽氧膠，上述不具有乙烯基之聚矽氧油為選自二甲基聚矽氧油、苯基甲基聚矽氧油、及氟聚矽氧油所組成之群中之至少1種，上述導熱填充劑包含氮化鋁粒子，且包含作為硬化成分之過氧化物，將上述基質成分設為100質量份時，具有乙烯基之聚矽氧基礎聚合物為50~90質量份。
  2. 如請求項1所述之導熱性聚矽氧組成物，其中，相對於上述基質成分100質量份，導熱填充劑為600~2000質量份。
  3. 如請求項1所述之導熱性聚矽氧組成物，其中，於將上述導熱填充劑設為100質量份時，氮化鋁粒子為10~100質量份。
  4. 如請求項1所述之導熱性聚矽氧組成物，其中，上述導熱填充劑進而包含氧化鋁粒子。
  5. 如請求項1所述之導熱性聚矽氧組成物，其中，上述導熱填充劑之平均粒徑為0.1~20μm。
  6. 如請求項1所述之導熱性聚矽氧組成物，其中，上述導熱性聚矽氧組成物不含補強性二氧化矽。
  7. 一種導熱性聚矽氧片材，其係將請求項1至6中任一項所述之導 熱性聚矽氧組成物塗佈於玻璃布之上漿片材之至少一面上之導熱性聚矽氧片材，其特徵在於，上述導熱性聚矽氧片材之厚度為0.1~1mm。
  8. 如請求項7所述之導熱性聚矽氧片材，其中，於上述玻璃布之上漿片材之兩面塗佈有導熱性聚矽氧組成物。
  9. 一種導熱性聚矽氧片材之製造方法，其係請求項7之導熱性聚矽氧片材之製造方法，且，於請求項1至6中任一項所述之導熱性聚矽氧組成物中加入稀釋液而製成塗佈液，使上述塗佈液含浸於玻璃布中，於乾燥後進行加熱硬化而製成上漿片材，於上述玻璃布之上漿片材之至少一面塗佈上述塗佈液，於乾燥後進行加熱硬化。
  10. 如請求項9所述之導熱性聚矽氧片材之製造方法，其中，上述塗佈為刮刀塗布。
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CN102220006B (zh) * 2011-04-28 2012-09-26 天津大学 混合填充型导热硅橡胶复合材料及其制备方法
JP6214094B2 (ja) * 2014-06-10 2017-10-18 信越化学工業株式会社 熱伝導性シート
CN105315672A (zh) * 2015-12-07 2016-02-10 德阳烯碳科技有限公司 一种含纳米碳材料的硅橡胶垫复合材料的制备方法
JP6610429B2 (ja) * 2016-05-24 2019-11-27 信越化学工業株式会社 熱伝導性シリコーン組成物、その硬化物及びその製造方法
CN109564906B (zh) * 2016-07-26 2023-08-15 信越化学工业株式会社 导热性片材

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017226724A (ja) * 2016-06-20 2017-12-28 信越化学工業株式会社 熱伝導性シリコーンパテ組成物
TW201823362A (zh) * 2016-10-18 2018-07-01 日商信越化學工業股份有限公司 熱傳導性矽氧組成物

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