TWI609053B - Thermal sheet - Google Patents
Thermal sheet Download PDFInfo
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- TWI609053B TWI609053B TW102124310A TW102124310A TWI609053B TW I609053 B TWI609053 B TW I609053B TW 102124310 A TW102124310 A TW 102124310A TW 102124310 A TW102124310 A TW 102124310A TW I609053 B TWI609053 B TW I609053B
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Description
本發明係關於一種導熱性片。
為了防止驅動時伴隨著發熱之IC(integrated circuit)晶片等發熱體之故障,而使發熱體介隔導熱性片與散熱片等散熱體密合。近年來,提出有如下方法作為提高此種導熱性片之導熱性之方法:使用磁場產生裝置,使於熱硬化性樹脂中分散有纖維狀填料之層狀熱硬化性樹脂組成物中之該纖維狀填料配向於層之厚度方向,之後使熱硬化性樹脂硬化而製造導熱性片(專利文獻1)。該導熱性片成為如下構成:全纖維狀填料之50~100%之纖維狀填料的端部露出於片之表面,當用於發熱體與散熱體之間時,纖維狀填料之露出之端部會沉入導熱性片內。
專利文獻1:日本專利第4814550號
然而,專利文獻1之導熱性片存在如下問題:全纖維狀填料之約一半以上之纖維狀填料配向於片之厚度方向,因此即便使纖維狀填料沉入,纖維狀填料彼此接觸之頻率亦不多,從而熱阻無法充分地下降。又,根據導熱性片應用於發熱體與散熱體之間之條件,亦有露出之纖維狀填料
之端部未沉入片內之問題。相反地為了使露出之纖維狀填料之端部完全地沉入片內,亦有存在如下情形之問題,即於將導熱性片配置於發熱體與散熱體之間時,不得不對該等施加如阻礙該等正常動作之負荷。
本發明之目的在於解決上述先前技術之問題點,而提供一種導熱性片,係纖維狀填料彼此接觸之頻率較高,且無露出之纖維狀填料之端部未沉入片內之情況,當配置於發熱體與散熱體之間時亦無需對該等施加如阻礙該等正常動作之負荷。
本發明人等假設使纖維狀填料配向於導熱性片之厚度方向係引起先前技術之問題點之主要原因,於該假設下對纖維狀填料之配向狀態進行研究,結果發現,將未配向於導熱性片之厚度方向之纖維狀填料於全纖維狀填料中之比率設為相對較高之特定範圍,藉此可達成上述目的,從而完成本發明。
即,本發明提供一種導熱性片,係含有纖維狀填料與黏合劑樹脂,且未配向於導熱性片之厚度方向之纖維狀填料於全纖維狀填料中之比率為45~95%。
本發明之導熱性片之未配向於導熱性片之厚度方向的纖維狀填料於全纖維狀填料中之比率成為45~95%。因此,導熱性片內纖維狀填料相互接觸之頻率變高,而熱阻下降。又,亦無露出之纖維狀填料之端部未沉入片內之情況,於配置於發熱體與散熱體之間時亦無需對該等施加如阻礙該等正常動作之負荷。又,可抑制彎折導熱性片時之龜裂產生。
本發明係一種導熱性片,係含有纖維狀填料與黏合劑樹脂者,且未配向於導熱性片之厚度方向之纖維狀填料於全纖維狀填料中之比率為45~95%。
構成導熱性片之纖維狀填料係用以使源自發熱體之熱效率良好地傳導至散熱體者。作為此種纖維狀填料,若平均徑過小,則擔心其比表面積變得過大,而使得製作導熱性片時之樹脂組成物之黏度變得過高,若平均徑過大,則擔心導熱性片之表面凹凸變大,而對發熱體或散熱體之密合性下降,因此平均徑較佳為8~12μm。又,若其縱橫比(長/徑)過小,則有導熱性片形成用組成物之黏度過高之傾向,若縱橫比過大,則有阻礙導熱性片之壓縮之傾向,因此縱橫比較佳為2~50,更佳為3~30。若特別著眼於纖維長度,則纖維長度較佳為15~800μm,更佳為40~250μm。
作為纖維狀填料之具體例,較佳為可列舉:碳纖維、金屬纖維(例如鎳、鐵等)、玻璃纖維、陶瓷纖維(例如氧化物(例如氧化鋁、二氧化矽等)、氮化物(例如氮化硼、氮化鋁等)、硼化物(例如硼化鋁等)、碳化物(例如碳化矽等)等非金屬系無機纖維)。
纖維狀填料係依導熱性片所要求之機械性質、熱性質、電性質等特性而選擇。其中,就顯示出高彈性率、良好之導熱性、高導電性、電波遮蔽性、低熱膨脹性等之方面而言,可較佳地使用瀝青(pitch)系碳纖
維。
纖維狀填料於導熱性片中之含量有如下傾向:若過少則導熱率變低,若過多則黏度變高,因此於導熱性片中較佳為16~40體積%,更佳為20~30體積%,且相對於構成導熱片之下述黏合劑樹脂100質量份,較佳為120~300質量份,更佳為130~250質量份。
再者,除纖維狀填料以外,亦可於無損本發明之效果之範圍內併用板狀填料、鱗片狀填料、球狀填料等。特別是就抑制纖維狀填料於導熱性片形成用組成物中二次凝聚之觀點而言,0.1~5μm直徑之球狀填料(較佳為球狀氧化鋁或球狀氮化鋁)之較佳範圍為30~60體積%,更佳為35~50體積%,且相對於纖維狀填料100質量份,較佳為併用100~900質量份。
黏合劑樹脂係將纖維狀填料保持於導熱性片內者,且依導熱性片所要求之機械強度、耐熱性、電性質等特性而選擇。作為此種黏合劑樹脂,可採用選自熱塑性樹脂、熱塑性彈性體、熱硬化性樹脂中者。
作為熱塑性樹脂,可列舉:聚乙烯、聚丙烯、乙烯-丙烯共聚物等乙烯-α烯烴共聚物、聚甲基戊烯、聚氯乙烯、聚偏二氯乙烯、聚乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、聚乙烯醇、聚乙烯醇縮醛、聚偏二氟乙烯及聚四氟乙烯等氟系聚合物、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚苯乙烯、聚丙烯腈、苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物(ABS,acrylonitrile-butadiene-styrene)樹脂、聚苯醚共聚物(PPE,polyphenylene ether)樹脂、改質PPE樹脂、脂肪族聚醯胺類、芳香族聚醯胺類、聚醯亞胺、聚醯胺醯亞胺、聚甲基丙烯酸、聚
甲基丙烯酸甲酯等聚甲基丙烯酸酯類、聚丙烯酸類、聚碳酸酯、聚苯硫醚、聚碸、聚醚碸、聚醚腈、聚醚酮、聚酮、液晶聚合物、聚矽氧樹脂、離子聚合物等。
作為熱塑性彈性體,可列舉:苯乙烯-丁二烯嵌段共聚物或其氫化物、苯乙烯-異戊二烯嵌段共聚物或其氫化物、苯乙烯系熱塑性彈性體、烯烴系熱塑性彈性體、氯乙烯系熱塑性彈性體、聚酯系熱塑性彈性體、聚胺基甲酸酯系熱塑性彈性體、聚醯胺系熱塑性彈性體等。
作為熱硬化性樹脂,可列舉:交聯橡膠、環氧樹脂、酚系樹脂、聚醯亞胺樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙酯(diallyl phthalate)樹脂等。作為交聯橡膠之具體例,可列舉:天然橡膠、丙烯酸系橡膠、丁二烯橡膠、異戊二烯橡膠、苯乙烯-丁二烯共聚合橡膠、腈橡膠、氫化腈橡膠、氯丁二烯橡膠、乙烯-丙烯共聚合橡膠、氯化聚乙烯橡膠、氯磺化聚乙烯橡膠、丁基橡膠、鹵化丁基橡膠、氟橡膠、胺基甲酸乙酯橡膠、及聚矽氧橡膠。
導熱性片除含有纖維狀填料與黏合劑樹脂外,亦可視需要而含有各種添加劑。
於本發明之導熱性片中,未配向於其厚度方向之纖維狀填料於全纖維狀填料中之比率為45~95%,較佳為60~90%。若該比率未達45%,則擔心片之厚度方向之導熱性變得不充分,若超過95%,則有相互接觸之纖維狀填料之比率較少,而導熱性片之導熱性變得不充分之傾向。
此處,所謂未配向於片之厚度方向之纖維狀填料係指纖維狀填料之長軸方向未平行於厚度方向之纖維狀填料。
未配向於厚度方向之纖維狀填料於全纖維狀填料中之比率可藉由如下方式求出,即對單位立方體(0.5mm見方)所含有之纖維狀填料進行顯微鏡觀察,從而計數其根數。具體而言係算出如下所述之值:對導熱性片之一剖面進行觀察時,可將“配置於厚度方向且可確認出特定長度之纖維狀填料之數”設為「配向於厚度方向之纖維狀填料」,求出其相對於全部纖維狀填料數之比率的值。該情形時,亦可將觀察之剖面數設為至少2個方向(縱橫)以上,以自該等獲得之平均值為基準而算出。
本發明之導熱性片可藉由具有以下步驟(A)~(C)之製造方法而製造。對每個步驟詳細地進行說明。
<步驟(A)>
首先,使纖維狀填料分散於黏合劑樹脂中,藉此製備導熱性片形成用組成物。該製備可藉由利用公知之方法將纖維狀填料、黏合劑樹脂、及視需要而調配之各種添加劑或揮發性溶劑均勻地混合而進行。
<步驟(B)>
繼而,藉由擠出成形法或模具成形法使所製備之導熱性片形成用組成物形成成形體塊。
作為擠出成形法、模具成形法,並無特別限制,可視導熱性片形成用組成物之黏度或導熱性片所要求之特性等,適當地從公知之各種擠出成形法、模具成形法中採用。
於擠出成形法中自模具擠出導熱性片形成用組成物時,或者於模具成形法中將導熱性片形成用組成物向模具壓入時,黏合劑樹脂會流動,一部分纖維狀填料會沿其流動方向進行配向,但大部分纖維狀填料之
配向變得無規則。
再者,於模具之前端安裝有長條之情形時,有相對於被擠出之成形體塊之寬度方向,於中央部纖維狀填料容易配向之傾向。另一方面,相對於成形體塊之寬度方向,周邊部受到長條壁之影響,從而纖維狀填料容易被無規則地配向。
成形體塊之大小.形狀可視求出之導熱性片之大小而決定。例如可列舉剖面之縱向大小為0.5~15cm且橫向大小為0.5~15cm的長方體。長方體之長度只要視需要決定即可。
<步驟(C)>
繼而,將形成之成形體塊切片成片狀。藉此可獲得導熱性片。於藉由切片而獲得之片表面(切片面)纖維狀填料露出。作為切片之方法,並無特別限制,可視成形體塊之大小或機械強度而自公知之切片裝置(較佳為超音波切割器)中進行適當選擇。作為成形體塊之切片方向,於成形方法為擠出成形法之情形時亦存在配向於擠出方向者,因此相對於擠出方向為60~120度、更佳為70~100度之方向。特佳為90度(垂直)之方向。
作為切片厚度,亦無特別限制,可視導熱性片之使用目的等而適當選擇。
<步驟(D)>
可視需要對獲得之導熱性片的切片面進行加壓。藉此可使導熱性片之表面平滑化,而使導熱性片對發熱體或散熱體之密合性提高。又,可將導熱性片壓縮,而使纖維狀填料彼此之接觸頻率增大。藉此可降低導熱性片之熱阻。作為加壓之方法,可使用由平盤與表面平坦之加壓頭所構成之一
對加壓裝置。又,亦可利用夾送輥(pinch roll)進行加壓。
作為加壓時之壓力,若過低,則有未加壓之情形與熱阻未變化之傾向,若過高,則有片延伸之傾向,因此加壓時之壓力較佳為2~8kgf/cm2,更佳為3~7kgf/cm2。
為了更提高加壓效果,縮短加壓時間,上述加壓較佳為於黏合劑樹脂之玻璃轉移溫度以上時進行。
加壓後之片厚由於壓縮而變薄,但若片之壓縮率[{(加壓前之片厚一加壓後之片厚)/加壓前之片厚}×100]過小,則有熱阻不會變小之傾向,若過大,則有片延伸之傾向,因此以壓縮率成為2~15%之方式進行加壓。
又,可藉由加壓而使片之表面變平滑。平滑之程度能以表面光澤度進行評價。若表面光澤度過低,則導熱性下降,因此較佳為於入射角60度反射角60度下經光澤計所測定之表面光澤度(光澤值)成為0.2以上之方式進行加壓。
此種導熱性片可提供一種感溫元件,其係為了將發熱體所產生之熱傳至散熱體而配置於該等之間之結構。作為發熱體,可列舉IC晶片、IC模組等,作為散熱體,可列舉由不鏽鋼等金屬材料形成之熱槽(heat sink)等。
實施例
實施例1
將聚矽氧A液(具有乙烯基之有機聚矽氧烷)、聚矽氧B液(具有氫矽基(hydrogen silyl)之有機聚矽氧烷)、氧化鋁粒子(平均粒徑3μm)、球狀
之氮化鋁(平均粒徑1μm)、及瀝青系碳纖維(平均長軸長度150μm、平均軸徑8μm)以表1所示之比率(體積份)均勻地進行混合,藉此製備導熱性片形成用聚矽氧樹脂組成物。
將該導熱性片形成用聚矽氧樹脂組成物灌入長方體狀之具有內部空間之模具中,於100℃之烘箱中加熱硬化6小時,藉此製作成形體塊。再者,於模具之內面以剝離處理面成為內側之方式貼附剝離聚對苯二甲酸乙二酯膜。
利用超音波切割器將獲得之成形體塊切片成0.5mm厚而獲得片。於該片之表面,因切片時之剪力故纖維狀填料之一部分露出於表面,並且於片表面形成有微小凹凸。其後,以成為表1之壓縮率之方式依據常法進行加壓。又,藉由電子顯微鏡觀察,確認瀝青系碳纖維相對於導熱性片之厚度方向朝向縱、橫、斜之各個方向,進而,對未配向於導熱性片之厚度方向之瀝青系碳纖維於全瀝青系碳纖維中之比率進行計數。將獲得之結果示於表1。
實施例2~11
按照表1之調配而製備導熱性片形成用聚矽氧樹脂組成物,除此以外,藉由與實施例1相同之操作而製作成形體塊,進而製作導熱性片。進而,對未配向於導熱性片之厚度方向之瀝青系碳纖維於全瀝青系碳纖維中之比率進行計數。將獲得之結果示於表1。
比較例1~4
按照表1之調配來製備導熱性片形成用聚矽氧樹脂組成物,進而,藉由日本特開2012-23335號公報之擠出成形法而製作導熱性片,切下瀝青系
碳纖維容易配向(厚度方向)之其中央部。進而,利用電子顯微鏡進行觀察,對未配向於厚度方向之瀝青系碳纖維於全瀝青系碳纖維中之比率進行計數。將獲得之結果示於表1。
<評價>
對獲得之導熱性片施加1kgf/cm2之荷重,使用依據ASTM-D5470之熱阻測定裝置而測定成為表1之壓縮率之時間點的熱阻(K/W)。將獲得之結果示於表1。期望熱阻為0.2(K/W)以下,經面積換算之值為0.65(K.cm2/W)以下。
表1之實施例1~11之導熱性片之未配向於導熱性片之厚度方向的碳纖維於全碳纖維中之比率為45~95%,因此熱阻顯示出較佳之較低值(0.2K/W以下(0.65K.cm2/W以下))。再者,根據實施例8~11之結果,即便碳纖維之平均纖維長度為40~250μm,亦可獲得良好之結果。
相對於此,比較例1~4之導熱性片之未配向於導熱性片之厚度方向的碳纖維於全碳纖維中之比率為5~40%,因此熱阻變得超過0.2K/W(0.65K.cm2/W)。
[產業上之可利用性]
本發明之導熱性片之未配向於其厚度方向的纖維狀填料於全纖維狀填料中之比率成為45~95%。因此,導熱性片內纖維狀填料相互接觸之頻率變高,熱阻下降。又,亦無露出之纖維狀填料之端部未沉入片內之情況,且於配置於發熱體與散熱體之間時亦無需對該等施加如阻礙該等正常動作之負荷。因此,本發明之導熱性片可用作用以配置於IC晶片或IC模組等發熱體與散熱體之間之導熱性片。
Claims (7)
- 一種導熱性片,係含有纖維狀填料與黏合劑樹脂者,且未配向於導熱性片之厚度方向之纖維狀填料之根數相對於纖維狀填料之總根數的比率為45~95%。
- 如申請專利範圍第1項之導熱性片,其中纖維狀填料之平均徑為8~12μm,且縱橫比為2~50。
- 如申請專利範圍第1或2項之導熱性片,其中纖維狀填料為瀝青系碳纖維。
- 如申請專利範圍第1或2項之導熱性片,其中纖維狀填料於導熱性片中之含量為16~40體積%。
- 如申請專利範圍第1或2項之導熱性片,其進而含有非纖維狀填料。
- 如申請專利範圍第5項之導熱性片,其中非纖維狀填料為球狀之氧化鋁或氮化鋁。
- 如申請專利範圍第1或2項之導熱性片,其中黏合劑樹脂為聚矽氧樹脂。
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TW201012912A (en) * | 2008-05-23 | 2010-04-01 | Hitachi Chemical Co Ltd | Heat radiation sheet and heat radiation device |
TW201008988A (en) * | 2008-07-31 | 2010-03-01 | Toray Industries | Prepreg, preform, moldings and manufacturing method of prepreg |
TW201209972A (en) * | 2010-06-17 | 2012-03-01 | Sony Chemical & Inf Device | Thermally conductive sheet and process for producing same |
Cited By (1)
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US10515870B1 (en) | 2018-05-30 | 2019-12-24 | Unimicron Technology Corp. | Package carrier having a mesh gas-permeable structure disposed in the through hole |
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KR20210150605A (ko) | 2021-12-10 |
US20150166771A1 (en) | 2015-06-18 |
CN105482456A (zh) | 2016-04-13 |
CN107043538A (zh) | 2017-08-15 |
EP2871674A1 (en) | 2015-05-13 |
KR20180082635A (ko) | 2018-07-18 |
HK1222406A1 (zh) | 2017-06-30 |
EP2871674B1 (en) | 2020-12-02 |
KR20150035783A (ko) | 2015-04-07 |
TW201418366A (zh) | 2014-05-16 |
EP2871674A4 (en) | 2016-02-17 |
CN103748674A (zh) | 2014-04-23 |
KR102558979B1 (ko) | 2023-07-25 |
JP2014033193A (ja) | 2014-02-20 |
CN107043538B (zh) | 2022-05-27 |
JP5541399B2 (ja) | 2014-07-09 |
KR20200030637A (ko) | 2020-03-20 |
US10106672B2 (en) | 2018-10-23 |
WO2014010520A1 (ja) | 2014-01-16 |
EP3790044A1 (en) | 2021-03-10 |
EP3790044B1 (en) | 2023-10-11 |
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