TW202245022A - 熱固性片材及切晶黏晶膜 - Google Patents

熱固性片材及切晶黏晶膜 Download PDF

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TW202245022A
TW202245022A TW111111134A TW111111134A TW202245022A TW 202245022 A TW202245022 A TW 202245022A TW 111111134 A TW111111134 A TW 111111134A TW 111111134 A TW111111134 A TW 111111134A TW 202245022 A TW202245022 A TW 202245022A
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Taiwan
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thermosetting
thermosetting sheet
mass
parts
mentioned
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TW111111134A
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English (en)
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小島麗奈
市川智昭
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日商日東電工股份有限公司
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Publication of TW202245022A publication Critical patent/TW202245022A/zh

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Abstract

本發明之熱固性片材為包含熱固性樹脂及熱塑性樹脂者，使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下。

Description

熱固性片材及切晶黏晶膜
本發明係關於一種熱固性片材及切晶黏晶膜。
以往，已知使熱固性片材覆著於被接著體而使用。
上述熱固性片材例如用於使半導體元件接著(覆著)於具有半導體元件之搭載區域之基板(用於黏晶)(例如下述專利文獻1)。即，上述熱固性片材例如在半導體裝置之製造中使用。 專利文獻1中，作為此種熱固性片材，揭示有包含導電性粒子及熱固性樹脂之熱固性片材。
在如上所述之半導體裝置之製造中，例如以在半導體晶圓之一個面(與電路形成面處於相反側之面)貼附有熱固性片材之狀態，對上述半導體晶圓及上述熱固性片材進行切割，藉此可獲得複數個在一個面貼附有半導體元件之熱固性片材。 並且，在一個面貼附有半導體元件之熱固性片材藉由在規定溫度(例如70℃)下將另一個面臨時接著於上述基板之安裝半導體元件之區域後，在高於此之溫度(例如200℃)下進行熱固化，從而接著於上述基板(正式接著)。即，上述半導體元件以介隔有上述熱固性片材之狀態接著於上述基板。 [先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2019-21813號公報
[發明所欲解決之問題]
且說，使上述熱固性片材之另一面正式接著於上述基板後(例如在200℃下接著之後)，有上述熱固性片材之另一面側之一部分會從作為被接著體之上述基板剝離之情況。 從上述熱固性片材對被接著體之接著可靠性之方面而言，不期望產生此種剝離。 又，在如上所述之半導體裝置中，若產生此種剝離，則經由上述導電性粒子之電傳導及熱傳導變得不充分，故不佳。 然而，關於抑制上述熱固性片材從作為被接著體之上述基板剝離，難言進行了充分研究。
再者，如上所述之熱固性片材之剝離之問題在被接著體為具有半導體元件之搭載區域之基板以外之情形時亦同樣可能發生。
因此，本發明之課題在於，提供能夠在熱固化後相對地抑制從被接著體之剝離之熱固性片材、及具備該熱固性片材之切晶黏晶膜。 [解決問題之技術手段]
本發明之熱固性片材係包含熱固性樹脂及熱塑性樹脂者， 使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下。
上述熱固性片材中，較佳為， 相對於上述熱固性樹脂100質量份，包含60質量份以上且500質量份以下之上述熱塑性樹脂。
上述熱固性片材中，較佳為， 進而包含導電性粒子。
上述熱固性片材中，較佳為， 進而包含揮發成分。
上述熱固性片材中，較佳為， 相對於上述熱固性樹脂100質量份，進而包含10質量份以上且300質量份以下之揮發成分。
本發明之切晶黏晶膜具備： 在基材層上積層黏著劑層而成之切晶帶、及 積層在上述切晶帶之上述黏著劑層上之熱固性片材， 上述熱固性片材為上述任一熱固性片材。
以下針對本發明之一個實施方式進行說明。
[熱固性片材] 本實施方式之熱固性片材包含熱固性樹脂及熱塑性樹脂。 又，本實施方式之熱固性片材在使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下。 再者，以下，有時對使溫度從25℃變化至200℃時之厚度之變化率賦予Rc這一參考標記。
如上所述，藉由包含熱固性樹脂及熱塑性樹脂且使溫度從25℃變化至200℃時之厚度之變化率Rc為0%以上且10%以下，從而在使上述熱固性片材熱固化並正式接著於上述被接著體時，能夠相對地抑制上述熱固性片材發生收縮。 並且，由於能夠相對地抑制上述熱固性片材發生收縮，從而在熱固化中，能夠相對地減小上述熱固性片材中產生之內部應力(固化收縮應力及熱收縮應力)，因此能夠抑制由於該內部應力而使上述熱固性片材從上述被接著體剝離。 又，由於包含上述熱塑性樹脂，因此在使上述熱固性片材熱固化後，亦能夠使上述熱固性片材具有相對低之彈性。 藉此，在熱固化後亦能夠確保上述熱固性片材與上述被接著體之密接性。
使溫度從25℃變化至200℃時之厚度之變化率Rc較佳為1%以上、更佳為3%以上。 再者，如上所述，使溫度從25℃變化至200℃時之厚度之變化率Rc之上限值為10%。
使溫度從25℃變化至200℃時之厚度之變化率Rc可藉由如下方式求出。 具體而言，在熱機械分析(TMA)中，使溫度從25℃變化至200℃時，測定25℃下之上述熱固性片材之厚度T1，並且測定剛升溫至200℃後之上述熱固性片材之厚度T2，使用該等測定值T1及T2，藉由下述式計算，藉此可求出。 Rc＝(T2－T1)/T1×100 再者，在與25℃相比，上述熱固性片材剛升溫至200℃後發生膨脹時，Rc為正值，在與25℃相比，上述熱固性片材剛升溫至200℃後發生收縮時，Rc為負值。 又，在與25℃相比，上述熱固性片材剛升溫至200℃後既不膨脹亦不收縮時，Rc之值為0。
熱機械分析可按照以下之條件進行。 熱機械分析之條件・熱機械分析裝置：TA Instruments Japan公司製造、型號Q400 ・探針：微膨脹探針 ・測定模式：壓縮膨脹 ・升溫條件：用60分鐘從25℃升溫至200℃，在200℃下保持1小時後，用30分鐘降溫至25℃。 ・測定氣氛：氮氣(N 2) ・負載：0.012 N(恆定負載) ・供試體：將積層複數片熱固性片材而獲得之第1熱固性片材積層體在溫度70℃、壓力6 kN之條件下加壓60秒而獲得厚度3 mm之第2熱固性片材積層體後，用4 mm
Figure 02_image001
之衝頭對該第2熱固性片材積層體進行沖裁，獲得厚度3 mm×4 mm
Figure 02_image001
之供試體。 再者，上述基於熱機械分析裝置之測定係藉由如下方式進行：將在雙面分別配置有鋁板(俯視圓形狀。厚度0.1 mm。平面尺寸5 mm
Figure 02_image001
)之上述供試體以一側之鋁板抵接之方式載置於上述熱機械分析裝置之載台上，然後從另一側之鋁板(上方之鋁板)側用上述探針施加負載。 又，Rc可將針對2個供試體求出之值進行算術平均而求得。
本實施方式之熱固性片材較佳為相對於上述熱固性樹脂100質量份包含60質量份以上且500質量份以下之上述熱塑性樹脂。 藉由使上述熱塑性樹脂之含量為上述範圍，能夠進一步抑制上述熱固性片材從被接著體之剝離。
本實施方式之熱固性片材更佳為相對於上述熱固性樹脂100質量份包含90質量份以上之上述熱塑性樹脂。 又，本實施方式之熱固性片材更佳為相對於上述熱固性樹脂100質量份包含400質量份以下、進而較佳為包含300質量份以下之上述熱塑性樹脂。
作為上述熱固性樹脂，例如可例舉環氧樹脂、酚樹脂、胺基樹脂、不飽和聚酯樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂、及熱固性聚醯亞胺樹脂等。該等之中，較佳為使用環氧樹脂。
作為環氧樹脂，例如可例舉雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、茀型、苯酚酚醛清漆型、甲酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥基苯基甲烷型、四酚基乙烷型、乙內醯脲型、異氰尿酸三縮水甘油酯型、及縮水甘油胺型之環氧樹脂。該等之中，較佳為使用雙酚A型環氧樹脂及甲酚酚醛清漆型環氧樹脂之至少一者，更佳為組合雙酚A型環氧樹脂及甲酚酚醛清漆型環氧樹脂使用。 作為雙酚A型環氧樹脂，可例舉脂肪族改性雙酚A型環氧樹脂。
對於作為環氧樹脂之固化劑之酚樹脂，例如可例舉酚醛清漆型酚樹脂、可溶酚醛型酚樹脂、聯苯型酚樹脂、及聚對羥基苯乙烯等聚羥基苯乙烯。上述酚樹脂中，較佳為使用聯苯型酚樹脂。
又，作為熱固性樹脂，亦可使用具有熱固性官能基之熱塑性樹脂。作為具有熱固性官能基之熱塑性樹脂，例如可例舉含熱固性官能基之丙烯酸系樹脂。作為含熱固性官能基之丙烯酸系樹脂中之丙烯酸系樹脂，可例舉包含來源於(甲基)丙烯酸酯之單體單元之樹脂。 在具有熱固性官能基之熱塑性樹脂中，根據熱固性官能基之種類來選擇固化劑。
作為上述熱塑性樹脂，例如可例舉天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、聚醯胺6、或聚醯胺6,6等聚醯胺樹脂、苯氧基樹脂、丙烯酸系樹脂、PET、或PBT等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、氟樹脂等。上述熱塑性樹脂可僅使用一種，亦可組合兩種以上使用。作為上述熱塑性樹脂，從離子性雜質少且耐熱性高、因而容易確保基於熱固性片材之連接可靠性之觀點出發，較佳為丙烯酸系樹脂。
上述丙烯酸系樹脂較佳為包含來源於(甲基)丙烯酸酯之單體單元作為質量比率最多之單體單元之聚合物。作為(甲基)丙烯酸酯，例如可例舉(甲基)丙烯酸烷基酯、(甲基)丙烯酸環烷基酯、及(甲基)丙烯酸芳基酯等。上述丙烯酸系樹脂亦可包含來源於能夠與(甲基)丙烯酸酯共聚之其他成分之單體單元。作為上述其他成分，例如可例舉含羧基單體、酸酐單體、含羥基單體、含縮水甘油基單體、含磺酸基單體、含磷酸基單體、丙烯醯胺、丙烯腈等含官能基單體、或各種多官能性單體等。 上述丙烯酸系樹脂較佳為含羧基之丙烯酸系聚合物。
本實施方式之熱固性片材如上所述，在包含上述熱固性樹脂及上述熱塑性樹脂之基礎上，使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下，藉此在藉由使上述熱固性片材熱固化而接著於被接著體後，能夠相對地抑制上述熱固性片材之一部分從上述被接著體剝離，關於其原因雖然不一定明確，但本發明人等對其原因作如下推測。
熱固性片材具有熱固化之特性，通常含有熱固性樹脂。 並且，認為熱固性樹脂通常在以相對較高之交聯密度進行交聯之同時熱固化，因此對於包含熱固性樹脂之熱固性片材而言，在使其熱固化而接著於被接著體時會發生體積收縮，隨著該體積收縮，上述熱固性片材之一部分從上述被接著體剝離。 與此相對，本實施方式之熱固性片材除了含有熱固性樹脂，亦含有熱塑性樹脂，因此認為藉由該熱塑性樹脂能夠緩和熱固性樹脂以相對較高之交聯密度進行交聯。即，認為在上述熱固性片材中能夠形成相對地寬鬆之交聯結構。 又，本實施方式之熱固性片材中，使溫度從25℃變化至200℃時之厚度之變化率Rc(剛升溫至200℃後之上述熱固性片材之厚度T2相對於25℃下之上述熱固性片材之厚度T1之變化率)不會為負值，且被調整為如上所述之數值範圍(0%以上且10%以下)，因此，認為亦抑制了因厚度之變化率Rc之值變得過大(上述熱固性片材過度膨脹)而導致上述熱固性片材之一部分從上述被接著體剝離。 藉此，本發明人等推測，本實施方式之熱固性片材在使其熱固化而接著於被接著體後，亦抑制其一部分從上述被接著體剝離。
本實施方式之熱固性片材藉由在上述熱固性片材中適當調整上述熱固性樹脂之含有比率與上述熱塑性樹脂之含有比率，從而能夠適當調整而獲得厚度之變化率Rc。 更具體而言，在上述熱固性片材中，藉由提高上述熱塑性樹脂之含有比率(藉由在上述熱固性片材中相對地降低上述熱固性樹脂之含有比率)，能夠適當調整厚度之變化率Rc之值。 再者，若過度提高上述熱塑性樹脂之含有比率，則由於上述熱固性片材之熱固化會變得難以進行、或厚度之變化率Rc之值變得過大(過度膨脹)，上述熱固性片材對上述被接著體之接著可靠性難免會變差，因此需要適當調整上述熱塑性樹脂之含有比率而使得厚度之變化率Rc為如上所述之數值範圍(0%以上且10%以下)。 又，如後所述，在本實施方式之熱固性片材包含導電性粒子之情形時，在上述熱固性片材中，上述導電性粒子之含有比率越高，則上述熱固性樹脂、或上述熱塑性樹脂等有機成分在上述熱固性片材中所占之含有比率越低，上述熱固性樹脂造成之上述熱固性片材之體積收縮程度越低。 因此，本實施方式之熱固性片材除了包含上述熱固性樹脂及上述熱塑性樹脂以外進而包含上述導電性粒子時，藉由適當調整該等之含有比率，能夠將厚度之變化率Rc適當調整為如上所述之數值範圍(0%以上且10%以下)。
本實施方式之熱固性片材在接著於具有半導體元件之搭載區域之基板使用時(用於半導體裝置之製造時)，該熱固性片材較佳為除了包含上述熱固性樹脂及上述熱塑性樹脂以外進而包含導電性粒子。 又，用於半導體裝置之製造時，本實施方式之熱固性片材較佳為除了包含上述導電性粒子以外進而包含揮發成分。 再者，本申請說明書中，導電性粒子係指按照JIS K 0130(2008)測得之電導率為100 μS/cm以下之粒子。
藉由使本實施方式之熱固性片材進而包含導電性粒子，從而不僅能夠抑制上述熱固性片材從被接著體之剝離，亦能夠經由上述導電性粒子使上述熱固性片材發揮電傳導性及熱傳導性。 又，藉由使本實施方式之熱固性片材除了包含導電性粒子以外進而包含揮發成分，從而在上述熱固性片材之熱固化中，能夠藉由使上述揮發成分揮發而減少上述熱固性片材之體積。 並且，與上述熱固性片材之體積減少之部分相應地，上述導電性粒子彼此在上述熱固性片材中成為較近之位置關係，因此在上述熱固性片材中容易藉由上述導電性粒子彼此而形成熱傳導路徑。 藉此，能夠使固化後之上述熱固性片材之熱傳導性相對提高。
本實施方式之熱固性片材較佳為相對於上述熱固性樹脂100質量份包含700質量份以上、更佳為包含1000質量份以上、進而較佳為包含2000質量份以上之上述導電性粒子。 又，本實施方式之熱固性片材較佳為相對於上述熱固性樹脂100質量份包含45000質量份以下、更佳為包含16000質量份以下、進而較佳為包含10000質量份以下、特佳為包含8000質量份以下之上述導電性粒子。 特別是相對於上述熱固性樹脂100質量份包含上述導電性粒子16000質量份以下時，上述熱固性片材會進一步維持片材形狀。
本實施方式之熱固性片材較佳為相對於上述熱固性樹脂100質量份包含10質量份以上且300質量份以下之上述揮發成分。 藉由使上述揮發成分之含量為上述範圍，從而在上述熱固性片材中更容易藉由上述導電性粒子彼此而形成熱傳導路徑。 藉此，能夠使固化後之上述熱固性片材之熱傳導性進一步提高。 本實施方式之熱固性片材更佳為相對於上述熱固性樹脂100質量份包含20質量份以上之上述揮發成分。 又，本實施方式之熱固性片材更佳為相對於上述熱固性樹脂100質量份包含250質量份以下、進而較佳為包含200質量份以下、特佳為包含100質量份以下之上述揮發成分。
上述導電性粒子較佳為包含銀粒子。 作為上述銀粒子之形狀，例如可使用薄片狀、針狀、長絲狀、球狀、扁平狀(包括鱗片狀)之粒子，該等之中，較佳為使用球狀之粒子。 作為上述銀粒子，藉由使用球狀之粒子，從而能夠在熱固性片材中提高上述銀粒子之分散性。
上述銀粒子可為包含銀元素及作為不可避免之雜質元素而包含之其他元素(金屬元素等)之銀粒子，亦可為實施了表面處理(例如矽烷偶合處理)之銀粒子。作為銀粒子之表面處理劑，可例舉脂肪酸系、或胺系、環氧系等之被覆劑。作為用脂肪酸系被覆劑進行了表面處理之銀粒子之市售品，可例舉DOWA ELECTRONICS MATERIALS公司製造之AG-2-8F等，作為用環氧系被覆劑進行了表面處理之銀粒子之市售品，可例舉三井金屬礦業公司製造之HP02等。 再者，以下有時將用脂肪酸系、或胺系、環氧系等之被覆劑進行了表面處理之銀粒子稱為被覆劑處理銀粒子。 本實施方式之熱固性片材中，作為上述銀粒子，較佳為使用被覆劑處理銀粒子。藉由使用被覆劑處理銀粒子作為上述銀粒子，能夠提高與上述熱固性片材所含之樹脂成分(熱固性樹脂及熱塑性樹脂)之親和性，因此上述銀粒子變得容易分散在上述熱固性片材中。
上述導電性粒子除了包含銀粒子以外亦可包含鎳粒子、銅粒子、鋁粒子、炭黑、奈米碳管、利用金或銀等金屬對作為芯(核)之金屬粒子之表面進行鍍覆而成之粒子(以下亦稱為鍍覆金屬粒子)、及利用金屬被覆作為芯(核)之樹脂粒子之表面而成之粒子(以下亦稱為金屬被覆樹脂粒子)等。該等導電性粒子可僅使用一種、亦可組合兩種以上使用。
作為鍍覆金屬粒子，例如可使用以鎳粒子或銅粒子作為核並利用金、銀等貴金屬鍍覆該核之表面而成之粒子。 作為金屬被覆樹脂粒子，例如可使用以樹脂粒子作為核，利用鎳、金等金屬被覆該核之表面而成之粒子。 本實施方式之熱固性片材包含銀粒子以外之導電性粒子時，作為該導電性粒子，較佳為使用鍍覆金屬粒子，作為鍍覆金屬粒子，較佳為使用以銅粒子為核並利用銀鍍覆該核之表面而成之粒子(銀被覆銅粒子)。作為銀被覆銅粒子之市售品，可例舉對三井金屬礦業公司製造之商品名1200Y(銅粒子)塗佈20質量%銀粒子而成之粒子、對三井金屬礦業公司製造之商品名MA-C03K(銅粒子)塗佈20質量%銀粒子而成之粒子、DOWA ELECTRONICS MATERIALS公司製造之商品名AOP-TCY-2(EN)等。 本實施方式之熱固性片材包含銀粒子以外之導電性粒子時，銀粒子在導電性粒子100質量份中所占之質量份較佳為10質量份以上且95質量份以下、更佳為20質量份以上且90質量份以下。
作為銀粒子以外之導電性粒子之形狀，例如可使用薄片狀、針狀、長絲狀、球狀、扁平狀(包括鱗片狀)之粒子，該等之中，較佳為使用球狀之粒子。 藉由使用球狀之粒子作為銀粒子以外之導電性粒子，在熱固性片材中，能夠提高除銀粒子以外之導電性粒子之分散性。 此處，球狀粒子與扁平狀粒子相比，比表面積小，因此若使用球狀粒子作為銀粒子以外之導電性粒子，則銀粒子以外之導電性粒子與銀粒子之接觸面積變小，從電傳導性及熱傳導性之觀點而言亦認為不利。 然而，本實施方式之熱固性片材由於包含揮發成分，因此藉由在上述熱固性片材之熱固化中使上述揮發成分揮發，固化後之上述熱固性片材之體積減少(上述熱固性片材體積收縮)，銀粒子以外之導電性粒子與銀粒子成為較近之位置關係。 因此，即使在使用球狀粒子作為銀粒子以外之導電性粒子之情形時，亦能夠充分確保銀粒子以外之導電性粒子與銀粒子之接觸面積，藉此，能夠充分確保電傳導性及熱傳導性。 再者，上述對三井金屬礦業公司製造之商品名1200Y塗佈20質量%銀粒子而成之粒子、對三井金屬礦業公司製造之商品名MA-C03K塗佈20質量%銀粒子而成之粒子、及DOWA ELECTRONICS MATERIALS公司製造之商品名AOP-TCY-2(EN)均係分類為球狀之粒子。
作為揮發成分，可例舉包含1個以上羥基且沸點為250℃以上之有機化合物。該有機化合物之沸點較佳為350℃以下。作為此種有機化合物，可例舉萜烯化合物。作為揮發成分，在萜烯化合物中，較佳為下述式(1)所示之異冰片基環己醇。再者，異冰片基環己醇係沸點為308～318℃之有機化合物，在200 mL/分鐘之氮氣氣流下以10℃/分鐘之升溫條件從室溫(23±2℃)升溫至600℃時，具有從100℃以上起重量大幅減少、在245℃下揮發消失(無法確認其以上之重量減少)之性質，並且具有在25℃下顯示出1000000 mPa·s之極高之黏度、但在60℃下顯示出1000 mPa・s以下之相對較低之黏度之性質。再者，重量減少係將測定開始溫度(室溫)下之重量減少率設為0%時之值。 如上所述，異冰片基環己醇在25℃下顯示出如上所述之極高之黏度，因此在室溫下能夠維持片材形狀，但由於在60℃下顯示出如上所述之相對較低之黏度，因此具有黏性。即，包含異冰片基環己醇之熱固性片材在室溫下片材形狀之維持性優異，在60℃以上之溫度下會變得具有黏性。 此處，將貼附於熱固性片材之一個面之半導體元件安裝於金屬引線框等時，通常在60～80℃之溫度下經由熱固性片材而將半導體元件臨時接著(臨時固定)於金屬引線框等被接著體，但由於異冰片基環己醇如上所述在60℃以上具有黏性，因此在本實施方式之熱固性片材包含異冰片基環己醇作為揮發成分之情形時，熱固性片材對金屬引線框等被接著體之臨時接著性進一步提高。即，在臨時接著之狀態下，可抑制半導體元件之安裝位置發生偏離、或熱固性片材從被接著體隆起。 因此，在使熱固性片材熱固化而將半導體元件接著於被接著體時，能夠高可靠性地進行接著。
[化1]
Figure 02_image004
從使樹脂成分之固化反應充分進行、或提高固化反應速度之觀點而言，本實施方式之熱固性片材可含有熱固化觸媒。作為熱固化觸媒，例如可例舉咪唑系化合物、三苯基膦系化合物、胺系化合物、及三鹵硼烷系化合物。
對於本實施方式之熱固性片材，固化前之上述熱固性片材中之上述導電性粒子之粒子填充率P 1較佳為30體積%以上、更佳為40體積%以上、進而較佳為50體積%以上。 上述粒子填充率P 1較佳為70體積%以下、更佳為60體積%以下。
又，對於本實施方式之熱固性片材，固化後之上述熱固性片材中之上述導電性粒子之粒子填充率P 2較佳為40體積%以上、更佳為50體積%以上、進而較佳為60體積%以上。 上述粒子填充率P 2較佳為80體積%以下、更佳為75體積%以下。 藉由使上述粒子填充率P 2滿足上述數值範圍，能夠進一步提高固化後之熱固性片材之散熱性。 再者，粒子填充率係指導電性粒子在每單位體積中所占之比率，關於上述粒子填充率，可如以下說明般，針對對熱固性片材進行機械研磨而露出之截面，使用場發射型電子顯微鏡，藉由拍攝任意截面區域內之SEM圖像而獲得反射電子圖像作為圖像資料，對該圖像資料進行圖像解析，藉此求出。
上述粒子填充率P 1可按照以下之程序來求出。 (1)對固化前之熱固性片材進行機械研磨而使截面露出，對於該露出之截面，使用離子拋光裝置(例如日本電子股份有限公司製造、商品名：Cross Section Polisher SM-09010)進行離子拋光。 (2)使用場發射型掃描電子顯微鏡(例如Hitachi High Technology公司製造、商品名SU8020)拍攝進行了離子拋光之露出截面中之任意截面區域內之SEM圖像(由掃描型電子顯微鏡獲得之圖像)，獲得反射電子圖像作為圖像資料。拍攝條件可將加速電壓設為5 kV、將倍率設為5000倍。 (3)對於獲得之圖像資料，使用圖像解析軟體(例如ImageJ)進行2值化為金屬部分及樹脂部分之自動2值化處理。 (4)由2值化後之圖像求出導電性粒子部分之合計面積與整體(導電性粒子部分＋樹脂部分)之面積，將導電性粒子部分之合計面積除以整體之面積，藉此對固化後之熱固性片材求出導電性粒子之粒子填充率P 1。 再者，上述粒子填充率P 1較佳為藉由將針對進行了離子拋光之露出截面中之5處截面區域求出之填充率進行算術平均來求出。 又，上述粒子填充率P 2亦可對固化後之熱固性片材進行與上述同樣之操作而求出。
本實施方式之熱固性片材之厚度較佳為5 μm以上、更佳為10 μm以上、進而較佳為20 μm以上。又，熱固性片材之厚度較佳為150 μm以下、更佳為100 μm以下、進而較佳為80 μm以下。 藉由使熱固性片材之厚度為150 μm以下，能夠進一步提高熱傳導性。 熱固性片材之厚度例如可藉由使用針盤指示器(PEACOCK公司製造、型號R-205)測定隨機選擇之任意5處之厚度並對該等厚度進行算術平均來求出。
本實施方式之熱固性片材較佳為固化後之熱導率為3 W/m・K以上。 藉由使固化後之熱導率滿足上述數值範圍，能夠進一步提高固化後之上述熱固性片材之導電性。 再者，本實施方式之熱固性片材中，固化後之熱導率之上限值通常為100 W/m・K。 關於固化後之熱導率，可將本實施方式之熱固性片材一邊利用加壓蒸煮器裝置施加0.5 MPa之壓力一邊在200℃下處理1小時而使其熱固化，對於熱固化之熱固性片材，藉由下述式來算出。
[數1] 熱導率(W/m·K)＝熱擴散率(m 2/s)×比熱(J/g·℃)×比重(g/cm 3)
上述式中之熱擴散率(m 2/s)可利用TWA法(溫度波熱分析法、測定裝置：ai-Phase Mobile、ai-Phase公司製造)來測定。 又，上述式中之比熱(J/g・℃)可藉由DSC法來測定。比熱測定可使用SII Nanotechnology公司製造之DSC6220在升溫速度10℃/分鐘、溫度範圍20～300℃之條件下進行，基於獲得之資料，利用JIS手冊(比熱容測定方法K-7123)中記載之方法算出比熱。 進而，上述式中之比重可利用阿基米德法來測定。
本實施方式之熱固性片材根據需要亦可含有1種或2種以上之其他成分。作為其他成分，例如可例舉填料分散劑、阻燃劑、矽烷偶合劑、及離子捕捉劑。
[切晶黏晶膜] 繼而，一邊參照圖1，一邊對切晶黏晶膜20進行說明。再者，在以下說明中，關於與熱固性片材重複之部分，不再重複其說明。
如圖1所示，本實施方式之切晶黏晶膜20具備在基材層1上積層有黏著劑層2之切晶帶10、及積層在切晶帶10之黏著劑層2上之熱固性片材3。 切晶黏晶膜20中，半導體元件係貼附於熱固性片材3上。半導體元件可為裸晶圓。 貼附於本實施方式之切晶黏晶膜20之裸晶圓藉由刀片切割、DBG(Dicing Before Grinding，切割後研磨)、或SDBG(Stealth Dicing Before Grinding，隱形切割後研磨)等被割斷為複數個裸晶片。並且，在如前所述地進行割斷時，與裸晶圓一起，熱固性片材3亦被割斷。熱固性片材3被割斷為相當於經單片化之複數個裸晶片之尺寸的大小。藉此，可獲得複數個附熱固性片材3之裸晶片。
切晶黏晶膜20之熱固性片材3如前所述，包含熱固性樹脂及熱塑性樹脂、且使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下。
基材層1支持黏著劑層2及積層在黏著劑層2上之熱固性片材3。基材層1包含樹脂。作為樹脂，可例舉：聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物等烯烴系樹脂；乙烯-乙酸乙烯酯共聚物(EVA)、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物等以乙烯作為單體成分之共聚物；聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)等聚酯；丙烯酸系樹脂；聚氯乙烯(PVC)；聚胺基甲酸酯；聚碳酸酯；聚苯硫醚(PPS)；聚醯胺、全芳香族聚醯胺(聚芳醯胺)等醯胺系樹脂；聚醚醚酮(PEEK)；聚醯亞胺；聚醚醯亞胺；聚偏二氯乙烯；ABS(丙烯腈-丁二烯-苯乙烯共聚物)；纖維素系樹脂；聚矽氧樹脂；氟樹脂等。 該等之中，較佳為包含聚對苯二甲酸乙二酯。
基材層1可包含1種上述樹脂，亦可包含2種以上之上述樹脂。
作為基材層1之材料，可例舉上述樹脂之交聯物等聚合物(例如塑膠膜)。上述塑膠膜可在未延伸下使用，亦可使用根據需要而實施了單軸或雙軸之延伸處理者。若為利用藉由延伸處理等而賦予了熱收縮性之樹脂片，則在切割後藉由使該基材層1熱收縮，能夠減小黏著劑層2與熱固性片材3之接著面積，從而實現使半導體晶片(半導體元件)之回收容易。
對於基材層1之表面，為了提高與鄰接之層之密接性、保持性等，可實施通常之表面處理。作為此種表面處理，可例舉：鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離放射線處理等化學或物理處理，利用底塗劑之塗佈處理等。
基材層1之厚度較佳為1 μm以上且1000 μm以下、更佳為10 μm以上且500 μm以下、進而較佳為20 μm以上且300 μm以下、特佳為30 μm以上且200 μm以下。 基材層1之厚度可與上述熱固性片材3之厚度同樣地使用針盤指示器(PEACOCK公司製造、型號R-205)求出。
基材層1可包含各種添加劑。作為各種添加劑，例如可例舉著色劑、填充劑、增塑劑、防老化劑、抗氧化劑、界面活性劑、阻燃劑等。
作為用於形成黏著劑層2之黏著劑，無特別限定，例如可使用丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑。作為上述感壓性黏著劑，從半導體晶圓或玻璃等怕被污染之電子零件之利用超純水或醇等有機溶劑之潔淨清洗性等方面出發，較佳為以丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑。
作為上述丙烯酸系聚合物，例如可例舉使用(甲基)丙烯酸烷基酯及(甲基)丙烯酸環烷基酯之1種或2種以上作為單體成分之丙烯酸系聚合物等。作為(甲基)丙烯酸烷基酯，例如可使用甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數為1～30、特別是碳數為4～18之直鏈狀或支鏈狀之烷基酯等。作為(甲基)丙烯酸環烷基酯，例如可使用環戊酯、環己酯等。 再者，(甲基)丙烯酸酯係指丙烯酸酯及甲基丙烯酸酯之至少一者，本發明之(甲基)全部表示與上述內容同樣之含義。
上述丙烯酸系聚合物出於凝集力、耐熱性等之改質之目的，根據需要可包含與能夠同上述(甲基)丙烯酸烷基酯或(甲基)丙烯酸環烷基酯共聚之其他單體成分對應之單元。作為此種單體成分，例如可例舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、巴豆酸等含羧基單體；馬來酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥甲基環己基)甲酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯氧基萘磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸單體；丙烯醯基磷酸2-羥基乙酯等含磷酸基單體；丙烯醯胺、丙烯腈等。該等能夠共聚之單體成分可使用1種或2種以上。該等能夠共聚之單體之使用量較佳為全部單體成分之40質量%以下。
進而，上述丙烯酸系聚合物為了使其交聯，根據需要還可包含多官能性單體等作為共聚用單體成分。作為此種多官能性單體，例如可例舉己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯等。該等多官能性單體亦可使用1種或2種以上。從黏著特性等方面出發，多官能性單體之使用量較佳為全部單體成分之30質量%以下。
上述丙烯酸系聚合物可藉由使單一單體或2種以上之單體混合物聚合來獲得。聚合可以溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等任意方法進行。從防止對清潔之被接著體之污染等方面出發，較佳為低分子量物質之含量小。從該方面而言，丙烯酸系聚合物之數均分子量較佳為30萬以上，更佳為40萬～300萬左右。
又，在上述黏著劑中，為了提高作為基礎聚合物之丙烯酸系聚合物等之數均分子量，可適當添加外部交聯劑。作為外部交聯方法之具體方式，可例舉添加多異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等交聯劑進行反應之方法。使用外部交聯劑之情形時，考慮與要交聯之基礎聚合物之平衡及作為黏著劑之使用用途來適當確定其使用量。一般而言，相對於上述基礎聚合物100質量份，外部交聯劑較佳為調配約5質量份以下，更佳為調配0.1～5質量份。
黏著劑除了上述成分以外，亦可根據需要而包含各種公知之增黏劑、防老化劑等添加劑。
黏著劑層2可藉由放射線固化型黏著劑形成。放射線固化型黏著劑能夠藉由紫外線等放射線之照射而增大交聯度，從而容易地降低其黏著力。即，藉由由放射線固化型黏著劑形成黏著劑層2，在切割前，不對黏著劑層2照射放射線並預先將熱固性片材3充分接著於黏著劑層2，在切割後，對黏著劑層2照射放射線來降低黏著劑層2之黏著力，藉此能夠容易地拾取(回收)半導體晶片(半導體元件)。
放射線固化型黏著劑只要具有碳-碳雙鍵等放射線固化性之官能基且顯示出黏著性，則可無特別限制地使用。作為放射線固化型黏著劑，例如可例舉在丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑中調配放射線固化性之單體成分、或低聚物成分而獲得之添加型之放射線固化型黏著劑。
作為上述放射線固化性之單體成分，例如可例舉胺基甲酸酯(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，作為上述放射線固化性之低聚物成分，可例舉胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，其分子量適宜為100～30000左右之範圍。上述放射線固化性之單體成分、或上述放射線固化性之低聚物成分之調配量較佳為設為在照射放射線後能夠適宜地降低黏著劑層2之黏著力之量。一般而言，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100質量份，上述放射線固化性之單體成分、或上述放射線固化性之低聚物成分之調配量例如較佳為5～500質量份，更佳為40～150質量份。
又，作為放射線固化型黏著劑，除了上述之添加型之放射線固化型黏著劑以外，亦可例舉內在型之放射線固化型黏著劑，該內在型之放射線固化型黏著劑使用在聚合物側鏈或主鏈中或者在主鏈末端具有碳-碳雙鍵之聚合物作為基礎聚合物。上述內在型之放射線固化型黏著劑無需含有作為低分子成分之低聚物成分等，或者上述低聚物成分等之含量較少。因此，在使用上述內在型之放射線固化型黏著劑之情形時，可抑制上述低聚物成分等在黏著劑層2中經時地移動。其結果，能夠使黏著劑層2具有相對穩定之層結構。
上述具有碳-碳雙鍵之基礎聚合物只要具有碳-碳雙鍵且具有黏著性，則可無特別限制地使用。作為此種基礎聚合物，較佳為以丙烯酸系聚合物作為基本骨架之聚合物。作為丙烯酸系聚合物之基本骨架，可例舉上述丙烯酸系聚合物。
向上述丙烯酸系聚合物導入碳-碳雙鍵之方法無特別限制，可採用各種方法，但若採用將碳-碳雙鍵導入至聚合物側鏈之方法，則分子設計變得容易。例如可例舉如下方法：預先使丙烯酸系聚合物與具有官能基之單體進行共聚後，使具有可與該官能基反應之官能基及碳-碳雙鍵之化合物在維持碳-碳雙鍵之放射線固化性之狀態下進行縮合反應或加成反應。
作為該等官能基之組合之例，可例舉：羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸酯基等。該等官能基之組合中，從反應追蹤之容易程度之方面而言，適宜為羥基與異氰酸酯基之組合。又，該等官能基之組合只要為生成上述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則任一官能基位於丙烯酸系聚合物側或上述具有碳-碳雙鍵之化合物側均可，在上述較佳之組合之情形時，適宜的是：丙烯酸系聚合物具有羥基，上述具有碳-碳雙鍵之化合物具有異氰酸酯基。該情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，例如可例舉甲基丙烯醯基異氰酸酯、異氰酸2-甲基丙烯醯氧基乙酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。又，作為丙烯酸系聚合物，可使用使上述含羥基單體、或2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚之醚系化合物等共聚而獲得之聚合物。
上述內在型之放射線固化型黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(特別是丙烯酸系聚合物)，但亦可以不使特性變差之程度調配上述放射線固化性之單體成分、或上述放射線固化性之低聚物成分。通常，相對於基礎聚合物100質量份，以30質量份以下之範圍、較佳為以1～10質量份之範圍包含上述放射線固化性之低聚物成分等。
在上述放射線固化型黏著劑中，在藉由紫外線等進行固化之情形時含有光聚合起始劑。作為光聚合起始劑，例如可例舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1等苯乙酮系化合物；苯偶姻乙醚、苯偶姻異丙醚、大茴香偶姻甲醚等苯偶姻醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(O-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯基苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；9-氧硫𠮿
Figure 111111134-001
、2-氯9-氧硫𠮿
Figure 111111134-001
、2-甲基9-氧硫𠮿
Figure 111111134-001
、2,4-二甲基9-氧硫𠮿
Figure 111111134-001
、異丙基9-氧硫𠮿
Figure 111111134-001
、2,4-二氯9-氧硫𠮿
Figure 111111134-001
、2,4-二乙基9-氧硫𠮿
Figure 111111134-001
、2,4-二異丙基9-氧硫𠮿
Figure 111111134-001
等9-氧硫𠮿
Figure 111111134-001
系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100質量份，光聚合起始劑之調配量例如為0.05～20質量份。
又，作為放射線固化型黏著劑，例如可例舉日本專利特開昭60-196956號公報中揭示之含有具有2個以上不飽和鍵之加成聚合性化合物、具有環氧基之烷氧基矽烷等光聚合性化合物與羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽系化合物等光聚合起始劑之橡膠系黏著劑、或丙烯酸系黏著劑等。
照射放射線時，在發生由氧導致之固化阻礙之情形時，理想的是對放射線固化型之黏著劑層2之表面用某種方法將氧氣(空氣)阻斷。例如可例舉用隔離膜被覆上述黏著劑層2之表面之方法、或在氮氣氣氛中進行紫外線等放射線之照射之方法等。
黏著劑層2之厚度無特別限定，從兼顧防止晶片切斷面之缺損及熱固性片材3之固定保持性之觀點而言，較佳為1～50 μm，更佳為2～30 μm，進而較佳為5～25 μm。
[半導體裝置] 本實施方式之半導體裝置具備：具有半導體元件之搭載區域之基板、及搭載於上述半導體元件之搭載區域之半導體元件，上述半導體元件經由熱固性片材搭載於上述基板之上述半導體元件之搭載區域。 本實施方式之半導體裝置中，上述半導體元件藉由使上述熱固性片材發生熱固化而搭載於上述基板之上述半導體元件之搭載區域。
本實施方式之半導體裝置中，使上述熱固性片材熱固化前，上述熱固性片材對於上述基板之接合率JR1(以下亦稱為熱固化前接合率JR1)較佳為85%以上、更佳為90%以上。 本實施方式之半導體裝置中，使上述熱固性片材熱固化後，上述熱固性片材對於上述基板之接合率JR2(以下亦稱為熱固化後接合率JR2)較佳為80%以上、更佳為90%以上。 本實施方式之半導體裝置中，熱固化後接合率JR2相對於熱固化前接合率JR1之比率較佳為80%以上、更佳為90%以上、進而較佳為95%以上。 本實施方式之半導體裝置中，較佳為熱固化前接合率JR1為85%以上、熱固化後接合率JR2為80%以上、且熱固化後接合率JR2相對於熱固化前接合率JR1之比率為80%以上，更佳為熱固化前接合率JR1為90%以上、熱固化後接合率JR2為90%以上、且熱固化後接合率JR2相對於熱固化前接合率JR1之比率為90%以上，進而較佳為熱固化前接合率JR1為95%以上、熱固化後接合率JR2為90%以上、且熱固化後接合率JR2相對於熱固化前接合率JR1之比率為95%以上。
本說明書中，熱固性片材對於基板之接合率係指：相對於要安裝在上述半導體元件之搭載區域之上述熱固性片材之總面積，上述熱固性片材在上述半導體元件之搭載區域中實際安裝之面積之比率。
作為本實施方式之半導體裝置之一例，可例舉如圖2所示地構成之半導體裝置。 如圖2所示，半導體裝置30具備：具有被劃分為俯視下大致矩形狀之晶片座31a及從晶片座31a之兩端側延伸之一對引線部31b、31b之引線框基板31；以積層於熱固性片材3之狀態安裝於引線框基板31之晶片座31a之半導體元件32；將半導體元件32與一對引線部31b、31b電連接之一對金屬線33、33；及將晶片座31a整體、一對引線部31b、31b之一部分、積層於熱固性片材3之半導體元件32整體及一對金屬線33、33整體收容在內部之中空狀之封裝體34；在半導體元件32等與封裝體34之間之空隙中填充有模塑樹脂35。 即，在如圖2所示之半導體裝置30中，引線框基板31成為具有半導體元件之搭載區域之基板，晶片座31a成為半導體元件之搭載區域。
又，半導體裝置30中，一對引線部31b、31b以如下方式構成：其一端側配置在晶片座31a之兩端之上表面側，在沿著與晶片座31a之上表面平行之方向(以下亦稱為水平方向)延伸後，進一步延伸至與晶片座31a之上表面垂直之方向之下方(以下亦簡稱為垂直下方)，一對引線部31b、31b在水平方向上延伸之部分貫穿封裝體34。 即，半導體裝置30中，一對引線部31b、31b在水平方向上延伸之部分之一部分收容於封裝體34之內部，水平方向之延伸部分之剩餘部分及延伸至垂直下方之部分之整體露出封裝體34之外部。
並且，如圖2所示，半導體裝置30安裝於在離開表面之位置具備一對電極41、41之配線基板40而使用。 更詳細而言，半導體裝置30將一對引線部31b、31b之延伸至垂直下方之部分之一部分使用焊料分別接合於一對電極41、41，從而安裝於配線基板40而使用。
本實施方式之半導體裝置中，上述熱固性片材如前所述為包含熱固性樹脂及熱塑性樹脂、且使溫度從25℃變化至200℃時之厚度變化率為0%以上且10%以下之熱固性片材。
上述熱固性片材對於上述基板之接合率可按照以下之程序求出。 (1)將在一個面安裝有矽晶片(裸晶片)之熱固性片材(或積層複數個熱固性片材而成之積層體)之另一個面安裝於具有半導體元件之搭載區域之基板之上述半導體元件搭載區域，獲得接合率評價用試驗體。 (2)使用超音波影像裝置(Hitachi Kenki FineTech公司製造、型號：FineSAT FS200II。以下亦稱為SAT)，藉由反射法對上述接合率評價用試驗體進行拍攝而獲得SAT圖像。關於拍攝，以上述超音波影像裝置之波形監視器中映出之上述基板與上述熱固性片材之接合部分之回波相匹配之方式調整柵極，將像素設定為1、增益設定為25 dB、並將Z軸高度設定為11.34 mm而進行。 (3)對於獲得之SAT圖像，使用圖像解析軟體ImageJ，進行2值化為上述基板與上述熱固性片材之接合部分(以下亦稱接合部分)、及上述基板與上述熱固性片材之非接合部分(以下亦稱非接合部分)之自動2值化處理。閾值設定為82。 (4)根據2值化後之圖像求出接合部分之面積與非接合部分之面積，將接合部分面積之值除以將接合部分面積與非接合部分面積合計而得之值，然後乘以數值100，藉此算出上述熱固性片材相對於上述基板之接合率。 再者，在2值化後之圖像中，接合部分用黑色表示，非接合部分用白色表示。
由本說明書揭示之事項包括以下內容。
(1) 一種熱固性片材，其為包含熱固性樹脂及熱塑性樹脂者， 使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下。
根據該構成，由於包含熱固性樹脂及熱塑性樹脂、且使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下，因此在使上述熱固性片材熱固化而正式接著於上述被接著體時，能夠抑制上述熱固性片材發生收縮。 並且，藉由抑制上述熱固性片材發生收縮，在熱固化中，能夠相對地減小上述熱固性片材中產生之內部應力(固化收縮應力及熱收縮應力)，因此能夠相對地抑制上述熱固性片材從被接著體之剝離。 又，由於包含上述熱塑性樹脂，因此在使上述熱固性片材熱固化後，亦能夠使上述熱固性片材具有相對低之彈性。 藉此，在熱固化後亦能夠確保上述熱固性片材與上述被接著體之密接性。
(2) 如上述(1)記載之熱固性片材，其中， 相對於上述熱固性樹脂100質量份，包含60質量份以上且500質量份以下之上述熱塑性樹脂。
根據該構成，能夠進一步抑制上述熱固性片材從被接著體之剝離。
(3) 如上述(1)或(2)記載之熱固性片材， 其進而包含導電性粒子。
根據該構成，除了能夠抑制上述熱固性片材從被接著體之剝離以外，亦能夠經由上述導電性粒子而使上述熱固性片材發揮電傳導性及熱傳導性。
(4) 如上述(3)記載之切晶黏晶膜， 其進而包含揮發成分。
根據該構成，由於進而包含揮發成分，因此在上述熱固性片材之熱固化中，能夠藉由使上述揮發成分揮發而減少上述熱固性片材之體積。 並且，與上述熱固性片材之體積減少之量相應地，上述導電性粒子彼此在上述熱固性片材中成為較近之位置關係，因此在上述熱固性片材中容易藉由上述導電性粒子彼此而形成熱傳導路徑。 藉此，能夠使固化後之上述熱固性片材之熱傳導性相對提高。 再者，藉由上述揮發成分揮發而產生之體積收縮(即，揮發所造成之體積收縮)與藉由上述熱固性樹脂熱固化而產生之體積收縮(即，熱固化所造成之體積收縮)相比，對上述熱固性片材從被接著體之剝離帶來之影響小。 因此，即使在產生了揮發所造成之體積收縮之情形時，亦成為上述熱固性片材從被接著體之剝離相對被抑制之狀態。
(5) 如上述(4)記載之切晶黏晶膜，其中， 相對於上述熱固性樹脂100質量份，進而包含10質量份以上且300質量份以下之揮發成分。
根據該構成，在上述熱固性片材中更容易藉由上述導電性粒子彼此而形成熱傳導路徑。 藉此，能夠使固化後之上述熱固性片材之熱傳導性進一步提高。
(6) 一種切晶黏晶膜，其具備： 在基材層上積層黏著劑層而成之切晶帶、及 積層在上述切晶帶之上述黏著劑層上之熱固性片材， 上述熱固性片材為如上述(1)至(5)中任一項記載之熱固性片材。
根據該構成，上述切晶黏晶膜之上述熱固性片材從被接著體(具有半導體元件之搭載區域之基板)之剝離被抑制。
再者，本發明之熱固性片材及切晶黏晶膜不限定於上述實施方式。又，本發明之熱固性片材及切晶黏晶膜不受上述作用效果之限定。本發明之熱固性片材及切晶黏晶膜可在不脫離本發明主旨之範圍內進行各種變更。 [實施例]
繼而，舉出實施例對本發明進行更具體之說明。以下之實施例係用於對本發明進行更詳細之說明之例，並不限定本發明之範圍。
[實施例1] 使用混合攪拌機(基恩士股份有限公司製造、商品名：HM-500)，將按照以下表1之實施例1之項所示之質量比率包含各材料之混合物用「攪拌模式」進行攪拌混合，製備清漆。 上述利用混合攪拌機進行之攪拌混合分3個階段進行。具體而言，首先，將包含熱固性樹脂及熱塑性樹脂之一次混合物攪拌混合3分鐘(一次攪拌)，繼而，將向上述一次混合物中添加導電性粒子及揮發材料而獲得之二次混合物攪拌混合6分鐘(二次攪拌)，進而，將向上述二次混合物中添加觸媒及溶劑而獲得之三次混合物攪拌混合3分鐘(三次攪拌)，藉此進行。 將該清漆塗佈於離型處理膜(三菱化學股份有限公司製造、商品名：MRA38、厚度38 μm)之一個面後，在溫度100℃下使其乾燥2分鐘，獲得厚度30 μm之熱固性片材。 再者，作為以下之表1所示之各材料，使用以下之物質。 ・酚樹脂 明和化成股份有限公司製造之MEHC-7851S(聯苯型酚樹脂、苯酚當量209 g/eq) ・固體環氧樹脂 新日鐵住金化學股份有限公司製造之KI-3000-4(甲酚酚醛清漆型多官能環氧樹脂、環氧當量200 g/eq) ・液態環氧樹脂 三菱化學股份有限公司製造之YL980(雙酚A型環氧樹脂、環氧當量180～190 g/eq) ・銀(Ag)被覆銅(Cu)粒子 DOWA ELECTRONICS MATERIALS公司製造之商品名AOP-TCY-2(EN)(對球狀之銅粒子塗佈20質量%銀粒子而成之粒子。粒子形狀為球狀。) ・銀(Ag)粒子 DOWA ELECTRONICS MATERIALS公司製造之AG-2-8F(用脂肪酸系被覆劑進行了表面處理之銀粒子。粒子形狀為球狀。) ・揮發材料(異冰片基環己醇(MTPH)) Nippon Terpene Chemicals製造之MTPH ・丙烯酸系樹脂溶液 Nagase ChemteX公司製造之Teisan Resin SG-70L(含有MEK及甲苯作為溶劑、固體成分12.5%、玻璃轉移溫度-13℃、重均分子量90萬、酸值5 mg/KOH、含羧基之丙烯酸系共聚物) ・偶合劑 信越化學工業股份有限公司製造之KBE-846(雙(三乙氧基甲矽烷基丙基)四硫化物) ・觸媒 北興化學工業股份有限公司製造之TPP-MK(四對甲苯基硼酸四苯基鏻) ・溶劑 甲基乙基酮(MEK) 又，關於熱塑性樹脂(丙烯酸系樹脂。以下亦稱TMR。)相對於100質量份熱固性樹脂(環氧樹脂(固體及液態)與酚樹脂。以下亦稱TSR。)之質量比率(質量份)、揮發材料(異冰片基環己醇)相對於100質量份熱固性樹脂之質量比率(質量份)、及導電性粒子相對於100質量份熱固性樹脂之質量比率(質量份)，示於以下之表2。 進而，關於銀被覆銅粒子及銀粒子在100質量份導電性粒子(銀被覆銅粒子及銀粒子)中所占之質量比率，示於以下之表3。
[實施例2] 獲得按照以下之表1之實施例2之項所示之質量比率包含各材料之混合物，除此以外，與實施例1同樣地獲得實施例2之熱固性片材。
[實施例3] 獲得按照以下之表1之實施例3之項所示之質量比率包含各材料之混合物，除此以外，與實施例1同樣地獲得實施例3之熱固性片材。
[實施例4] 獲得按照以下之表1之實施例4之項所示之質量比率包含各材料之混合物，除此以外，與實施例1同樣地獲得實施例4之熱固性片材。
[實施例5] 獲得按照以下之表1之實施例5之項所示之質量比率包含各材料之混合物，除此以外，與實施例1同樣地獲得實施例5之熱固性片材。
[比較例1] 獲得按照以下之表1之比較例1之項所示之質量比率包含各材料之混合物，除此以外，與實施例1同樣地獲得比較例1之熱固性片材。
[比較例2] 獲得按照以下之表1之比較例2之項所示之質量比率包含各材料之混合物，除此以外，與實施例1同樣地獲得比較例2之熱固性片材。
[表1]
   單位 實施例1 實施例2 實施例3 實施例4
酚樹脂 質量份 0.84 0.50 0.50 0.74
固體環氧樹脂 質量份 0.55 0.33 0.40 0.60
液態環氧樹脂 質量份 0.23 0.14 0.07 0.11
銀被覆銅粒子 質量份 13.1 13.2 16.1 14.4
銀粒子 質量份 30.7 30.9 37.7 33.6
異冰片基環己醇(MTPH) 質量份 0.81 0.81 0.36 0.72
丙烯酸系樹脂溶液 質量份 13.0 18.1 18.2 11.6
偶合劑 質量份 0.12 0.12 0.11 0.11
觸媒 質量份 0.010 0.010 0.010 0.010
甲基乙基酮(MEK、溶劑) 質量份 8.0 3.5 5.9 14.2
   單位 實施例5 比較例1 比較例2   
酚樹脂 質量份 0.84 1.17 1.06   
固體環氧樹脂 質量份 0.39 0.77 0.48   
液態環氧樹脂 質量份 0.39 0.33 0.48   
銀被覆銅粒子 質量份 11.5 13.1 16.2   
銀粒子 質量份 26.8 30.5 37.9   
異冰片基環己醇(MTPH) 質量份 0.36 0.81 0.72   
丙烯酸系樹脂溶液 質量份 13.0 7.77 6.94   
偶合劑 質量份 0.11 0.12 0.11   
觸媒 質量份 0.010 0.010 0.010   
甲基乙基酮(MEK、溶劑) 質量份 2.6 12.3 21.2   
[表2]
      實施例1 實施例2 實施例3 實施例4
熱固性樹脂 固體環氧樹脂 34.0質量份 34.0質量份 41.2質量份 41.4質量份
液態環氧樹脂 14.2質量份 14.4質量份 7.2質量份 7.6質量份
酚樹脂 51.9質量份 51.5質量份 51.5質量份 51.0質量份
總計 100質量份 100質量份 100質量份 100質量份
熱塑性樹脂(丙烯酸系樹脂) 99.9質量份 233.6質量份 234.5質量份 99.7質量份
揮發材料(MTPH) 50質量份 83.5質量份 37.1質量份 49.7質量份
導電性粒子 2703質量份 4546質量份 5546質量份 3310質量份
      實施例5 比較例1 比較例2   
熱固性樹脂 固體環氧樹脂 24.1質量份 33.9質量份 23.8質量份   
液態環氧樹脂 24.1質量份 14.5質量份 23.8質量份   
酚樹脂 51.9質量份 51.5質量份 52.5質量份   
總計 100質量份 100質量份 100質量份   
熱塑性樹脂(丙烯酸系樹脂) 100.3質量份 42.8質量份 42.9質量份   
揮發材料(MTPH) 22.2質量份 35.7質量份 35.6質量份   
導電性粒子 2364質量份 1921質量份 2678質量份   
＜導電性粒子之填充率＞ 按照以下之程序，對固化前之各例之熱固性片材求出導電性粒子之粒子填充率P 1。 (1)對固化前之熱固性片材進行機械研磨而使截面露出，對於該露出之截面，使用離子拋光裝置(日本電子股份有限公司製造、商品名：Cross Section Polisher SM-09010)進行離子拋光。 (2)使用場發射型掃描電子顯微鏡SU8020(Hitachi High Technology公司製造)拍攝進行了離子拋光之露出截面中之任意截面區域內之SEM圖像(由掃描型電子顯微鏡獲得之圖像)，獲得反射電子圖像作為圖像資料。拍攝條件係將加速電壓設為5 kV、將倍率設為5000倍。 (3)對於獲得之圖像資料，使用圖像解析軟體ImageJ進行2值化為金屬部分及樹脂部分之自動2值化處理。 (4)由2值化後之圖像求出金屬部分之合計面積與整體(金屬部分＋樹脂部分)之面積，將金屬部分之合計面積除以整體之面積，藉此對固化後之熱固性片材求出導電性粒子之粒子填充率P 1。 再者，上述粒子填充率P 1係藉由將針對進行了離子拋光之露出截面中之5處截面區域求出之粒子填充率進行算術平均來求出。 將針對固化前之各例之熱固性片材求出上述粒子填充率P 1之結果示於以下之表3。 又，對於固化後之各例之熱固性片材，亦與上述同樣地求出導電性粒子之粒子填充率P 2。 將針對固化後之各例之熱固性片材求出上述粒子填充率P 2之結果示於以下之表3。
＜熱固性片材之熱導率＞ 對於各例之熱固性片材，一邊利用加壓蒸煮器裝置施加0.5 MPa之壓力，一邊在200℃下處理1小時而使其熱固化。對於經熱固化之各例之熱固性片材，藉由下述式來算出熱導率。
[數2] 熱導率(W/m·K)＝熱擴散率(m 2/s)×比熱(J/g·℃)×比重(g/cm 3)
熱擴散率α(m 2/s)係利用TWA法(溫度波熱分析法、測定裝置：ai-Phase Mobile、ai-Phase公司製造)來測定。 比熱C p(J/g・℃)係藉由DSC法來測定。比熱測定係使用SII Nanotechnology公司製造之DSC6220，在升溫速度10℃/分鐘、溫度範圍20～300℃之條件下進行，基於獲得之資料，利用JIS手冊(比熱容測定方法K-7123)中記載之方法算出比熱。 比重係利用阿基米德法來測定。 將針對各例之固化後之熱固性片材算出熱導率之結果示於以下之表3。
＜接合率＞ 針對各例之熱固性片材，測定對於基板之接合率。 接合率之測定時，將各例之熱固性片材切成5 cm見方並將5 cm見方之熱固性片材積層10片後，在真空下(壓力3.3 kPa)壓製，藉此獲得厚度300 μm之片材積層體，製作在該片材積層體之一個面安裝有切割成5 cm見方之裸晶片之附裸晶片之片材積層體。 對於基板之接合率之測定係按照以下之步驟進行。 (1)將在一個面安裝有裸晶片之片材積層體之另一面安裝於引線框基板(Cu引線框基板)之晶片座，獲得接合率評價用試驗體。 (2)使用超音波影像裝置(Hitachi Kenki FineTech公司製造、型號：FineSAT FS200II。以下亦稱為SAT)，藉由反射法對上述接合率評價用試驗體進行拍攝而獲得SAT圖像。關於拍攝，以上述超音波影像裝置之波形監視器中映出之上述基板與上述熱固性片材之接合部分之回波相匹配之方式調整柵極，將像素設定為1、增益設定為25 dB、及將Z軸高度設定為11.34 mm而進行。 (3)對於獲得之SAT圖像，使用圖像解析軟體ImageJ，進行2值化為上述引線框基板與上述片材積層體之接合部分(以下亦簡稱為接合部分)、及上述引線框基板與上述片材積層體之非接合部分(以下亦簡稱為非接合部分)之自動2值化處理。閾值設定為82。 (4)根據2值化後之圖像求出接合部分之面積與非接合部分之面積，將接合部分面積除以將接合部分面積與非接合部分面積合計而得之值，然後乘以數值100，藉此算出片材積層體對於上述引線框基板(抵接於上述引線框基板之熱固性片材對於上述引線框基板)之接合率。 再者，在2值化後之圖像中，接合部分用黑色表示，非接合部分用白色表示。
將針對各例之熱固性片材測定對於基板(引線框基板)之接合率之結果示於以下之表3。
＜厚度之變化率Rc＞ 針對各例之熱固性片材，如下所述地求出使溫度從25℃變化至200℃時之厚度之變化率Rc。 具體而言，在熱機械分析(TMA)中，使溫度從25℃變化至200℃時，測定25℃下之上述熱固性片材之厚度T1，並且測定剛升溫至200℃後之上述熱固性片材之厚度T2，使用該等測定值T1及T2，藉由下述式計算，藉此求出。 Rc＝(T2－T1)/T1×100
熱機械分析係按照以下之條件進行。 熱機械分析之條件 ・熱機械分析裝置：TA Instruments Japan公司製造、型號Q400 ・探針：微膨脹探針 ・測定模式：壓縮膨脹 ・升溫條件：用60分鐘從25℃升溫至200℃，在200℃下保持1小時後，用30分鐘降溫至25℃。 ・測定氣氛：氮氣(N 2) ・負載：0.012 N(恆定負載) ・供試體：將積層有多片熱固性片材之第1熱固性片材積層體在溫度70℃、壓力6 kN之條件下加壓60秒而獲得厚度3 mm之第2熱固性片材積層體後，用4 mm
Figure 02_image001
之衝頭對該第2熱固性片材積層體進行沖裁，獲得厚度3 mm×4 mm
Figure 02_image001
之供試體。 再者，上述基於熱機械分析裝置之測定係藉由如下方式進行：將在雙面分別配置有鋁板(俯視圓形狀。厚度0.1 mm。平面尺寸5 mm
Figure 02_image001
)之上述供試體以一側之鋁板抵接之方式載置於上述熱機械分析裝置之載台上，然後從另一側之鋁板(上方之鋁板)側用上述探針施加負載。 又，Rc係將針對2個供試體求出之值進行算術平均而求得。
將針對各例之熱固性片材測定厚度變化率Rc之結果示於以下之表3。 又，將表示對各例之熱固性片材進行熱機械分析時獲得之厚度變化率Rc之變遷之曲線圖示於圖3A及3B。
[表3]
   單位 實施例1 實施例2 實施例3 實施例4
導電性粒子 銀粒子種類 - AG-2-8F AG-2-8F AG-2-8F AG-2-8F
銀粒子在100質量份導電性粒子中所占之質量份 質量份 70 70 70 70
銀被覆銅粒子種類 - AOP-TCY-2(EN) AOP-TCY-2(EN) AOP-TCY-2(EN) AOP-TCY-2(EN)
銀被覆銅粒子在100質量份導電性粒子中所占之質量份 質量份 30 30 30 30
TMR相對於100質量份TSR之質量份 質量份 99.9 233.6 234.5 99.7
MTPH相對於100質量份TSR之質量份 質量份 50 83.5 37.1 49.7
固化前之熱固性片材之粒子填充率P1 vol% 55 55 63 60
固化後之熱固性片材之粒子填充率P2 vol% 62.5 60.9 65.1 64.9
固化後之熱固性片材之熱導率 W/m·K 11.1 8.7 8.5 13.0
固化前之接合率JR1 % 98.4 95.4 86.5 99.7
固化後之接合率JR2 % 96.9 94.2 85.1 92.0
JR2/JR1×100 % 98.5 98.8 98.4 92.3
剛升溫至200℃後之厚度之變化率Rc % 5.0 7.1 5.8 2.8
   單位 實施例5 比較例1 比較例2   
導電性粒子 銀粒子種類 - AG-2-8F AG-2-8F AG-2-8F   
銀粒子在100質量份導電性粒子中所占之質量份 質量份 70 70 70   
銀被覆銅粒子種類 - AOP-TCY-2(EN) AOP-TCY-2(EN) AOP-TCY-2(EN)   
銀被覆銅粒子在100質量份導電性粒子中所占之質量份 質量份 30 30 30   
TMR相對於100質量份TSR之質量份 質量份 100.3 42.8 42.9   
MTPH相對於100質量份TSR之質量份 質量份 22.2 35.7 35.6   
固化前之熱固性片材之粒子填充率P1 vol% 55 55 63   
固化後之熱固性片材之粒子填充率P2 vol% 57.5 62.7 67.2   
固化後之熱固性片材之熱導率 W/m·K 4.2 14.5 19.6   
固化前之接合率JR1 % 98.8 98.7 92.6   
固化後之接合率JR2 % 98.8 76.8 20.6   
JR2/JR1×100 % 100.0 77.83 22.2   
剛升溫至200℃後之厚度之變化率Rc % 4.5 -4.4 -1.8   
由表3可知，對於各實施例之熱固性片材，固化前之接合率JR1均顯示85%以上之高值，又，固化後之接合率JR2均顯示85%以上之高值，並且固化後之接合率JR2相對於固化前之接合率JR1之比率亦顯示90%以上之高值。 與此相對，對於比較例1之熱固性片材，可知雖然固化前之接合率JR1顯示98.70%之高值，但固化後之接合率JR2顯示76.8%之低值，又，固化後之接合率JR2相對於固化前之接合率JR1之比率為77.8%，亦大幅降低。 又，對於比較例2之熱固性片材，同樣獲知雖然固化前之接合率JR1顯示92.6%之高值，但固化後之接合率JR2顯示20.6%這一明顯低之值，又，固化後之接合率JR2相對於固化前之接合率JR1之比率亦顯示22.2%這一明顯低之值。 進而，針對熱固性片材，將固化前後之SAT圖像(使用超音波影像裝置拍攝之SAT圖像)之一例(實施例5及比較例2)示於圖4A～4D，但對於實施例5之熱固性片材(圖4A及4B)，固化後在端緣側完全未確認到剝離。 與此相對，對於比較例2之熱固性片材(圖4C及4D)，固化後確認到從端緣側之大幅剝離，並且確認到僅中央附近接合之狀態。 如上所述，根據SAT圖像亦可知，實施例之熱固性片材與比較例之熱固性片材在從被接著體之剝離性之方面確認到有意義差。 並且，從厚度之變化率Rc之值而言，實施例1之熱固性片材為5.0%、實施例2之熱固性片材為7.1%、實施例3之熱固性片材為5.8%、實施例4之熱固性片材為2.8%、實施例5之熱固性片材為4.5%，均為0%以上且10%以下之範圍內，與此相對，比較例1及2之熱固性片材中，厚度之變化率Rc分別為-4.4%及-1.8%，處於0%以上且10%以下之範圍外。 根據該等結果可掌握，藉由在使熱固性片材包含熱固性樹脂及熱塑性樹脂之基礎上，進一步使厚度之變化率Rc為0%以上且10%以下之範圍，從而該熱固性片材可相對地抑制熱固化後從被接著體之剝離。
又，由表3可知，對於實施例1～5之熱固性片材，藉由使固化後之熱固性片材之粒子填充率P 2為50體積%以上，可獲得高於4 W/m・K之充分之熱導率。
又，觀察圖3A及3B可知，對於比較例1及2之熱固性片材，厚度變化率Rc隨著加熱溫度之上升均大致顯示為負值並持續減少。 進而，對於比較例1及2之熱固性片材，可知厚度之變化率Rc在為了使熱固化反應進一步進行而保持溫度為200℃之期間顯示出進一步減少之傾向，在該保持溫度之期間，比較例1之熱固性片材最小顯示-6.7%之值，比較例2之熱固性片材最小顯示-5.6%之值。 並且，對於比較例1及2之熱固性片材，可知厚度之變化率Rc隨著保持溫度200℃後之冷卻造成之樹脂成分之體積收縮，顯示為進一步大之負值(比較例1之熱固性片材最小為-7.9%，比較例2之熱固性片材最小為-7.3%)。
與此相對，觀察圖3A及3B可知，對於實施例1～5之熱固性片材，厚度之變化率Rc隨著加熱溫度之上升，均有大致顯示為正值並增加之傾向(詳細而言，對於實施例1之熱固性片材，厚度之變化率Rc從50℃以上起顯示為正值，對於實施例2及4之熱固性片材，厚度之變化率Rc從剛開始加熱後顯示為正值，對於實施例3及5之熱固性片材，厚度之變化率Rc從30℃以上起顯示為正值)，在100℃以上且200℃以下之溫度範圍顯示出最大值(實施例1之熱固性片材最大為3.9%，實施例2之熱固性片材最大為8%，實施例3之熱固性片材最大為5.8%，實施例4之熱固性片材最大為3%，實施例5之熱固性片材最大為4.5%)。 又，對於實施例1～3之熱固性片材，可知厚度之變化率Rc雖然在為了使熱固化反應進一步進行而保持溫度為200℃之期間顯示出減少之傾向，但均持續顯示為正值。 並且，對於實施例1及2之熱固性片材，可知厚度之變化率Rc雖然隨著由保持溫度200℃後之冷卻造成之樹脂成分之體積收縮而成為進而小之值，但仍然持續顯示為正值，與此相對，對於實施例3之熱固性片材，厚度之變化率Rc雖然由於保持溫度200℃後之冷卻而顯示為負值(最小為-2.3%)，但顯示了高於比較例1及2之熱固性片材之厚度之變化率Rc之值。 又，對於實施例4及5之熱固性片材，可知厚度之變化率Rc雖然在為了使熱固化反應進一步進行而保持溫度為200℃之期間顯示出減少而成為負值之傾向，進而由於保持溫度200℃後之冷卻而顯示為更小之負值(實施例4之熱固性片材最小為-5.3%，實施例5之熱固性片材最小為-4.9%)，但顯示了高於比較例1及2之熱固性片材之厚度之變化率Rc之值。
考慮上述結果可掌握到：本實施方式之熱固性片材較佳為在使溫度從25℃變化至200℃時，在50℃以上且200℃以下之溫度範圍內，厚度之變化率Rc大於0%(顯示為正值)。 又，對於本實施方式之熱固性片材可掌握到：在使溫度從25℃變化至200℃時，較佳為在100℃以上且200℃以下之溫度範圍內顯示出最大值，並且該最大值較佳為3%以上。 再者，認為由於固體環氧樹脂通常在80～100℃開始軟化，因此熱固性片材藉由如上所述地在80℃～100℃之溫度下使厚度變化率Rc顯示為正值，該熱固性片材以提高了與被接著體之密接性之狀態進行熱固化反應，因此與被接著體之接著性進一步提高，即，熱固化後之從被接著體之剝離進一步被抑制。
1:基材層 2:黏著劑層 3:熱固性片材 10:切晶帶 20:切晶黏晶膜 30:半導體裝置 31:引線框基板 31a:晶片座 31b:引線部 32:半導體元件 33:金屬線 34:封裝體 35:模塑樹脂 40:配線基板 41:電極
圖1為示出本發明之一個實施方式之切晶黏晶膜之構成之剖視圖。 圖2為示出本發明之一個實施方式之半導體裝置之構成之剖視圖。 圖3A為示出對實施例1及2、以及比較例1之熱固性片材進行熱機械分析時獲得之厚度之變化率Rc之變遷之曲線圖。 圖3B為示出對實施例3～5、及比較例2之熱固性片材進行熱機械分析時獲得之厚度之變化率Rc之變遷之曲線圖。 圖4A為對實施例5之熱固性片材在固化前拍攝之SAT圖像。 圖4B為對實施例5之熱固性片材在固化後拍攝之SAT圖像。 圖4C為對比較例2之熱固性片材在固化前拍攝之SAT圖像。 圖4D為對比較例2之熱固性片材在固化後拍攝之SAT圖像。
1:基材層
2:黏著劑層
3:熱固性片材
10:切晶帶
20:切晶黏晶膜

Claims (6)

  1. 一種熱固性片材，其係包含熱固性樹脂及熱塑性樹脂者， 使溫度從25℃變化至200℃時之厚度之變化率為0%以上且10%以下。
  2. 如請求項1之熱固性片材，其中相對於上述熱固性樹脂100質量份，包含60質量份以上且500質量份以下之上述熱塑性樹脂。
  3. 如請求項1或2之熱固性片材，其進而包含導電性粒子。
  4. 如請求項3之熱固性片材，其進而包含揮發成分。
  5. 如請求項4之熱固性片材，其中相對於上述熱固性樹脂100質量份，包含10質量份以上且300質量份以下之上述揮發成分。
  6. 一種切晶黏晶膜，其具備： 在基材層上積層黏著劑層而成之切晶帶、及 積層在上述切晶帶之黏著劑層上之熱固性片材， 上述熱固性片材為如請求項1至5中任一項之熱固性片材。
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