以下，對本發明之一實施形態之密封片材用樹脂組合物、密封片材、及半導體裝置進行詳細說明。 [密封片材用樹脂組合物] 本實施形態之密封片材用樹脂組合物之特徵在於含有：(A)結晶性環氧樹脂及/或液狀環氧樹脂、(B)酚樹脂硬化劑、(C)硬化促進劑、(D)無機填充材料、及(E)含酮亞胺基之矽烷化合物。 首先，對本實施形態之密封片材用樹脂組合物(以下，亦簡稱為樹脂組合物)之各成分進行說明。 本實施形態中使用之(A)成分之環氧樹脂係結晶性環氧樹脂及/或液狀環氧樹脂。結晶性環氧樹脂係指具有於常溫(25℃)下為固體且顯示結晶狀態，於熔融時黏度大幅度下降之性質之環氧樹脂。結晶性環氧樹脂之熔點較佳為80～150℃，更佳為90～130℃。又，液狀環氧樹脂係指於常溫(25℃)下為液狀或半固體狀態之環氧樹脂，例如可列舉於常溫(25℃)下具有流動性之環氧樹脂。液狀環氧樹脂之25℃下之黏度較佳為10,000 mPa·s以下，更佳為1,000～6,000 mPa·s。 再者，上述結晶性環氧樹脂之熔點可藉由DSC(differential scanning calorimetry，示差掃描熱量測定)之吸熱峰進行測定。又，上述液狀環氧樹脂之25℃下之黏度可藉由旋轉式黏度計進行測定。 上述(A)成分之結晶性環氧樹脂及液狀環氧樹脂(以下，亦簡稱為(A)成分之環氧樹脂)可不受分子結構、分子量等之限制地使用，其中，較佳為聯苯型環氧樹脂、雙酚A型環氧樹脂及雙酚F型環氧樹脂。該等可使用1種，亦可將2種以上混合而使用。 再者，聯苯型環氧樹脂係具有聯苯骨架之環氧樹脂，但本實施形態中之聯苯骨架亦包含將聯苯環中之至少一個芳香族環氫化而成者。 作為聯苯型環氧樹脂之具體例，例如可列舉4,4'-雙(2,3-環氧丙氧基)聯苯、4,4'-雙(2,3-環氧丙氧基)-3,3',5,5'-四甲基聯苯、使表氯醇與4,4'-聯苯二酚或4,4'-(3,3',5,5'-四甲基)聯苯二酚之類的聯苯二酚化合物進行反應而獲得之環氧樹脂等。該等之中，較佳為4,4'-雙(2,3-環氧丙氧基)-3,3',5,5'-四甲基聯苯、4,4'-(3,3',5,5'-四甲基)聯苯之縮水甘油醚。聯苯型環氧樹脂可使用1種，亦可將2種以上混合而使用。 若例示用作聯苯型環氧樹脂之市售品，則例如可列舉三菱化學(股)製造之YX-4000(環氧當量185，熔點105℃)、三菱化學(股)製造之YX-4000K(環氧當量185，熔點105℃)、三菱化學(股)製造之YX-4000H(環氧當量193，熔點105℃)、三菱化學(股)製造之YL-6121H(環氧當量175，熔點125℃)(以上均為商品名)等。 又，作為雙酚A型環氧樹脂，具體而言，可列舉DIC(股)製造之EXA-850CRP(環氧當量173，25℃黏度4500 mPa·s)等。作為雙酚F型環氧樹脂，具體而言，可列舉新日鐵住金化學(股)製造之YDF-8170C(環氧當量160，25℃黏度1250 mPa·s)等。 除上述(A)成分之環氧樹脂以外，於無損本發明之效果之範圍內，可併用用作密封材料之環氧樹脂。 再者，於併用上述結晶性環氧樹脂及液狀環氧樹脂以外之環氧樹脂之情形時，其調配量相對於(A)成分之環氧樹脂100質量份，較佳為設為30質量份以下，更佳為設為20質量份以下，進而較佳為設為10質量份以下。 本實施形態中使用之(B)成分之酚樹脂硬化劑只要為於分子中具有2個以上之可與上述(A)成分之環氧樹脂中之環氧基進行反應之酚性羥基者，則可使用，並無特別限制。具體而言，可列舉使苯酚、烷酚等酚類與甲醛或多聚甲醛進行反應而獲得之苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等酚醛清漆型酚樹脂、將該等酚醛清漆型酚樹脂環氧化或丁基化而成之改性酚醛清漆型酚樹脂、二環戊二烯改性酚樹脂、對二甲苯改性酚樹脂、苯酚芳烷基樹脂、萘酚芳烷基樹脂、三苯酚烷烴型酚樹脂、多官能型酚樹脂等。其中，較佳為使用酚醛清漆型酚樹脂、三苯酚烷烴型酚樹脂。該等可使用1種，亦可將2種以上混合而使用。 上述(B)成分之酚樹脂硬化劑之調配量較佳為(B)成分之酚樹脂硬化劑所具有之酚性羥基數(b)相對於上述(A)成分之環氧樹脂所具有之環氧基數(a)之比[(b)/(a)]成為0.3以上且1.5以下之範圍，更佳為成為0.5以上且1.2以下之範圍。若比[(b)/(a)]為0.3以上，則可提昇硬化物之耐濕可靠性，若為1.5以下，則可提高硬化物之強度。 本實施形態中使用之(C)成分之硬化促進劑係促進(A)成分之環氧樹脂與(B)成分之酚樹脂硬化劑之硬化反應之成分。(C)成分之硬化促進劑只要為發揮上述作用者，則可使用公知之硬化促進劑，並無特別限制。 作為上述(C)成分之硬化促進劑，具體而言，可列舉：2-甲基咪唑、2-乙基咪唑、2-異丙基咪唑、2-十一烷基咪唑、1,2-二甲基咪唑、2,4-二甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、4-甲基咪唑、4-乙基咪唑、2-苯基-4-羥基甲基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑等咪唑類；1,8-二氮雜雙環[5.4.0]十一烯-7(DBU)、1,5-二氮雜雙環[4.3.0]壬烯、5,6-二丁基胺基-1,8-二氮雜雙環[5.4.0]十一烯-7等二氮雜雙環化合物及該等之鹽；三乙基胺、三伸乙基二胺、苄基二甲基胺、α-甲基苄基二甲基胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三級胺類；三甲基膦、三乙基膦、三丁基膦、二苯基膦、三苯基膦、三(對甲基苯基)膦、三(壬基苯基)膦、甲基二苯基膦、二丁基苯基膦、三環己基膦、雙(二苯基膦基)甲烷、1,2-雙(二苯基膦基)乙烷等有機膦化合物等。該等之中，就流動性及成形性良好之觀點而言，較佳為咪唑類，更佳為2-苯基-4-甲基-5-羥基甲基咪唑。該等可使用1種，亦可將2種以上混合而使用。 上述(C)成分之硬化促進劑之調配量較佳為相對於樹脂組合物整體為0.1～5質量%之範圍，更佳為0.2～1質量%之範圍。若(C)成分之調配量為0.1質量%以上，則可充分獲得硬化性之促進效果，若為5質量%以下，則可提昇成形品之耐濕可靠性。 本實施形態中使用之(D)成分之無機填充材料係填充至樹脂組合物中而調整樹脂組合物之黏度或提高製成下述密封片材時之操作性及成形性之成分。作為上述(D)成分之無機填充材料，只要為該種樹脂組合物中通常使用之公知之無機填充材料，則可使用，並無特別限制。 關於上述(D)成分之無機填充材料，具體而言，例如可列舉：熔融二氧化矽、結晶二氧化矽、破碎二氧化矽、合成二氧化矽、氧化鋁、氧化鈦、氧化鎂等氧化物粉末；氫氧化鋁、氫氧化鎂等氫氧化物粉末；氮化硼、氮化鋁、氮化矽等氮化物粉末等。該等無機填充材料可使用1種，亦可將2種以上混合而使用。 作為上述(D)成分之無機填充材料，就提高密封片材之操作性或成形性之觀點而言，上述例示之中，較佳為二氧化矽粉末，更佳為熔融二氧化矽，尤佳為球狀熔融二氧化矽。又，亦可併用熔融二氧化矽及熔融二氧化矽以外之二氧化矽，於該情形時，熔融二氧化矽以外之二氧化矽之比率較佳為設為未達二氧化矽粉末整體之30質量%。 上述(D)成分之無機填充材料之平均粒徑較佳為0.5～40 μm，更佳為1～30 μm，進而較佳為5～30 μm。又，進而較佳為(D)成分之無機填充材料之最大粒徑為105 μm以下。 若平均粒徑為0.5 μm以上，則可抑制樹脂組合物之流動性之下降，使成形性良好。又，若平均粒徑為40 μm以下，則可抑制使樹脂組合物硬化而獲得之成形品之翹曲，或防止尺寸精度之下降。又，若最大粒徑為105 μm以下，則可使樹脂組合物之成形性良好。 再者，於本說明書中，(D)成分之無機填充材料之平均粒徑例如可藉由雷射繞射式粒度分佈測定裝置求出，平均粒徑係利用該裝置測得之粒度分佈中累計體積成為50%之粒徑(d50)。 上述(D)成分之無機填充材料之調配量相對於樹脂組合物整體，較佳為70～95質量%之範圍，更佳為75～90質量%之範圍。若無機填充材料之調配量為70質量%以上，則可抑制樹脂組合物之線膨脹係數之增大，可提高成形品之尺寸精度、耐濕性、機械強度等。若無機填充材料之調配量為95質量%以下，則可抑制樹脂組合物之熔融黏度之增大而抑制流動性之下降，並且可提高成形性。又，可使將該樹脂組合物成形而獲得之密封片材不易破裂。 本實施形態中使用之(E)成分之含酮亞胺基之矽烷化合物係於1分子中具有酮亞胺基及烷氧基之化合物，藉由於樹脂組合物中含有該(E)成分，而可提高硬化物之接著力。 上述(E)成分之含酮亞胺基之矽烷化合物只要於1分子中具有酮亞胺基及烷氧基，則並無特別限定，就提高硬化物之接著力之觀點而言，較佳為下述通式(1)所表示之化合物。 [化1]
上述通式(1)中，R
1～R
4分別獨立地表示碳數1～5之烷基，具體而言，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、各種戊基等。其中，就市場中之獲取容易性之觀點而言，較佳為甲基、乙基、丙基、丁基。 R
5表示碳數1～10、較佳為碳數1～5之伸烷基。該伸烷基可為直鏈狀、支鏈狀中之任一者，例如可列舉亞甲基、伸乙基、伸丙基、三亞甲基、伸丁基、伸戊基等。其中，較佳為伸乙基、三亞甲基。 a表示0～2之整數，較佳為0。 上述(E)成分之含酮亞胺基之矽烷化合物於成形時之高溫條件下容易水解而生成一級胺。水解所需之水係吸附於二氧化矽表面之水便充分，但亦可預先與純水進行混合。又，可單獨使用亦可與其他矽烷偶合劑併用。 作為上述通式(1)所表示之含酮亞胺基之矽烷化合物之具體例，可列舉N-(1-甲基亞乙基)-3-(三乙氧基矽烷基)-1-丙胺、N-(1,3-二甲基亞丁基)-3-(三乙氧基矽烷基)-1-丙胺、N-(1-甲基亞丙基)-3-(三乙氧基矽烷基)-1-丙胺、N-(1-甲基亞乙基)-3-(甲基二乙氧基矽烷基)-1-丙胺、N-(1,3-二甲基亞丁基)-3-(甲基二乙氧基矽烷基)-1-丙胺、N-(1-甲基亞丙基)-3-(甲基二乙氧基矽烷基)-1-丙胺、N-(1-甲基亞乙基)-3-(乙基二乙氧基矽烷基)-1-丙胺、N-(1,3-二甲基亞丁基)-3-(乙基二乙氧基矽烷基)-1-丙胺、N-(1-甲基亞丙基)-3-(乙基二乙氧基矽烷基)-1-丙胺、N-(1-甲基亞乙基)-3-(甲基二甲氧基矽烷基)-1-丙胺、N-(1,3-二甲基亞丁基)-3-(甲基二甲氧基矽烷基)-1-丙胺、N-(1-甲基亞丙基)-3-(甲基二甲氧基矽烷基)-1-丙胺、N-(1-甲基亞乙基)-2-(三乙氧基矽烷基)-1-乙胺、N-(1,3-二甲基亞丁基)-2-(三乙氧基矽烷基)-1-乙胺、N-(1-甲基亞丙基)-2-(三乙氧基矽烷基)-1-乙胺、N-(1-甲基亞乙基)-2-(甲基二乙氧基矽烷基)-1-乙胺、N-(1,3-二甲基亞丁基)-2-(甲基二乙氧基矽烷基)-1-乙胺、N-(1-甲基亞丙基)-2-(甲基二乙氧基矽烷基)-1-乙胺、N-(1-甲基亞乙基)-2-(乙基二乙氧基矽烷基)-1-乙胺、N-(1,3-二甲基亞丁基)-2-(乙基二乙氧基矽烷基)-1-乙胺、N-(1-甲基亞丙基)-2-(乙基二乙氧基矽烷基)-1-乙胺、N-(1-甲基亞乙基)-2-(甲基二甲氧基矽烷基)-1-乙胺、N-(1,3-二甲基亞丁基)-2-(甲基二甲氧基矽烷基)-1-乙胺、N-(1-甲基亞丙基)-2-(甲基二甲氧基矽烷基)-1-乙胺等。其中，就市場中之獲取容易性之觀點而言，較佳為N-(1,3-二甲基亞丁基)-3-(三乙氧基矽烷基)-1-丙胺。 該等含酮亞胺基之矽烷化合物可使用1種，亦可將2種以上組合而使用。 上述(E)成分之含酮亞胺基之矽烷化合物於成形時之高溫條件下容易水解而生成一級胺，並且生成矽烷醇基。一級胺與上述(A)成分之環氧樹脂進行反應，並且矽烷醇基與存在於上述(D)成分之無機填充材料表面之羥基進行縮合反應，藉此硬化樹脂與無機填充材料之結合變得牢固。其結果，於將本實施形態之樹脂組合物用作半導體裝置之密封材料之情形時，其硬化物與矽晶片等之接著性變得牢固。 關於上述(E)成分之含酮亞胺基之矽烷化合物相對於樹脂組合物總量之含量，就其硬化物對矽晶片等之接著性之提昇、孔隙等成形不良之抑制及經濟性之平衡等觀點而言，較佳為於0.5～2.0質量%、更佳為於0.8～1.5質量%之範圍內選定。 若例示用作上述(E)成分之含酮亞胺基之矽烷化合物之市售品，則例如作為N-(1,3-二甲基亞丁基)-3-(三乙氧基矽烷基)-1-丙胺，可列舉Shin-Etsu Silicones(股)製造之KBE-9103、JNC(股)製造之Sila-Ace S340、東麗道康寧(股)製造之Z-6860等。 於本實施形態之樹脂組合物中，除以上之各成分以外，於不阻礙本實施形態之效果之範圍內，亦可調配該種樹脂組合物中通常調配之成分，例如：偶合劑；合成蠟、天然蠟、高級脂肪酸、高級脂肪酸之金屬鹽等脫模劑；碳黑、鈷藍等著色劑；聚矽氧油、聚矽氧橡膠等低應力賦予劑；鋁碳酸鎂類；離子捕捉劑等。 作為偶合劑，可列舉環氧矽烷系、胺基矽烷系、脲基矽烷系、乙烯基矽烷系、烷基矽烷系、有機鈦酸酯系、鋁醇鹽系等之偶合劑等。該等可使用1種，亦可將2種以上混合而使用。 作為上述偶合劑，就成形性、阻燃性、硬化性等觀點而言，較佳為胺基矽烷系偶合劑，尤佳為γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、(N-苯基-γ-胺基丙基)三甲氧基矽烷等。 於使用偶合劑之情形時，其調配量較佳為成為樹脂組合物整體之0.01質量%以上且3.0質量%以下之範圍，更佳為成為0.1質量%以上且1質量%以下之範圍。若偶合劑之調配量為0.01質量%以上，則可提昇成形性，若為3.0質量%以下，則可抑制成形時產生發泡，抑制成形品產生孔隙或表面鼓出等。 本實施形態之樹脂組合物係將(A)結晶性環氧樹脂及/或液狀環氧樹脂、(B)酚樹脂硬化劑、(C)硬化促進劑、(D)無機填充材料、(E)含酮亞胺基之矽烷化合物、及上述視需要調配之各種成分利用混合機等充分混合(乾摻)後，藉由熱輥或捏合機等混練裝置進行熔融混練，冷卻後，粉碎成適當之大小。粉碎方法並無特別限制，可使用通常之粉碎機，例如Speed Mill、切磨機、球磨機、旋風磨機、錘磨機、振磨機、切碎機、砂磨機等。其中，較佳為使用Speed Mill。粉碎物其後可藉由篩分分級或空氣分級等而調整為具有特定之粒度分佈之粒子集合體。 [密封片材] 其次，對本實施形態之密封片材進行說明。 本實施形態之密封片材係以上述密封片材用樹脂組合物為材料並使其成形為片狀而獲得之片狀成形體。該密封片材例如藉由將本實施形態之樹脂組合物於加壓構件間進行加熱熔融並進行壓縮而成形為片狀而獲得。更具體而言，於聚酯膜等耐熱性之脫模膜上，以成為大致均勻之厚度之方式供給上述樹脂組合物而形成樹脂層後，一面使樹脂層加熱軟化一面藉由輥及熱壓機進行壓延。此時，於樹脂層上亦配置聚酯膜等耐熱性膜。以此方式將樹脂層壓延成所需之厚度後，進行冷卻固化，將耐熱性膜剝離，進而視需要切斷為所需之大小、形狀。藉此，可獲得任意大小之密封片材。 再者，使樹脂層軟化時之加熱溫度通常為80～150℃左右。若加熱溫度未達80℃，則熔融混合變得不充分，若超過150℃，則有硬化反應過度進行而於加熱硬化時成形性下降之虞。 本實施形態之密封片材藉由高化式流變儀於溫度175℃、負載10 kg(剪切應力1.23×10
5Pa)之條件下測定之熔融黏度較佳為2～50 Pa·s，更佳為3～20 Pa·s。若熔融黏度為2 Pa·s以上，則可抑制毛邊之產生，若為50 Pa·s以下，則填充性提昇，而可抑制孔隙或未填充部分之產生。 本實施形態之密封片材適於半導體元件等零件之密封，根據其密封對象之零件之大小等，適當調整其大小而設置。該密封片材之大小可任意製作，例如較佳為200×200 mm～600×600 mm等。又，該密封片材較佳為厚度為0.1～2.0 mm。若厚度為0.1 mm以上，則無破裂之虞，操作性優異，亦可無障礙而容易地進行向壓縮成形用模具中之搬入。又，若厚度為2.0 mm以下，則亦不會存在半導體密封時模具內之密封片材之熔融延遲而使成形變得不良之情況。 [半導體裝置] 本實施形態之半導體裝置具備藉由上述密封片材密封之元件。該半導體裝置可藉由對固定於基板上之半導體元件，使用上述密封片材藉由壓縮成形進行密封而進行製造。以下，記載該方法之一例。 首先，針對安裝有半導體元件之基板，使其由2片上述密封片材夾入而於半導體元件上覆蓋密封片材，並配置於壓縮成形用模具之模腔內之特定位置，以特定之溫度、特定之壓力進行壓縮成形。成形條件較佳為設為溫度100～190℃、壓力4～12 MPa。成形後，以130～190℃之溫度進行2～8小時左右之後硬化。藉由該加熱硬化，密封片材密接於半導體元件並硬化，從而可製造將半導體元件以不與外部環境接觸之方式密封之樹脂密封型之半導體裝置。 以此方式獲得之半導體裝置即便較薄亦容易操作，且藉由使用成形性優異之密封片材之壓縮成形進行密封，因此即便為薄型亦可具備較高之品質及較高之可靠性。 再者，本實施形態之半導體裝置中密封之半導體元件為公知之半導體元件即可，因此並無特別限定，例如可例示IC(Integrated Circuit，積體電路)、LSI(Large Scale Integration，大型積體電路)、二極體、閘流體、電晶體等。尤其是，於利用先前之密封材料難以密封之密封後之厚度成為0.1～1.5 mm之類的半導體元件之情形時，使用上述密封片材之半導體裝置之製造方法尤其有用。 [實施例] 其次，藉由實施例，對本發明進行具體說明，但本發明並不受該等例之任何限定。再者，以下之實施例及比較例中使用之材料係如表1所示。 (實施例1～6、比較例1～3) 將各原料以成為表2所示之組成之方式於常溫(25℃)下進行混合，繼而，使用熱輥以80～130℃進行加熱混練。冷卻後，使用Speed Mill進行粉碎而製備密封片材用樹脂組合物。 將所獲得之密封片材用樹脂組合物由包含聚酯之脫模膜夾持，放置於80℃之熱板間，以10 MPa之壓力進行1分鐘加熱及加壓，而製作厚度0.5 mm之密封片材。 進而，使用所獲得之密封片材進行半導體晶片之密封。即，首先，自所獲得之密封片材切出150 mm×30 mm之片材。將該切出之密封片材放置於壓縮成形用模具內，於其上重疊安裝有半導體晶片之基板，進而於其上重疊上述密封片材，於8.0 MPa之加壓下、175℃且30分鐘之條件下進行壓縮成形。其後，進行175℃、4小時之後硬化，而製造半導體裝置。 針對上述各實施例及比較例中所獲得之密封片材用樹脂組合物、密封片材、及半導體裝置(製品)，利用下述所示之方法對各種特性進行評價。將其結果一併表示於表2。再者，表2中，空欄表示未調配。 [表1]
表1 材料 商品名、製造商 備註 結晶性環氧樹脂I YX-4000H 三菱化學(股) 聯苯型環氧樹脂 環氧當量：193 g/eq. 熔點：105℃ 結晶性環氧樹脂II YL-6121H 三菱化學(股) 聯苯型環氧樹脂 環氧當量：175 g/eq. 熔點：125℃ 液狀環氧樹脂I EXA-850CRP DIC(股) 雙酚A型環氧樹脂 環氧當量：173 g/eq. 黏度：4500 mPa·s 液狀環氧樹脂II YDF-8170C 新日鐵住金化學(股) 雙酚F型環氧樹脂 環氧當量：160 g/eq. 黏度：1250 mPa·s 固體環氧樹脂 CNE-200ELB-65 長春人造樹脂(股) 鄰甲酚酚醛清漆型環氧樹脂 環氧當量：198 g/eq. 酚樹脂I Shonol BRG-556 昭和電工(股) 苯酚酚醛清漆型酚樹脂 羥基當量：105 g/eq. 酚樹脂II MEH-7500 明和化成(股) 三苯酚甲烷型酚樹脂 羥基當量：97 g/eq. 熔融二氧化矽I FB-105 Denka(股) 平均粒徑：12 μm 最大分割粒徑*1：75 μm 熔融二氧化矽II FB-875FC Denka(股) 平均粒徑：23 μm 最大分割粒徑*1：55 μm 熔融二氧化矽III SC-4500SQ Admatechs(股) 平均粒徑：1 μm 含酮亞胺基之矽烷化合物 KBE-9103 Shin-Etsu Silicones(股) N-(1,3-二甲基亞丁基)-3-(三乙氧基矽烷基)-1-丙胺 矽烷偶合劑 Z-6883 東麗道康寧(股) (N-苯基-γ-胺基丙基)三甲氧基矽烷 硬化促進劑 2P4MHZ 四國化成工業(股) 2-苯基-4-甲基-5-羥基甲基咪唑 著色劑 MA-600 三菱化學(股) 碳黑 脫模劑 巴西棕櫚蠟1號 ＊1：使用網眼75 μm之篩進行分級。 [表2]
表2 單位 實施例 比較例 1 2 3 4 5 6 1 2 3 組成 環氧樹脂 (A)成分 結晶性環氧樹脂I 質量% 7.5 7.5 7.5 7.5 7.5 結晶性環氧樹脂Ⅱ 質量% 7.5 液狀環氧樹脂I 質量% 7.5 液狀環氧樹脂Ⅱ 質量% 7.5 固體環氧樹脂 質量% 7.5 酚樹脂 硬化劑 (B)成分 酚樹脂I 質量% 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 酚樹脂Ⅱ 質量% 3.5 硬化促進劑 (C)成分 硬化促進劑 質量% 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 無機填充劑 (D)成分 熔融二氧化矽I 質量% 80 80 80 80 80 80 80 80 熔融二氧化矽Ⅱ 質量% 80 熔融二氧化矽III 質量% 8 8 8 8 8 8 8 8 8 含酮亞胺基之矽烷化合物 (E)成分 含酮亞胺基之矽烷化合物 質量% 1 1 1 1 1 1 1 其他成分 矽烷偶合劑 質量% 1 著色劑 質量% 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 脫模劑 質量% 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 物性 密封片材用樹脂組合物 螺旋流動 [cm] 195 203 189 213 225 222 143 197 121 凝膠時間(175℃) [s] 45 46 45 40 49 51 41 46 45 高化式流變黏度 [Pa·s] 6 8 7 5 5 4 12 6 13 密封片材 可撓性 初始 [s] 0 0 0 0 0 0 ＞600 0 0 25℃/168h後 [s] 248 244 268 252 201 220 ＞600 ＞600 222 玻璃轉移點 [℃] 118 120 158 124 110 108 136 115 117 彎曲強度(25℃) [MPa] 174 176 178 178 171 168 178 176 165 彎曲彈性模數(25℃) [GPa] 26 25 27 25 24 24 25 25 23 吸水率(PCT)121℃/24h [%] 0.42 0.46 0.47 0.47 0.51 0.53 0.48 0.42 0.46 與矽晶片之接著力 [MPa] ＞20 ＞20 ＞20 ＞20 ＞20 ＞20 ＞20 16 14 半導體裝置 耐回焊性(MSL LV.3) 不良數/總個數 0/20 0/20 0/20 0/20 0/20 0/20 16/20 0/20 14/20 耐濕可靠性(PCT) 不良數/總個數 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 2/20 高溫放置可靠性(HAST) 不良數/總個數 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 3/20 ＜樹脂組合物＞ (1)螺旋流動 使用依據EMMI標準之模具，以溫度175℃、壓力9.8 MPa進行轉移成形，進行測定。 (2)凝膠時間 依據JIS C 2161之7.5.1所規定之凝膠化時間A法，將約1 g之密封片材用樹脂組合物塗佈於175℃之熱板上，利用攪拌棒進行攪拌，測定直至成為凝膠狀而無法進行攪拌之時間。 (3)高化式流變黏度 藉由流動特性評價裝置(島津製作所(股)製造，製品名：流變儀CFT-500型)，測定溫度175℃、負載10 kg(剪切應力1.23×10
5Pa之環境下)之熔融黏度。 ＜密封片材＞ (1)可撓性 切出寬度10 mm、長度50 mm、厚度0.5 mm之密封片材，夾住自一端起15 mm之部分，於架台上安放於高度18 mm，測定直至由於自重而片材之一端與架台上表面接觸之時間(初始)。 又，另外切出寬度10 mm、長度50 mm、厚度0.5 mm之密封片材，於25℃下放置168小時後，同樣地，夾住自一端起15 mm之部分，於架台上安放於高度18 mm，測定直至由於自重而片材之一端與架台上表面接觸之時間。 ＜硬化物＞ (1)玻璃轉移點(Tg) 利用於175℃下進行3分鐘加熱使之硬化而獲得之硬化物製作棒狀之樣品，藉由熱分析裝置(TMA)(Seiko Instruments(股)製造，製品名：TMA SS-150)，於升溫速度10℃/分鐘之條件下進行升溫並測定TMA圖，根據2個切線之交點求出。 (2)彎曲強度、彎曲彈性模數 針對以與上述(1)相同之方式製作之樣品，依據JIS K 6911，於溫度25℃下進行測定。 (3)吸水率 於12 MPa之加壓下、175℃且2分鐘之條件下進行壓縮成形，繼而，進行175℃、8小時之後硬化而獲得直徑50 mm、厚度3 mm之圓板狀之硬化物。將該硬化物於127℃、0.25 MPa之飽和水蒸氣中放置24小時，求出處理前後增加之質量，利用下式算出。 吸水率(%)＝增加之質量(g)/硬化物之初始質量(g) (4)與矽晶片之接著力 於矽晶片上將密封片材以成形溫度150℃、成形壓力100 kg/cm
2進行10分鐘轉移成形為1邊2 mm之正方形狀。對所獲得之成形品施加剪力，將斷裂時之剪力設為接著力。 ＜製品(半導體裝置)＞ (1)耐回焊性(MSL試驗) 對半導體裝置進行以下試驗，即，以85℃、85%RH進行72小時吸濕處理後，於240℃之紅外線回焊爐中加熱90秒鐘之試驗(MSL試驗：Level 3)，調查不良(剝離及裂痕)之產生率(試樣數＝20)。 (2)耐濕可靠性(壓力鍋試驗：PCT) 針對半導體裝置，於壓力鍋內，於127℃、0.25 MPa之條件下，使之吸水72小時後，進行240℃、90秒鐘之蒸氣回焊，調查不良(開路不良)之產生率(試樣數＝20)。 (3)高溫放置可靠性(高度加速壽命試驗：HAST) 將半導體裝置於180℃之恆溫槽中放置1000小時，調查不良(開路不良)之產生率(試樣數＝20)。 根據表2可明確，本實施形態之密封片材即便於常溫下長時間放置亦具有柔軟性，具有良好之操作性，又，與矽晶片接著亦良好。 又，可確認使用該密封片材而製造之半導體裝置於MSL試驗、壓力鍋試驗、高度加速壽命試驗之任一試驗中均可獲得良好之結果，係作為樹脂密封型半導體裝置具有較高之可靠性者。 [產業上之可利用性] 本發明之密封片材即便厚度變薄，操作性或成形性亦優異。因此，作為經薄型化之半導體元件之壓縮成形用密封材料有用，可製造高品質且可靠性較高之樹脂密封型半導體裝置。 又，除半導體元件以外，亦可用作以不暴露於外部環境之方式對零件等進行密封之密封片材。
Hereinafter, the resin composition for a sealing sheet, the sealing sheet, and the semiconductor device according to the embodiment of the present invention will be described in detail. [Resin Composition for Sealing Sheet] The resin composition for a sealing sheet of the present embodiment is characterized by containing (A) a crystalline epoxy resin and/or a liquid epoxy resin, and (B) a phenol resin curing agent. (C) a hardening accelerator, (D) an inorganic filler, and (E) a ketimine-containing decane compound. First, each component of the resin composition for a sealing sheet (hereinafter, also simply referred to as a resin composition) of the present embodiment will be described. The epoxy resin-based crystalline epoxy resin and/or liquid epoxy resin of the component (A) used in the present embodiment. The crystalline epoxy resin is an epoxy resin which has a property of being solid at normal temperature (25 ° C) and exhibiting a crystalline state and having a large viscosity at the time of melting. The melting point of the crystalline epoxy resin is preferably from 80 to 150 ° C, more preferably from 90 to 130 ° C. In addition, the liquid epoxy resin is an epoxy resin which is in a liquid or semi-solid state at normal temperature (25 ° C), and examples thereof include an epoxy resin having fluidity at normal temperature (25 ° C). The viscosity of the liquid epoxy resin at 25 ° C is preferably 10,000 mPa·s or less, more preferably 1,000 to 6,000 mPa·s. Further, the melting point of the crystalline epoxy resin can be measured by an endothermic peak of DSC (differential scanning calorimetry). Further, the viscosity of the liquid epoxy resin at 25 ° C can be measured by a rotary viscometer. The crystalline epoxy resin and the liquid epoxy resin (hereinafter, also referred to simply as the epoxy resin of the component (A)) of the component (A) can be used without being restricted by molecular structure, molecular weight, etc., and preferably, Benzene type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin. These may be used alone or in combination of two or more. Further, the biphenyl type epoxy resin is an epoxy resin having a biphenyl skeleton, but the biphenyl skeleton in the present embodiment also includes hydrogenation of at least one aromatic ring in the biphenyl ring. Specific examples of the biphenyl type epoxy resin include 4,4'-bis(2,3-epoxypropoxy)biphenyl and 4,4'-bis(2,3-epoxypropoxy group). )-3,3',5,5'-tetramethylbiphenyl, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3',5,5'-four An epoxy resin obtained by reacting a biphenyldiol compound such as methyl)biphenol or the like. Among these, 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl, 4,4'-(3, A glycidyl ether of 3',5,5'-tetramethyl)biphenyl. One type of the biphenyl type epoxy resin may be used, or two or more types may be used in combination. For example, a commercially available product of a biphenyl type epoxy resin is exemplified by YX-4000 (epoxy equivalent weight 185, melting point 105 ° C) manufactured by Mitsubishi Chemical Corporation, and YX-4000K manufactured by Mitsubishi Chemical Corporation. (epoxy equivalent 185, melting point 105 ° C), YX-4000H (epoxy equivalent 193, melting point 105 ° C) manufactured by Mitsubishi Chemical Corporation, YL-6121H (epoxy equivalent 175, melting point 125) manufactured by Mitsubishi Chemical Corporation °C) (all of the above are trade names) and so on. Further, specific examples of the bisphenol A type epoxy resin include EXA-850 CRP (epoxy equivalent 173, 25 ° C viscosity 4500 mPa·s) manufactured by DIC. Specific examples of the bisphenol F-type epoxy resin include YDF-8170C (epoxy equivalent 160, 25 ° C viscosity 1250 mPa·s) manufactured by Nippon Steel & Co., Ltd. In addition to the epoxy resin of the above component (A), an epoxy resin used as a sealing material may be used in combination within the range not impairing the effects of the present invention. In the case where the epoxy resin other than the crystalline epoxy resin or the liquid epoxy resin is used in combination, the blending amount is preferably 30 mass% based on 100 parts by mass of the epoxy resin of the component (A). The amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. The phenol resin curing agent of the component (B) used in the present embodiment is a phenolic hydroxyl group which has two or more reactive groups with the epoxy group in the epoxy resin of the component (A). It can be used without particular limitation. Specific examples thereof include a phenol novolak resin obtained by reacting a phenol such as phenol or an alkylphenol with formaldehyde or paraformaldehyde, and a novolac type phenol resin such as a cresol novolak resin, and the novolac type phenol resin. Epoxidized or butylated phenolic phenol resin, dicyclopentadiene modified phenol resin, p-xylene modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, trisphenol An alkane type phenol resin, a polyfunctional phenol resin or the like. Among them, a novolac type phenol resin or a triphenyl alkane type phenol resin is preferably used. These may be used alone or in combination of two or more. The blending amount of the phenol resin hardener of the component (B) is preferably a phenolic hydroxyl group of the phenol resin hardener of the component (B) (b) and a ring of the epoxy resin of the component (A). The ratio [(b)/(a)] of the number of oxygen groups (a) is in the range of 0.3 or more and 1.5 or less, and more preferably in the range of 0.5 or more and 1.2 or less. When the ratio [(b)/(a)] is 0.3 or more, the moisture resistance reliability of the cured product can be improved, and if it is 1.5 or less, the strength of the cured product can be improved. The curing accelerator of the component (C) used in the present embodiment is a component which accelerates the curing reaction of the epoxy resin of the component (A) and the phenol resin curing agent of the component (B). The hardening accelerator of the component (C) is not particularly limited as long as it exhibits the above-described effects, and a known curing accelerator can be used. Specific examples of the curing accelerator of the component (C) include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-undecylimidazole, and 1,2-di Methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 4-methylimidazole, 4-ethylimidazole, 2-phenyl-4-hydroxyl Methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl- 4,5-Dihydroxymethylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazoles such as imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole Class; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene, 5,6-dibutylamino group- a diazabicyclo compound such as 1,8-diazabicyclo[5.4.0]undecene-7 and the salts thereof; triethylamine, triethylamine, benzyldimethylamine, α -methylbenzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol Tertiary amines; trimethylphosphine, triethylphosphine, tributylphosphine, diphenylphosphine, triphenylphosphine, tris(p-methylphenyl)phosphine, tris(nonylphenyl)phosphine, A An organic phosphine compound such as diphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine, bis(diphenylphosphino)methane or 1,2-bis(diphenylphosphino)ethane. Among these, from the viewpoint of good fluidity and moldability, an imidazole is preferred, and 2-phenyl-4-methyl-5-hydroxymethylimidazole is more preferred. These may be used alone or in combination of two or more. The amount of the curing accelerator of the component (C) is preferably in the range of 0.1 to 5% by mass, more preferably 0.2 to 1% by mass based on the total amount of the resin composition. When the amount of the component (C) is 0.1% by mass or more, the effect of promoting the hardenability can be sufficiently obtained, and when it is 5% by mass or less, the moisture resistance reliability of the molded article can be improved. The inorganic filler of the component (D) used in the present embodiment is a component which is filled in the resin composition to adjust the viscosity of the resin composition or to improve the workability and formability when the following sealing sheet is produced. The inorganic filler as the component (D) can be used as long as it is a known inorganic filler which is generally used in the resin composition, and is not particularly limited. Specific examples of the inorganic filler of the component (D) include oxides such as molten cerium oxide, crystalline cerium oxide, crushed cerium oxide, synthetic cerium oxide, aluminum oxide, titanium oxide, and magnesium oxide. Powder; hydroxide powder such as aluminum hydroxide or magnesium hydroxide; nitride powder such as boron nitride, aluminum nitride or tantalum nitride. These inorganic fillers may be used alone or in combination of two or more. The inorganic filler as the component (D) is preferably a cerium oxide powder, more preferably a molten cerium oxide, from the viewpoint of improving the handleability or formability of the sealing sheet. It is a spherical molten cerium oxide. Further, cerium oxide other than molten cerium oxide and molten cerium oxide may be used in combination, and in this case, the ratio of cerium oxide other than molten cerium oxide is preferably set to 30 masses which are less than the entire cerium oxide powder. %. The inorganic filler of the component (D) preferably has an average particle diameter of 0.5 to 40 μm, more preferably 1 to 30 μm, still more preferably 5 to 30 μm. Further, it is preferable that the inorganic filler of the component (D) has a maximum particle diameter of 105 μm or less. When the average particle diameter is 0.5 μm or more, the fluidity of the resin composition can be suppressed from being lowered, and the moldability can be improved. In addition, when the average particle diameter is 40 μm or less, it is possible to suppress warpage of the molded article obtained by curing the resin composition or to prevent deterioration in dimensional accuracy. Moreover, when the maximum particle diameter is 105 μm or less, the moldability of the resin composition can be improved. Further, in the present specification, the average particle diameter of the inorganic filler of the component (D) can be determined, for example, by a laser diffraction type particle size distribution measuring apparatus, and the average particle diameter is accumulated in the particle size distribution measured by the apparatus. The volume becomes 50% of the particle size (d50). The blending amount of the inorganic filler of the component (D) is preferably in the range of 70 to 95% by mass, more preferably in the range of 75 to 90% by mass, based on the entire resin composition. When the blending amount of the inorganic filler is 70% by mass or more, the increase in the linear expansion coefficient of the resin composition can be suppressed, and the dimensional accuracy, moisture resistance, mechanical strength, and the like of the molded article can be improved. When the blending amount of the inorganic filler is 95% by mass or less, the increase in the melt viscosity of the resin composition can be suppressed, the decrease in fluidity can be suppressed, and the moldability can be improved. Further, the sealing sheet obtained by molding the resin composition can be prevented from being broken. The ketimine group-containing decane compound of the component (E) used in the present embodiment is a compound having a ketimine group and an alkoxy group in one molecule, and the resin composition contains the component (E). It can increase the adhesion of the hardened material. The ketimine group-containing decane compound of the above (E) component is not particularly limited as long as it has a ketimine group and an alkoxy group in one molecule, and is preferably a viewpoint of improving the adhesion of the cured product. A compound represented by the following formula (1). [Chemical 1] In the above formula (1), R 1 to R 4 each independently represent an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Isobutyl, second butyl, tert-butyl, various pentyl groups, and the like. Among them, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred from the viewpoint of ease of availability in the market. R 5 represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. The alkylene group may be any of a linear chain and a branched chain, and examples thereof include a methylene group, an ethylidene group, a propyl group, a trimethylene group, a butyl group, and a pentyl group. Among them, an ethyl group and a trimethylene group are preferred. a represents an integer of 0 to 2, preferably 0. The ketimine-containing decane compound of the above (E) component is easily hydrolyzed under high temperature conditions at the time of molding to form a primary amine. The water required for the hydrolysis is sufficient to adsorb water on the surface of the ceria, but it may be mixed with pure water in advance. Further, it may be used alone or in combination with other decane coupling agents. Specific examples of the ketimine group-containing decane compound represented by the above formula (1) include N-(1-methylethylidene)-3-(triethoxydecyl)-1-propylamine. , N-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine, N-(1-methylpropylene)-3-(triethoxydecane) -1 -propylamine, N-(1-methylethylidene)-3-(methyldiethoxydecyl)-1-propylamine, N-(1,3-dimethylbutylene)- 3-(methyldiethoxydecyl)-1-propylamine, N-(1-methylpropylene)-3-(methyldiethoxydecyl)-1-propylamine, N-(1 -methylethylidene)-3-(ethyldiethoxydecyl)-1-propylamine, N-(1,3-dimethylbutylene)-3-(ethyldiethoxydecylalkyl) )-1-propylamine, N-(1-methylpropylene)-3-(ethyldiethoxydecyl)-1-propylamine, N-(1-methylethylidene)-3-( Methyldimethoxydecyl)-1-propylamine, N-(1,3-dimethylbutylidene)-3-(methyldimethoxydecyl)-1-propylamine, N-(1- Methyl propylene)-3-(methyldimethoxydecyl)-1-propylamine, N-(1-methylethylidene)-2-(triethoxydecyl)-1-B Amine, N-(1,3-dimethylbutylene)-2-(triethoxydecyl)-1-ethylamine, N-(1- Methyl propylene)-2-(triethoxydecyl)-1-ethylamine, N-(1-methylethylidene)-2-(methyldiethoxydecyl)-1- Ethylamine, N-(1,3-dimethylbutylene)-2-(methyldiethoxydecyl)-1-ethylamine, N-(1-methylpropylidene)-2-( Methyldiethoxydecyl)-1-ethylamine, N-(1-methylethylidene)-2-(ethyldiethoxydecyl)-1-ethylamine, N-(1, 3-dimethylbutylene)-2-(ethyldiethoxydecyl)-1-ethylamine, N-(1-methylpropylidene)-2-(ethyldiethoxydecylalkyl) )-1-ethylamine, N-(1-methylethylidene)-2-(methyldimethoxydecyl)-1-ethylamine, N-(1,3-dimethylbutylene) 2-(Methyldimethoxydecyl)-1-ethylamine, N-(1-methylpropylene)-2-(methyldimethoxydecyl)-1-ethylamine, and the like. Among them, N-(1,3-dimethylbutylidene)-3-(triethoxydecyl)-1-propylamine is preferred from the viewpoint of ease of availability in the market. These ketimine-containing decane compounds may be used alone or in combination of two or more. The ketimine-containing decane compound of the above (E) component is easily hydrolyzed under high temperature conditions at the time of molding to form a primary amine, and a stanol group is formed. The primary amine is reacted with the epoxy resin of the above component (A), and the stanol group is subjected to a condensation reaction with a hydroxyl group present on the surface of the inorganic filler of the component (D), whereby the combination of the hardened resin and the inorganic filler becomes Firm. As a result, when the resin composition of the present embodiment is used as a sealing material for a semiconductor device, the adhesion between the cured product and the tantalum wafer or the like is strong. With respect to the content of the ketimine group-containing decane compound of the above (E) component relative to the total amount of the resin composition, the adhesion of the cured product to the ruthenium wafer or the like, the formation of pores and the like, and the balance of economy are balanced. From the viewpoints, it is preferably selected in the range of 0.5 to 2.0% by mass, more preferably 0.8 to 1.5% by mass. If a commercially available product of a ketimine-containing decane compound used as the above component (E) is exemplified, for example, it is N-(1,3-dimethylbutylene)-3-(triethoxydecylalkyl). Examples of the 1-propylamine include KBE-9103 manufactured by Shin-Etsu Silicones Co., Ltd., Sila-Ace S340 manufactured by JNC Co., Ltd., Z-6860 manufactured by Toray Dow Corning Co., Ltd., and the like. In the resin composition of the present embodiment, in addition to the above respective components, components which are usually formulated in such a resin composition, such as a coupling agent; synthetic wax, may be blended in a range which does not inhibit the effects of the present embodiment. , natural wax, higher fatty acid, metal salt of higher fatty acid release agent; carbon black, cobalt blue and other colorants; polyoxygenated oil, polyoxyxene rubber and other low stress imparting agents; aluminum magnesium carbonate; ion trapping agent, etc. . The coupling agent may, for example, be a coupling agent such as an epoxy decane type, an amino decane type, a urea decane type, a vinyl decane type, an alkyl decane type, an organic titanate type, or an aluminum alkoxide type. These may be used alone or in combination of two or more. The coupling agent is preferably an amine-based decane coupling agent, and more preferably γ-aminopropyltrimethoxydecane or γ-aminopropyl, from the viewpoints of moldability, flame retardancy, and curability. Triethoxy decane, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, (N-phenyl-γ-aminopropyl)trimethoxy Decane and so on. In the case of using a coupling agent, the amount thereof is preferably in the range of 0.01% by mass or more and 3.0% by mass or less based on the entire resin composition, and more preferably in the range of 0.1% by mass or more and 1% by mass or less. When the amount of the coupling agent is 0.01% by mass or more, the moldability can be improved. When the amount is 3.0% by mass or less, foaming during molding can be suppressed, and voids or surface bulging of the molded article can be suppressed. The resin composition of the present embodiment is (A) a crystalline epoxy resin and/or a liquid epoxy resin, (B) a phenol resin curing agent, (C) a curing accelerator, (D) an inorganic filler, (E) The ketimine compound-containing decane compound and the above-mentioned various components to be blended as needed are thoroughly mixed (dry blended) by a mixer or the like, and then melt-kneaded by a kneading device such as a hot roll or a kneader, cooled, and pulverized into appropriate The size. The pulverization method is not particularly limited, and a usual pulverizer such as a Speed Mill, a cutter mill, a ball mill, a cyclone mill, a hammer mill, a vibrating mill, a chopper, a sand mill, or the like can be used. Among them, it is preferred to use Speed Mill. The pulverized material can then be adjusted to a particle aggregate having a specific particle size distribution by sieving classification or air classification or the like. [Sealing Sheet] Next, the sealing sheet of the present embodiment will be described. The sealing sheet of the present embodiment is a sheet-shaped formed body obtained by molding the resin composition for a sealing sheet into a sheet shape. The sealing sheet is obtained by, for example, heating and melting the resin composition of the present embodiment between the pressing members and compressing them into a sheet shape. More specifically, the resin composition is supplied to the release film having heat resistance such as a polyester film so as to have a substantially uniform thickness, and then the resin layer is heated and softened by a roll and hot pressing. The machine is calendered. At this time, a heat resistant film such as a polyester film is also disposed on the resin layer. After the resin is laminated to a desired thickness in this manner, it is cooled and solidified, and the heat-resistant film is peeled off, and further cut into a desired size and shape as necessary. Thereby, a sealing sheet of any size can be obtained. Further, the heating temperature at the time of softening the resin layer is usually about 80 to 150 °C. When the heating temperature is less than 80 ° C, the melt mixing becomes insufficient. When the heating temperature exceeds 150 ° C, the curing reaction proceeds excessively, and the moldability deteriorates during heat curing. The sealing sheet of the present embodiment preferably has a melt viscosity of 2 to 50 Pa·s as measured by a high-temperature rheometer at a temperature of 175 ° C and a load of 10 kg (shear stress: 1.23 × 10 5 Pa). More preferably 3 to 20 Pa·s. When the melt viscosity is 2 Pa·s or more, generation of burrs can be suppressed, and if it is 50 Pa·s or less, the filling property is improved, and generation of voids or unfilled portions can be suppressed. The sealing sheet of the present embodiment is suitable for sealing a component such as a semiconductor element, and is appropriately adjusted in size according to the size of the component to be sealed. The size of the sealing sheet can be arbitrarily produced, and is, for example, preferably 200 × 200 mm to 600 × 600 mm. Further, the sealing sheet preferably has a thickness of 0.1 to 2.0 mm. When the thickness is 0.1 mm or more, the film is not broken, and the workability is excellent, and the mold can be easily carried into the mold for compression molding without any trouble. Moreover, when the thickness is 2.0 mm or less, there is no possibility that the sealing of the sealing sheet in the mold at the time of semiconductor sealing is delayed, and the molding is deteriorated. [Semiconductor Device] The semiconductor device of the present embodiment includes an element sealed by the sealing sheet. The semiconductor device can be manufactured by sealing a semiconductor element fixed to a substrate by compression molding using the above-mentioned sealing sheet. An example of this method will be described below. First, a substrate on which a semiconductor element is mounted is sandwiched between two sheets of the sealing sheet, and a sealing sheet is placed on the semiconductor element, and placed at a specific position in a cavity of the compression molding die at a specific temperature. The specific pressure is compression molded. The molding conditions are preferably a temperature of 100 to 190 ° C and a pressure of 4 to 12 MPa. After the molding, it is cured at a temperature of 130 to 190 ° C for about 2 to 8 hours. By this heat curing, the sealing sheet is in close contact with the semiconductor element and hardened, whereby a resin-sealed type semiconductor device in which the semiconductor element is sealed without being in contact with the external environment can be manufactured. The semiconductor device obtained in this manner is easy to handle even if it is thin, and is sealed by compression molding using a sealing sheet having excellent moldability. Therefore, even a thin type can have high quality and high reliability. In addition, the semiconductor device to be sealed in the semiconductor device of the present embodiment is not particularly limited as long as it is a known semiconductor device. For example, an IC (Integrated Circuit) or an LSI (Large Scale Integration) can be exemplified. Circuit), diode, thyristor, transistor, etc. In particular, in the case where the thickness after sealing using the sealing material which is difficult to seal with the prior sealing material is a semiconductor element of 0.1 to 1.5 mm, the manufacturing method of the semiconductor device using the above-mentioned sealing sheet is particularly useful. [Examples] Next, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. Further, the materials used in the following examples and comparative examples are shown in Table 1. (Examples 1 to 6 and Comparative Examples 1 to 3) Each of the raw materials was mixed at a normal temperature (25 ° C) so as to have a composition shown in Table 2, and then heated and kneaded at 80 to 130 ° C using a hot roll. After cooling, it was pulverized using a Speed Mill to prepare a resin composition for a sealing sheet. The obtained resin composition for a sealing sheet was sandwiched between a release film containing polyester, placed between hot plates at 80 ° C, and heated and pressurized at a pressure of 10 MPa for 1 minute to prepare a thickness of 0.5 mm. Seal the sheet. Further, the obtained sealing sheet was used to seal the semiconductor wafer. Namely, first, a sheet of 150 mm × 30 mm was cut out from the obtained sealing sheet. The cut sealing sheet was placed in a mold for compression molding, a substrate on which a semiconductor wafer was mounted thereon, and the sealing sheet was superposed thereon, and pressed at 175 ° C for 30 minutes under a pressure of 8.0 MPa. Compression molding is carried out under the conditions. Thereafter, the film was cured at 175 ° C for 4 hours to fabricate a semiconductor device. The resin composition for a sealing sheet, the sealing sheet, and the semiconductor device (product) obtained in each of the above Examples and Comparative Examples were evaluated for various characteristics by the methods described below. The results are shown together in Table 2. Furthermore, in Table 2, the blank column indicates that it is not allocated. [Table 1] Table 1 Material Trade name, manufacturer Remarks Crystalline epoxy resin I YX-4000H Mitsubishi Chemical Co., Ltd. Biphenyl type epoxy resin Epoxy equivalent: 193 g/eq. Melting point: 105 ° C Crystalline epoxy Resin II YL-6121H Mitsubishi Chemical Co., Ltd. Biphenyl type epoxy resin Epoxy equivalent: 175 g/eq. Melting point: 125 °C Liquid epoxy resin I EXA-850CRP DIC (share) Bisphenol A type epoxy ring Oxygen equivalent: 173 g/eq. Viscosity: 4500 mPa·s Liquid epoxy resin II YDF-8170C Nippon Steel & Sumitomo Chemical Co., Ltd. Bisphenol F epoxy resin Epoxy equivalent: 160 g/eq. Viscosity: 1250 mPa·s solid epoxy resin CNE-200ELB-65 Changchun artificial resin (strand) o-cresol novolac type epoxy resin epoxy equivalent: 198 g/eq. Phenolic resin I Shonol BRG-556 Showa Denko (stock) Phenol novolac Clear phenolic resin hydroxyl equivalent: 105 g/eq. Phenol resin II MEH-7500 Minghe Chemical Co., Ltd. Trisphenol methane phenol resin hydroxyl equivalent: 97 g/eq. Molten cerium oxide I FB-105 Denka (share) average Particle size: 12 μm Maximum split size *1:75 μm Melted ruthenium dioxide II FB-875FC Denka (strand) Average particle size: 23 μm Maximum split particle size *1:55 μm Melt Cerium oxide III SC-4500SQ Admatechs (strand) Average particle size: 1 μm Ketone-based decane compound KBE-9103 Shin-Etsu Silicones (share) N-(1,3-dimethylbutylene)-3- (triethoxydecyl)-1-propanamine decane coupling agent Z-6883 Toray Dow Corning (share) (N-phenyl-γ-aminopropyl) trimethoxy decane hardening accelerator 2P4MHZ Shikoku Chemical Industry ( Strand) 2-Phenyl-4-methyl-5-hydroxymethylimidazole colorant MA-600 Mitsubishi Chemical Co., Ltd. Carbon black release agent Carnauba wax No.1*1: Classification using a mesh 75 μm sieve . [Table 2] Table 2 Unit Example Comparative Example 1 2 3 4 5 6 1 2 3 Composition Epoxy Resin (A) Component Crystalline Epoxy Resin I% by mass 7.5 7.5 7.5 7.5 7.5 Crystalline Epoxy Resin II% by mass 7.5 Liquid epoxy resin I% by mass 7.5 Liquid epoxy resin II% by mass 7.5 Solid epoxy resin mass% 7.5 Phenolic resin hardener (B) Component Phenolic resin I% by mass 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Phenolic resin II Quality % 3.5 Hardening accelerator (C) Hardening accelerator mass % 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Inorganic filler (D) Ingredient cerium oxide I Mass % 80 80 80 80 80 80 80 80 Fused cerium oxide II Mass % 80 Molten cerium oxide III mass% 8 8 8 8 8 8 8 8 8 ketone imine group decane compound (E) component ketone imine group decane compound mass% 1 1 1 1 1 1 1 other components矽 偶 coupling agent mass % 1 colorant mass % 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 release agent mass % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 The resin composition for the physical sealing sheet spiral flow [cm] 195 203 189 213 225 222 143 197 121 Gel time (175 ° C) [s] 45 46 45 40 49 51 41 46 45 High-grade Viscosity [Pa·s] 6 8 7 5 5 4 12 6 13 Seal sheet flexibility initial [s] 0 0 0 0 0 0 >600 0 0 25°C/168h after [s] 248 244 268 252 201 220 >600 >600 222 Glass Transfer Point [°C] 118 120 158 124 110 108 136 115 117 Bending Strength (25°C) [MPa] 174 176 178 178 171 168 178 176 165 Bending Elastic Modulus (25°C) [GPa] 26 25 27 25 24 24 25 25 23 Water absorption (PCT) 121°C/24h [%] 0.42 0.46 0.47 0.47 0.51 0.53 0.48 0.42 0.46 Adhesion to 矽 wafer [MPa] >20 >20 >20 >20 >20 >20 >20 16 14 Solderability of semiconductor devices (MSL LV.3) Number of defects / total number 0/20 0/20 0/20 0/20 0/20 0/20 16/20 0/20 14/20 Resistance Wet Reliability (PCT) Bad Number / Total Number 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 2/20 High Temperature Placement Reliability (HAST) Bad Number / Total Number 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 3/20 <Resin composition> (1) Spiral flow using a mold according to EMMI standard at a temperature of 175 ° C The measurement was carried out by transfer molding at a pressure of 9.8 MPa. (2) Gel time According to the gelation time A method prescribed in 7.7.1 of JIS C 2161, about 1 g of the resin composition for a sealing sheet is applied onto a hot plate at 175 ° C, and a stir bar is used. The mixture was stirred and measured until it became a gel and the stirring could not be performed. (3) The high-grade rheological viscosity is measured by a flow characteristic evaluation device (manufactured by Shimadzu Corporation, product name: rheometer CFT-500), measuring temperature 175 ° C, load 10 kg (shear stress 1.23 × 10) Melt viscosity in a 5 Pa environment). <Sealing sheet> (1) Flexibility Cut out a sealing sheet with a width of 10 mm, a length of 50 mm, and a thickness of 0.5 mm, and clamp a portion of 15 mm from one end, and place it on the gantry at a height of 18 mm. The time (initial) at which one end of the sheet comes into contact with the upper surface of the gantry due to its own weight. Further, a sealing sheet having a width of 10 mm, a length of 50 mm, and a thickness of 0.5 mm was cut out, and after standing at 25 ° C for 168 hours, the portion 15 mm from the one end was sandwiched and placed on the gantry at a height of 18 Mm, the time until one end of the sheet comes into contact with the upper surface of the gantry due to its own weight. <Cured product> (1) Glass transition point (Tg) A sample obtained by heating at 175 ° C for 3 minutes by heating to obtain a rod-shaped sample by a thermal analysis device (TMA) (Seiko Instruments) Manufactured, product name: TMA SS-150), the temperature was raised at a temperature increase rate of 10 ° C / min, and the TMA map was measured, and the intersection of the two tangent lines was determined. (2) Flexural strength and flexural modulus The sample prepared in the same manner as in the above (1) was measured at a temperature of 25 ° C in accordance with JIS K 6911. (3) The water absorption rate was compression-molded under the pressure of 12 MPa at 175 ° C for 2 minutes, and then hardened at 175 ° C for 8 hours to obtain a circular plate-like hardening having a diameter of 50 mm and a thickness of 3 mm. Things. The cured product was allowed to stand in saturated steam of 0.25 ° C and 0.25 MPa for 24 hours, and the mass increased before and after the treatment was determined and calculated by the following formula. Water absorption rate (%) = increased mass (g) / initial mass of the hardened material (g) (4) The bonding force with the tantalum wafer was placed on the tantalum wafer at a forming temperature of 150 ° C, a forming pressure of 100 kg / cm 2 The transfer was carried out for 10 minutes to form a square shape of 1 side and 2 mm. A shear force is applied to the obtained molded article, and the shear force at the time of fracture is set as the adhesion force. <Product (semiconductor device)> (1) Reflow resistance (MSL test) The semiconductor device was subjected to the following tests, that is, an infrared reflow furnace at 240 ° C after performing a moisture absorption treatment at 85 ° C and 85% RH for 72 hours. The test was carried out for 90 seconds (MSL test: Level 3), and the incidence of defects (peeling and cracking) was investigated (number of samples = 20). (2) Moisture resistance reliability (pressure cooker test: PCT) For a semiconductor device, in a pressure cooker, after absorbing water for 72 hours at 127 ° C and 0.25 MPa, steam reflow at 240 ° C for 90 seconds is performed. The incidence of poor investigation (poor opening) (number of samples = 20). (3) High-temperature placement reliability (high-acceleration life test: HAST) The semiconductor device was placed in a thermostat at 180 ° C for 1000 hours, and the rate of occurrence of defective (open circuit failure) (number of samples = 20) was investigated. As is clear from Table 2, the sealing sheet of the present embodiment has flexibility even when left at a normal temperature for a long period of time, and has good handleability, and is also excellent in adhesion to a tantalum wafer. Moreover, it was confirmed that the semiconductor device manufactured using the sealing sheet can obtain good results in any of the MSL test, the pressure cooker test, and the highly accelerated life test, and has high reliability as a resin-sealed type semiconductor device. By. [Industrial Applicability] The sealing sheet of the present invention is excellent in handleability and moldability even when the thickness is reduced. Therefore, it is useful as a sealing material for compression molding of a thinned semiconductor element, and it is possible to manufacture a high-quality and highly reliable resin-sealed semiconductor device. Further, in addition to the semiconductor element, it can also be used as a sealing sheet for sealing a part or the like without being exposed to the external environment.