.201215583 六、發明說明 【發明所屬之技術領域】 本發明係有關陶瓷混合物及使用其所成含有陶瓷之熱 傳導性樹脂薄片。更詳細爲，本發明係有關賦予高熱傳導 性樹脂薄片之陶瓷混合物.，及使用該陶瓷混合物而得，自 發熱體將熱傳達至散熱構件用之熱傳導性樹脂薄片，特別 是形成自半導體元件等之發熱體將熱傳達至散熱構件，且 具有絕緣層機能之熱傳導性樹脂層用之熱傳導性樹脂薄 片。 【先前技術】 近年來對使用於各種電子機器等之1C等之電子構件 要求提升其積體度。又，爲了對應電子機器等之小型化需 求’而將IC等之電子構件高密度配置於小空間時，筐體 內相對於發熱之散熱對策將成爲大問題。即，1C等之電 子構件會因溫度上升而變動電子構件之特性造成機器錯誤 動作及使電子構件本身故障。 另外相對於以高速化發展之CPU爲首之半導體顯示 器等所發生之發熱量增加，各種電子機器等之裝置仍往小 型輕量化及薄型化進展。因此爲了維持其性能及機能，需 充分去除所發生之熱，而要求有效率之散熱系統。 對自電氣、電子機器之發熱部將熱傳達至散熱構件之 熱傳導性樹脂層要求具有高熱傳導性、絕緣性及接合性 下，係使用熱硬化性樹脂添加無機塡充物所得之熱傳導性 -5- 201215583 樹脂組成物。 例如已知動力組件中，設置於搭載電力半導體元件之 導體框架之背面，與構成散熱部之金屬板之間的熱傳導性 樹脂層係使用，含有無機塡充物之熱硬化性樹脂薄片及塗 佈膜之技術（例如參考專利文獻1)。 又，已知介於CPU等之發熱性電子構件與散熱片之 間的熱傳導性樹脂層爲，塡充高熱傳導性之無機粉體所得 之熱硬化性樹脂薄片（例如參考專利文獻2)。 如專利文獻2所示，無機粉體用之球狀氧化鋁粒子易 分散，可高度塡充，故非常適合作爲使用於熱傳導性薄片 之熱傳導性塡充物。因此開始檢討組合其他熱傳導性塡充 物所得之物及變更有機基質，使熱傳導性塡充物具有更高 塡充度得高熱傳導性（例如參考專利文獻3及4)。 專利文獻5曾揭示，可發揮高散熱特性之無機粉末 爲，由含有無機質粉末，與平均粒徑小於該球狀無機質粉 末之非球狀無機質粉末之混合粉末形成，平均粒徑爲5至 5 Ομηι之無機粉末。但實際進行評估時，由二氧化矽、氧 化鋁、碳化矽及氮化鋁中所選出之組合能否可得到與其他 無機粉末相同之效果仍未確定。 又，高度塡充如氧化鋁般之比重較高之塡充物時會加 重熱傳導性樹脂薄片本身，而有難對應電子機器等之小型 化、輕量化之問題。 另外伴隨著電子機器等之小型化，而促使熱傳導性樹 脂薄片薄膜化時可能會降低絕緣破壞特性。又，具有高熱 -6- 201215583 傳導性之氮化鋁含有相對於大氣中之水分爲不安定而難處 理，且價格高，同樣地熱傳導性優良之碳化矽會有絕緣破 壞特性差之問題。 例如專利文獻6曾揭示，粒徑5 μ m之氮化矽與粒徑 7μπι之氮化硼之倂用系的熱傳導性樹脂薄片，但因氮化矽 粒徑太小而難均勻分散，故有未必能得到倂用效果之問 題。又該文獻也曾揭示碳化矽與氮化硼之倂用系之熱傳導 性樹脂薄片，但使用碳化矽之系之絕緣破壞特性差。 專利文獻 專利文獻1:日本特開2001-196495號公報 專利文獻2:日本特開2003-253136號公報 專利文獻3 :日本特開平1 1 - 8 7 9 5 8號公報 專利文獻4:日本特開2 000-1 61 6號公報 專利文獻5:日本特開2007-70474號公報 專利文獻6:日本專利第4089636號公報 【發明內容】 發明所欲解決之課題 本發明係該狀況下完成之發明，其目的爲提供可賦予 具有比先前更優良之熱傳導率，同時可謀求薄片重量輕量 化，及具有優良加工性，且絕緣破壞特性良好之熱傳導性 樹脂薄片之陶瓷混合物’及使用該陶瓷混合物而具有上述 特徵之含有陶瓷混合物之熱傳導性樹脂薄片。 201215583 解決課題之方法 本發明者們爲了逢成前述目的經專心硏究後，發現下 述見解。 首先鱗片狀六方晶氮化硼粒子爲，具有高熱傳導性之 物’但不易分散於有機基質中，而有加工性差之缺點。因 此藉由混合流動性良好之球狀氧化鋁粒子，易使鱗片狀六 方晶氮化硼粒子分散，可提升加工性。又，利用鱗片狀六 方晶氮化硼粒子於面方向具有高熱傳導性之特性，以球狀 氧化鋁粒子爲骨材，將其配向於熱傳導性薄片之厚度方向 可得高熱傳導率。又，因不使用絕緣破壞特性差之碳化 矽，而使用氧化鋁，可得優良絕緣破壞特性。 藉由上述見解，以一定比例含有具有特定粒徑之鱗片 狀六方晶氮化硼粒子，與具有特定粒徑之球狀氧化鋁粒子 所得之陶瓷混合物作爲熱傳導性塡充物用時，既使單獨使 用氧化鋁粒子及氮化硼粒子，也可得具有比先前更優良之 熱傳導率，同時可謀求薄片重量輕量化，且具有優良加工 性之熱傳導性樹脂薄片。 即，本發明如下所述。 [1] —種陶瓷混合物，其爲體積基準之D50(50體積％ 粒徑）爲10至55 μιη之球狀氧化鋁粒子，與體積基準之 D50爲30μπι以下之鱗片狀六方晶氮化硼粒子之混合物’ 其特徵爲，前述鱗片狀六方晶氮化硼粒子之含有比例爲5 至3 0質量％。 [2] 如[1 ]所記載之陶瓷混合物，其中鱗片狀六方晶氮 201215583 化硼粒子之體積基準之D50爲5至30μηι。 [3] —種含有陶瓷之熱傳導性樹脂薄片，其特徵爲， 由含有有機基質1〇至7〇體積％，與[1]或[2]所記載之陶 瓷混合物3 0至9 0體積％之樹脂組成物經成型所得者。 [4] 如[3]所記載之含有陶瓷之熱傳導性樹脂薄片，其 中，前述球狀氧化鋁之體積基準之D50，相對於前述鱗片 狀六方晶氮化硼粒子之體積基準之D50爲3至7倍。 [5] 如[3]所記載之含有陶瓷之熱傳導性樹脂薄片，其 中，前述陶瓷混合物中前述球狀氧化鋁粒子之體積基準之 D5 0爲45至55 μιη，該陶瓷混合物於前述樹脂組成物中之 含有比例爲7 0至8 0體積％。 [6] 如[5]所記載之含有陶瓷之熱傳導性樹脂薄片，其 中’前述陶瓷混合物中前述鱗片狀六方晶氮化硼粒子之含 有比例爲6至2 5質量％，該陶瓷混合物於前述樹脂組成 物中之含有比例爲75至80體積％。 [7] 如[6]所記載之含有陶瓷之熱傳導性樹脂薄片，其 中’熱傳導率爲7W/m · Κ以上。 [8 ]如[5 ]所記載之含有陶瓷之熱傳導性樹脂薄片，其 中前述陶瓷混合物中前述鱗片狀六方晶氮化硼粒子之含有 比例爲1 5至2 5質量％，該陶瓷混合物於前述樹脂組成物 中之含有比例爲70至80質量％。 [9]如[8]所記載之含有陶瓷之熱傳導性樹脂薄片，其 中，熱傳導率爲9W/m . K以上。 Π〇]如[4]至[9]中任何一項所記載之含有陶瓷之熱傳 201215583 導性樹脂薄片’其中，前述有機基質含有硬化 脂。 [11]如[4]至[9]中任何一項所記載之含有陶 導性樹脂薄片’其中，前述有機基質含有硬化性 樹脂。 發明之效果 本發明可提供賦予具有比先前更優良之熱傳 時可圖薄片重量輕量化，具有優良加工性，且絕 性良好之熱傳導性樹脂薄片之陶瓷混合物，及使 混合物而具有上述特徵之熱傳導性樹脂薄片。 實施發明之形態 首先將說明本發明之陶瓷混合物。 [陶瓷混合物] 本發明之陶瓷混合物爲，提供具有比先前更 傳導率，同時可圖薄片重量輕量化，且加工性優 導性樹脂薄片用之熱傳導性塡充物，其爲體積基 爲10至55μιη之球狀氧化鋁粒子，與體積基準； 3 0 μηι以下之鱗片狀六方晶氮化硼粒子之混合物 爲，前述鱗片狀六方晶氮化硼粒子之含有比例爲 質量％。 性環氧樹 瓷之熱傳 聚较氧院 導率，同 緣破壞特 用該陶瓷 優良之熱 良之熱傳 準之 D50 之D5 0爲 ，其特徵 5至 30 -10- 201215583 (球狀氧化鋁粒子） 構成本發明之陶瓷混合物之2種成分中一方成分之氧 化鋁粒子爲，熱傳導性良好之球狀或非球狀之物。本發明 之陶瓷混合物中’考量另一成分之後述之鱗片狀六方晶氮 化硼粒子於有機基質中不易分散之觀點，該氧化鋁粒子係 使用流動性良好之球狀氧化鋁粒子。該球狀氧化鋁粒子係 指’氧化鋁粉末中粒子形狀爲球狀乃至近似球狀之形狀之 粉末。 又’本發明中「球狀」係以平均球形度評估。平均球 形度可使用例如西施美公司製商品名「FPIA-1 0000」等之 流動式粒子像分析裝置”以下述方法測定。首先由粒子像 測定粒子之投影面積（A)與周長（PM)。以對應周長（PM)之 真圓面積爲（B)時，該粒子之球形度可以a/B表示。又假 設爲持有與試料粒子之周長（PM)相同之周長之真圓時 ΡΜ = 2 π r、Β= π r2，因此，冗 Χ(ΡΜ/2 7Γ )2，故可以球形 度=Α/Β = Αχ4 7Γ (PM)2算出各個粒子之球形度。測定由其所 任意選出之1 00個以上粒子，以其平均値作爲平均球形 度。本發明之「球狀」可爲，上述球形度爲0.93至1.00 之範圍者，又若一般市售品中指明爲球狀或球形之物則符 合該範圍。 該球狀氧化鋁粒子之體積基準之D50，就相對於陶瓷 混合物之有機基質之分散性，及所得熱傳導性樹脂薄片之 丨生扣等觀點需爲10至55μιη’較佳爲25至55μηι，更佳爲 45至55 μιη。又’就上述觀點較佳爲粒度分布明顯之球狀 -11 - 201215583 氧化鋁粒子。 又’本發明之體積基準之D50可利用庫爾特計數器 法或雷射衍射散亂法等測定。例如球狀氧化鋁粒子時較佳 爲’藉由庫爾特計數器法測定，鱗片狀六方晶氮化硼粒子 時較佳爲，藉由雷射衍射散亂法測定。 (鱗片狀六方晶氮化硼粒子） 構成本發明之陶瓷混合物之另一方成分之鱗片狀六方 晶氮化硼粒子係使用，體積基準之D50爲30μπι以下之 物。體積基準之D50超過30μιη時，有機基質中鱗片狀粒 子相對於厚度方向易平行配向而使所得之熱傳導性樹脂薄 片不易得到所希望之熱傳導性。 該鱗片狀六方晶氮化硼粒子之體積基準之D50較佳 爲5至30μπι，更佳爲5至15μηι。體積基準之D50未達 5μηι時，會提升含有有機基質及陶瓷混合物之樹脂組成物 之黏度，而降低加工性。 體積基準之D50不超過30μιη之範圍內，使用持有較 大體積基準之D5 0之鱗片狀六方晶氮化硼粒子時可得， 至少粒子間之界面更易傳達熱之效果。 此時之「鱗片狀」係指，如圖1 (Α)之平面圖所示， 鱗片狀六方晶氮化硼粒子10之長徑L，與圖1(A)之Χ-Χ 剖面圖（圖1(B))所示之該粒子10之厚度r(平均厚度）之比 (長寬比（L : r)爲5 : 1至20 : 1之形態。 該鱗片狀六方晶氮化硼中含有大量不純物（例如B2〇3) -12- 201215583 時，使用硬化所需之有機基質時會成爲阻礙硬化之要因。 又，會成爲降低所得熱傳導性樹脂薄片之熱傳導性之要 因。因此就此觀點，該鱗片狀六方晶氮化硼中不可避免混 入之不純物B2〇3含量較佳爲〇.〇1至〇.1質量％,更佳爲 0.01 至 0.05 質量 ％。 本發明之陶瓷混合物中該鱗片狀六方晶氮化硼粒子之 含量需爲5至30質量％。該含量超過30質量％時，會增 加含有有機基質及陶瓷混合物之樹脂組成物之黏度，而成 爲降低加工性之要因。又’鱗片狀六方晶氮化硼粒子爲高 價物’因此其含量超過3 0質量％將不利於商業性。就該 觀點，陶瓷混合物中該鱗片狀六方晶氮化硼粒子之含量較 佳爲3 0質量％以下。又’未達5質量％時將無法賦予優良 之熱傳導性。含量較佳爲6至2 5質量％，又以1 〇至2 5 質量％爲佳，更佳爲1 5至2 5質量％，特佳爲1 8至2 5質 量％ » 球狀氧化鋁粒子之體積基準之D50相對於鱗片狀六 方晶氮化硼粒子之體積基準之D50較佳爲3至7倍，更 佳爲4至6倍。3至7倍時，比較單獨使用球狀氧化鋁粒 子及單獨使用鱗片狀六方晶氮化硼粒子時，可明顯得到高 熱傳導率。 爲了提高前述球狀氧化鋁粒子及鱗片狀六方晶氮化硼 粒子相對於有機基質之分散性，與加工性等，必要時可使 用各種偶合劑等實施表面處理。 •13- 201215583 (偶合劑） 偶合劑如，矽烷系、鈦酸鹽系'鋁系等，其中就效果 觀點較佳爲矽烷系偶合劑、矽烷系偶合劑特佳爲使用r -胺基丙基三甲氧基矽烷、r-胺基丙基三乙氧基矽烷、r-(2-胺基乙基）胺基丙基三甲氧基矽烷、r -(2-胺基乙基）胺 基丙基三乙氧基矽烷、r-苯胺基丙基三甲氧基矽烷、r-苯胺基丙基三乙氧基矽烷、N- /3 -(N-乙烯基苄基胺基乙 基）-r-胺基丙基三甲氧基矽烷及乙烯基苄基胺 基乙基）-r -胺基丙基三乙氧基矽烷等之胺基矽烷化合 物。 其次將說明本發明之含有陶瓷之熱傳導性樹脂薄片。 [含有陶瓷之熱傳導性樹脂薄片] 本發明之含有陶瓷之熱傳導性樹脂薄片爲，特徵係由 含有有機基質10至70體積％，與前述本發明之陶瓷混合 物30至90體積％之樹脂組成物經成型所得。 陶瓷混合物超過90體積％(有機基質未達10體積％) 時，會因有機基質太少而難形成樹脂組成物，陶瓷混合物 未達30體積％(有機基質超過90體積％)時，有機基質內 塡充物相互間將難接觸，會降低熱傳導性，而難得到散熱 所必需之熱傳導率。 本發明之含有陶瓷之熱傳導性樹脂薄片就優良熱傳導 率、薄片重量輕量化、良好加工性及絕緣破壞特性之觀 點，較佳爲下述第1態樣及第2態樣中任何一種。 -14- 201215583 即，第1態樣爲’陶瓷混合物中鱗片狀六方晶氮化硼 粒子之含有比例爲6至2 5質量％ ’該陶瓷混合物於前述 樹脂組成物中之含有比例爲7 5至8 0體積％之含有陶瓷之 熱傳導性樹脂薄片。該態樣可使熱傳導率爲7W/m · K以 上。 又，第2態樣爲，陶瓷混合物中前述鱗片狀六方晶氮 化硼粒子之含有比例爲1 5至2 5質量％，該陶瓷混合物於 前述樹脂組成物中之含有比例爲70至8 0體積％之含有 陶瓷之熱傳導性樹脂薄片。該態樣可使熱傳導率爲 9W/m · K 以上。 (有機基質） 本發明之含有陶瓷之熱傳導性樹脂薄片（以下單稱爲 「熱傳導性樹脂薄片」）所使用的有機基質，可因應熱傳 導性樹脂薄片之機械強度、耐熱性、耐久性、柔軟性、可 撓性等之要求特性，自先前熱傳導性樹脂薄片中作爲有機 基質用之各種熱硬化性樹脂、熱塑性樹脂、熱塑性彈性體 等之中適當選用。此等有機基質可使用一種，或二種以上 組合使用，但本發明特別適用硬化性環氧樹脂及硬化性聚 砂氧院樹脂。 <硬化性環氧樹脂> 本發明之熱傳導性樹脂薄片中作爲有機基質用之硬化 性環氧樹脂，就陶瓷混合物相對於有機基質之分散性之觀 -15- 201215583 點較佳爲’常溫下液狀之環氧樹脂，及常溫下固體狀之低 軟化點環氧樹脂。 該硬化性環氧樹脂可爲，.一分子中具有2個以上環氧 基之化合物無特別限制，可自先前作爲環氧樹脂用之已知 化合物中適當選用任意之物。該類環氧樹脂如，雙酚A 型環氧樹脂、雙酚F型環氧樹脂、聚羧酸之縮水甘油醚、 環己烷衍生物藉由環氧化所得之環氧樹脂等。此等可單獨 使用一種，或二種以上組合使用。前述環氧樹脂中，就耐 熱性及作業性等之觀點較佳爲雙酚A型環氧樹脂、雙酚F 型環氧樹脂、環己烷衍生物藉由環氧化所得之環氧樹脂。 <環氧樹脂用硬化劑> 爲了硬化硬化性環氧樹脂，一般係使用環氧樹脂用硬 化劑。 該環氧樹脂用硬化劑無特別限制，可自先前作爲環氧 樹脂之硬化劑用之物中適當選用任意之物，例如胺系、苯 酚系、酸酐系等。 胺系硬化劑較佳如，二氰基二醯胺、m -伸苯基二胺、 4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基颯、m_二甲 苯二胺等之芳香族二胺等。 苯酚系硬化劑較佳如，苯酚酚醛清漆樹脂、甲酚酚醛 清漆樹脂、雙酚A型酚醛清漆樹脂、三嗪改性苯酚酚醛 清漆樹脂等。又，酸酐系硬化劑如，甲基六氫酞酸酐等之 脂環式酸酐、酞酸酐等之芳香族酸酐、二元脂肪族酸酐等 -16- 201215583 之脂肪族酸酐、氯菌酸酐等之鹵系酸酐等。 此等硬化劑可單獨使用一種，或二種以上組合使用。 該環氧樹脂用硬化劑之使用量，就硬化性與硬化樹脂物性 之平衡性等觀點，相對於前述硬化性環氧樹脂之當量比一 般選定爲0.5至1.5當量比，較佳爲0.7至1.3當量比。 <環氧樹脂用硬化促進劑> 本發明中，環氧樹脂用硬化劑於必要時可倂用環氧樹 脂用硬化促進劑。 該環氧樹脂用硬化促進劑無特別限制，可自先前作爲 環氧樹脂之硬化促進劑用之物中適當選用任意之物。例 如，2·乙基-4 -甲基咪唑、1-苄基-2 -甲基咪唑、2 -甲基咪 唑、2 -乙基咪唑、2 -異丙基咪唑、2 -苯基咪唑、2 -苯基_4· 甲基咪唑等之咪唑化合物、2,4,6-三（二甲基胺基甲基）苯 酚、三氟化硼胺錯合物、三苯基膦等。 此等硬化促進劑可單獨使用一種，或二種以上組合使 用。該環氧樹脂用硬化促進劑之使用量，就硬化促進性及 硬化樹脂物性之平衡性等觀點，相對於前述硬化性環氧樹 脂1〇〇質量份一般選定爲0.1至10質量份，較佳爲〇·4 至5質量份。 <硬化性聚矽氧烷樹脂> 硬化性聚矽氧烷樹脂可使用，加成反應Μ聚矽氧烷樹 脂與聚矽氧烷系交聯劑之混合物。加成反應型聚矽氧烷樹 -17- 201215583 脂如，自分子中具有官能基用之鏈烯基之聚有機矽氧烷中 所選出之至少1種。上述分子中具有官能基用之鏈烯基之 聚有機矽氧烷較佳如，以乙烯基爲官能基之聚二甲基矽氧 烷 '以己烯基爲官能基之聚二甲基矽氧烷及此等之混合物 聚矽氧烷系交聯劑如，一分子中具有至少2個矽與氫 鍵結所得之構造之聚有機矽氧烷。其具體例如，二甲基氫 二烯矽氧基末端封鏈二甲基矽氧烷-甲基氫二烯矽氧烷共 聚物、三甲基矽氧基末端封鏈二甲基矽氧烷-甲基氫矽氧 烷共聚物、三甲基矽氧烷基末端封鏈聚（甲基氫矽氧烷）、 聚（氫矽倍半噁烷）等。 又，硬化觸媒一般係使用鉑系化合物。該鉑系化合物 如，微粒子狀鉑、吸附於碳粉末載體之微粒子狀鉑、氯化 鉑酸、醇改質氯化鉑酸、氯化鈾酸之烯烴錯合物、鈀觸 媒、铑觸媒等。 (製作熱傳導性樹脂薄片） 本發明之熱傳導性樹脂薄片爲，使用有機基質與本發 明之陶瓷混合物，例如以下述方法製作。 首先將一定比例之球狀氧化鋁粒子，與鱗片狀六方晶 氮化硼粒子之混合物所形成之本發明之陶瓷混合物，分散 於適當溶劑中，調製濃度爲59至80質量％之陶瓷混合物 之懸浮液。 其次將有機基質加入該懸浮液中，使相對於該有機基 -18- 201215583 質與陶瓷混合物之合計量的前述陶瓷混合物之含 30至90體積％，調製樹脂組成物。 有機基質之主成分爲，使用硬化性環氧樹脂 硬化性環氧樹脂、環氧樹脂用硬化劑與必要時使 樹脂用硬化促進劑之混合物爲有機基質。 又，有機基質之主成分爲，使用硬化性聚矽 時係以加成反應型聚矽氧烷樹脂、聚矽氧烷系交 化觸媒之混合物爲有機基質。 熱傳導性塡充物係單獨使用球狀氧化鋁粒子 得到具有所希望之熱傳導性樹脂薄片，於有機基 需爲50體積％，較佳爲80體積％以上之高塡 因本發明之陶瓷混合物爲，球狀氧化鋁粒子與鱗 晶氮化硼粒子之混合物，故可以比使用球狀氧化 之塡充度發揮良好熱傳導性。 爲了得到更良好之熱傳導性，使陶瓷混合物 機基質與陶瓷混合物之合計量之含有比例爲30 3 %，或70至80體積％、75至80體積％時，可 優良之熱傳導率之熱傳導性樹脂薄片。 又，本發明中，陶瓷混合物、球狀氧化鋁粒 狀六方晶氮化硼粒子之體積基準之含有比例（體積 分率）可由，球狀氧化鋁粒子之比重（3.98)、鱗片 氮化硼粒子之比重（2.2 7)及所使用之各種樹脂， 取。 由上述調製所得之樹脂組成物中，有機基質 有比例爲 時係以骛 用之環氧 氧烷樹脂 聯劑與硬 時’爲了 質中至少 充度。但 片狀六方 鋁時更低 相對於有 [90體積 得具有更 子及鱗片 %、體積 狀六方晶 之比重求 及陶瓷混 19- 201215583 合物以外，必要時可含有其他添加劑。該其他添加劑如， 可塑劑、黏著劑、補強劑、著色劑、耐熱提升劑等。 樹脂組成物係藉由，以一般塗覆機等塗布於附離模層 之樹脂薄膜等之離模性薄膜等之上，利用遠紅外線輻射加 熱器、吹附溫風等乾燥而薄片化。 離模層係使用三聚氰胺樹脂等。又，樹脂薄膜係使用 聚對苯二甲酸乙二醇酯等之聚酯樹脂等。 另外有機基質爲硬化性基質時，前述所得之樹脂薄片 於必要時係藉由加壓下再加熱處理而硬化，得本發明之熱 傳導性樹脂薄片。 由此而得之本發明之熱傳導性樹脂薄片之厚度較佳爲 0.1 至 10mm，更佳爲 0.1 至 〇.3mm。 又，本發明之熱傳導性樹脂薄片中，熱傳導率較佳爲 3W/m· K以上，又以 7W/m. K以上爲佳，更佳爲 9W/m . K 以上。 又’絕緣破壞特性之指標之絕緣破壞電壓較佳爲 l_〇kV以上，更佳爲i.5kV以上。 本發明之熱傳導性樹脂薄片爲了提升作業性以及補強 目的’可於其單面、雙面或薄片內，層合或塡埋薄片狀、 纖維狀、網目狀構件。 由此而得之熱傳導性樹脂薄片可以’經剝離離模性薄 膜或以離模性薄膜爲保護薄膜之狀態’作爲供給熱傳導性 樹脂薄片使用之製品形態。 又’本發明之熱傳導性樹脂薄片可爲’熱傳導性樹脂 -20- 201215583 薄片之上面或下面另設置黏著性層而構成’如此可提高製 品使用時之便利性。 本發明之熱傳導性樹脂薄片係爲’將來自例如 MPU、動力電晶體、變壓器等之發熱性電子構件之熱傳熱 至散熱片或散熱風扇等之散熱構件用，挾持於發熱性電子 構件與散熱構件之間之物。藉此使發熱性構件與散熱構件 之間有良好傳熱性，可明顯減輕發熱性電子構件之錯誤動 作。 【實施方式】 實施例 其次將舉實施例更詳細說明本發明，但本發明非限定 於此等例。 又，球狀氧化鋁粒子及鱗片狀六方晶氮化硼粒子之體 積基準之D50，及各例所得之熱傳導性樹脂薄片之熱傳導 率係以下述方法測定。 (1) 球狀氧化鋁粒子及鱗片狀六方晶氮化硼粒子之體 積基準之D 5 0係以粒度分布計測定。其中鱗片狀六方晶 氮化硼粒子係使用西拉斯公司製，機種名「古拉紐7 1 5」 測定’氧化鋁係使用佩庫曼公司製，機種名 「Multisaizer」測定體積基準之〇50。 (2) 熱傳導性樹脂薄片之熱傳導率 使用艾菲滋（股）公司製’機種名「艾菲滋型」測定熱 擴散率後’乘以各自樹脂薄片之比熱與密度之理論値而算 -21 - 201215583 出之値。 實施例1至3 (1)調製含有有機基質與陶瓷混合物之樹脂組成物 有機基質係使用液狀硬化性環氧樹脂[日本環氧樹脂 公司製，商品名「jER828」、雙酚A型，環氧當量184-194g/eq，25°C之比重爲1.17]100質量份，與硬化劑爲咪 唑[四國化成公司製，商品名「2E4MZ-CN」]5質量份之倂 用物。又，陶瓷混合物係使用球狀氧化鋁粒子[昭和戴達 尼公司製，商品名「CB」]，與鱗片狀六方晶氮化硼粒子 [昭和電工公司製，商品名「UHP-1」，體積基準之D50 爲9μηι，長寬比（L: r)爲8: l(n = 30)]之質量比爲79:21 之混合物。 又，球狀氧化鋁粒子係各自使用體積基準之D50爲 Ιίμιη(記爲「A10S」）、28μπι 及 51μιη(記爲「A50S」）3 種 之物。又，如下述表1所示，以使用D50爲1 Ιμιη之球狀 氧化鋁粒子之例爲實施例1，使用D50爲28 μιη之球狀氧 化鋁粒子之例爲實施例2，使用D50爲5 1 μπι之球狀氧化 鋁粒子之例爲實施例3。 將前述陶瓷混合物 1〇〇質量份，與甲基乙基酮 (ΜΕΚ)45質量份（使用 A50S時）加入均化用不銹鋼製容器 中，於均化器內以轉速5 00 Orpm之條件攪拌混合2分鐘， 調製陶瓷混合物之懸浮液。（MEK係爲調整至塗布機可塗 布之黏度用，會因各自之系而使用量不同。以下有關 -22- 201215583 MEK之量將不記載）。 其次將前述有機基質加入該陶瓷混合物之懸浮液中， 使該有機基質中之陶瓷混合物含量爲70體積％後，有使 用均化器以轉速5000rpm之條件攪拌混合10分鐘，調製 樹脂組成物。 (2)製作熱傳導性樹脂薄片 使用塗布機將前述樹脂組成物以硬化膜厚爲500 μιη 以下之條件，塗布於寬10.5cm、長13cm之離模薄膜上， 靜置於設定爲4〇°C之乾燥機中30分鐘，蒸發溶劑MEK 進行乾燥，得3種薄片狀樹脂組成物。 其次各自介有另一離模薄膜，以120°C、IMPa之條 件壓合15分鐘，該3種薄片狀樹脂組成物，再硬化薄片 狀樹脂組成物，製作3種熱傳導性樹脂薄片。 測定所得之3種熱傳導性樹脂薄片之熱傳導率（30點 之平均値）。結果如下述表1所示。 實施例4、5 除了實施例1 (1)中，陶瓷混合物係使用球狀氧化鋁粒 子（前述）[體積基準之D50爲28μιη(實施例4)、51μιη(實施 例5)2種]，與鱗片狀六方晶氮化硼粒子（前述）之質量比爲 94: 6之混合物，且陶瓷混合物之含量爲全體之80體積 %外，進行同實施例1之操作，製作2種熱傳導性樹脂薄 片。 測定所得之2種熱傳導性樹脂薄片之熱傳導率，結果 -23- 201215583 如下述表1所示。 實施例6 除了實施例1 (1)中’陶瓷混合物係使用球狀氧化鋁粒 子（前述）[體積基準之D50爲51μιη]，與鱗片狀六方晶氮 化硼粒子（前述）之質量比爲94: 6之混合物，且陶瓷混合 物之含量爲全體之70體積％外，進行同實施例1之操 作，製作熱傳導性樹脂薄片。 測定所得之熱傳導性樹脂薄片之熱傳導率，結果如下 述表1所示。 實施例7 除了實施例1 (1)中，陶瓷混合物係使用球狀氧化鋁粒 子（前述）[體積基準之D50爲5 1 μιη] ’與鱗片狀六方晶氮 化硼粒子（前述）之質量比爲79 : 21之混合物，且陶瓷混 合物之含量爲全體之80體積％外’進行同實施例1之操 作，製作熱傳導性樹脂薄片。 測定所得之熱傳導性樹脂薄片之熱傳導率’結果如表 1所示。 -24- 201215583 表1 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 D50 (μηι) 球狀氧化 鋁粒子 11 28 51 28 51 51 51 鱗片狀六 方晶氮化 硼粒子 9 9 9 9 9 9 9 含有比※ (氧化鋁/氮化硼） 79/21 79/21 79/21 94/6 94/6 94/6 79/21 陶瓷混合物之含量 (體積％) 70 70 70 80 80 70 80 薄片之熱傳導率 (W/m · K) 3.4 5.9 9.1 5.3 7.1 5 10.2 ※含有比例爲體積基準（表3及5相同） 比較例1至4 (1)調製含有有機基質與球狀氧化鋁粒子之樹脂組成 物 除了實施例1(1)中，除了使用球狀氧化鋁粒子（前 述）[體積基準之D50爲Ιίμιη、21μπι(記爲「A20S」）、 28μιη、51μιη 4種]取代陶瓷混合物外，同實施例1(1)調製 球狀氧化鋁粒子之懸浮液。 又，如下述表2所示，以使用D5 0爲11 μιη之球狀氧 化鋁粒子之例爲比較例1，使用D5 0爲2 1 μιη之球狀氧化 鋁粒子之例爲比較例2，使用D50爲28μιη之球狀氧化鋁 粒子之例爲比較例3，使用D 5 0爲5 1 μιη之球狀氧化鋁粒 子之例爲比較例4。 其次除了將有機基質加入該球狀氧化鋁粒子之懸浮液 -25- 201215583 中，使該有機基質中之球狀氧化鋁粒子之含量爲80體積 %外，進行同實施例1 (1)之操作’調製4種樹脂組成物。 (2)製作熱傳導性樹脂薄片 使用前述（1)所得之4種樹脂組成物’進行同實施例 1 (2)之操作，製作4種熱傳導性樹脂薄片。 測定所得之4種熱傳導性樹脂薄片之熱傳導率，結果 如下述表2所示。 表2 比較例1 比較例2 比較例3 比較例4 D50 (μηι) 球狀氧化鋁粒子 11 21 28 51 陶瓷混合物之含量(體積％) 80 80 80 80 薄片之熱傳導率(W/m · Κ) 3.8 4.1 3.3 4.7 由表1及表2得知，以陶瓷混合物作爲熱傳導性塡充 物，所得的實施例1至7之本發明之熱傳導性樹脂薄片中 陶瓷混合物之塡充量各自爲70體積％、80體積％時，熱 傳導率爲3.4至l〇.2W/m· K。 相對地塡充80體積％之僅使用球狀氧化鋁粒子之熱 傳導性塡充材料所得的比較例之熱傳導性樹脂薄片中，熱 傳導率爲3.8至4.7 W/m · K。 比較球狀氧化鋁粒子之體積基準之D50爲28μίη及 5 1 μηι時之實施例與比較例之熱傳導性樹脂薄片的熱傳導 率，結果球狀氧化鋁粒子之體積基準之D50爲28 μηι時， 相對於實施例2及4之熱傳導率各自爲5·9 W/m · Κ及 -26- 201215583 5.3 W / m · Κ，比較例3爲3 · 3 W / m · Κ，比實施例低。 又，球狀氧化鋁粒子之體積基準之D5 0爲51 μιη時， 相對於實施例3及7之熱傳導率爲9.1 W/m . Κ及10.2 W/m · K，比較例4爲4.7W/m · K，明顯比實施例低。 因此球狀氧化鋁粒子與鱗片狀六方晶氮化硼粒子之混 合物之本發明之陶瓷混合物，比較單獨使用球狀氧化鋁粒 子時，可爲更優良之熱傳導性塡充物。 比較例5 (1) 調製含有有機基質與球狀氧化鋁粒子之樹脂組成 物 同比較例2(1)調製球狀氧化鋁粒子之懸浮液。 其次除了將有機基質加入該球狀氧化鋁粒子之懸浮液 中，使該有機基質中之球狀氧化鋁粒子含量爲7〇體積％ 外，進行同比較例2 ( 1 )之操作，調製樹脂組成物。 (2) 製作熱傳導性樹脂薄片 使用前述（1)所得之樹脂組成物，進行同比較例2(2) 之操作，製作熱傳導性樹脂薄片。'測定所得之熱傳導性樹 脂薄片之熱傳導率。結果如下述表3所示。 -27- 201215583 表3 比較例5 D50 (μηι) 球狀氧化鋁粒子 (A50S) 51 球狀氧化鋁粒子 (A10S) 11 含有比率 (A50S/A10S) 94/6 陶瓷混合物之含量(體積％) 70 薄片之熱傳導率(W/m · Κ) 5.3 比較例6 (1) 調製含有有機基質與鱗片狀六方晶氮化硼粒 樹脂組成物 除了實施例1 (1)中’僅使用鱗片狀六方晶氮化硼 (前述）[體積基準之D50爲9μπι]取代陶瓷混合物外， 施例1 (1)調製球狀氧化鋁粒子之懸浮液。 其次除了將有機基質加入該球狀氧化鋁粒子之懸 中，使該有機基質中之球狀氧化鋁粒子之含量爲7〇 %外，進行同實施例1 (1)之操作’調製樹脂組成物。 (2) 製作熱傳導性樹脂薄片 使用前述（1)所得之樹脂，組成物’進行同實施例 之操作，製作熱傳導性樹脂薄片。'測定所得之熱傳導 脂薄片之熱傳導率。結果如下述表4所示。 子之 粒子 同實 浮液 體積 1(2) 性樹 -28- 201215583 表4 比較例6 D50 (μιη) 鱗片狀六方晶氮 化硼粒子 9 陶瓷混合物之含量(體積％) 70 薄片之熱傳導率(W/m · Κ) 5.5 由表3及表4得知，取代氮化硼組合小粒徑之球狀氧 化鋁之物，及係以氮化硼爲塡充物，幾乎無法改善熱傳導 性。 比較例7 除了實施例3中，陶瓷混合物係使用球狀氧化鋁粒子 (前述）[體積基準之D50爲51μιη]，與鱗片狀六方晶氮化 硼粒子（前述）之質量比爲97 : 3之混合物，且陶瓷混合物 之含量爲全體之7 〇體積％外，進行同實施例1之操作， 製作熱傳導性樹脂薄片。 測定所得之熱傳導性樹脂薄片之熱傳導率，結果如下 述表5所示。 表5 比較例7 D50 (μπι) 球狀氧化鋁粒子 51 鱗片狀六方晶氮 化硼粒子 9 含有比例(氧化鋁/氮化硼） 97/3 陶瓷混合物之含量(體積％) 70 薄片之熱傳導率(W/m · Κ) 5.5 -29 - 201215583 由表5得知’氮化硼之質量比未達本申請書之下限値 之3質量％者，將無法改善熱傳導率。 實施例8至14及比較例8至1 1 (1 )調製含有有機基質及陶瓷混合物之樹脂組成物 有機基質係使用液狀硬化性環氧樹脂[日本環氧樹脂 公司製’商品名「耶皮可828」，雙酚A型]100質量份， 與硬化劑用之1-氰基乙基-2-甲基咪唑[四國化成公司製， 商品名「裘艾左2PN-CN」]1質量份之倂用物。又，陶瓷 混合物係使用下述表6所記載之粒子。 將前述陶瓷混合物（依下述表7所示添加），與甲基乙 基酮（MEK) 101質量份加入均化用不銹鋼製容器中，於均 化器內以轉速5000rpm之條件攪拌混合2分鐘，調製陶瓷 混合物之懸浮液。 其次將前述有機基質加入該陶瓷混合物之懸浮液中， 使該有機基質中之陶瓷混合物含量如下述表6所示之量， 再使用均化器以轉速5 OOOrpm之條件攪拌混合10分鐘， 調製樹脂組成物。 (2)製作熱傳導性樹脂薄片 將與上述熱硬化性樹脂組成物同體積之〇!^爲5μιτι之 粒子狀氮化矽塡充劑{SN-7，電氣化學工業（股）}加入上述 熱硬化性樹脂組成物之溶液中進行預混。其後使用三座滾 軸混練該預混物，得上述熱硬化性樹脂組成物之溶液中均 -30- 201215583 勻分散上述塡充劑之複合物。 其次以刮刀法將上述複合物塗布於厚100μηι之單面 經離模處理之聚對苯二甲酸乙二醇酯薄片之離模處理面 上，再以110°c加熱乾燥處理15分鐘，製作厚80μιη之Β 級狀態之熱傳導性樹脂薄片。 接著以1 2 0 °C 1小時與1 6 0 °C 3小時之條件加熱上述熱 傳導性樹脂薄片，製作熱傳導性樹脂薄片。 同實施例1等測定所得之熱傳導性樹脂薄片之熱傳導 率（3 0點之平均値）。結果如下述表6所示。 -31 - 201215583 比較例 11 i Os 0/100 0/100 〇 寸 比較例 10 1 100/0 100/0 〇 <N — 比較例 9 00 (N 1 100/0 100/0 〇 — 比較例 8 1 100/0 100/0 〇 <N cn 實施例 14 «ο 〇\ 68/32 79/21 〇 實施例 13 00 (Ν Os 68/32 79/21 〇 ON uS 實施例 12 σ\ 68/32 79/21 〇 寸 ΓΟ 實施例 11 as 80/20 88/12 〇 實施例 10 90/10 94/6 〇 實施例 9 00 <Ν 90/10 94/6 〇 CN 實施例 8 90/10 94/6 〇 m ΓΟ 球狀氧化鋁 粒子 mg 籙喊 ^ S ^ ffiW 另輕鹦_ IKE DC · · · · § ^ ^ 陶瓷混合物之含量 (體積％) 薄片之熱傳導率 (W/m · K) D50 (μιη) -32- 201215583 評估熱傳導性樹脂薄片之絕緣破壞特性 以接著面積爲30x30mm2之條件將熱傳導性樹脂薄片 接著於銅板（40x40x5mm3)與鋁板（30x30x5mm3)之間製作試 驗片。依 JIS C 2110之耐電壓試驗方法’以規定電壓 1 . 5 k V、規定時間6 0秒之條件測定試驗片。未絕緣破壞者 爲合格（〇），經絕緣破壞者爲不合格（X) ° 又，依實施例1 ’以下述表7所示之添加率各自製作 熱傳導性樹脂薄片。同實施例1測定熱傳導性樹脂薄片之 熱傳導率，結果如下述表7所示。 -33- 201215583 表7 陶瓷幻 昆合物 氧化鋁/ 氮化硼 碳化砂/ 氮化硼 熱傳導性樹脂薄 片之各成分之添 加率 質量分率 (體積分率） (%) 球狀氧化鋁粒子 (A50S) 69(48) 0(0) 碳化矽粒子 〇(〇) 64(48) 鱗片狀六方晶 氮化硼粒子 (UHP-1) 18(22) 21(22) 有機成分 (樹脂、其他） 13(30) 15(30) 合計 100(100) 100(100) 熱傳導性樹脂薄 片之陶瓷添加率 質量分率 (體積分率） (%) 球狀氧化鋁粒子 (A50S) 79(68) 0⑼ 碳化矽粒子 〇(〇) 75(68) 鱗片狀六方晶 氮化硼粒子 (UHP-1) 21(32) 25(32) 合計 100(100) 100(100) 絕緣破壞特性 〇 X 薄片之熱傳導率(W/m · K) 8.3 5.2 ※碳化矽粒子爲使用富吉米（股）公司製之商品名 「GC#500」。 ※各成分之添加率中（）之數値係爲體積分率。 產業上利用可能性 本發明之陶瓷混合物適用爲熱傳導性塡充物。又，使 用該熱傳導性塡充物所得之本發明之熱傳導性樹脂薄片可 作爲，自例如MPU及動力電晶體、變壓器等之發熱性電 -34- 201215583 子構件將熱傳熱至散熱風扇及散熱片等之散熱構件用。 又，熱傳導性樹脂薄片之絕緣破壞特性良好，因此可充分 對應電子機器等伴隨小型化之熱傳導性樹脂薄片薄膜化。 【圖式簡單說明】 圖1爲，說明鱗片狀六方晶氮化硼粒子之「鱗片狀」 形態之圖，圖1(A)爲平面圖，圖1(B)爲圖1(A)中X-X剖 面圖。 【主要元件符號說明】 1 〇 :鱗片狀六方晶氮化硼粒子 L :長徑 r :厚度 -35-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic mixture and a thermally conductive resin sheet containing the ceramic. More specifically, the present invention relates to a ceramic mixture for imparting a high heat conductive resin sheet, and a ceramic conductive mixture, which is used to transfer heat from a heat generating body to a heat conductive resin sheet for a heat radiating member, particularly a semiconductor element or the like. The heat-generating resin sheet for the heat conductive resin layer having the function of the insulating layer is transmitted to the heat radiating member. [Prior Art] In recent years, it has been demanded to increase the degree of integration of electronic components such as 1C used in various electronic devices. In addition, when electronic components such as ICs are placed in a small space at a high density in accordance with the demand for miniaturization of electronic equipment and the like, heat dissipation measures against heat generation in the casing are a big problem. In other words, the electronic component such as 1C changes the characteristics of the electronic component due to an increase in temperature, causing a malfunction of the machine and causing the electronic component itself to malfunction. In addition, the amount of heat generated by semiconductor displays such as CPUs that are being developed with high speed has increased, and devices such as various electronic devices have been reduced in size and thickness. Therefore, in order to maintain its performance and function, it is necessary to fully remove the heat generated, and an efficient heat dissipation system is required. The thermal conductivity of a thermally conductive resin layer that transmits heat to a heat-dissipating member of an electric or electronic device to a heat-dissipating member is required to have high thermal conductivity, insulation, and bonding properties, and thermal conductivity obtained by adding an inorganic filler to a thermosetting resin -5 - 201215583 Resin composition. For example, a known power module is provided on a back surface of a conductor frame on which a power semiconductor element is mounted, a thermally conductive resin layer between a metal plate constituting a heat dissipation portion, and a thermosetting resin sheet containing an inorganic filler and coating. A technique of a film (for example, refer to Patent Document 1). In addition, it is known that a thermally conductive resin layer interposed between a heat-generating electronic component such as a CPU and a heat sink is a thermosetting resin sheet obtained by charging a high thermal conductivity inorganic powder (for example, refer to Patent Document 2). As disclosed in Patent Document 2, the spherical alumina particles for inorganic powders are easily dispersed and highly entangled, so that they are very suitable as thermally conductive fillers for use in thermally conductive sheets. Therefore, it has been reviewed to combine the contents obtained by combining other thermally conductive chelates and to change the organic matrix so that the thermally conductive entangled material has higher enthalpy and high thermal conductivity (for example, refer to Patent Documents 3 and 4). Patent Document 5 discloses that an inorganic powder which exhibits high heat dissipation characteristics is formed of a mixed powder containing an inorganic powder and an aspherical inorganic powder having an average particle diameter smaller than the spherical inorganic powder, and an average particle diameter of 5 to 5 Ομηι Inorganic powder. However, in the actual evaluation, it is still undetermined whether the combination selected from cerium oxide, aluminum oxide, cerium carbide and aluminum nitride can obtain the same effect as other inorganic powders. Further, when the filler having a high specific gravity such as alumina is highly filled, the thermally conductive resin sheet itself is increased, and it is difficult to cope with the problem of miniaturization and weight reduction of an electronic device or the like. In addition, with the miniaturization of electronic equipment and the like, it is possible to reduce the dielectric breakdown characteristics when the thermal conductive resin sheet is thinned. Further, aluminum nitride having high heat -6 - 201215583 conductivity is difficult to handle with respect to moisture in the atmosphere, and is expensive, and the same high thermal conductivity of carbonized tantalum has a problem of poor insulation damage characteristics. For example, Patent Document 6 discloses that a tantalum nitride having a particle diameter of 5 μm and a boron nitride having a particle diameter of 7 μm are used as a thermally conductive resin sheet, but since the particle size of tantalum nitride is too small, it is difficult to uniformly disperse. It may not be possible to get the effect of the effect. Further, this document also discloses a thermally conductive resin sheet of tantalum carbide and boron nitride, but the insulation failure characteristics of the tantalum carbide system are inferior. Patent Document 1: JP-A-2001-196495 Patent Document 2: JP-A-2003-253136 Patent Document 3: Japanese Patent Laid-Open Publication No. Hei No. Hei No. 1 - 8 7 9 5 8 Patent Document 4: Japanese Patent Laid-Open The present invention is an invention completed in this state, and the subject matter to be solved by the present invention is as follows: Patent Document 5: JP-A-2007-70474. The purpose of the invention is to provide a ceramic mixture of a thermally conductive resin sheet which can provide a thermal conductivity which is superior to the prior art, and which can reduce the weight of the sheet, and which has excellent processability and excellent dielectric breakdown properties, and has a ceramic mixture. A thermally conductive resin sheet containing a ceramic mixture of the above characteristics. 201215583 Method for Solving the Problem The present inventors discovered the following findings after focusing on the above-mentioned objectives. First, the scaly hexagonal boron nitride particles are those having high thermal conductivity, but are not easily dispersed in the organic matrix, and have the disadvantage of poor workability. Therefore, by mixing the spherical alumina particles having good fluidity, the scaly hexagonal boron nitride particles are easily dispersed, and the workability can be improved. Further, the scaly hexagonal boron nitride particles have high thermal conductivity in the surface direction, and spherical alumina particles are used as the aggregate, and the thermal conductivity can be obtained by aligning them in the thickness direction of the thermally conductive sheet. Further, since aluminum carbide is used without using carbonization defects having poor dielectric breakdown characteristics, excellent dielectric breakdown characteristics can be obtained. According to the above findings, when a scaly hexagonal boron nitride particle having a specific particle diameter is contained in a certain ratio and a ceramic mixture obtained from spherical alumina particles having a specific particle diameter is used as a thermally conductive entangled material, even if it is used alone By using the alumina particles and the boron nitride particles, it is possible to obtain a thermally conductive resin sheet which has a thermal conductivity higher than that of the prior art and which is light in weight and excellent in workability. That is, the present invention is as follows. [1] A ceramic mixture which is a volume-based D50 (50 vol% particle diameter) of spherical alumina particles of 10 to 55 μm, and a volume-based D50 of scaly hexagonal boron nitride particles of 30 μm or less. The mixture is characterized in that the content of the scaly hexagonal boron nitride particles is from 5 to 30% by mass. [2] The ceramic mixture according to [1], wherein the scaly hexagonal nitrogen 201215583 boronized particles have a D50 of 5 to 30 μm. [3] A ceramic-containing thermally conductive resin sheet characterized by containing from 1 to 7 vol% of the organic matrix, and from 30 to 90% by volume of the ceramic mixture described in [1] or [2] The resin composition is molded. [4] The thermally conductive resin sheet containing ceramics according to [3], wherein a D50 of a volume basis of the spherical alumina is 3 to a volume basis of a volume basis of the scaly hexagonal boron nitride particles 7 times. [5] The thermally conductive resin sheet containing ceramics according to [3], wherein the volume of the spherical alumina particles in the ceramic mixture is D50 of 45 to 55 μm, and the ceramic mixture is in the resin composition. The content ratio in the medium is 70 to 80% by volume. [6] The ceramic-containing thermally conductive resin sheet according to [5], wherein the content of the scaly hexagonal boron nitride particles in the ceramic mixture is 6 to 25 mass%, and the ceramic mixture is in the resin The content ratio in the composition is from 75 to 80% by volume. [7] The thermally conductive resin sheet containing ceramics according to [6], wherein the thermal conductivity is 7 W/m·Κ or more. [8] The ceramic-containing thermally conductive resin sheet according to [5], wherein a content ratio of the scaly hexagonal boron nitride particles in the ceramic mixture is 15 to 25 mass%, and the ceramic mixture is in the resin The content ratio in the composition is from 70 to 80% by mass. [9] The thermally conductive resin sheet containing ceramics according to [8], wherein the thermal conductivity is 9 W/m·K or more. The ceramic-containing heat transfer 201215583 conductive resin sheet as described in any one of [4] to [9] wherein the organic matrix contains a hardening grease. [11] The ceramic-containing resin sheet as described in any one of [4] to [9] wherein the organic substrate contains a curable resin. Advantageous Effects of Invention The present invention can provide a ceramic mixture of a thermally conductive resin sheet which is lighter in weight than a conventionally preferred heat transfer sheet, has excellent processability, and is excellent in extrinsability, and has the above characteristics in a mixture. Thermally conductive resin sheet. Mode for Carrying Out the Invention First, the ceramic mixture of the present invention will be explained. [Ceramic Mixture] The ceramic mixture of the present invention is provided with a heat conductive filler for a resin sheet having a lighter weight than that of the prior art and having a light weight of the sheet, and having a volume basis of 10 to The mixture of the spherical alumina particles of 55 μm and the volume basis; and the mixture of the scaly hexagonal boron nitride particles of 300 μm or less is such that the content ratio of the scaly hexagonal boron nitride particles is 3% by mass. The thermal conductivity of the epoxy resin is higher than that of the oxygen, and the same edge is destroyed by the heat of the ceramic. The D50 of D50 is characterized by 5 to 30 -10- 201215583 (spherical alumina) Particles: The alumina particles constituting one of the two components of the ceramic mixture of the present invention are spherical or non-spherical materials having good thermal conductivity. In the ceramic mixture of the present invention, the scaly hexagonal boron nitride particles described later in the other component are less likely to be dispersed in the organic matrix, and the alumina particles are spherical alumina particles having good fluidity. The spherical alumina particles refer to a powder in which the shape of the particles in the alumina powder is spherical or even spherical. Further, in the present invention, "spherical" is evaluated by an average sphericity. The average sphericity can be measured by the following method using, for example, a flow type particle image analyzer of a product name "FPIA-1 0000" manufactured by Seiko Co., Ltd. First, the projected area (A) and circumference (PM) of the particles are measured from the particle image. When the true circular area of the corresponding perimeter (PM) is (B), the sphericity of the particle can be expressed as a/B. It is also assumed to be a true circle having the same circumference as the circumference (PM) of the sample particle. = 2 π r, Β = π r2, therefore, it is redundant (ΡΜ/2 7Γ )2, so the sphericity of each particle can be calculated by sphericity = Α / Β = Αχ 4 7 Γ (PM) 2. The measurement is arbitrarily selected. The average enthalpy of the 00 or more particles is the average sphericity. The "spherical shape" of the present invention may be such that the sphericity is in the range of 0.93 to 1.00, and if it is specified as a spherical or spherical shape in a general commercial product. The object is in line with this range. The D50 of the volume reference of the spherical alumina particles is preferably from 10 to 55 μm, preferably from 25 to 55 μm, from the viewpoint of the dispersibility of the organic matrix of the ceramic mixture and the twinning of the obtained thermally conductive resin sheet. Good for 45 to 55 μιη. Further, it is preferable that the above-mentioned viewpoint is a spherical -11 - 201215583 alumina particle having a remarkable particle size distribution. Further, the D50 of the volume standard of the present invention can be measured by a Coulter counter method or a laser diffraction scattering method. For example, spherical alumina particles are preferably measured by a Coulter counter method, and scaly hexagonal boron nitride particles are preferably measured by a laser diffraction scattering method. (Scale-like hexagonal boron nitride particles) The scaly hexagonal boron nitride particles constituting the other component of the ceramic mixture of the present invention are used, and the D50 of the volume standard is 30 μm or less. When the D50 of the volume standard exceeds 30 μm, the scaly particles in the organic matrix are easily aligned in the direction of the thickness, so that the obtained thermally conductive resin sheet is less likely to have a desired thermal conductivity. The volume basis of the scaly hexagonal boron nitride particles preferably has a D50 of 5 to 30 μm, more preferably 5 to 15 μm. When the D50 of the volume standard is less than 5 μm, the viscosity of the resin composition containing the organic matrix and the ceramic mixture is increased, and the workability is lowered. When the D50 of the volume standard is not more than 30 μm, it is obtained by using scaly hexagonal boron nitride particles having a relatively large volume of D50, and at least the interface between the particles is more likely to convey the effect of heat. The "scaly" at this time means that the long diameter L of the scaly hexagonal boron nitride particle 10 is as shown in the plan view of Fig. 1 (Α), and the Χ-Χ cross-sectional view of Fig. 1(A) (Fig. 1) (B)) The ratio of the thickness r (average thickness) of the particles 10 (the aspect ratio (L: r) is 5:1 to 20:1. The scaly hexagonal boron nitride contains a large amount. In the case of an impurity (for example, B2〇3) -12 to 201215583, the use of an organic substrate required for hardening may become a factor that hinders hardening. Further, it may become a factor for lowering the thermal conductivity of the obtained thermally conductive resin sheet. Therefore, in view of this, the scale The content of the impurity B2〇3 which is inevitably mixed in the hexagonal crystal boron nitride is preferably from 〇.〇1 to 0.1% by mass, more preferably from 0.01 to 0.05% by mass. The scaly hexagonal crystal in the ceramic mixture of the present invention The content of the boron nitride particles needs to be 5 to 30% by mass. When the content exceeds 30% by mass, the viscosity of the resin composition containing the organic matrix and the ceramic mixture is increased, which is a factor for lowering workability. The boron nitride particles are high-priced materials', so their content exceeds 30% by mass. In view of the above, the content of the scaly hexagonal boron nitride particles in the ceramic mixture is preferably 30% by mass or less. Further, when it is less than 5% by mass, excellent thermal conductivity cannot be imparted. It is preferably 6 to 25 mass%, more preferably 1 〇 to 2 5 mass%, still more preferably 15 to 25 mass%, particularly preferably 18 to 25 mass% » spherical alumina particles The D50 of the volume reference D50 is preferably 3 to 7 times, more preferably 4 to 6 times, relative to the volume basis of the scaly hexagonal boron nitride particles. When 3 to 7 times, the spherical alumina particles are used alone. When scaly hexagonal boron nitride particles are used alone, high thermal conductivity can be obtained. In order to improve the dispersibility of the spherical alumina particles and the scaly hexagonal boron nitride particles with respect to the organic matrix, it is necessary to have workability and the like. The surface treatment can be carried out by using various coupling agents, etc. • 13-201215583 (coupling agent) A coupling agent such as a decane type or a titanate type 'aluminum type, etc., and among them, a decane type coupling agent and a decane type couple are preferable. It is especially good to use r-aminopropyl trimethyl Baseline, r-aminopropyltriethoxydecane, r-(2-aminoethyl)aminopropyltrimethoxydecane, r-(2-aminoethyl)aminopropyltriethyl Oxydecane, r-anilinopropyltrimethoxydecane, r-anilinopropyltriethoxydecane, N-/3-(N-vinylbenzylaminoethyl)-r-aminopropyl Aminodecane compounds such as trimethoxymethoxynonane and vinylbenzylaminoethyl)-r-aminopropyltriethoxydecane. Next, a ceramic-containing thermally conductive resin sheet of the present invention will be described. [Ceramic-Conducting Thermal Conductive Resin Sheet] The ceramic-containing thermally conductive resin sheet of the present invention is characterized in that it is composed of a resin composition containing 10 to 70% by volume of the organic substrate and 30 to 90% by volume of the ceramic mixture of the present invention. Molded. When the ceramic mixture exceeds 90% by volume (the organic substrate is less than 10% by volume), the resin composition is difficult to form due to too little organic matrix. When the ceramic mixture is less than 30% by volume (the organic matrix exceeds 90% by volume), the organic matrix is The ruthenium will be difficult to contact with each other, which will reduce the thermal conductivity and make it difficult to obtain the thermal conductivity necessary for heat dissipation. The ceramic-containing thermally conductive resin sheet of the present invention preferably has any of the following first aspect and second aspect in terms of excellent thermal conductivity, light weight loss, good workability, and dielectric breakdown characteristics. -14- 201215583 That is, the first aspect is that the content ratio of the scaly hexagonal boron nitride particles in the ceramic mixture is 6 to 25 mass%, and the content of the ceramic mixture in the resin composition is 75 to 80% by volume of a ceramic-containing thermally conductive resin sheet. This aspect allows the thermal conductivity to be 7 W/m · K or more. Further, in the second aspect, the content ratio of the scaly hexagonal boron nitride particles in the ceramic mixture is 15 to 25 mass%, and the content of the ceramic mixture in the resin composition is 70 to 80 % of a thermally conductive resin sheet containing ceramics. This aspect allows the thermal conductivity to be 9 W/m · K or more. (Organic Substrate) The organic matrix used for the ceramic-containing thermally conductive resin sheet (hereinafter referred to simply as "thermally conductive resin sheet") can be used for mechanical strength, heat resistance, durability, and flexibility of the thermally conductive resin sheet. The required properties such as flexibility and the like are appropriately selected from various thermosetting resins, thermoplastic resins, thermoplastic elastomers and the like used as an organic substrate in the conventional thermally conductive resin sheet. These organic substrates may be used alone or in combination of two or more, but the present invention is particularly suitable for a curable epoxy resin and a curable polyoxygen resin. <Curable Epoxy Resin> The curable epoxy resin used as the organic matrix in the thermally conductive resin sheet of the present invention preferably has a viewpoint of dispersibility of the ceramic mixture with respect to the organic substrate -15 - 201215583 A liquid epoxy resin and a solid low-softening point epoxy resin at room temperature. The curable epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, and any of the known compounds previously used as the epoxy resin can be appropriately selected. Such epoxy resins are, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ethers of polycarboxylic acids, epoxy resins obtained by epoxidation of cyclohexane derivatives, and the like. These may be used alone or in combination of two or more. Among the above-mentioned epoxy resins, an epoxy resin obtained by epoxidation is preferred from the viewpoints of heat resistance, workability, and the like, as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a cyclohexane derivative. <Hardware for Epoxy Resin> In order to cure the curable epoxy resin, a hardener for epoxy resin is generally used. The curing agent for the epoxy resin is not particularly limited, and may be any one selected from the prior art as a curing agent for an epoxy resin, for example, an amine type, a phenol type, an acid anhydride type or the like. The amine hardener is preferably, for example, dicyanodiamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylphosphonium, m An aromatic diamine such as xylene diamine or the like. The phenolic curing agent is preferably, for example, a phenol novolak resin, a cresol novolac resin, a bisphenol A novolak resin, a triazine-modified phenol novolac resin or the like. Further, the acid anhydride-based curing agent is an alicyclic acid anhydride such as methyl hexahydrophthalic anhydride, an aromatic acid anhydride such as phthalic anhydride, a dibasic aliphatic acid anhydride or the like, an aliphatic acid anhydride such as -16 to 201215583, or a halogen such as chloric acid anhydride. An acid anhydride or the like. These hardeners may be used alone or in combination of two or more. The equivalent amount of the curable epoxy resin is generally selected to be 0.5 to 1.5 equivalent ratio, preferably 0.7 to 1.3, in terms of the amount of the curing agent for the epoxy resin, and the balance between the curability and the physical properties of the cured resin. Equivalent ratio. <Curing Agent for Epoxy Resin> In the present invention, a curing agent for an epoxy resin may be used as a curing accelerator for an epoxy resin if necessary. The hardening accelerator for the epoxy resin is not particularly limited, and any of them may be appropriately selected from those previously used as a hardening accelerator for an epoxy resin. For example, 2·ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 2 - an imidazole compound such as phenyl_4. methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, a boron trifluoride complex, triphenylphosphine or the like. These hardening accelerators may be used alone or in combination of two or more. The amount of the curing accelerator for the epoxy resin is preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass, per part by mass of the curable epoxy resin, from the viewpoints of the balance between the curing property and the physical properties of the cured resin. It is 4 to 5 parts by mass. <Curable Polyoxyalkylene Resin> A curable polydecane resin can be used, and an addition reaction is a mixture of a polyoxyalkylene resin and a polyoxyalkylene crosslinking agent. The addition reaction type polyoxyalkylene tree -17-201215583 is at least one selected from the group consisting of polyorganosiloxanes having an alkenyl group for a functional group in the molecule. The polyorganosiloxane having an alkenyl group for a functional group in the above molecule is preferably, for example, a polydimethylsiloxane having a hexenyl group as a functional group. Alkane and a mixture of such polyoxyalkylene-based crosslinking agents, for example, a polyorganosiloxane having a structure in which at least two anthracene and hydrogen are bonded in one molecule. Specifically, for example, a dimethylhydrogendienyloxy end-terminated dimethyl methoxy oxane-methylhydrodiene decane copolymer, a trimethyl decyloxy terminal dimethyl methoxy oxane- A methylhydroquinone copolymer, a trimethylphosphonium alkyl terminal-blocked poly(methylhydroquinone), a poly(hydroquinone sesquioxane), or the like. Further, the curing catalyst generally uses a platinum compound. The platinum-based compound is, for example, microparticulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified platinic acid, an olefin complex of uranium chloride, a palladium catalyst, and a touch Media and so on. (Production of thermally conductive resin sheet) The thermally conductive resin sheet of the present invention is produced by using the organic substrate and the ceramic mixture of the present invention, for example, by the following method. First, a ceramic mixture of the present invention formed by mixing a certain proportion of spherical alumina particles with scaly hexagonal boron nitride particles is dispersed in a suitable solvent to prepare a suspension of a ceramic mixture having a concentration of 59 to 80% by mass. liquid. Next, an organic substrate is added to the suspension to prepare a resin composition in an amount of 30 to 90% by volume based on the total amount of the above-mentioned ceramic mixture of the organic group -18-201215583 and the ceramic mixture. The main component of the organic matrix is an organic matrix using a curable epoxy resin curable epoxy resin, a curing agent for an epoxy resin, and a curing accelerator for a resin if necessary. Further, the main component of the organic matrix is an organic matrix in which a mixture of an addition reaction type polyoxane resin and a polyoxyalkylene type crosslinking catalyst is used in the case of using a curable polyfluorene. The thermally conductive chelating agent is obtained by using spherical alumina particles alone to obtain a desired heat conductive resin sheet, and the organic group needs to be 50% by volume, preferably 80% by volume or more, because the ceramic mixture of the present invention is Since the mixture of the spherical alumina particles and the smectite boron nitride particles can exhibit good thermal conductivity than the use of spherical oxidation. In order to obtain better thermal conductivity, the content of the ceramic mixture machine matrix and the ceramic mixture is 30%, or 70 to 80% by volume, and 75 to 80% by volume, and the thermal conductivity resin having excellent thermal conductivity is obtained. Sheet. Further, in the present invention, the volume ratio of the ceramic mixture and the spherical alumina granular hexagonal boron nitride particles (volume fraction) may be, the specific gravity of the spherical alumina particles (3.98), and the scale boron nitride particles. The specific gravity (2.2 7) and the various resins used are taken. In the resin composition obtained by the above-mentioned preparation, the ratio of the organic matrix is such that the epoxy oxyalkylene resin is used in combination with the hard aging to at least charge. However, in the case of flaky hexagonal aluminum, it may contain other additives as necessary, in addition to having a specific gravity of 90% and having a volume of hexagonal crystals and a ceramic mixture of 19-201215583. The other additives are, for example, plasticizers, adhesives, reinforcing agents, colorants, heat-resistant enhancers, and the like. The resin composition is applied to a release film or the like of a resin film or the like which is attached to the mold layer by a general coating machine or the like, and is dried by a far-infrared radiant heater or a blown warm air. A melamine resin or the like is used as the release layer. Further, as the resin film, a polyester resin such as polyethylene terephthalate or the like is used. When the organic substrate is a curable matrix, the resin sheet obtained as described above is cured by reheating under pressure, if necessary, to obtain a thermally conductive resin sheet of the present invention. The thickness of the thermally conductive resin sheet of the present invention thus obtained is preferably from 0.1 to 10 mm, more preferably from 0.1 to 3.3 mm. Further, in the thermally conductive resin sheet of the present invention, the thermal conductivity is preferably 3 W/m·K or more, more preferably 7 W/m·K or more, and still more preferably 9 W/m·K or more. Further, the dielectric breakdown voltage of the index of the dielectric breakdown characteristic is preferably l_〇kV or more, more preferably i.5 kV or more. The thermally conductive resin sheet of the present invention can laminate or bury a sheet-like, fibrous or mesh-like member on one side, both sides or in a sheet for the purpose of improving workability and reinforcement. The thermally conductive resin sheet thus obtained can be used as a product for supplying a thermally conductive resin sheet in a state in which the release film is peeled off or the release film is used as a protective film. Further, the thermally conductive resin sheet of the present invention may be formed by providing an adhesive layer on the upper or lower side of the sheet of the "thermal conductive resin -20-201215583". Thus, the convenience in use of the article can be improved. The heat conductive resin sheet of the present invention is a heat dissipating member that transfers heat from a heat generating electronic component such as an MPU, a power transistor, or a transformer to a heat sink or a heat radiating fan, and is held by the heat generating electronic component and the heat sink. The object between the components. Thereby, good heat transfer between the heat generating member and the heat radiating member is achieved, and the malfunction of the heat generating electronic member can be remarkably reduced. [Embodiment] EXAMPLES Next, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Further, D50 of the volume basis of the spherical alumina particles and the scaly hexagonal boron nitride particles, and the thermal conductivity of the thermally conductive resin sheet obtained in each of the examples were measured by the following methods. (1) The volume of the spherical alumina particles and the scaly hexagonal boron nitride particles is measured by a particle size distribution meter. The scaly hexagonal boron nitride particles were manufactured by Silas, and the model name "Gulain 7 1 5" was measured. 'The alumina system was made by Pekkaman, and the model name "Multisaizer" was used to measure the volume basis. . (2) The thermal conductivity of the heat-conductive resin sheet is measured by multiplying the specific heat and density of the respective resin sheets by measuring the thermal diffusivity of the model name "Effie type" manufactured by Philippine Co., Ltd. - 201215583 Out of the box. Examples 1 to 3 (1) Preparation of a resin composition containing an organic matrix and a ceramic mixture The organic matrix is a liquid curable epoxy resin [manufactured by Nippon Epoxy Co., Ltd., trade name "jER828", bisphenol A type, ring The oxygen equivalent is 184-194 g/eq, and the specific gravity at 25 ° C is 1.17] 100 parts by mass, and the curing agent is an amount of 5 parts by mass of an imidazole [manufactured by Shikoku Kasei Co., Ltd., trade name "2E4MZ-CN"). In addition, spherical alumina particles (trade name "CB" manufactured by Showa Daidani Co., Ltd.) and scaly hexagonal boron nitride particles (product name "UHP-1" manufactured by Showa Denko Co., Ltd.) are used for the ceramic mixture. The reference has a D50 of 9μηι and an aspect ratio (L: r) of 8: l (n = 30)] with a mass ratio of 79:21. Further, each of the spherical alumina particles is a volume-based D50 of Ιίμιη (referred to as "A10S"), 28μπι and 51μιη (denoted as "A50S"). Further, as shown in the following Table 1, an example in which spherical alumina particles having a D50 of 1 μm is used is the first embodiment, and a spherical alumina particle having a D50 of 28 μm is used as the example 2, and the D50 is 5 An example of the spherical alumina particles of 1 μm is Example 3. 1 part by mass of the above ceramic mixture, and 45 parts by mass of methyl ethyl ketone (ΜΕΚ) (in the case of using A50S) were placed in a stainless steel container for homogenization, and stirred and mixed in a homogenizer at a rotation speed of 500 rpm. A suspension of the ceramic mixture was prepared for 2 minutes. (MEK is used for adjusting the viscosity that can be applied to the coater. It will be used differently depending on the system. The following -22-201215583 MEK will not be recorded). Next, the organic substrate was added to the suspension of the ceramic mixture so that the content of the ceramic mixture in the organic substrate was 70% by volume, and the mixture was stirred and mixed for 10 minutes at a rotational speed of 5000 rpm using a homogenizer to prepare a resin composition. (2) Preparation of thermally conductive resin sheet The resin composition was applied to a release film having a width of 10.5 cm and a length of 13 cm under the conditions of a cured film thickness of 500 μm or less using a coater, and was set to 4 ° C. In a drier for 30 minutes, the solvent MEK was evaporated and dried to obtain three kinds of flaky resin compositions. Next, each of the release film was interposed, and the three kinds of flaky resin compositions were pressed at 120 ° C and 1 MPa for 15 minutes to cure the sheet-like resin composition, thereby producing three kinds of thermally conductive resin sheets. The thermal conductivity (average enthalpy of 30 points) of the obtained three kinds of thermally conductive resin sheets was measured. The results are shown in Table 1 below. Examples 4 and 5 In the example 1 (1), the spherical alumina particles (the above) were used as the ceramic mixture [the D50 of the volume basis was 28 μm (Example 4) and 51 μm (Example 5)], and Two kinds of thermally conductive resin sheets were produced by the same operation as in Example 1 except that the mass ratio of the scaly hexagonal boron nitride particles (described above) was 94:6, and the content of the ceramic mixture was 80% by volume. The thermal conductivity of the obtained two types of thermally conductive resin sheets was measured, and as a result, -23 to 201215583 are shown in Table 1 below. Example 6 In the example 1 (1), the 'ceramic mixture was obtained by using spherical alumina particles (described above) [the D50 of the volume basis was 51 μm], and the mass ratio of the scaly hexagonal boron nitride particles (described above) was 94. A mixture of 6 and a ceramic mixture of 70% by volume of the whole were subjected to the same operation as in Example 1 to prepare a thermally conductive resin sheet. The thermal conductivity of the obtained thermally conductive resin sheet was measured, and the results are shown in Table 1 below. Example 7 In the example 1 (1), the ceramic mixture was a mass ratio of spherical alumina particles (described above) [D50 of a volume basis of 5 1 μm] and scaly hexagonal boron nitride particles (described above). A mixture of 79:21 and a ceramic mixture content of 80% by volume of the whole was subjected to the same operation as in Example 1 to prepare a thermally conductive resin sheet. The results of measuring the thermal conductivity of the obtained thermally conductive resin sheet were shown in Table 1. -24- 201215583 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 D50 (μηι) Spherical alumina particles 11 28 51 28 51 51 51 Scale-like hexagonal boron nitride Particle 9 9 9 9 9 9 9 Content ratio ※ (alumina/boron nitride) 79/21 79/21 79/21 94/6 94/6 94/6 79/21 Content of ceramic mixture (% by volume) 70 70 70 80 80 70 80 Thermal conductivity of sheet (W/m · K) 3.4 5.9 9.1 5.3 7.1 5 10.2 * The ratio is based on volume (the same in Tables 3 and 5) Comparative Examples 1 to 4 (1) Modulation contains organic matrix and sphere In the resin composition of the alumina particles, in addition to the spherical oxide particles (described above), the D50 is Ιίμιη, 21 μm (denoted as "A20S"), 28 μm, and 51 μm. A suspension of spherical alumina particles was prepared in the same manner as in Example 1 (1) instead of the ceramic mixture. Further, as shown in the following Table 2, a case of using spherical alumina particles having a D50 of 11 μm as Comparative Example 1 and a case of using spherical alumina particles having a D50 of 2 1 μm as Comparative Example 2 were used. An example in which spherical alumina particles having a D50 of 28 μm is Comparative Example 3, and a spherical alumina particle having a D 50 of 5 1 μη is used as Comparative Example 4. Next, the operation of the same as in Example 1 (1) was carried out except that the organic matrix was added to the suspension of the spherical alumina particles - 25 to 201215583, and the content of the spherical alumina particles in the organic matrix was 80% by volume. 'Modify four resin compositions. (2) Preparation of thermally conductive resin sheet Four kinds of thermally conductive resin sheets were produced by the same operation as in Example 1 (2) using the four kinds of resin compositions obtained in the above (1). The thermal conductivity of the four kinds of thermally conductive resin sheets obtained was measured, and the results are shown in Table 2 below. Table 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 D50 (μηι) Spherical alumina particles 11 21 28 51 Content of ceramic mixture (% by volume) 80 80 80 80 Thermal conductivity of flakes (W/m · Κ) 3.8 4.1 3.3 4.7 It is known from Tables 1 and 2 that the ceramic mixture is used as the thermally conductive entangled material, and the charge amounts of the ceramic mixture in the thermally conductive resin sheet of the present invention obtained in Examples 1 to 7 are each 70% by volume. At 80% by volume, the thermal conductivity is 3.4 to 1 W.2 W/m·K. The thermal conductivity resin sheet of the comparative example obtained by directly charging 80% by volume of the thermally conductive chelating material using only spherical alumina particles had a thermal conductivity of 3.8 to 4.7 W/m·K. When the D50 of the volume reference of the spherical alumina particles was 28 μίη and 5 1 μηι, the thermal conductivity of the thermally conductive resin sheets of the examples and the comparative examples was compared, and as a result, the D50 of the volume reference of the spherical alumina particles was 28 μηι, The thermal conductivities of Examples 2 and 4 were each 5·9 W/m·Κ and -26-201215583 5.3 W / m · Κ, and Comparative Example 3 was 3 · 3 W / m · Κ, which was lower than that of the examples. Further, when the volume of D5 0 of the spherical alumina particles was 51 μm, the thermal conductivity with respect to Examples 3 and 7 was 9.1 W/m. Κ and 10.2 W/m · K, and Comparative Example 4 was 4.7 W/ m · K, significantly lower than the embodiment. Therefore, the ceramic mixture of the present invention in which a mixture of spherical alumina particles and scaly hexagonal boron nitride particles is used is a more excellent thermal conductive filler than when spherical alumina particles are used alone. Comparative Example 5 (1) A resin composition containing an organic matrix and spherical alumina particles was prepared. A suspension of spherical alumina particles was prepared in the same manner as in Comparative Example 2 (1). Next, except that an organic matrix was added to the suspension of the spherical alumina particles so that the content of the spherical alumina particles in the organic matrix was 7 vol%, the operation of Comparative Example 2 (1) was carried out to prepare a resin composition. Things. (2) Preparation of thermally conductive resin sheet The resin composition obtained in the above (1) was subjected to the same operation as in Comparative Example 2 (2) to prepare a thermally conductive resin sheet. 'Measure the thermal conductivity of the resulting thermally conductive resin sheet. The results are shown in Table 3 below. -27- 201215583 Table 3 Comparative Example 5 D50 (μηι) Spherical alumina particles (A50S) 51 Spherical alumina particles (A10S) 11 Content ratio (A50S/A10S) 94/6 Content of ceramic mixture (% by volume) 70 Thermal Conductivity of Sheet (W/m · Κ) 5.3 Comparative Example 6 (1) Modification of a resin composition containing an organic matrix and scaly hexagonal boron nitride particles except that in Example 1 (1), only scaly hexagonal nitrogen was used. In addition to the ceramic mixture, boron (the aforementioned) [D50 of the volume basis is substituted for the mixture of the ceramics, Example 1 (1) prepares a suspension of spherical alumina particles. Next, the operation of the same as in Example 1 (1) was carried out except that the organic matrix was added to the suspension of the spherical alumina particles so that the content of the spherical alumina particles in the organic matrix was 7% by weight. . (2) Preparation of heat conductive resin sheet The resin obtained in the above (1), the composition ' was subjected to the same operation as in the Example to prepare a thermally conductive resin sheet. 'Measure the thermal conductivity of the resulting heat transfer grease sheet. The results are shown in Table 4 below. Particles with real floating volume 1(2) Sex tree-28- 201215583 Table 4 Comparative Example 6 D50 (μιη) Scale-like hexagonal boron nitride particles 9 Content of ceramic mixture (% by volume) 70 Thermal conductivity of flakes ( W/m · Κ) 5.5 It is known from Tables 3 and 4 that the substitution of boron nitride in combination with a spherical alumina having a small particle size and the use of boron nitride as a ruthenium hardly improve the thermal conductivity. Comparative Example 7 In Example 3, the ceramic mixture was a spherical alumina particle (described above) [D50 of a volume basis of 51 μm], and a mass ratio of scaly hexagonal boron nitride particles (described above) was 97:3. The mixture was subjected to the same operation as in Example 1 except that the content of the ceramic mixture was 7% by volume based on the whole, and a thermally conductive resin sheet was produced. The thermal conductivity of the obtained thermally conductive resin sheet was measured, and the results are shown in Table 5 below. Table 5 Comparative Example 7 D50 (μπι) Spherical alumina particles 51 Scale-like hexagonal boron nitride particles 9 Content ratio (alumina/boron nitride) 97/3 Content of ceramic mixture (% by volume) 70 Thermal conductivity of flakes (W/m · Κ) 5.5 -29 - 201215583 It is known from Table 5 that the mass ratio of boron nitride is less than 3 mass% of the lower limit of this application, and the thermal conductivity cannot be improved. Examples 8 to 14 and Comparative Examples 8 to 1 1 (1) Preparation of a resin composition containing an organic matrix and a ceramic mixture The organic matrix is a liquid curable epoxy resin [manufactured by Nippon Epoxy Co., Ltd.] 828", bisphenol A type] 100 parts by mass, and 1-cyanoethyl-2-methylimidazole for use as a curing agent [manufactured by Shikoku Kasei Co., Ltd., trade name "裘艾左2PN-CN"] 1 quality倂 倂 倂. Further, as the ceramic mixture, the particles described in the following Table 6 were used. The ceramic mixture (added as shown in Table 7 below) and 101 parts by mass of methyl ethyl ketone (MEK) were placed in a stainless steel container for homogenization, and stirred and mixed for 2 minutes in a homogenizer at a rotation speed of 5000 rpm. , preparing a suspension of the ceramic mixture. Next, the organic matrix is added to the suspension of the ceramic mixture, and the content of the ceramic mixture in the organic matrix is as shown in the following Table 6, and then stirred and mixed for 10 minutes at a rotation speed of 5 OOO rpm using a homogenizer to prepare a resin. Composition. (2) Preparation of a thermally conductive resin sheet The same amount of the above-mentioned thermosetting resin composition is added to the above-mentioned thermosetting resin in the same manner as the particulate niobium-filling agent {SN-7, electric chemical industry (share)} of 5 μm τι Premixing is carried out in a solution of the resin composition. Thereafter, the premix was kneaded using a three-seater roller to obtain a composite of the above-mentioned entangled agent in a solution of the above thermosetting resin composition in a range of -30 to 201215583. Then, the above composite was applied by a doctor blade method to a release-treated surface of a single-faced polyethylene terephthalate sheet having a thickness of 100 μm, and then dried by heating at 110 ° C for 15 minutes to prepare a thick layer. A thermally conductive resin sheet of a state of 80 μm. Then, the thermally conductive resin sheet was heated at 1 to 20 ° C for 1 hour and at 60 ° C for 3 hours to prepare a thermally conductive resin sheet. The thermal conductivity (average enthalpy of 30 points) of the thermally conductive resin sheet obtained in the same manner as in Example 1 was measured. The results are shown in Table 6 below. -31 - 201215583 Comparative Example 11 i Os 0/100 0/100 〇 Inch Comparative Example 10 1 100/0 100/0 〇 <N - Comparative Example 9 00 (N 1 100/0 100/0 〇 - Comparative Example 8 1 100/0 100/0 〇 <N cn Example 14 «ο 〇 \ 68/32 79/21 〇 Example 13 00 (Ν Os 68/32 79/21 〇 ON uS Example 12 σ\ 68/32 79/21 〇 inch 实施 Example 11 as 80/20 88/12 〇Example 10 90/10 94/6 〇Example 9 00 <Ν 90/10 94/6 〇CN Example 8 90/10 94/6 〇m ΓΟ Spherical alumina particles mg Shouting ^ S ^ ffiW Another light cockroach _ IKE DC · · · · § ^ ^ Ceramic mixture Content (% by volume) Thermal conductivity of the sheet (W/m · K) D50 (μιη) -32 - 201215583 Evaluation of the dielectric breakdown characteristics of the thermally conductive resin sheet The thermal conductive resin sheet was attached to the copper sheet under the condition of an area of 30 x 30 mm 2 ( A test piece was made between 40x40x5mm3) and an aluminum plate (30x30x5mm3). The test piece was measured in accordance with the withstand voltage test method of JIS C 2110 at a predetermined voltage of 1.5 kV for a predetermined time of 60 seconds. The uninsulated damage was judged to be acceptable (〇), and the insulation was broken (X) °, and the thermally conductive resin sheet was produced in accordance with the addition ratio shown in the following Table 7 in Example 1'. The thermal conductivity of the thermally conductive resin sheet was measured in the same manner as in Example 1. The results are shown in Table 7 below. -33- 201215583 Table 7 Addition rate of each component of ceramic illusion alumina/boron carbide carbonized sand/boron nitride thermal conductive resin sheet (volume fraction) (%) Spherical alumina particles ( A50S) 69(48) 0(0) bismuth carbide particles 〇(〇) 64(48) scaly hexagonal boron nitride particles (UHP-1) 18(22) 21(22) Organic components (resin, others) 13 (30) 15(30) Total 100(100) 100(100) Ceramic addition rate of thermal conductive resin sheet Mass fraction (volume fraction) (%) Spherical alumina particles (A50S) 79(68) 0(9) Tantalum carbide Particle 〇(〇) 75(68) Scale-like hexagonal boron nitride particles (UHP-1) 21(32) 25(32) Total 100(100) 100(100) Insulation failure characteristics 〇X Thermal conductivity of sheet (W /m · K) 8.3 5.2 ※ The niobium carbide particles are the trade name "GC#500" manufactured by Fujifilm Co., Ltd. * The number of () in the addition rate of each component is the volume fraction. Industrial Applicability The ceramic mixture of the present invention is suitably used as a thermally conductive entangled material. Moreover, the thermally conductive resin sheet of the present invention obtained by using the thermally conductive entangled material can be used as heat-generating heat-dissipating fan and heat-dissipating heat from a heat-generating electric-34-201215583 sub-member such as an MPU, a power transistor, or a transformer. For heat dissipation members such as sheets. Further, since the heat-conductive resin sheet has excellent dielectric breakdown properties, it can sufficiently cope with the thinning of the thermally conductive resin sheet which is reduced in size, such as an electronic device. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a "scaly" form of scaly hexagonal boron nitride particles, FIG. 1(A) is a plan view, and FIG. 1(B) is a XX cross section of FIG. 1(A). Figure. [Explanation of main component symbols] 1 〇 : scaly hexagonal boron nitride particles L : long diameter r : thickness -35-