[0011] 以下，詳細說明關於本發明。尚且，有將「導熱性聚矽氧組成物」略稱為「聚矽氧組成物」之情況。 [(A)成分] (A)成分之有機聚矽氧烷為本發明之聚矽氧組成物之主劑。作為與該有機聚矽氧烷中之矽原子鍵結之基，可舉出例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、十九基、二十基等之直鏈狀烷基；異丙基、第三丁基、異丁基、2-甲基十一基、1-己基庚基等之分枝鏈狀烷基；環戊基、環己基、環十二基等之環狀烷基；乙烯基、烯丙基、丁烯基、戊烯基、己烯基等之烯基；苯基、甲苯基、茬基等之芳基；苄基、苯乙基、2-(2,4,6-三甲基苯基)丙基等之芳烷基；3,3,3-三氟丙基、3-氯丙基等之鹵化烷基，較佳為烷基、烯基、芳基，特佳為甲基、乙烯基、苯基。 [0012] 有機聚矽氧烷於25℃之黏度並無限定，以20~100,000mPa・s之範圍內為佳，以50~100,000mPa・s為較佳，以50~50,000mPa・s為更佳，以100~50,000mPa・s為特佳。若黏度過低時，聚矽氧組成物之物理特性會有顯著降低之虞，若黏度過高時，則有聚矽氧組成物之操作作業性顯著降低之虞。 [0013] 有機聚矽氧烷之分子構造並無限定，可舉出例如，直鏈狀、分枝鏈狀、具有一部分分枝之直鏈狀、樹枝狀(樹枝狀高分子狀)，較佳為直鏈狀、具有一部分分枝之直鏈狀。作為此種有機聚矽氧烷，可舉出例如，具有該等分子構造之均聚物、由該等分子構造所構成之共聚物，或該等聚合物之混合物。 [0014] 作為此種有機聚矽氧烷，可舉出例如，分子鏈兩末端二甲基乙烯基矽氧基封端二甲基聚矽氧烷、分子鏈兩末端甲基苯基乙烯基矽氧基封端二甲基聚矽氧烷、分子鏈兩末端二甲基乙烯基矽氧基封端二甲基矽氧烷・甲基苯基矽氧烷共聚物、分子鏈兩末端二甲基乙烯基矽氧基封端二甲基矽氧烷・甲基乙烯基矽氧烷共聚物、分子鏈兩末端三甲基矽氧基封端二甲基矽氧烷・甲基乙烯基矽氧烷共聚物、分子鏈兩末端二甲基乙烯基矽氧基封端甲基(3,3,3-三氟丙基)聚矽氧烷、分子鏈兩末端矽醇基封端二甲基矽氧烷・甲基乙烯基矽氧烷共聚物、分子鏈兩末端矽醇基封端二甲基矽氧烷・甲基乙烯基矽氧烷・甲基苯基矽氧烷共聚物、由式：(CH3
)3
SiO1/2
所示之矽氧烷單位與式：(CH3
)2
(CH2
=CH)SiO1/2
所示之矽氧烷單位與式：CH3
SiO3/2
所示之矽氧烷單位與式：(CH3
)2
SiO2/2
所示之矽氧烷單位所構成之有機矽氧烷共聚物、分子鏈兩末端矽醇基封端二甲基聚矽氧烷、分子鏈兩末端矽醇基封端二甲基矽氧烷・甲基苯基矽氧烷共聚物、分子鏈兩末端三甲氧基矽氧基封端二甲基聚矽氧烷、分子鏈兩末端三甲氧基矽基封端二甲基矽氧烷・甲基苯基矽氧烷共聚物、分子鏈兩末端甲基二甲氧基矽氧基封端二甲基聚矽氧烷、分子鏈兩末端三乙氧基矽氧基封端二甲基聚矽氧烷、分子鏈兩末端三甲氧基矽基乙基封端二甲基聚矽氧烷，可單獨使用1種或可適宜組合使用2種以上。 [0015] 在聚矽氧組成物係藉由矽氫化反應進行硬化之情況，(A)成分係以(A-I)1分子中具有平均0.1個以上之矽原子鍵結烯基之有機聚矽氧烷為佳，以1分子中具有平均0.5個以上之矽原子鍵結烯基之有機聚矽氧烷為較佳，以1分子中具有平均0.8個以上之矽原子鍵結烯基之有機聚矽氧烷為更佳。此係由於1分子中之矽原子鍵結烯基之平均值若未滿上述範圍之下限時，則有取得之聚矽氧組成物變得不會充分硬化之傾向。作為此有機聚矽氧烷中之矽原子鍵結烯基，可例示如與前述相同之烯基，較佳為乙烯基。又，作為此有機聚矽氧烷中之烯基以外之與矽原子鍵結之基，可例示如與前述相同之直鏈狀烷基、分枝鏈狀烷基、環狀烷基、芳基、芳烷基、鹵化烷基，較佳為烷基、芳基，特佳為甲基、苯基。 [0016] 在聚矽氧組成物係藉由縮合反應進行硬化之情況，(A)成分為、(A-II)1分子中具有至少2個矽醇基或矽原子鍵結水解性基之有機聚矽氧烷。作為此有機聚矽氧烷中之矽原子鍵結水解性基，可舉出例如，甲氧基、乙氧基、丙氧基等之烷氧基；乙烯氧基、丙烯氧基、異丙烯氧基、1-乙基-2-甲基乙烯氧基等之烯氧基；甲氧基乙氧基、乙氧基乙氧基、甲氧基丙氧基等之烷氧基烷氧基；乙醯氧基、辛醯氧基等之醯氧基；二甲基酮肟基、甲基乙基酮肟基等之酮肟基；二甲基胺基、二乙基胺基、丁基胺基等之胺基；二甲基胺氧基、二乙基胺氧基等之胺氧基；N-甲基乙醯胺基、N-乙基乙醯胺基等之醯胺基。又，作為此有機聚矽氧烷中之矽醇基及矽原子鍵結水解性基以外之與矽原子鍵結之基，可例示如與前述相同之直鏈狀烷基、分枝鏈狀烷基、環狀烷基、烯基、芳基、芳烷基、鹵化烷基。 [0017] 在聚矽氧組成物係藉由使用有機過氧化物之自由基反應進行硬化之情況，(A)成分之有機聚矽氧烷並無限定，較佳為(A-III)1分子中具有至少1個矽原子鍵結烯基之有機聚矽氧烷。作為此有機聚矽氧烷中之鍵結於矽原子之基，可例示如與前述相同之直鏈狀烷基、分枝鏈狀烷基、環狀烷基、烯基、芳基、芳烷基、鹵化烷基，以烷基、烯基、芳基為佳，以甲基、乙烯基、苯基為較佳。 [0018] (A)成分之配合量在聚矽氧組成物中係以2.0~20.0質量%為佳，以2.0~19.0質量%為較佳。 [0019] [(B)成分] (B)成分係為平均球形度0.8以上，羥基為30個/nm2
以下，平均粒子徑10μm以上未滿50μm，且在雷射繞射型粒度分佈下96~150μm之粗粒子比例為全體之0.1~30質量%之球狀氧化鋁粉末。只要係滿足上述範圍者，亦可併用平均粒子徑相異之2種類以上之複數種類。 [0020] 氧化鋁粉末之結晶構造可為單結晶體、多結晶體之任一者，在從高導熱性之觀點，結晶相係以α相為理想，且比重係以3.7以上為理想。比重未滿3.7時，由於存在於粒子內部之空孔與低結晶相之比例變多，故有變得難以提高導熱率之憂慮。氧化鋁粉末之粒度調整係可藉由分級・混合操作來進行。 [0021] 平均球形度在0.8以上，以0.9以上為較佳。平均球形度未滿0.8時則有流動性降低之情況。平均球形度未滿0.8時，有粒子彼此之接觸變得顯著，片材表面之凹凸變大，界面熱阻抗增加而導致導熱率變差之傾向。上限並無特別限定，越接近球(平均球形度1)越佳。 [0022] 本發明中之平均球形度係可將掃描型電子顯微鏡所攝影之粒子圖像導入於圖像解析裝置、例如JEOL公司製商品名「JSM-7500F」，藉由以下操作進行測量。即，從相片測量粒子之投影面積(X)與周圍長(Z)。將對應周圍長(Z)之真圓之面積設為(Y)時，該粒子之球形度係可表示作為X/Y。因此，若假設具有與試料粒子之周圍長(Z)相同之周圍長之真圓時，由於Z=2πr、Y=πr2
，故變成Y=π×(Z/2π)2
，而各別之粒子球形度係可算出成球形度=X/Y=X×4π/Z2
。求出藉此所得之任意之粒子100個之球形度，並將該平均值作為平均球形度。 [0023] 羥基為30個/nm2
以下，以25個/nm2
以下為佳。下限並無特別限定，可設成5個/nm2
。表面羥基超過30個/nm2
時，則有對聚矽氧組成物之填充性變差，且導熱率變差之傾向。 [0024] 本發明中之上述羥基數，即表面羥基濃度係可藉由卡爾-費雪電量滴定法，使用例如三菱化學公司製商品名「微量水分測量裝置CA-100」進行測量。具體而言，將試料0.3~1.0g放入水分汽化裝置，供給經脫水處理之氬氣作為載氣，並同時以電熱器進行加熱昇溫。在卡爾-費雪電量測量法中，將溫度超過200℃至900℃為止所產生之水分定義成表面羥基量。從經測量之水分量與比表面積來算出表面羥基之濃度。 [0025] 平均粒子徑為10μm以上未滿50μm，以20μm以上未滿50μm為佳。平均粒子徑若未滿10μm，則有由於粒子彼此之接觸變少，粒子間接觸熱阻抗之增加而導熱率變差之憂慮。又，若為50μm以上，則有片材表面之凹凸變大，界面熱阻抗增加而導致導熱率變差之憂慮。 [0026] (B)成分在雷射繞射型粒度分佈下96~150μm之粗粒子比例佔(B)成分全體之0.1~30質量%，以0.1~10質量%為佳。藉由作成上述範圍，可同時取得所欲之厚度與高導熱性。96~150μm之粗粒子比例若未滿全體之0.1質量%時，在100~150μm下不會成為所欲之厚度，且無法達成高導熱性，在30質量%以上時，在100~150μm下雖可達成所欲之厚度，但有(B)成分之填充性變差之傾向。 [0027] 本發明中之平均粒子徑係可使用雷射繞射式粒度分佈測量裝置，例如，島津製作所製「雷射繞射式粒度分佈測量裝置SALD-2300」進行測量。評價試樣係在玻璃燒杯添加50cc之純水與進行測量之導熱性粉末5g，使用刮勺進行攪拌，其後以超音波洗淨機進行分散處理10分鐘。使用滴管將經進行分散處理之導熱性材料之粉末之溶液，一滴一滴添加至裝置之採樣部，等待穩定直到變得能測量吸光度為止。藉此操作在吸光度變得穩定之時間點下進行測量。從使用雷射繞射式粒度分佈測量裝置中之檢測器所檢測出之粒子所得之繞射/散射光之光強度分佈之資料計算出粒度分佈。平均粒子徑係對所測量之粒子徑之值乘上相對粒子量(差分%)，除以相對粒子量之合計(100%)來求得。尚且，平均粒子徑為粒子之平均直徑。又，96μm以上之粗粒子比例係亦可從全體之粒度分佈來容易求得。 [0028] [(C)成分] (C)成分為平均粒子徑0.1~5μm，較佳為0.5~2μm之氧化鋁粉末，可為球狀亦可為無規則形狀。尚且，球狀以外者則為無規則形狀。在不損及本發明之範圍內，可單獨使用1種，亦可併用平均粒子徑相異之2種類以上之複數種類。平均粒子徑若未滿0.1μm，則有由於粒子彼此之接觸變少，粒子間接觸熱阻抗之增加而導致導熱率變差之傾向。又，超過5μm時，有片材表面之凹凸變大，界面熱阻抗增加而導致導熱率變差之傾向。尚且，(C)成分為球狀時，與(B)成分同樣地，以平均球形度0.8以上，羥基係30個/nm2
以下為佳。尚且，平均粒子徑、平均球形度、羥基之測量方法係與(B)成分相同。 [0029] 上述(B)成分與(C)成分之配合比例體積比為5：5~9.5：0.5，以6：4~9：1為較佳。(B)成分之比例以體積比計若小於5((B)成分與(C)成分合計為10，以下相同)時，有(B)成分及(C)成分之填充性變差之傾向。另一方面，(C)成分之比例若大於9.5時，有(B)成分及(C)成分變得難以緻密地填充，且導熱性減少之傾向。 [0030] (B)成分與(C)成分之合計配合量在聚矽氧組成物中為50體積%以上未滿80體積%，以60體積%以上未滿80體積%為佳。配合量若未滿50體積%，有聚矽氧組成物之導熱性變得不充分之情況，若在80體積%以上，則有導熱性填料之填充變得困難且變成油灰(putty-like)狀之情況。 [0031] [(D)成分] 本發明更包含(D)矽烷耦合劑，且(B)成分及(C)成分係以受到(D)矽烷耦合劑表面處理為佳。 [0032] (D-1) 作為(D)矽烷耦合劑，可舉出如乙烯基系矽烷耦合劑、環氧系矽烷耦合劑、丙烯酸系矽烷耦合劑，以及長鏈烷基系矽烷耦合劑等，可單獨使用1種或可適宜組合2種以上來使用。其中亦以長鏈烷基系矽烷耦合劑為佳，以癸基三甲氧基矽烷為佳。 [0033] 作為由(D-I)成分所成之(B)成分、(C)成分之表面處理方法，可採用如使用流體噴嘴之噴霧方式、具有剪切力之攪拌方式、球磨機、混合機等之乾式法、水系或有機溶劑系等之濕式法。攪拌式係在不造成球狀氧化鋁粉末破壞之程度下進行。乾式法中之系統內溫度或處理後之乾燥溫度係因應表面處理劑之種類，在表面處理劑不會揮發或分解之區域下適宜決定，如為80~180℃。 [0034] (D-I)成分之處理使用量係相對於(B)成分及(C)成分之合計100質量份，以0.1~5質量份為佳。若少於0.1質量份時，其效果較小，且即使多過5質量份，也不會展現對應於使用量之效果。 [0035] 作為(D)成分，可舉出如(D-II)下述一般式(1)所示之1分子中至少含有1個矽基且在25℃之黏度為0.01~30Pa・s之有機聚矽氧烷。(式中，R1
係獨立為未取代或取代之1價烴基，R2
係獨立為烷基、烷氧基烷基、烯基或醯基，a為0、1或2。) [0036] 作為(D-II)成分，可舉出如下述一般式(2)所示之有機聚矽氧烷。(式中，R1
係獨立為未取代或取代之1價烴基，R2
係獨立為烷基、烷氧基烷基、烯基或醯基，b為2~100之整數，a為0、1或2)。 [0037] 式(1)、(2)中，R1
係獨立為未取代或取代之以碳數1~10為佳，較佳為1~6，更佳為1~3之1價烴基，作為其之例，可舉出如直鏈狀烷基、分枝鏈狀烷基、環狀烷基、烯基、芳基、芳烷基、鹵化烷基。作為直鏈狀烷基，可舉出例如，甲基、乙基、丙基、己基、辛基、癸基等。作為分枝鏈狀烷基，可舉出例如，異丙基、異丁基、tert-丁基、2-乙基己基等。作為環狀烷基，可舉出例如，環戊基、環己基等。作為烯基，可舉出例如，乙烯基、烯丙基等。作為芳基，可舉出例如，苯基、甲苯基等。作為芳烷基，可舉出例如，2-苯基乙基、2-甲基-2-苯基乙基等。作為鹵化烷基，可舉出例如，3,3,3-三氟丙基、2-(九氟丁基)乙基、2-(十七氟辛基)乙基等。作為R1
，以甲基、苯基為佳。 [0038] 式(1)、(2)中，R2
係獨立為烷基、烷氧基烷基、烯基或醯基。作為烷基，可舉出例如，與R1
中所例示者相同之直鏈狀烷基、分枝鏈狀烷基、環狀烷基。作為烷氧基烷基，可舉出例如，甲氧基乙基、甲氧基丙基等。作為烯基，可舉出例如，與R1
中所例示者相同者。碳數係以1~8者為佳。作為醯基，可舉出例如，乙醯基、辛醯基等。R2
係以烷基為佳，特別係以甲基、乙基為佳。b為2~100之整數，較佳為5~50。a為0、1或2，較佳為0。 [0039] 作為(D-II)成分之有機聚矽氧烷之適宜具體例，可舉出如下述者。(式中，Me為甲基)。 [0040] (D-II)成分之有機聚矽氧烷在25℃之黏度通常為0.01~30Pa・s，以0.01~10Pa・s為佳。黏度低於0.01Pa・s時，有變得容易導致從聚矽氧組成物產生漏油，且變得容易流延之憂慮。黏度大於30mPa・s時，有取得之聚矽氧組成物之流動性顯著變差而導致塗佈作業性惡化之憂慮。尚且，此黏度係使用旋轉黏度計所得之測量值(以下相同)。 [0041] (D-II)成分之配合量在相對於(A)成分100質量份而言，以5~900質量份為佳，以10~900質量份為較佳，以20~700質量份為更佳。 [0042] [(E)成分] 本發明之聚矽氧組成物中，以相對於聚矽氧組成物之總量，配合(E)中心粒子徑之最大值為150μm以上，SiO2
含量為50質量%以上之球狀玻璃珠或不規則形狀玻璃10質量%以下為佳。(E)成分之特徵在於中心粒子徑之最大值大於(B)成分之平均粒子徑，其上限並無特別限定，但可設成300μm以下。在配合(E)成分時，即便為極少量，仍能將導熱性聚矽氧組成物作成所欲之150μm以上之硬化厚度。作為材料，可舉出如鹼石灰玻璃、鹼石灰二氧化矽玻璃、或硼矽酸玻璃。從硬化厚度之均勻性之觀點，比起不規則形狀(E)成分係以球狀為佳，(E)成分為球狀玻璃珠時，平均球形度與(B)成分同樣係以0.8以上為佳。 [0043] (E)成分係以在不損及本發明範圍內少量添加為佳，具體而言，為了不使導熱性聚矽氧組成物之導熱率顯著降低，相對於聚矽氧組成物之總量，(F)成分量係以10質量%以下(0~10質量%)為佳。尚且，中心粒子徑之測量係能以雷射繞射法例如使用島津製作所製「雷射繞射式粒度分佈測量裝置SALD-2300」進行測量。 [0044] 本發明之導熱性聚矽氧組成物係可直接為該狀態，亦可更配合硬化劑而作成硬化性之組成物。 [0045] 在作成硬化性導熱性聚矽氧組成物之際，可舉出如以下之3形態，可作成基質聚合物之有機聚矽氧烷(A)係使用上述(A-I)~(A-III)成分之有機聚矽氧烷，且配合上述導熱性填充材(B)及(C)者。 [I]加成反應硬化型導熱性聚矽氧組成物 [II]縮合反應硬化型導熱性聚矽氧組成物 [III]有機過氧化物硬化型導熱性聚矽氧組成物 從快速硬化且不產生副生成物之觀點，以[I]加成反應硬化型導熱性聚矽氧組成物為佳。以下具體地展示關於各別之組成物。 [0046] [I]加成反應硬化型導熱性聚矽氧組成物 在聚矽氧組成物為藉由矽氫化反應進行硬化之加成反應硬化型導熱性聚矽氧組成物之情況，上述(A)係使用上述所示之(A-I)成分，且更包含下述成分者，硬化劑為下述(F)及(G)成分。 (F)交聯劑係為具有至少2個直接鍵結於矽原子之氫原子之有機氫聚矽氧烷、 (G)鉑族金屬系硬化觸媒、 (H)因應必要之加成反應控制劑 [0047] [(F)成分] 具有至少2個直接鍵結於矽原子之氫原子之有機氫聚矽氧烷係作用作為交聯劑之成分。作為鍵結於有機氫聚矽氧烷之矽原子鍵之基，可例示如與前述相同之直鏈狀烷基、分枝鏈狀烷基、環狀烷基、芳基、芳烷基、鹵化烷基，較佳為烷基、芳基，特佳為甲基、苯基。(F)成分在25℃之黏度並無限定，以1~100,000mPa・s之範圍為佳，以1~5,000mPa・s之範圍為較佳。(F)成分之分子構造並無限定，可舉出例如，直鏈狀、分枝鏈狀、具有一部分分枝之直鏈狀、環狀、樹枝狀(樹枝狀高分子狀)。作為此種有機聚矽氧烷，可舉出例如，具有該等分子構造之均聚物、由該等分子構造所構成之共聚物，或該等之混合物。 [0048] 作為(F)成分，可舉出例如，分子鏈兩末端二甲基氫矽氧基封端二甲基聚矽氧烷、分子鏈兩末端三甲基矽氧基封端二甲基矽氧烷・甲基氫矽氧烷共聚物、分子鏈兩末端二甲基氫矽氧基封端二甲基矽氧烷・甲基氫矽氧烷共聚物、由式：(CH3
)3
SiO1/2
所示之矽氧烷單位與式：(CH3
)2
HSiO1/2
所示之矽氧烷單位與式：SiO4/2
所示之矽氧烷單位所構成之有機矽氧烷共聚物，可單獨使用1種或可適宜組合2種以上來使用。 [0049] (F)成分之配合量係為使聚矽氧組成物硬化所必需之量，具體而言，相對於(A-I)成分中之矽原子鍵結烯基1莫耳，以(F)成分中之矽原子鍵結氫原子成為0.1~10莫耳範圍內之量為佳，更以成為0.1~5莫耳範圍內之量為佳，特別係以成為0.1~3.0莫耳範圍內之量為佳。此係由於若本成分之含量成為未滿上述範圍之下限之量時，有取得之聚矽氧組成物變得不會充分硬化之傾向，另一方面若超過上述範圍之上限時，則有取得之聚矽氧硬化物變得非常硬質，且表面產生多數龜裂之情況。 [0050] (G)鉑族金屬系硬化觸媒為促進聚矽氧組成物之硬化用之觸媒，可舉出例如，氯化鉑酸、氯化鉑酸之醇溶液、鉑之烯烴錯合物、鉑之烯基矽氧烷錯合物、鉑之羰基錯合物。 [0051] (G)成分之配合量為使聚矽氧組成物硬化所必需之量，具體而言，相對於(A-I)成分而言，(G)成分中之鉑金屬以質量單位計成為0.01~1,000ppm之範圍內之量為佳，特別係以成為0.1~500ppm之範圍內之量為佳。此係由於(G)成分之配合量未滿上述範圍之下限時，取得之聚矽氧組成物有變得不會充分硬化之傾向，另一方面即使配合超過上述範圍之上限，取得之聚矽氧組成物之硬化速度仍不會顯著提升。 [0052] (H)硬化反應抑制劑 為了調節聚矽氧組成物之硬化速度且提升操作作業性，可配合硬化反應抑制劑。作為硬化反應抑制劑，可舉出如2-甲基-3-丁炔-2-醇、2-苯基-3-丁炔-2-醇、1-乙炔基-1-環己醇等之乙炔系化合物；3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔等之烯-炔化合物；其他胼系化合物、膦系化合物、硫醇系化合物等，可單獨使用1種或可適宜組合2種以上來使用。 [0053] (H)成分之配合量並無特別限定，相對於聚矽氧組成物，以0.0001~1.0質量%為佳。藉由作成上述範圍，聚矽氧組成物之作業性或硬化速度會變得更加合適。 [0054] [II]縮合反應硬化型導熱性聚矽氧組成物 在聚矽氧組成物為縮合反應硬化型導熱性聚矽氧組成物之情況，上述(A)係使用上述所示之(A-II)成分，且更包含下述成分者，硬化劑為下述(I)成分。 (I)1分子中具有至少3個之矽原子鍵結水解性基之矽烷或其部分水解物、 (J)因應必要之縮合反應用觸媒 [0055] 作為(I)成分中之矽原子鍵結水解性基，可例示如與前述相同之烷氧基、烷氧基烷氧基、醯氧基、酮肟基、烯氧基、胺基、胺氧基、醯胺基。又，於此矽烷之矽原子除上述之水解性基以外，亦可鍵結例如與前述相同之直鏈狀烷基、分枝鏈狀烷基、環狀烷基、烯基、芳基、芳烷基、鹵化烷基。作為此種矽烷或其部分水解物，可舉出例如，甲基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、乙基正矽酸酯。 [0056] (I)成分之配合量係使聚矽氧組成物硬化所必需之量，具體而言，相對於(A-II)成分100質量份，以0.01~20質量份之範圍內為佳，特別係以0.1~10質量份之範圍內為佳。此係由於若該矽烷或其部分水解物之含量為未滿上述範圍之下限之量時，有取得之聚矽氧組成物之儲藏安定性降低之憂慮，另一方面，若超過上述範圍之上限之量時，有取得之聚矽氧組成物之硬化顯著變慢之憂慮。 [0057] (J)成分為任意之成分，在將例如具有胺氧基、胺基、酮肟基等之水解性基之矽烷使用作為硬化劑時，則為非必須者。作此種縮合反應用觸媒，可舉出例如，四丁基鈦酸酯、四異丙基鈦酸酯等之有機鈦酸酯；二異丙氧基雙(乙醯基乙酸)鈦、二異丙氧基雙(乙基乙醯乙酸酯)鈦等之有機鈦螯合物化合物；參(乙醯基丙酮酸)鋁、參(乙基乙醯乙酸)鋁等之有機鋁化合物；四(乙醯基丙酮酸)鋯、四丁酸鋯等之有機鋁化合物；二丁基錫二辛酸酯、二丁基錫二月桂酸酯、丁基錫-2-乙基己酸酯等之有機錫化合物；環烷酸錫、油酸錫、丁基酸錫、環烷酸鈷、硬脂酸鋅等之有機羧酸之金屬鹽；己基胺、磷酸十二基胺等之胺化合物、及其之鹽；苄基三乙基銨乙酸鹽等之4級銨鹽；乙酸鉀、硝酸鋰等之鹼金屬之低級脂肪酸鹽；二甲基羥基胺、二乙基羥基胺等之二烷基羥基胺；含胍基之有機矽化合物。 [0058] 在配合(J)成分之情況，其配合量只要係使聚矽氧組成物硬化所必需之量即可，具體而言，相對於(A)成分100質量份，以0.01~20質量份之範圍內為佳，特別係以0.1~10質量份之範圍內為佳。此係由於在該觸媒為必需之情況，該觸媒之含量未滿上述範圍之下限時，則有取得之聚矽氧組成物變得不會充分硬化之傾向，另一方面在超出上述範圍之上限時，則有取得之聚矽氧組成物之儲藏安定性降低之傾向。 [0059] [III]有機過氧化物硬化型導熱性聚矽氧組成物 在聚矽氧組成物為有機過氧化物硬化型導熱性聚矽氧組成物之情況，上述(A)係使用上述所示之(A-III)成分，且更包含下述成分者，硬化劑為下述(K)成分。 (K)有機過氧化物 [0060] 作為(K)有機過氧化物，可舉出例如，苄醯基過氧化物、二異丙苯基過氧化物、2,5-二甲基雙(2,5-t-丁基過氧基)己烷、二-t-丁基過氧化物、過苯甲酸t-丁基酯。 [0061] (K)成分之配合量係使聚矽氧組成物硬化所必需之量，具體而言，相對於上述(A-III)成分之有機聚矽氧烷100質量份，以0.1~5質量份之範圍為佳。(K)成分之配合量未滿上述範圍之下限時，則有取得之聚矽氧組成物變得不會充分硬化之傾向，另一方面即使配合超過上述範圍之上限之量，取得之聚矽氧組成物之硬化速度仍不會顯著上升，且反而會有變成空隙之原因之憂慮。 [0062] 更進一步，本發明之聚矽氧組成物在不損及本發明之目的範圍內，亦可含有其他任意之成分，例如，氧化鋅、氣相二氧化矽、沉降性二氧化矽、氣相氧化鈦等之填充劑，此填充劑表面係藉由有機矽化合物而受到疏水化處理之填充劑；3-環氧丙氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷等之接著賦予劑；其他，顏料、染料、螢光染料、耐熱添加劑、三唑系化合物等之難燃性賦予劑、塑化劑。尚且，在不損及本發明之效果範圍內，亦可配合(B)成分以外之導熱性填充材，可舉出例如，鋁粉末、銅粉末、銀粉末、鎳粉末、金粉末、氧化鋅粉末、氧化鎂粉末、氮化硼粉末、氮化鋁粉末、金剛石粉末、碳粉末等。 [0063] [製造方法] 本發明之聚矽氧組成物係可藉由使上述各成分之規定量進行均勻混合來調製。可舉出例如，一種製造導熱性聚矽氧組成物之方法，其係包含混合 (A)有機聚矽氧烷、 (B)平均球形度0.8以上，羥基為30個/nm2
以下，平均粒子徑10μm以上未滿50μm，在雷射繞射型粒度分佈下96~150μm之粗粒子比例佔(B)成分全體之0.1~30質量%之球狀氧化鋁粉末，及 (C)平均粒子徑0.1~5μm之球狀或無規則形狀氧化鋁粉末之步驟； 其中上述(B)成分與(C)成分之配合比例體積比((B)：(C))為5：5~9.5：0.5，(B)成分與(C)成分之合計量佔組成物中50體積%以上未滿80體積%，組成物於25℃之導熱率根據ISO 22007-2之熱碟法為1.2W/m・K以上未滿5.5W/m・K，組成物於25℃之黏度在使用螺旋式黏度計以旋轉數10rpm測量時為5~800Pa・s。並且，亦可包含混合任意成分之步驟。 [0064] [導熱性聚矽氧組成物] 導熱性聚矽氧組成物之導熱率係根據ISO 22007-2之熱碟法為1.2W/m・K以上未滿5.5W/m・K，以1.5~5.5W/m・K為較佳。測量溫度為25℃。 [0065] 又，導熱性聚矽氧組成物於25℃之黏度在使用螺旋式黏度計以旋轉數10rpm測量時為5~800Pa・s，以30~600Pa・s為佳。 [0066] [硬化物] 在聚矽氧組成物為硬化性者之情況，使其硬化之方法並無限定，可舉出例如，使聚矽氧組成物成形後，在常溫下放置之方法；使聚矽氧組成物成形後，加熱至40~200℃之方法，且可取得聚矽氧彈性體成形品。又，藉此所得之聚矽氧橡膠之性狀並無限定，可舉出例如，膠狀、低硬度之橡膠狀、或高硬度之橡膠狀。其硬化厚度係以150μm以上為佳。上限並無特別限定，在考慮使用本組成物之發熱性電子零件之大小時，以5mm以下為佳。尚且，硬化物之硬度係使聚矽氧組成物成為6mm硬化厚度之方式流入成形模具，在100℃下使其硬化1小時。其次，將6mm厚度之硬化物重疊2枚並以阿斯克(Asker)C硬度計進行測量時，以3~90為佳，以5~80為較佳。 [0067] 硬化物於150℃之導熱率根據ISO 22007-2之熱碟法係以0.7W/m・K以上未滿4.0W/m・K為佳，以1.0W/m・K以上未滿4.0W/m・K為較佳。並且，硬化物於25℃之導熱率根據ISO 22007-2之熱碟法為1.2W/m・K以上未滿5.5W/m・K，以1.5~5.5W/m・K為較佳。尚且，25℃，150℃中係指測量溫度，藉由在150℃具有如上述之導熱率，即可取得在高溫時之導熱性優異者。 又，將横軸設為溫度，縱軸設為導熱率時，將在25℃與150℃中取得之導熱率予以製圖而得之一次直線中，從各溫度所推定之導熱率亦係包括在本發明中。 ［實施例］ [0068] 以下，展示實施例及比較例來具體說明本發明，但本發明並非係受到下述實施例所限制者。尚且，下述式中，Me為甲基。 [0069] 實施例及比較例所使用之成分係如下述所示。 首先，準備以下之各成分。 (A)成分 A-1：25℃之黏度為400mPa・s，兩末端經二甲基乙烯基矽基封端，且Vi基量為0.018moL/100g之二甲基聚矽氧烷 A-2：信越化學工業製KF-54，比重(25℃)為1.07，動黏度(25℃)為400mm2
/s之分子鏈兩末端三甲基矽氧基封端二甲基矽氧烷・二苯基矽氧烷共聚物 A-3：信越化學工業製KF-50-1,000cs，比重(25℃)為1.00，動黏度(25℃)為1,000mm2
/s之分子鏈兩末端三甲基矽氧基封端二甲基矽氧烷・二苯基矽氧烷共聚物 [0070] (B)成分 具有下述表所示性質之球狀氧化鋁在此表示之粗粒含有率係指在雷射繞射型粒度分佈下取得之相對於粒度分佈全體之96~150μm之粗粒子比例 [0071] (C)成分 具有下述表所示性質之球狀或無規則形狀氧化鋁[0072] (D)成分 D-1：下述式所示之有機聚矽氧烷[0073] (E)成分 E-1：Potters Ballotini製MIL粒度系列M-9(中心粒子徑之最大值為180μm)、SiO2
含量為99.4質量%之球狀玻璃珠 [0074] (F)成分 F-1：下述式所示之有機氫聚矽氧烷F-2：下述式所示之有機氫聚矽氧烷[0075] (G)成分 G-1：鉑濃度為1質量%之氯化鉑酸-1,3-二乙烯基四甲基二矽氧烷錯合物 [0076] (H)成分 H-1：1-乙炔基-1-環己醇之50%甲苯溶液 [0077] [實施例1~16、比較例1~16] 使用上述成分，以下述所示方法調製聚矽氧組成物，並使用此聚矽氧組成物來取得導熱性成型物。使用該等藉由下述所示之方法進行評價。將其結果併記於表中。 [0078] 以下述表3~6所示之配合量，如以下操作般地將上述成分予以混合，而取得聚矽氧組成物。即，在5公升框式混合機(gate mixer)(井上製作所(股)製、商品名：5公升行星式混合機)中，以表1所示之配合量取用(A)、(B)、(C)、(D)成分，在150℃下脫氣加熱混合2小時。其後，冷卻直到常溫(25℃)為止，添加(G)成分，在室溫(25℃)下混合直到均勻為止，其後添加(H)成分，在室溫(25℃)下混合直到均勻為止。更添加(E)及(F)成分，在室溫下脫氣氣混合使其均勻。對於藉此所得之聚矽氧組成物，藉由下述所示之方法評價初期黏度、硬化後硬度、硬化前後之導熱率。將其結果併記於表中。 [0079] [初期黏度評價] 聚矽氧組成物之初期黏度為25℃之值，該測量係使用螺旋式黏度計：MALCOM黏度計(型號PC-10AA、旋轉數10rpm)。 [硬化後硬度評價] 使聚矽氧組成物流入會成為6mm硬化厚度之成形模具，在100℃下使其硬化1小時。其次，將6mm厚度之硬化物予以2枚重疊，並使用阿斯克(Asker)C硬度計進行測量。 [導熱率評價] 使用京都電子工業(股)製熱碟法熱物性測量裝置TPS 2500 S，測量25℃之聚矽氧組成物之硬化前之導熱率(根據ISO 22007-2之熱碟法)。 並且，使聚矽氧組成物流入會成為6mm硬化厚度之成形模具，在100℃下使其硬化1小時。對於取得之6mm厚度之硬化物，測量25℃及150℃之硬化物之導熱率。 [0080][0081][0082][0083] [0011] Hereinafter, the present invention will be described in detail. In addition, the "thermally conductive polysiloxane composition" may be referred to as a "polysiloxane composition". [(A) component] The organopolysiloxane of the (A) component is the main agent of the polysiloxane composition of the present invention. Examples of the group bonded to a silicon atom in the organic polysiloxane include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl , Undecyl, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, icosyl, etc. Branched chain alkyl groups such as alkyl, tert-butyl, isobutyl, 2-methylundecyl, 1-hexylheptyl; cyclic alkyl groups such as cyclopentyl, cyclohexyl, cyclododecyl, etc. ; Alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl; aryl groups such as phenyl, tolyl, stubyl; benzyl, phenethyl, 2- (2,4 Aralkyl groups such as 1,6-trimethylphenyl) propyl, etc .; halogenated alkyl groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, etc., preferably alkyl, alkenyl, aryl Particularly preferred are methyl, vinyl, and phenyl. [0012] The viscosity of the organic polysiloxane at 25 ° C is not limited, and is preferably in the range of 20 to 100,000 mPa · s, more preferably 50 to 100,000 mPa · s, and more preferably 50 to 50,000 mPa · s. Good, especially 100 ~ 50,000mPa · s. If the viscosity is too low, the physical properties of the polysiloxane composition may be significantly reduced. If the viscosity is too high, the workability of the polysiloxane composition may be significantly reduced. [0013] The molecular structure of the organic polysiloxane is not limited, and examples thereof include linear, branched, linear, partially branched, and dendritic (dendritic) polymers. It is linear and has a branched linear shape. Examples of such an organic polysiloxane include a homopolymer having such a molecular structure, a copolymer composed of such a molecular structure, or a mixture of these polymers. [0014] Examples of such an organopolysiloxane include dimethylvinylsiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, and methylphenylvinylsilicon at both ends of the molecular chain. Oxygen-terminated dimethylpolysiloxane, dimethyl vinyl siloxane-terminated siloxane and methylphenylsiloxane copolymers at both ends of the molecular chain, dimethyl at both ends of the molecular chain Vinylsiloxy-terminated dimethylsiloxane, methylvinylsiloxane copolymer, trimethylsiloxy-terminated dimethylsiloxane, methylvinylsiloxane, both ends of the molecular chain Copolymer, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) polysiloxane at both ends of molecular chain, silanol-terminated dimethylsiloxy at both ends of molecular chain Alkane · methylvinylsiloxane copolymer, silanol-terminated dimethylsiloxane, methylvinylsiloxane, methylphenylsiloxane copolymer at both ends of the molecular chain, by the formula: ( CH 3 ) 3 SiO 1/2 Siloxane unit and formula shown: (CH 3 ) 2 (CH 2 = CH) SiO 1/2 Siloxane unit and formula shown: CH 3 SiO 3/2 Siloxane unit and formula shown: (CH 3 ) 2 SiO 2/2 Organosiloxane copolymers composed of the shown siloxane units, silanol-terminated dimethylpolysiloxane at both ends of the molecular chain, silanol-terminated dimethylpolysiloxane at both ends of the molecular chain · Copolymer of methylphenylsiloxane, trimethoxysiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, trimethoxysilyl-terminated dimethylsiloxane at both ends of the molecular chain Phenylsiloxane copolymer, methyldimethoxysiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, triethoxysiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain The alkane and trimethoxysilylethyl-terminated dimethylpolysiloxane at both ends of the molecular chain may be used alone or in a suitable combination of two or more. [0015] In the case where the polysiloxane composition is hardened by a hydrosilylation reaction, the (A) component is an organopolysiloxane having an average of 0.1 or more silicon atoms bonded to an alkenyl group in one molecule of (AI) Preferably, an organic polysiloxane having an average of more than 0.5 silicon atom-bonded alkenyl groups in one molecule is preferable, and an organic polysiloxane having an average of more than 0.8 silicon atom-bonded alkenyl groups in one molecule is preferable Alkanes are more preferred. This is because if the average value of the silicon atom-bonded alkenyl group in one molecule is less than the lower limit of the above range, the obtained polysiloxane composition tends not to be sufficiently hardened. Examples of the silicon atom-bonded alkenyl group in this organic polysiloxane include the same alkenyl group as described above, and preferably a vinyl group. Examples of the organic polysiloxane-based bond to a silicon atom other than the alkenyl group include a linear alkyl group, a branched chain alkyl group, a cyclic alkyl group, and an aryl group as described above. , Aralkyl, and halogenated alkyl are preferably alkyl and aryl, particularly preferably methyl and phenyl. [0016] When the polysiloxane composition is hardened by a condensation reaction, the component (A) is an organic compound having at least two silanol groups or silicon atom-bondable hydrolyzable groups in one molecule of (A-II). Polysiloxane. Examples of the silicon atom-bondable hydrolyzable group in this organic polysiloxane include alkoxy groups such as methoxy, ethoxy, and propoxy groups; vinyloxy, propyleneoxy, and isopropenyloxy Alkenyloxy groups such as methyl, 1-ethyl-2-methylvinyloxy; alkoxyalkoxy groups such as methoxyethoxy, ethoxyethoxy, and methoxypropoxy; etc. Alkoxy groups such as alkoxy and octyloxy; ketooximes such as dimethylketoxime, methylethylketoxime; dimethylamino, diethylamino, and butylamino Amine groups such as dimethylamino, dimethylamino, diethylamino, and the like; amines such as N-methylacetamido and N-ethylacetamido. Examples of the organic polysiloxane group other than the silanol group and the silicon atom-bondable hydrolyzable group include a straight-chain alkyl group and a branched-chain alkane group as described above. Radical, cyclic alkyl, alkenyl, aryl, aralkyl, haloalkyl. [0017] In the case where the polysiloxane composition is hardened by a radical reaction using an organic peroxide, the organopolysiloxane of the component (A) is not limited, and preferably (A-III) 1 molecule An organopolysiloxane having at least one silicon atom bonded to an alkenyl group therein. Examples of the group bonded to a silicon atom in this organic polysiloxane include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, and an aralkyl group, which are the same as those described above. As the alkyl group and the halogenated alkyl group, an alkyl group, an alkenyl group and an aryl group are preferred, and a methyl group, a vinyl group and a phenyl group are more preferred. [0018] The compounding amount of the component (A) in the polysiloxane composition is preferably 2.0 to 20.0% by mass, and more preferably 2.0 to 19.0% by mass. [(B) component] (B) The component system has an average sphericity of 0.8 or more, and the number of hydroxyl groups is 30 / nm 2 Hereinafter, the spherical alumina powder having an average particle diameter of 10 μm or more and less than 50 μm, and a coarse particle ratio of 96 to 150 μm in a laser diffraction type particle size distribution is 0.1 to 30% by mass of the whole. As long as it satisfies the above range, two or more types having different average particle diameters may be used in combination. [0020] The crystal structure of the alumina powder may be either a single crystal or a polycrystal. From the viewpoint of high thermal conductivity, the crystalline phase is preferably an α phase, and the specific gravity is preferably 3.7 or more. When the specific gravity is less than 3.7, there is a concern that it becomes difficult to improve the thermal conductivity because the ratio of the pores existing in the particles to the low-crystalline phase increases. The particle size adjustment of the alumina powder can be performed by classification and mixing operations. [0021] The average sphericity is 0.8 or more, and preferably 0.9 or more. When the average sphericity is less than 0.8, the fluidity may decrease. When the average sphericity is less than 0.8, there is a tendency for particles to come into contact with each other, the unevenness on the surface of the sheet becomes larger, the interface thermal resistance increases, and the thermal conductivity tends to deteriorate. The upper limit is not particularly limited, and the closer to the sphere (average sphericity 1), the better. [0022] The average sphericity in the present invention is a particle image photographed by a scanning electron microscope, which can be introduced into an image analysis device, for example, a brand name "JSM-7500F" manufactured by JEOL, and measured by the following operation. That is, the projected area (X) and the surrounding length (Z) of the particles are measured from the photograph. When the area of a true circle corresponding to the surrounding length (Z) is set to (Y), the sphericity of the particle can be expressed as X / Y. Therefore, if a true circle having the same perimeter length (Z) as the perimeter length of the sample particles is assumed, since Z = 2πr, Y = πr 2 , So it becomes Y = π × (Z / 2π) 2 , And the sphericity of each particle can be calculated as sphericity = X / Y = X × 4π / Z 2 . The sphericity of 100 arbitrary particles thus obtained was obtained, and the average value was used as the average sphericity. 30 hydroxyl groups / nm 2 Below, at 25 / nm 2 The following is better. The lower limit is not particularly limited, and can be set to 5 / nm 2 . Surface hydroxyl groups exceed 30 / nm 2 In this case, there is a tendency that the filling property to the polysiloxane composition is deteriorated and the thermal conductivity is deteriorated. [0024] In the present invention, the above-mentioned hydroxyl number, that is, the surface hydroxyl concentration can be measured by Karl-Fisher titration using, for example, a brand name "micro-moisture measuring device CA-100" manufactured by Mitsubishi Chemical Corporation. Specifically, 0.3 to 1.0 g of the sample is put into a moisture vaporization device, and dehydration-treated argon gas is supplied as a carrier gas, and at the same time, the temperature is increased by heating with an electric heater. In the Karl-Fisher power measurement method, the amount of water generated until the temperature exceeds 200 ° C to 900 ° C is defined as the amount of surface hydroxyl groups. The surface hydroxyl concentration was calculated from the measured water content and specific surface area. [0025] The average particle diameter is preferably 10 μm or more and less than 50 μm, and preferably 20 μm or more and less than 50 μm. If the average particle diameter is less than 10 μm, there is a concern that the contact between the particles will be reduced, the thermal resistance between the particles will increase, and the thermal conductivity will be deteriorated. Moreover, if it is 50 micrometers or more, there exists a possibility that the unevenness | corrugation of the surface of a sheet | seat will become large, the interface thermal resistance will increase, and thermal conductivity may worsen. [0026] The proportion of coarse particles of 96 to 150 μm of the component (B) in the laser diffraction type particle size distribution accounts for 0.1 to 30% by mass of the entire (B) component, and preferably 0.1 to 10% by mass. By forming the above range, a desired thickness and high thermal conductivity can be obtained at the same time. If the proportion of coarse particles of 96 to 150 μm is less than 0.1% by mass of the whole, the desired thickness will not be achieved at 100 to 150 μm and high thermal conductivity cannot be achieved. At 30% by mass or more, the thickness will be 100 to 150 μm. The desired thickness can be achieved, but the filling property of the component (B) tends to deteriorate. [0027] The average particle diameter in the present invention can be measured using a laser diffraction particle size distribution measurement device, for example, "Laser diffraction particle size distribution measurement device SALD-2300" manufactured by Shimadzu Corporation. In the evaluation sample, 50 cc of pure water and 5 g of thermally conductive powder to be measured were added to a glass beaker, stirred with a spatula, and then subjected to a dispersion treatment with an ultrasonic cleaner for 10 minutes. Use a dropper to add a solution of the powder of the thermally conductive material that has been subjected to the dispersion treatment to the sampling section of the device, and wait for stabilization until it becomes possible to measure the absorbance. With this operation, measurement is performed at a time point when the absorbance becomes stable. The particle size distribution is calculated from the data of the light intensity distribution of the diffracted / scattered light obtained using the particles detected by the detector in the laser diffraction type particle size distribution measurement device. The average particle diameter is obtained by multiplying the value of the measured particle diameter by the relative particle amount (% difference) and dividing by the total of the relative particle amount (100%). Moreover, the average particle diameter is the average diameter of a particle. The coarse particle ratio of 96 μm or more can be easily obtained from the entire particle size distribution. [(C) component] (C) The component is an alumina powder having an average particle diameter of 0.1 to 5 μm, preferably 0.5 to 2 μm, and may be spherical or irregular. Moreover, the shape other than a sphere is an irregular shape. Within the scope of not impairing the present invention, one type may be used alone, or two or more types having different average particle diameters may be used in combination. If the average particle diameter is less than 0.1 μm, there is a tendency that the thermal conductivity of the particles will be deteriorated because the contact between the particles will decrease and the thermal resistance between the particles will increase. When the thickness exceeds 5 μm, the unevenness on the surface of the sheet increases, and the thermal resistance at the interface increases, which tends to cause the thermal conductivity to deteriorate. In addition, when the component (C) is spherical, the average sphericity is 0.8 or more and the number of hydroxyl groups is 30 / nm as in the case of the component (B). 2 The following is better. In addition, the measurement method of average particle diameter, average sphericity, and hydroxyl group is the same as that of (B) component. [0029] The mixing ratio volume ratio of the component (B) and the component (C) is 5: 5 to 9.5: 0.5, and 6: 4 to 9: 1 is preferable. If the ratio of the (B) component is less than 5 in volume ratio (the total of the (B) component and the (C) component is 10, the same applies hereinafter), the filling properties of the (B) component and the (C) component tend to deteriorate. On the other hand, when the ratio of the (C) component is more than 9.5, it is difficult to fill the (B) component and the (C) component densely and the thermal conductivity tends to decrease. [0030] The total blending amount of the component (B) and the component (C) is preferably 50 vol% or more and 80 vol% or less, and preferably 60 vol% or more and 80 vol% or less in the polysiloxane composition. If the blending amount is less than 50% by volume, the thermal conductivity of the polysiloxane composition may be insufficient. If it is more than 80% by volume, filling with a thermally conductive filler becomes difficult and putty-like. Situation. [(D) component] The present invention further contains (D) a silane coupling agent, and the (B) component and (C) component are preferably subjected to (D) a silane coupling agent surface treatment. (D-1) Examples of the (D) silane coupling agent include a vinyl silane coupling agent, an epoxy silane coupling agent, an acrylic silane coupling agent, and a long-chain alkyl silane coupling agent. It can be used singly or in combination of two or more kinds. Among them, a long-chain alkyl silane coupling agent is preferred, and decyltrimethoxysilane is preferred. [0033] As a surface treatment method of the (B) component and the (C) component made of the (DI) component, for example, a spray method using a fluid nozzle, a stirring method with a shear force, a ball mill, a mixer, or the like can be used. Dry method, wet method such as water-based or organic solvent-based. The stirring system is performed to such an extent that the spherical alumina powder is not damaged. The temperature in the system in the dry method or the drying temperature after the treatment is appropriately determined in the region where the surface treatment agent will not volatilize or decompose according to the type of surface treatment agent, such as 80 ~ 180 ° C. [0034] The amount of the (DI) component to be used is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total of the components (B) and (C). If it is less than 0.1 parts by mass, the effect is small, and even if it exceeds 5 parts by mass, the effect corresponding to the amount used will not be exhibited. [0035] Examples of the component (D) include those having at least one silicon group in a molecule represented by the following general formula (1) as in (D-II) and having a viscosity at 25 ° C. of 0.01 to 30 Pa · s. Organic polysiloxane. (Where, R 1 Is an unsubstituted or substituted monovalent hydrocarbon group, R 2 Is independently alkyl, alkoxyalkyl, alkenyl or fluorenyl, and a is 0, 1 or 2. [0036] Examples of the (D-II) component include an organic polysiloxane represented by the following general formula (2). (Where, R 1 Is an unsubstituted or substituted monovalent hydrocarbon group, R 2 Is independently an alkyl group, an alkoxyalkyl group, an alkenyl group or a fluorenyl group, b is an integer from 2 to 100, and a is 0, 1 or 2). In formulas (1) and (2), R 1 A monovalent hydrocarbon group having 1 to 10 carbon atoms, which is independently unsubstituted or substituted, is preferably 1 to 6, and more preferably 1 to 3. As examples thereof, linear alkyl groups, Branched chain alkyl, cyclic alkyl, alkenyl, aryl, aralkyl, haloalkyl. Examples of the linear alkyl group include methyl, ethyl, propyl, hexyl, octyl, and decyl. Examples of the branched chain alkyl group include isopropyl, isobutyl, tert-butyl, and 2-ethylhexyl. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include 2-phenylethyl and 2-methyl-2-phenylethyl. Examples of the halogenated alkyl group include 3,3,3-trifluoropropyl, 2- (nonafluorobutyl) ethyl, and 2- (heptadecafluorooctyl) ethyl. As R 1 Of these, methyl and phenyl are preferred. [0038] In the formulae (1) and (2), R 2 System is independently alkyl, alkoxyalkyl, alkenyl or fluorenyl. Examples of the alkyl group include R and R. 1 The same examples of straight chain alkyl groups, branched chain alkyl groups, and cyclic alkyl groups exemplified in the above. Examples of the alkoxyalkyl group include methoxyethyl and methoxypropyl. Examples of the alkenyl group include R and R. 1 Those exemplified in the same. The carbon number is preferably from 1 to 8. Examples of the fluorenyl group include ethenyl and octyl. R 2 An alkyl group is preferred, and a methyl group and an ethyl group are particularly preferred. b is an integer from 2 to 100, preferably from 5 to 50. a is 0, 1, or 2, preferably 0. [0039] Preferred specific examples of the organopolysiloxane as the (D-II) component include the following. (Wherein Me is methyl). [0040] The viscosity of the organopolysiloxane of the (D-II) component at 25 ° C. is usually 0.01 to 30 Pa · s, preferably 0.01 to 10 Pa · s. When the viscosity is less than 0.01 Pa · s, there is a concern that oil leakage from the polysiloxane composition is likely to occur, and castability is liable to occur. When the viscosity is more than 30 mPa · s, the fluidity of the obtained polysiloxane composition is significantly deteriorated, which may cause deterioration of coating workability. Moreover, the viscosity is a measurement value obtained by using a rotary viscometer (the same applies hereinafter). [0041] The content of the (D-II) component is preferably 5 to 900 parts by mass, more preferably 10 to 900 parts by mass, and 20 to 700 parts by mass relative to 100 parts by mass of the component (A). For the better. [(E) component] In the polysiloxane composition of the present invention, the maximum value of (E) center particle diameter is 150 μm or more relative to the total amount of the polysiloxane composition, and SiO 2 Spherical glass beads or irregularly shaped glass with a content of 50% by mass or more are preferably 10% by mass or less. The component (E) is characterized in that the maximum value of the central particle diameter is larger than the average particle diameter of the component (B). The upper limit is not particularly limited, but may be set to 300 μm or less. When the (E) component is blended, the thermally conductive polysiloxane composition can be made into a desired hardened thickness of 150 μm or more even in a very small amount. Examples of the material include soda-lime glass, soda-lime silica glass, and borosilicate glass. From the viewpoint of the uniformity of the hardened thickness, the spherical shape is better than the irregular shape (E) component, and when the (E) component is spherical glass beads, the average sphericity is 0.8 or more as the (B) component. good. [0043] The component (E) is preferably added in a small amount within the scope of the present invention. Specifically, in order not to significantly reduce the thermal conductivity of the thermally conductive polysiloxane composition, compared with the polysiloxane composition, The total amount of (F) component is preferably 10% by mass or less (0 to 10% by mass). In addition, the measurement of the central particle diameter can be performed by a laser diffraction method using, for example, a "laser diffraction type particle size distribution measurement device SALD-2300" manufactured by Shimadzu Corporation. [0044] The thermally conductive polysiloxane composition of the present invention may be directly in this state, or a hardening agent may be further added to form a hardenable composition. [0045] In the case of forming a hardenable thermally conductive polysiloxane composition, the following three forms can be cited. The organopolysiloxane (A) which can be used as a matrix polymer is the one using the above (AI) to (A- III) An organopolysiloxane containing components and blended with the thermally conductive fillers (B) and (C). [I] Addition reaction hardening type thermally conductive polysiloxane composition [II] Condensation reaction hardening type thermally conductive polysiloxane composition [III] Organic peroxide hardening type thermally conductive polysiloxane composition rapidly hardens without From the viewpoint of generating byproducts, the [I] addition reaction-hardening type thermally conductive polysiloxane composition is preferred. Specific compositions will be shown below. [1] In the case where the addition reaction-hardening type thermally conductive polysiloxane composition is an addition reaction-hardening type thermally conductive polysiloxane composition that is hardened by a hydrosilylation reaction, the above ( A) In the case where the (AI) component shown above is used and further includes the following components, the hardener is the following (F) and (G) components. (F) Crosslinking agent is an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to a silicon atom, (G) a platinum group metal-based hardening catalyst, and (H) an addition reaction control as necessary [0047] [(F) component] An organohydrogenpolysiloxane system having at least two hydrogen atoms directly bonded to a silicon atom acts as a component of a crosslinking agent. Examples of the group of a silicon atom bond bonded to an organohydrogenpolysiloxane include the same linear alkyl groups, branched alkyl groups, cyclic alkyl groups, aryl groups, aralkyl groups, and halogenated groups as described above. The alkyl group is preferably an alkyl group or an aryl group, and particularly preferably a methyl group or a phenyl group. The viscosity of the (F) component at 25 ° C is not limited, but is preferably in the range of 1 to 100,000 mPa · s, and more preferably in the range of 1 to 5,000 mPa · s. The molecular structure of the component (F) is not limited, and examples thereof include a linear shape, a branched chain shape, a linear shape having a part of branches, a ring shape, and a dendritic shape (dendritic polymer shape). Examples of such an organic polysiloxane include a homopolymer having such a molecular structure, a copolymer consisting of such a molecular structure, or a mixture of these. [0048] Examples of the component (F) include dimethylhydrosiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, and trimethylsiloxy-terminated dimethyl at both ends of the molecular chain. Siloxane · methylhydrosilane copolymer, dimethylhydrosiloxy-terminated dimethylsiloxanes · methylhydrosiloxane copolymer at both ends of the molecular chain, formula: (CH 3 ) 3 SiO 1/2 Siloxane unit and formula shown: (CH 3 ) 2 HSiO 1/2 Siloxane unit and formula shown: SiO 4/2 The organosiloxane copolymer composed of the shown siloxane units can be used singly or in combination of two or more kinds. [0049] The compounding amount of the component (F) is an amount necessary to harden the polysiloxane composition, and specifically, 1 mole of the silicon atom-bonded alkenyl group in the component (AI) is represented by (F) The amount of silicon atom-bonded hydrogen atoms in the composition is preferably in the range of 0.1 to 10 mol, more preferably in the range of 0.1 to 5 mol, especially in the range of 0.1 to 3.0 mol. Better. This is because if the content of this component is less than the lower limit of the above range, the obtained polysiloxane composition tends to not sufficiently harden. On the other hand, if it exceeds the upper limit of the above range, it may be obtained. The silicone hardened material becomes very hard, and most of the surface cracks occur. (G) The platinum group metal-based hardening catalyst is a catalyst for promoting hardening of the polysiloxane composition, and examples thereof include platinum chloride, an alcohol solution of platinum chloride, and an olefin complex of platinum. Compounds, platinum alkenyl siloxane complexes, platinum carbonyl complexes. [0051] The compounding amount of the component (G) is an amount necessary to harden the polysiloxane composition, and specifically, the platinum metal in the component (G) becomes 0.01 relative to the (AI) component in mass units. The amount in the range of ~ 1,000 ppm is preferable, and the amount in the range of 0.1 to 500 ppm is particularly preferable. This is because when the blending amount of the (G) component is less than the lower limit of the above range, the obtained polysiloxane composition tends not to be sufficiently hardened. The hardening rate of the oxygen composition is still not significantly improved. (H) Hardening reaction inhibitor In order to adjust the hardening speed of the polysiloxane composition and improve the workability, a hardening reaction inhibitor may be added. Examples of the hardening reaction inhibitor include 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol. Acetylene-based compounds; 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne, and other ene-alkyne compounds; other fluorene-based compounds, phosphine-based compounds, The thiol-based compound or the like may be used alone or in a suitable combination of two or more. [0053] The blending amount of the (H) component is not particularly limited, and it is preferably 0.0001 to 1.0% by mass relative to the polysiloxane composition. By setting it as the said range, the workability or hardening speed of a polysiloxane composition becomes more suitable. [II] Condensation reaction-hardening thermally conductive polysiloxane composition In the case where the polysiloxane composition is a condensation-reaction-hardening thermally conductive polysiloxane composition, the above-mentioned (A) uses the above-mentioned (A) -II) component, and further including the following component, the hardener is the following (I) component. (I) Silane or a partial hydrolyzate thereof having at least 3 silicon atom-bondable hydrolyzable groups in one molecule, (J) A catalyst for a necessary condensation reaction [0055] As a silicon atom bond in the component (I) Examples of the hydrolyzable group include an alkoxy group, an alkoxyalkoxy group, a fluorenyloxy group, a ketoxime group, an alkenyloxy group, an amine group, an amineoxy group, and a fluorenylamino group as described above. In addition to the above hydrolyzable group, the silicon atom of the silane may be bonded to, for example, the same linear alkyl group, branched alkyl group, cyclic alkyl group, alkenyl group, aryl group, and aromatic group as described above. Alkyl, halogenated alkyl. Examples of such a silane or a partial hydrolyzate thereof include methyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, and ethyl orthosilicate. [0056] The compounding amount of the component (I) is an amount necessary to harden the polysiloxane composition, and specifically, it is preferably within a range of 0.01 to 20 parts by mass relative to 100 parts by mass of the component (A-II). In particular, it is preferably within a range of 0.1 to 10 parts by mass. This is because if the content of the silane or a part of the hydrolysate thereof is less than the lower limit of the above range, there is a concern that the storage stability of the obtained polysilicone composition will be reduced. On the other hand, if it exceeds the upper limit of the above range When the amount is large, there is a concern that the hardening of the obtained polysiloxane composition is significantly slowed. [0057] The component (J) is an optional component, and it is not necessary when a silane having a hydrolyzable group such as an amine group, an amine group, or a ketoxime group is used as a hardener. Examples of the catalyst for such a condensation reaction include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; titanium diisopropoxybis (ethylenylacetate); Organo-titanium chelate compounds such as isopropoxy bis (ethyl acetoacetate) titanium; organoaluminum compounds such as ginsyl (ethylpyruvate) and ginsyl (ethyl acetoacetate); four (Acetylpyruvate) organoaluminum compounds such as zirconium, zirconium tetrabutyrate, etc .; organotin compounds such as dibutyltin dicaprylate, dibutyltin dilaurate, butyltin-2-ethylhexanoate, etc .; naphthenes Metal salts of organic carboxylic acids such as tin acid, tin oleate, tin butylate, cobalt naphthenate, zinc stearate; amine compounds such as hexylamine, dodecylamine phosphate, and their salts; benzyl Grade 4 ammonium salts such as triethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dialkylhydroxyamines such as dimethylhydroxylamine and diethylhydroxylamine; Organic silicon compounds. [0058] When the component (J) is blended, the blending amount may be an amount necessary to harden the polysiloxane composition. Specifically, it is 0.01 to 20 masses based on 100 mass parts of the (A) component. The content is preferably within a range of 0.1 to 10 parts by mass. This is because when the catalyst is necessary, when the content of the catalyst is less than the lower limit of the above range, the obtained polysiloxane composition tends to not sufficiently harden, and on the other hand, it exceeds the above range. When the upper limit is exceeded, the storage stability of the obtained polysiloxane composition tends to decrease. [III] In the case where the polysiloxane composition is an organic peroxide-hardened thermally conductive polysiloxane composition, the above (A) uses the above-mentioned In the case where the component (A-III) is shown and further includes the following components, the hardener is the following (K) component. (K) Organic peroxide [0060] Examples of the (K) organic peroxide include benzylfluorenyl peroxide, dicumyl peroxide, 2,5-dimethylbis (2 , 5-t-butylperoxy) hexane, di-t-butylperoxide, t-butylperbenzoate. [0061] The compounding amount of the (K) component is an amount necessary to harden the polysiloxane composition. Specifically, it is 0.1 to 5 parts with respect to 100 parts by mass of the organic polysiloxane of the (A-III) component. The range of parts by mass is preferred. (K) When the blending amount of the components is less than the lower limit of the above range, the obtained polysilicon oxide composition tends not to be sufficiently hardened. On the other hand, even if the blended amount exceeds the upper limit of the above range, the obtained polysilicon composition tends to not sufficiently harden. The hardening rate of the oxygen composition will not increase significantly, and there will be anxiety about the cause of the void. [0062] Furthermore, the polysiloxane composition of the present invention may contain other arbitrary components, such as zinc oxide, fumed silica, precipitated silica, A filler such as fumed titanium oxide. The surface of this filler is a filler that is hydrophobized by an organic silicon compound; 3-glycidoxypropyltrimethoxysilane, 3-methacryloxy Adhesives such as propyltrimethoxysilane; others, flame retardants and plasticizers such as pigments, dyes, fluorescent dyes, heat-resistant additives, and triazole compounds. In addition, as long as the effect of the present invention is not impaired, a thermally conductive filler other than the component (B) may be blended, and examples thereof include aluminum powder, copper powder, silver powder, nickel powder, gold powder, and zinc oxide powder. , Magnesium oxide powder, boron nitride powder, aluminum nitride powder, diamond powder, carbon powder, etc. [Manufacturing Method] The polysiloxane composition of the present invention can be prepared by uniformly mixing a predetermined amount of each of the components described above. For example, a method for producing a thermally conductive polysiloxane composition is obtained by mixing (A) an organic polysiloxane, (B) an average sphericity of 0.8 or more, and 30 hydroxyl groups per nm. 2 Below, a spherical alumina powder having an average particle diameter of 10 μm or more and less than 50 μm, and a coarse particle proportion of 96 to 150 μm in the laser diffraction type particle size distribution, which accounts for 0.1 to 30% by mass of the entire (B) component, and (C) Step of spherical or irregular alumina powder having an average particle diameter of 0.1 to 5 μm; wherein the mixing ratio volume ratio ((B): (C)) of the above (B) component to (C) component is 5: 5 to 9.5 : 0.5, the total amount of (B) component and (C) component accounts for more than 50% by volume and less than 80% by volume of the composition, and the thermal conductivity of the composition at 25 ° C is 1.2W / according to the hot dish method of ISO 22007-2 Above m · K is less than 5.5 W / m · K, and the viscosity of the composition at 25 ° C is 5 to 800 Pa · s when measured with a spiral viscometer at 10 rpm. Further, a step of mixing arbitrary components may be included. [Thermal conductive polysiloxane composition] The thermal conductivity of the thermal conductive polysiloxane composition is 1.2 W / m · K or more and less than 5.5 W / m · K in accordance with the hot disc method of ISO 22007-2. 1.5 ~ 5.5W / m ・ K is preferable. The measurement temperature was 25 ° C. [0065] The viscosity of the thermally conductive polysiloxane composition at 25 ° C. is 5 to 800 Pa · s, and preferably 30 to 600 Pa · s when measured with a spiral viscometer at a rotation number of 10 rpm. [Hardened material] In the case where the polysiloxane composition is hardenable, the method of hardening it is not limited, and examples thereof include a method in which the polysiloxane composition is formed and then left at room temperature; After the polysiloxane composition is formed, it is heated to 40 to 200 ° C, and a polysiloxane elastomer molded product can be obtained. In addition, the properties of the silicone rubber thus obtained are not limited, and examples thereof include a gel-like shape, a low-hardness rubber shape, and a high-hardness rubber shape. The hardened thickness is preferably 150 μm or more. The upper limit is not particularly limited. When considering the size of the exothermic electronic component using the composition, it is preferably 5 mm or less. In addition, the hardness of the hardened material is such that the polysiloxane composition flows into the molding die so as to have a hardened thickness of 6 mm, and is hardened at 100 ° C for 1 hour. Second, when 2 pieces of 6mm hardened material are stacked and measured with an Asker C hardness meter, it is preferably 3 to 90, and more preferably 5 to 80. [0067] The thermal conductivity of the hardened material at 150 ° C is preferably 0.7 W / m · K or less and less than 4.0 W / m · K according to the hot dish method of ISO 22007-2, and 1.0 W / m · K or less. 4.0W / m ・ K is better. In addition, the thermal conductivity of the cured product at 25 ° C is 1.2 W / m · K or more and less than 5.5 W / m · K, and preferably 1.5 to 5.5 W / m · K according to the hot disc method of ISO 22007-2. In addition, 25 ° C and 150 ° C refer to the measurement temperature. By having the above-mentioned thermal conductivity at 150 ° C, one having excellent thermal conductivity at high temperature can be obtained. When the horizontal axis is the temperature and the vertical axis is the thermal conductivity, the thermal conductivity obtained at 25 ° C and 150 ° C is plotted as a single straight line. The thermal conductivity estimated from each temperature is also included in the graph. In the present invention. [Examples] [0068] Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited by the following examples. In the following formula, Me is a methyl group. [0069] The components used in the examples and comparative examples are as follows. First, the following components are prepared. (A) Component A-1: dimethylpolysiloxane A-2 having a viscosity of 400 mPa · s at 25 ° C, both ends of which are terminated with dimethylvinylsilyl group, and a Vi group amount of 0.018moL / 100g : KF-54, manufactured by Shin-Etsu Chemical Industry, with specific gravity (25 ° C) of 1.07 and dynamic viscosity (25 ° C) of 400mm 2 / s of both ends of the molecular chain of trimethylsiloxy-terminated dimethylsiloxane and diphenylsilane copolymer A-3: KF-50-1,000cs manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity (25 ° C) 1.00, dynamic viscosity (25 ° C) is 1,000mm 2 / s molecular chain trimethylsiloxy-terminated dimethylsiloxane-diphenylsiloxane copolymer at both ends [0070] (B) Spherical alumina having the properties shown in the following table The coarse particle content ratio shown here refers to a coarse particle ratio of 96 to 150 μm relative to the entire particle size distribution obtained under a laser diffraction type particle size distribution. [0071] (C) A component having a ball having the properties shown in the following table Shaped or irregular shaped alumina (D) Component D-1: Organic polysiloxane represented by the following formula (E) Component E-1: MIL particle size series M-9 made by Potters Ballotini (the maximum value of the central particle diameter is 180 μm), SiO 2 Spherical glass beads with a content of 99.4% by mass [0074] (F) Component F-1: Organic hydrogen polysiloxane represented by the following formula F-2: Organic hydrogen polysiloxane represented by the following formula (G) Component G-1: Platinum chloride-1,3-divinyltetramethyldisilaxane complex having a platinum concentration of 1% by mass [0076] (H) Component H-1 : 50% toluene solution of 1-ethynyl-1-cyclohexanol [0077] [Examples 1-16, Comparative Examples 1-16] Using the above components, a polysiloxane composition was prepared in the following manner and used This polysiloxane composition is used to obtain a thermally conductive molded article. Evaluation was performed by the method shown below using these. The results are recorded in a table. [0078] With the compounding amounts shown in the following Tables 3 to 6, the above components were mixed as described below to obtain a polysiloxane composition. That is, in a 5 liter gate mixer (manufactured by Inoue Seisakusho Co., Ltd., trade name: 5 liter planetary mixer), (A) and (B) were used at the mixing amounts shown in Table 1. , (C) and (D) components, degassed and heated and mixed at 150 ° C for 2 hours. After that, it was cooled down to normal temperature (25 ° C), and the component (G) was added, and mixed at room temperature (25 ° C) until uniform, and then the component (H) was added, and mixed at room temperature (25 ° C) until uniform. until. The components (E) and (F) were further added, and degassed and mixed at room temperature to make it uniform. The polysiloxane composition thus obtained was evaluated for initial viscosity, hardness after hardening, and thermal conductivity before and after hardening by the methods described below. The results are recorded in a table. [Evaluation of Initial Viscosity] The initial viscosity of the polysiloxane composition was a value of 25 ° C. This measurement was performed using a spiral viscometer: MALCOM viscometer (model PC-10AA, rotation number 10 rpm). [Evaluation of Hardness After Hardening] The silicone composition was fed into a molding die having a hardened thickness of 6 mm, and was hardened at 100 ° C for 1 hour. Next, two pieces of hardened material having a thickness of 6 mm were overlapped and measured using an Asker C hardness tester. [Evaluation of thermal conductivity] Thermal conductivity before curing of polysilicone composition at 25 ° C was measured using TPS 2500 S, a thermo-physical property measuring device manufactured by Kyoto Electronics Industry Co., Ltd. (based on ISO 22007-2 hot-disk method) . In addition, the polysiloxane composition was fed into a molding die having a hardened thickness of 6 mm, and was hardened at 100 ° C for 1 hour. For the obtained hardened material having a thickness of 6 mm, the thermal conductivity of the hardened material at 25 ° C and 150 ° C was measured. [0080] [0081] [0082] [0083]