201204786 六、發明說明： 【發明所屬之技術領域】 本發明係關於硬化性有機聚矽氧烷組成物及半 置，詳細而言，係關於用以形成即使在高溫/低溫 循環條件下，耐龜裂性亦良好之硬化物之硬化性有 氧烷組成物，以及藉由該硬化物被覆半導體元件且 佳之半導體裝置。 【先前技術】 半導體裝置係使用在各種領域中，構成半導體 半導體元件等亦處在各種環境下，有時會大幅地受 響。爲人所知者，尤其在將LED通電及點燈時，會 遽的溫度上升而使LED元件受到熱衝擊。所以會因 件的重覆點燈及熄滅而使LED元件暴露在嚴苛的溫 中。 以此般LED元件爲首之半導體元件的密封材料 是使用環氧樹脂。然而，由於環氧樹脂的彈性率高 線可能受到溫度循環等所造成的應力影響而產生斷 是在環氧樹脂中產生龜裂。此外，尤其當用作爲發 的密封材料時，起因於環氧樹脂對LED晶片所造成 ’而存在著因半導體材料的結晶結構崩解所導致之 率的降低之疑慮。 作爲該對策，係已循例採用下列既定方法者， 室溫硬化型的聚矽氧烷橡膠用作爲緩衝材，並以環 導體裝 的溫度 機聚矽 可靠度 裝置之 到該影 引起急 LED元 度循環 ，一般 ，接合 線，或 光元件 的應力 發光效 亦即將 氧樹脂 -5- 201204786 將其外側密封之方法。然而，此方法中爲人所知者，由於 環氧樹脂未黏著於聚矽氧烷樹脂，所以仍會藉由溫度循環 等應力而在環氧樹脂與聚矽氧烷樹脂之界面產生剝離，或 是取光效率隨時間經過而極度降低。 因此，係有人提出使用聚矽氧烷樹脂作爲取代環氧樹 脂之材料者（例如參照專利文獻1、2及3 )。聚矽氧烷樹 脂，由於耐熱性、耐候性、耐變色性較環氧樹脂佳，所以 近年來以藍色LED、白色LED爲中心來使用之例子乃逐漸 增加。 然而，此等聚矽氧烷樹脂，與環氧樹脂相比，雖然彈 性率低，但彎曲強度等機械特性亦低，故具有由於將LED 通電及點燈時所產生之熱衝擊而容易產生龜裂之問題。 〔先前技術文獻〕 〔專利文獻〕 [專利文獻1]日本特開平1 1-1619號公報 [專利文獻2]日本特開2002-265787號公報 [專利文獻3]日本特開2004-1 861 68號公報 【發明內容】 (發明所欲解決之課題） 本發明係鑒於上述情形而創作出之發明，其係以提供 一種具有高透明性，且尤其對熱衝擊具有高耐性，即使在 嚴苛的溫度循環下亦不易產生龜裂之硬化性有機聚矽氧烷 組成物者爲目的。 201204786 (用以解決課題之手段） 爲了解決上述課題，本發明係提供一種硬化性有機聚 矽氧烷組成物，其特徵爲至少含有： (A-Ι):於1分子中至少具有2個經矽原子鍵結的烯 基’並且具有含有由下列一般式（1)表示之矽氧烷單位 5〜70莫耳％的分枝構造之有機聚矽氧烷， R S i Ο 3 /2 (1 ) (式中，R爲取代或非取代的一價烴基），及 (A-II ):於1分子中至少具有2個經矽原子鍵結的烯 基，並且具有含有由上述一般式（1)表示之矽氧烷單位 至少超過70莫耳％的分枝構造之有機聚矽氧烷， 其中，（A-Ι)及（A-II)的含量以重量單位計爲（八-I )/( A-Π ) =1 /99-99/1 的量； (B):由下列平均組成式（2)表示，於1分子中至 少具有2個經矽原子鍵結的氫原子，且在25 °C時的黏度爲 lOOOmPas以下之直鏈狀有機氫聚矽氧烷， R 1 aHb S i 0(4-a-b )/2 (2) (式中，R1爲扣除脂肪族不飽和烴基之取代或非取代 的一價烴基，a、b爲滿足 0.7SaS2.1、O.OlSbSl.O、且 0.8 S a + b各2.9之正數）， 其中，鍵結於該砂原子的氫原子數，相對於每1個（ A-Ι)及（A-II)成分中之經砂原子鍵結的嫌基之合計數’ 爲0.3-10個之量；以及 201204786 (C):加成反應觸媒，其含量爲觸媒量。 此般本發明之硬化性有機聚矽氧烷組成物，其耐變色 性佳，故具有高透明性，尤其對熱衝擊具有高耐性，即使 在嚴苛的溫度循環下亦不易產生龜裂或剝離。 此時，係以前述（A-Ι)成分在25 °c時爲液狀，並且 前述（A-II)成分在25°C時爲固體狀者爲佳。 如此，若在25°C時（A-Ι)成分爲液狀且（A-II)成分 爲固體狀，則更容易具有耐熱衝擊性及強度。 此外，此時前述（A-I) 、（A-II)及（B)的各成分 ，較佳係於1分子中具有至少1個經矽原子鍵結的芳基。 如此，若於（A-I) ~(B)之各成分的1分子中具有至 少1個經矽原子鍵結的芳基，則可得到作爲聚矽氧烷樹脂 所需的硬度及強度，並且硬化後之被覆保護材的耐熱性或 低溫特性、透明性特別良好，且熱衝擊試驗時亦可得到可 靠度。 此外，本發明係提供一種半導體裝置，其特徵爲：藉 由前述硬化性有機聚矽氧烷組成物的硬化物來被覆半導體 元件。 如此，若使用耐熱衝擊性特高且透明性佳之本發明之 硬化性有機聚矽氧烷組成物來被覆半導體元件，則所得之 半導體裝置可應用在各領域中且具有用性。 此時，前述半導體元件較佳爲發光元件。 本發明之硬化性有機聚矽氧烷組成物，尤其對熱衝擊 具有高耐性而不易產生龜裂，因此如前述般，特別適合於 -8- 201204786 作爲用以被覆處在嚴苛的溫度循環下的發光元件之密封材 料。 發明之效果： 如以上所說明，本發明之硬化性有機聚矽氧烷組成物 ，其硬化物的耐衝擊性特高，且透明性佳。因此，係有用 於作爲發光二極體元件及其他光學裝置用或光學零件用之 材料，且進一步有用於作爲電機及電子、OA機器、汽車 、精密機械等各種領域中之封裝材料。 【實施方式】 以下更詳細地說明本發明。 如上述般，以往所使用之半導體元件用密封材料，乃 具有由於將LED通電及點燈時所產生之熱衝擊而容易產生 龜裂之問題，因而要求即使在嚴苛的溫度循環下亦不易產 生龜裂或剝離之密封材料。 因此，本發明者們進行精心探討，結果發現到，藉由 組合具有分枝單位含量不同的2種分枝構造之有機聚矽氧 烷，可達成上述課題，因而完成一種硬化性有機聚矽氧烷 組成物。 亦即，本發明之硬化性有機聚矽氧烷組成物的特徵爲 至少含有： (A-Ι):於1分子中至少具有2個經矽原子鍵結的烯 基’並且具有含有由下列一般式（1)表示之矽氧烷單位 -9 - 201204786 5〜7 0莫耳％的分枝構造之有機聚矽氧烷， RSi〇3/2 (1) (式中，R爲取代或非取代的一價烴基），及 (A-II ):於1分子中至少具有2個經矽原子鍵結的烯 基，並且具有含有由上述一般式（1)表示之矽氧烷單位 至少超過70莫耳％的分枝構造之有機聚矽氧烷， 其中，（A-Ι)及（A-II)的含量以重量單位計爲（八-I ) / ( A-II ) =1/99~99/1 的量； (B ):由下列平均組成式（2 )表示，於1分子中至 少具有2個經矽原子鍵結的氫原子，且在25 °C時的黏度爲 lOOOmPas以下之直鏈狀有機氫聚矽氧烷， R 1 a H b s i Ο ( 4 - a-b )/2 (2 ) (式中，R1爲扣除脂肪族不飽和烴基之取代或非取代 的一價烴基，a、b爲滿足 0.7Sa$2.1、O.OlSbSl.O、且 0.8 S a + b$ 2.9之正數）， 其中，鍵結於該矽原子的氫原子數，相對於每1個（ A-I )及（A-II)成分中之經矽原子鍵結的烯基之合計數’ 爲0.3〜1 0個之量；以及 (C):加成反應觸媒，其含量爲觸媒量。 以下詳細說明本發明之各成分。 以下亦有將（A-I )成分與（A_II )合稱爲（A )成分 時。 < (A-I )成分 > -10- 201204786 (A-I )成分’係於丨分子中至少具有2個經矽原子鍵 結的稀基’並且具有由下列—般式（1)表示之矽氧烷單 位5〜7 0莫耳％，較佳是具有在2yc時爲液狀的分枝構造之 有機聚矽氧烷。（A-Ι)成分，爲將對熱衝擊具有高耐性 且即使在嚴苛的溫度循環下亦不易產生龜裂之特性，賦予 至本發明組成物之成分。因此，該RSi〇3/2單位的含量爲 5〜70莫耳％ ’尤佳爲20〜60莫耳％。低於5莫耳％時，無法充 份地得到硬化物的耐衝擊性，高於7 0莫耳％時，2 5 t時難 以良好地保持液狀狀態。 R S i 〇 3 /2 (1) 其他砂氧院單位，可列舉出R2Si02/2單位、R3Si01/2單 位、Si04/2單位（式中，R爲同一或不同種之取代或非取代 的一價烴基）。此時，R的一部分可由經基及/或院氧基所 取代。 此等當中，較佳爲R2Si02/2單位及/或113310 U 2單位。 上述一般式（1)中，R所表示之鍵結於矽原子之取代 或非取代的一價烴基，通常爲碳數1〜20，特佳爲1〜10之非 取代或取代的一價烴基，此般烴基，具體可列舉出甲基、 乙基、丙基、丁基、戊基、己基、環己基、庚基等之烷基 ;苯基、甲苯基、二甲苯基、萘基等之芳基；苄基、苯乙 基等之芳烷基；乙烯基、烯丙基、丁烯基、戊烯基 '己烯 基、庚烯基等之烯基等的不飽和烴基；氯甲基、3-氯丙基 、3，3,3 -三氟丙基等之鹵化垸基等。 於（A-I )成分的1分子中，必須含有至少2個經矽原 -11 - 201204786 子鍵結的稀基’此外’於此等全部R中，烯基爲〇1〜2〇莫 耳％ ’較佳爲0.5〜1〇莫耳％。當烯基的含量爲〇.卜“莫耳％ 時’可得到作爲聚矽氧烷樹脂的適當硬度，且耐龜裂性更 佳。 此外’ （A-Ι)成分之經矽原子鍵結的全部有機基中 ’較佳係含有經矽原子鍵結的芳基，尤佳爲5〜100莫耳％, 特佳爲10〜100莫耳％。芳基特佳爲苯基。 < (A-II)成分〉 (A-II)成分’係於1分子中至少具有2個經矽原子鍵 結的燃基’並且具有由上述—般式（1) (RSi〇3/2)表示 之砂氧院單位至少超過7〇莫耳％，較佳是具有在25t時爲 固體狀的分枝構造之有機聚矽氧烷。（A-II )成分，爲將 強度賦予至本發明組成物之成分。因此，該RSi〇3/2單位的 含量須至少超過7 0莫耳％，-尤佳爲7 5莫耳％以上》 .其他矽氧烷單位，與（A-I )成分相同，可列舉出 R2Si02/2單位、R3Si〇1/2單位、si〇4/2單位，此外，式中的 R與上述相同。 (A-Η)成分中，於（A-II )成分的1分子中必須含有 至少2個經矽原子鍵結的烯基，此外，於此等全部R中，烯 基爲1〜30莫耳％ ’較佳爲5~2〇莫耳％。當烯基的含量爲 1〜3 0莫耳％時，可得到特別適合作爲聚矽氧烷樹脂的硬度 ’且耐龜裂性更佳。 此外’ （A-II )成分之經矽原子鍵結的全部有機基中 -12- 201204786 ’較佳係含有經矽原子鍵結的芳基，尤佳爲5〜1〇〇莫耳％， 特佳爲1 0〜1 00莫耳％。芳基特佳爲苯基。 此等當中’較佳爲RzSiO2,2單位及/或R3SiOW2單位。 (A-II)成分的調配量’是本成分相對於（a-〗）成分 之含量比以重量單位計爲1/99〜99/1之量，較佳爲 10/90~90/10之量’特佳爲20/80~80/20之量《此係由於當 (A-II )成分的含量未達上述範圍的下限時，所得之硬化 物的強度有降低之傾向之故。另一方面，超過上述範圍的 上限時’所得之組成物的處理操作性降低，或是所得之硬 化物的強度有變得極硬之傾向之故。 本發明中，上述一般式（1)表示之矽氧烷單位，（ A-Ι)成分所含有者與（A-II)成分所含有者可爲相同或不 同。 < (B )成分> (B)成分之有機氫聚矽氧烷，是由下列平均組成式 (2)表示，於1分子中至少具有2個經矽原子鍵結的氫原 子，且在25°C時的黏度爲lOOOmPas以下，通常爲 0.5〜lOOOmPas，較佳爲1〜500mPas之直鏈狀有機氫聚矽氧 烷。 R 1 a H b S i Ο ( 4 - a - b )/2 (2) (式中，R 1爲扣除脂肪族不飽和烴基之取代或非取代 的一價烴基，a、b爲滿足 0.7SaS2.1、O.OlSbSl.O、且 0.8 S a + b S 2.9之正數） -13- 201204786 在此，R1較佳爲碳數1~12，特佳爲碳數1~10之扣除脂 肪族不飽和烴基之取代或非取代的一價烴基，此般烴基， 具體可列舉出甲基、乙基、丙基、丁基、戊基、己基、環 己基、庚基等之烷基：苯基、甲苯基、二甲苯基、萘基等 之芳基；苄基、苯乙基等之芳烷基；氯甲基、3-氯丙基、 3，3,3 -二氣丙基等之鹵化院基等。此外，a、b爲滿足0.7S 2.1，較佳爲 l.OSag 2.0，O.OlgbS 1.0，較佳爲 0.02 SbSl.O，尤佳爲 O.lOSbSl.O，且 〇_8S a + b S 2.9，較佳 爲1.01Sa + bS2.8，尤佳爲1.6Sa + bS2.7之正數，當b未 達0.01時，無法得到作爲聚矽氧烷樹脂的充分硬度。 該有機氫聚矽氧烷，其分子結構並無特別限制，但較 佳爲直鏈狀，就與（A)成分之相溶性、硬化物的物性等 觀點來看，鍵結於矽原子之R1與Η (氫原子）中，苯基爲5 莫耳％以上，較佳爲10〜50莫耳％。R1中爲苯基以外時，較 佳爲甲基。 此外，（Β)成分之有機氫聚矽氧烷的調配量，較佳 是以鍵結於該矽原子的氫原子數，相對於每1個（Α)成分 中之鍵結於矽原子的烯基之合計數，爲0.3~10個之量來調 配。此係由於未達〇·3個時，硬化不足，超過1〇個時，硬 化物變得過脆之故。較佳爲0.5〜5個。 < (C )成分> (C)成分之加成反應觸媒，爲（Α)成分與（Β)成 分的加成反應中之進行交聯的觸媒，該例子可列舉出氯鈾 14- 201204786 酸、氯鈾酸與一價醇之反應物、氯鉑酸之烯烴錯合物 鉑酸與乙烯矽氧烷之配位化合物，鉑黑等之鈾系觸媒 外有鈀系觸媒、铑系觸媒等，就觸媒效率高之方面來 通常使用鉑觸媒。此外，尤其在本用途中使用在電子 之密封型led的製作時，較佳爲不會有腐蝕金屬的疑 低氯觸媒，當中較佳爲經不含氯成分之二乙烯基四甲 矽氧烷、二乙烯基二苯基二甲基二矽氧烷等所改質者 此等加成反應觸媒可單獨使用1種或倂用2種以上 該加成反應觸媒的調配量，爲作用爲觸媒之有效 觸媒量），較佳是相對於（A)成分與（B)成分的合 爲l~1000ppm。lppm以上時，可使硬化以適度的速度 ，lOOOppm以下時，亦不會使可作業時間過度縮短， 化物不易黃變而具經濟性。特佳爲5〜1 0 Op p m。 <任意成分> 本發明之組成物中，作爲上述（A ) ~ ( C )成分 之任意成分，例如，均可使用被視爲對加成反應觸媒 硬化抑制效果之化合物之以往所知的控制劑化合物。 化合物，可例示出三苯基膦等之含磷化合物，三丁胺 甲基伸已二胺、苯並三唑等之含氮化合物，含硫化合 乙炔系化合物，含有2個以上的烯基之化合物，氫過 化合物，馬來酸衍生物等。控制劑化合物所帶來之硬 遲效果的程度，係因控制劑化合物之化學結構而有極 同，所以控制劑化合物的添加量，較佳係針對所使用 、氯 、此 看， 領域 慮之 基二 量（ 計量 進行 且硬 以外 具有 此般 或四 物， 氧基 化延 大不 之各 -15- 201204786 控制劑化合物來調整爲最適量，一般而言，室溫下可得到 長期儲存安定性且不會阻礙硬化之範圍內的量，通常相對 於（A-Ι)成分與（A-II)成分的合計1〇〇質量份，是以〇,5 質量份以下，較佳爲0.01〜0.3質量份的量來使用。 此外，本發明之組成物中，亦可含有用以提升該黏著 性之黏著賦予劑。該黏著賦予劑，較佳是於1分子中具有 至少1個鍵結於矽原子的烷氧基之有機矽化合物。該烷氧 基可例示出甲氧基、乙氧基、丙氧基、丁氧基、甲氧乙氧 基，特佳爲甲氧基。此外，該有機矽化合物之鍵結於矽原 子的烷氧基以外之基，可列舉出與例示作爲R基者相同， 通常爲碳數1〜12，較佳爲碳數卜10之非取代或經鹵素取代 的一價烴基，除此之外，可列舉出γ-環氧丙氧基丙基、β-(3，4-環氧環己基）乙基等之經環氧官能基取代的烷基、 氫原子等，較佳可列舉出甲基、乙基、丙基、苯基、乙烯 基、氫原子、γ-環氧丙氧基丙基。 此外，本發明係提供一種藉由上述本發明之硬化性有 機聚矽氧烷組成物所被覆保護之半導體裝置。 本發明之半導體裝置的一例，可列舉出第1圖所示者 ，但並不限定於此。在此，第1圖中，1爲殼體，2爲發光 元件，3、4爲引線電極，5爲焊晶材，6爲金線，7爲密封 樹脂（本發明之組成物）。 此般本發明之半導體裝置8，由於裝置的耐熱、耐濕 、耐光性佳且裝置不會腐蝕，因此可提供一種可靠度佳之 半導體裝置，產業上乃具有極大優勢。 -16- 201204786 〔實施例〕 以下顯示實施例及比較例來具體說明本發明，但本發 明並不限定於下列實施例等。 [實施例1] 將具有由平均單位式：（PhSi03/2)〇.5[(CH2 = CH) MediOo.^oj^MesSiOo.5)〇.25表示之液狀分枝結構之有機 聚矽氧烷[在25 °C時的黏度爲35 OOmP as、經矽原子鍵結的 乙烯基之含有率=12·5莫耳％、經矽原子鍵結的全部有機基 中之經矽原子鍵結的苯基之含有率=25莫耳％、經標準苯乙 烯換算後的重量平均分子量=1200]50質量份、具有由 (PhSiOwh.sUCHfCWMezSiOo」]。」表示之固體狀分枝結 構之有機聚矽氧烷[經矽原子鍵結的乙烯基之含有率=14.3 莫耳％、經矽原子鍵結的全部有機基中之經矽原子鍵結的 苯基之含有率=5 7莫耳％、經標準苯乙烯換算後的重量平均 分子量=23 50]50 質量份、具有 HMezSiCKPl^SiOhSiMezH 的 結構且黏度爲4mPas之有機氫聚矽氧烷30質量份、含有氯 鉛酸/1,3-二乙烯四甲基二矽氧烷錯合物以鉑原子含量計爲 1質量％之甲苯溶液0.06質量份、乙炔基環己醇0.05質量份 、及γ -環氧丙氧基丙基三甲氧矽烷3質量份均一地混合， 而調製出聚矽氧烷組成物（U)。在150 °C下將該聚矽氧烷 組成物（U )加熱4小時使其硬化，硬度以Shore D計爲60 201204786 [實施例2] 將具有由平均單位式：（PhSi03/2)〇.5[(CH2 = CH) "已28丨〇().5]〇.25(^^633丨〇().5)0.25表不之液狀分枝結構之有機 聚砂氧院[在25°C時的黏度爲3500mPas、經砂原子鍵結的 乙烯基之含有率=12.5莫耳％、經矽原子鍵結的有機基中之 經矽原子鍵結的苯基之含有率=2 5莫耳％、經標準苯乙烯換 算後的重量平均分子量=12〇〇]80質量份、具有由 (卩118丨〇3,2)。.75[(〇112 = ^11'1)^4623丨0。.5]。.25表不之固體狀分枝 結構之有機聚矽氧烷[經矽原子鍵結的乙烯基之含有率=17 莫耳％、經矽原子鍵結的全部有機基中之經矽原子鍵結的 苯基之含有率=50莫耳％、經標準苯乙烯換算後的重量平均 分子量=1 600] 20質量份、相對於經矽原子鍵結的氫原子、 苯基及甲基之合計具有30莫耳％的苯基之氫氣產生量 l4〇ml/g且黏度2〇mPaS之有機氫聚矽氧烷32質量份、含有 氯鈾酸/1，3 -二乙烯四甲基二矽氧烷錯合物以鈾原子含量計 爲1質量％之甲苯溶液0.5質量份、乙炔基環己醇0.05質量 份、及γ-環氧丙氧基丙基三甲氧矽烷3質量份均一地混合 ，而調製出聚矽氧烷組成物（V)。在150 °C下將該聚矽氧 烷組成物（V )加熱4小時使其硬化，硬度以Shore D計爲 6 5〇 [實施例3] 將具有由平均單位式：（PhSiO^h.^KCHpCH) -18- 201204786201204786 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition of a hardenable organopolyoxane and a semi-set, in particular, for forming a turtle resistant even under high temperature/low temperature cycling conditions A hardenable aerobic alkane composition of a cured product which is also excellent in cracking property, and a semiconductor device which is coated with a semiconductor element by the cured product. [Prior Art] Semiconductor devices are used in various fields, and semiconductor semiconductor devices and the like are also in various environments, and may be greatly affected. Known, especially when the LED is energized and lit, the temperature of the crucible rises and the LED element is thermally shocked. Therefore, the LED components are exposed to severe temperatures due to repeated lighting and extinction. The sealing material of the semiconductor element including the LED element is an epoxy resin. However, since the elastic modulus of the epoxy resin may be affected by stress caused by temperature cycling or the like, cracking occurs in the epoxy resin. Further, particularly when used as a sealing material for hair, there is a concern that the epoxy resin is caused by the epoxy resin on the LED wafer, and the rate of collapse of the crystal structure of the semiconductor material is lowered. As a countermeasure, the following established methods have been used, and a room temperature hardening type polyoxyalkylene rubber is used as a cushioning material, and a temperature device with a ring conductor is used for the reliability of the device to cause an acute LED factor. The cycle, in general, the bonding wire, or the stress illuminating effect of the optical component is also the method of sealing the outside of the epoxy resin-5-201204786. However, as is well known in the art, since the epoxy resin is not adhered to the polyoxyalkylene resin, peeling occurs at the interface between the epoxy resin and the polyoxyalkylene resin by stress such as temperature cycling, or It is the light extraction efficiency that is extremely reduced with time. Therefore, it has been proposed to use a polyoxyalkylene resin as a material for replacing an epoxy resin (for example, refer to Patent Documents 1, 2 and 3). As a result of the heat resistance, weather resistance, and discoloration resistance of the polyoxyalkylene resin, the use of blue LEDs and white LEDs has been increasing in recent years. However, these polyoxyalkylene resins have lower elastic modulus than epoxy resins, but have low mechanical properties such as bending strength. Therefore, they have a tendency to generate turtles due to thermal shock generated when the LEDs are energized and lighted. The problem of cracking. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-265787 [Patent Document 3] SUMMARY OF THE INVENTION (Problem to be Solved by the Invention) The present invention has been made in view of the above circumstances, and provides an object having high transparency and high resistance especially to thermal shock even at severe temperatures. For the purpose of cracking the hardened organopolyoxane composition which is not likely to be generated under circulation. 201204786 (Means for Solving the Problems) In order to solve the above problems, the present invention provides a curable organopolyoxane composition characterized by comprising at least: (A-Ι): having at least two passes in one molecule a hydrazine-bonded alkenyl group and having an organic polyoxane having a branched structure of 5 to 70 mol% of a decane unit represented by the following general formula (1), RS i Ο 3 /2 (1) (wherein R is a substituted or unsubstituted monovalent hydrocarbon group), and (A-II): an alkenyl group having at least two fluorene-bonded atoms in one molecule, and having a general formula (1) An organopolysiloxane having a branched structure of at least 70 mol%, wherein the content of (A-Ι) and (A-II) is (eight-I)/(by weight) A-Π) =1 /99-99/1 amount; (B): represented by the following average composition formula (2), having at least 2 hydrogen atoms bonded via a ruthenium atom in one molecule, and at 25 ° A linear organohydrogenpolyoxyalkylene having a viscosity of less than 100 mPas at C, R 1 aHb S i 0(4-ab )/2 (2) (wherein R1 is a substitution or a subtraction of an aliphatic unsaturated hydrocarbon group Replace a monovalent hydrocarbon group, a, b is a positive number satisfying 0.7 SaS2.1, O.OlSbSl.O, and 0.8 S a + b each 2.9, wherein the number of hydrogen atoms bonded to the sand atom is relative to each The sum of the sand-bonded susceptibility groups in the (A-Ι) and (A-II) components is 0.3-10; and 201204786 (C): the addition reaction catalyst, the content is The amount of catalyst. The curable organopolyoxane composition of the present invention has high discoloration resistance, so it has high transparency, and is particularly resistant to thermal shock, and is less likely to be cracked or peeled off even under severe temperature cycling. . In this case, it is preferred that the (A-II) component is liquid at 25 ° C, and the component (A-II) is solid at 25 ° C. As described above, when the component (A-Ι) is liquid at 25 ° C and the component (A-II) is solid, it is more likely to have thermal shock resistance and strength. Further, in this case, each of the components (A-I), (A-II) and (B) is preferably an aryl group having at least one atom bonded by a ruthenium atom in one molecule. Thus, if at least one arylene-bonded aryl group is contained in one molecule of each of (AI) to (B), the hardness and strength required as a polyoxyalkylene resin can be obtained, and after hardening The coated protective material is particularly excellent in heat resistance, low-temperature characteristics, and transparency, and can be obtained in a thermal shock test. Further, the present invention provides a semiconductor device characterized in that a semiconductor element is coated by a cured product of the curable organopolysiloxane composition. When the semiconductor element is coated with the curable organopolysiloxane composition of the present invention which is particularly high in thermal shock resistance and excellent in transparency, the obtained semiconductor device can be applied to various fields and has usability. In this case, the semiconductor element is preferably a light-emitting element. The composition of the curable organopolyoxane of the present invention is particularly resistant to thermal shock and is less prone to cracking, and therefore, as described above, is particularly suitable for use in the -8-201204786 for covering under severe temperature cycles. The sealing material of the light-emitting element. Advantageous Effects of Invention As described above, the curable organopolysiloxane composition of the present invention has a particularly high impact resistance and good transparency. Therefore, it is useful as a material for a light-emitting diode element and other optical devices or optical components, and further as a packaging material for various fields such as motors and electronics, OA machines, automobiles, and precision machinery. [Embodiment] Hereinafter, the present invention will be described in more detail. As described above, the sealing material for a semiconductor element used in the prior art has a problem that cracks are likely to occur due to thermal shock generated when the LED is energized and turned on, and therefore it is required to be hard to generate even under severe temperature cycling. Cracked or peeled sealing material. Therefore, the inventors of the present invention have conducted intensive studies and found that the above problems can be attained by combining organic polyoxoxanes having two kinds of branching structures having different branch unit contents, thereby completing a hardening organic polyfluorene oxide. Alkane composition. That is, the curable organopolyoxane composition of the present invention is characterized by containing at least: (A-Ι): having at least 2 alkenyl groups bonded via a ruthenium atom in one molecule and having a general The oxime unit represented by the formula (1)-9 - 201204786 5 to 7 0 mol % of the branched structure of the organopolyoxane, RSi 〇 3 / 2 (1) (wherein R is a substituted or unsubstituted Monovalent hydrocarbon group), and (A-II): having at least 2 alkenyl groups bonded via a ruthenium atom in one molecule, and having at least 70 units of a decane unit represented by the above general formula (1) An organopolysiloxane having a branched structure of the ear, wherein the contents of (A-Ι) and (A-II) are (eight-I) / (A-II) =1/99-99 in weight units (B): a linear chain having at least two hydrogen atoms bonded via a ruthenium atom in one molecule and having a viscosity of less than 1000 mPas at 25 ° C, represented by the following average composition formula (2) Organohydrogen polyoxyalkylene, R 1 a H bsi Ο ( 4 - ab ) / 2 (2 ) (wherein R 1 is a substituted or unsubstituted monovalent hydrocarbon group minus an aliphatic unsaturated hydrocarbon group, a, b is Meet 0.7Sa$2.1, O.OlSbS lO, and a positive number of 0.8 S a + b$ 2.9, wherein the number of hydrogen atoms bonded to the ruthenium atom is bonded to the ruthenium atom in each (AI) and (A-II) component The total number of alkenyl groups is from 0.3 to 10; and (C): addition reaction catalyst, the amount of which is the amount of the catalyst. The components of the present invention are described in detail below. The following also refers to the combination of the (A-I) component and (A_II) as the component (A). < (AI) component> -10- 201204786 The (AI) component 'is a dilute base having at least two ruthenium atoms bonded to a ruthenium molecule' and has a oxime represented by the following general formula (1) The unit is 5 to 70% by mole, preferably an organic polyoxyalkylene having a branched structure which is liquid at 2 yc. The (A-Ι) component is a component which imparts high resistance to thermal shock and is less likely to cause cracking even under severe temperature cycling, and is imparted to the composition of the present invention. Therefore, the content of the RSi 〇 3/2 unit is 5 to 70 mol% ‘especially 20 to 60 mol%. When the amount is less than 5 mol%, the impact resistance of the cured product cannot be sufficiently obtained. When the amount is more than 70 mol%, it is difficult to maintain the liquid state well at 25 t. RS i 〇3 /2 (1) Other units of the seroconverter include R2Si02/2 units, R3Si01/2 units, and Si04/2 units (wherein R is the same or different substituted or unsubstituted valence Hydrocarbyl). At this time, a part of R may be substituted by a base group and/or a hospitaloxy group. Among these, R2Si02/2 units and/or 113310 U 2 units are preferred. In the above general formula (1), the substituted or unsubstituted monovalent hydrocarbon group bonded to a halogen atom represented by R is usually an unsubstituted or substituted monovalent hydrocarbon group having a carbon number of 1 to 20, particularly preferably 1 to 10. Specific examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group or a heptyl group; and a phenyl group, a tolyl group, a xylyl group, a naphthyl group or the like. An aryl group; an aralkyl group such as a benzyl group or a phenethyl group; an unsaturated hydrocarbon group such as an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl 'hexenyl group or a heptenyl group; or a chloromethyl group; a halogenated fluorenyl group such as 3-chloropropyl or 3,3,3-trifluoropropyl. In one molecule of the (AI) component, it is necessary to contain at least two dilute groups which are bonded via the 矽-12-201204786 sub-group. In addition, all of these R are, and the alkenyl group is 〇1~2〇mole%' It is preferably 0.5 to 1% by mole. When the content of the alkenyl group is 〇. 卜 "% by mole", a suitable hardness as a polyoxyalkylene resin can be obtained, and crack resistance is better. Further, the (A-Ι) component is bonded by a ruthenium atom. Preferably, all of the organic groups contain an aryl group bonded via a ruthenium atom, particularly preferably from 5 to 100 mol%, particularly preferably from 10 to 100 mol%. The aryl group is preferably a phenyl group. -II) Ingredient > (A-II) component ' is a ruthenium having at least two ruthenium-bonded groups in one molecule and having sand represented by the above formula (1) (RSi 〇 3/2) The oxygen hospital unit is at least more than 7 mole %, preferably an organic polyoxyalkylene having a branched structure which is solid at 25 t. The component (A-II ) is a component which imparts strength to the composition of the present invention. Therefore, the content of the RSi 〇 3/2 unit must be at least 70% by mole, and more preferably 7.5 % by mole or more. Other siloxane units are the same as the (AI) component, and R2Si02 can be cited. /2 units, R3Si〇1/2 unit, si〇4/2 unit, and R in the formula is the same as above. (A-Η) component must contain at least one molecule of the (A-II) component. 2 prayer flags The sub-bonded alkenyl group, in addition, in all of R, the alkenyl group is 1 to 30 mol%, preferably 5 to 2 mol%. When the alkenyl group content is 1 to 30 mol% When it is obtained, it is particularly suitable as the hardness of the polyoxyalkylene resin, and the crack resistance is better. Further, the total organic group of the (A-II) component bonded by the ruthenium atom is -12-201204786' The aryl group having a ruthenium atom-bonded bond is preferably 5 to 1 〇〇 mol %, particularly preferably 10 to 1 00 mol %. The aryl group is preferably a phenyl group. Among these, 'preferable as RzSiO 2 2 units and/or R3SiOW2 unit. The amount of the component (A-II) is 'the content of the component relative to the (a-) component is 1/99 to 99/1 by weight, preferably The amount of 10/90 to 90/10 is particularly good for 20/80 to 80/20. This is because the strength of the cured product is obtained when the content of the (A-II) component does not reach the lower limit of the above range. On the other hand, when the temperature exceeds the upper limit of the above range, the handling operability of the obtained composition is lowered, or the strength of the obtained cured product tends to be extremely hard. The unit of the oxirane represented by the general formula (1) may be the same as or different from the component (A-II) contained in the component (A-II). <(B) component> The organohydrogen polyoxyalkylene is represented by the following average composition formula (2), and has at least two hydrogen atoms bonded via a ruthenium atom in one molecule, and has a viscosity of less than 100 mPas at 25 ° C, usually A linear organic hydrogen polyoxyalkylene having a concentration of from 0.5 to 100 mPas, preferably from 1 to 500 mPas. R 1 a H b S i Ο ( 4 - a - b ) / 2 (2) (wherein R 1 is a substituted or unsubstituted monovalent hydrocarbon group minus an aliphatic unsaturated hydrocarbon group, and a and b satisfy 0.7 SaS2 .1, O.OlSbSl.O, and a positive number of 0.8 S a + b S 2.9) -13- 201204786 Here, R1 is preferably a carbon number of 1 to 12, and particularly preferably a carbon number of 1 to 10. The substituted or unsubstituted monovalent hydrocarbon group of a saturated hydrocarbon group, and the like, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group or a heptyl group: a phenyl group; An aryl group such as tolyl, xylyl or naphthyl; an aralkyl group such as benzyl or phenethyl; a halogenated compound such as chloromethyl, 3-chloropropyl or 3,3,3-dipropylene Base. Further, a and b satisfy 0.7S 2.1, preferably l.OSag 2.0, O.OlgbS 1.0, preferably 0.02 SbSl.O, especially preferably O.lOSbSl.O, and 〇_8S a + b S 2.9 Preferably, it is 1.01Sa + bS2.8, and particularly preferably a positive number of 1.6Sa + bS2.7. When b is less than 0.01, sufficient hardness as a polyoxyalkylene resin cannot be obtained. The organic hydrogen polyoxyalkylene has a molecular structure of not particularly limited, but is preferably linear, and is bonded to the R1 of the ruthenium atom from the viewpoints of compatibility with the component (A) and physical properties of the cured product. In the case of hydrazine (hydrogen atom), the phenyl group is 5 mol% or more, preferably 10 to 50 mol%. When R1 is other than a phenyl group, it is preferably a methyl group. Further, the amount of the organohydrogen polyoxane of the (Β) component is preferably such that the number of hydrogen atoms bonded to the ruthenium atom is relative to the olefin bonded to the ruthenium atom per one (Α) component. The total number of bases is adjusted from 0.3 to 10. In this case, when the number is less than three, the hardening is insufficient, and when it exceeds one, the hardening becomes too brittle. It is preferably 0.5 to 5 pieces. <(C) component> The addition reaction catalyst of the component (C) is a catalyst which is crosslinked in the addition reaction of the (Α) component and the (Β) component, and examples thereof include uranium chloride 14 - 201204786 The reaction of acid, uranyl uric acid with monovalent alcohol, the olefin complex of chloroplatinic acid, the coordination compound of platinum acid and ethylene oxane, the uranium catalyst such as platinum black, and the palladium catalyst. In the case of a catalyst, etc., a platinum catalyst is usually used in terms of high catalyst efficiency. In addition, especially when used in the production of electronically sealed LEDs, it is preferred to have a suspected low-chlorine catalyst which does not corrode metals, and among them, it is preferably a vinylidene-free tetracarbonyl-free oxygen-free component. For the modification of the alkane, divinyldiphenyldimethyldioxane, etc., the addition reaction catalyst may be used alone or in combination of two or more kinds of the addition reaction catalyst. The amount of the effective catalyst for the catalyst is preferably from 1 to 1000 ppm with respect to the combination of the component (A) and the component (B). When it is lppm or more, it can be hardened at a moderate speed, and when it is less than 100 ppm, the working time is not excessively shortened, and the compound is not easily yellowed and economical. Particularly preferred is 5 to 1 0 Op p m. <Optional component> As the component of the above (A) to (C) component, for example, a compound which is considered to be a compound for inhibiting the addition reaction catalyst hardening effect can be used as the composition of the present invention. Control agent compound. The compound may, for example, be a phosphorus-containing compound such as triphenylphosphine, a nitrogen-containing compound such as tributylamine methyl hexamethylenediamine or benzotriazole, or a sulfurized acetylene-based compound containing two or more alkenyl groups. Compounds, hydrogen peroxide compounds, maleic acid derivatives, and the like. The degree of hard late effect brought about by the control agent compound is extremely different due to the chemical structure of the control agent compound, so the amount of the control agent compound to be added is preferably based on the use, chlorine, and the field of consideration. Two quantities (measured and harder than this or four substances, oxylation extended each -15-201204786 control agent compound to adjust to the optimum amount, in general, long-term storage stability at room temperature and The amount in the range of hardening is not hindered, and is usually 1 part by mass based on the total of the (A-Ι) component and the (A-II) component, and is 〇, 5 parts by mass or less, preferably 0.01 to 0.3 mass. Further, the composition of the present invention may further contain an adhesion-imparting agent for enhancing the adhesion. The adhesion-imparting agent preferably has at least one bond to a ruthenium atom in one molecule. The alkoxy group organic oxime compound. The alkoxy group may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a methoxyethoxy group, and particularly preferably a methoxy group. Alkoxy group bonded to a ruthenium atom Examples of the external group include the unsubstituted or halogen-substituted monovalent hydrocarbon groups which are the same as those exemplified as the R group, and are usually a carbon number of 1 to 12, preferably a carbon number of 10, and may be exemplified. The alkyl group, the hydrogen atom or the like which is substituted with an epoxy functional group such as γ-glycidoxypropyl or β-(3,4-epoxycyclohexyl)ethyl is preferably a methyl group or an ethyl group. Further, the propyl group, the phenyl group, the vinyl group, the hydrogen atom, and the γ-glycidoxypropyl group. Further, the present invention provides a semiconductor protected by the above-described hardenable organopolyoxane composition of the present invention. Although an example of the semiconductor device of the present invention is shown in Fig. 1, the present invention is not limited thereto. Here, in Fig. 1, 1 is a casing, 2 is a light-emitting element, and 3 and 4 are leads. The electrode, 5 is a solder crystal, 6 is a gold wire, and 7 is a sealing resin (a composition of the present invention). Thus, the semiconductor device 8 of the present invention has good heat resistance, moisture resistance, light resistance, and corrosion resistance of the device. Therefore, it is possible to provide a semiconductor device with good reliability, which has great advantages in the industry. -16- 201204786 〔 EXAMPLES Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples and the like. [Example 1] It will have an average unit formula: (PhSi03/2) 〇.5 [( CH2 = CH) MediOo.^oj^MesSiOo.5) 有机.25 indicates the liquid branched structure of the organopolyoxyalkylene [the viscosity at 25 ° C is 35 OOmP as, the ruthenium atom bonded vinyl group The content rate = 12·5 mol%, the content of the phenyl group bonded via the ruthenium atom in all the organic groups bonded by the ruthenium atom = 25 mol%, and the weight average molecular weight after conversion by standard styrene = 1200] 50 parts by mass, having (PhSiOwh.s UCHfCWMezSiOo"]. The organic polyoxyalkylene represented by the solid branched structure [the content of the vinyl group bonded via a ruthenium atom = 14.3 mol%, and the benzene bonded via the ruthenium atom in all the organic groups bonded by the ruthenium atom The content of the base = 57 mol%, the weight average molecular weight after conversion by standard styrene = 23 50] 50 parts by mass, 30 parts by mass of the organic hydrogen polyoxyalkylene having a structure of HMezSiCKPl^SiOhSiMezH and a viscosity of 4 mPas, The chlorine-lead acid/1,3-diethylenetetramethyldioxane complex is 0.06 parts by mass of a toluene solution having a platinum atom content of 1% by mass, 0.05 parts by mass of ethynylcyclohexanol, and a γ-ring. 3 parts by mass of oxypropoxypropyltrimethoxy hydride was uniformly mixed to prepare a polyoxane composition (U). The polyoxyalkylene composition (U) was heated at 150 ° C for 4 hours to harden it, and the hardness was 60,047,047,86 as Shore D [Example 2] will have an average unit formula: (PhSi03/2). 5[(CH2 = CH) " has 28丨〇().5]〇.25(^^633丨〇().5) 0.25 The liquid poly-branched structure of the liquid poly-branched structure [at 25 The viscosity at °C is 3500 mPas, the content of vinyl groups bonded by sand atoms is =12.5 mol%, and the content of phenyl groups bonded via ruthenium atoms in the organic group bonded by ruthenium atoms = 2 5 Ear %, weight average molecular weight after conversion by standard styrene = 12 Å] 80 parts by mass, with (卩118丨〇3, 2). .75[(〇112 = ^11'1)^4623丨0. .5]. .25 indicates an organic polyoxyalkylene of a solid branched structure [the content of a vinyl group bonded via a ruthenium atom = 17 mol%, and a ruthenium atom bond in all organic groups bonded via a ruthenium atom The content of the phenyl group = 50 mol%, the weight average molecular weight after conversion by standard styrene = 1 600] 20 parts by mass, and the total of the hydrogen atom bonded to the ruthenium atom, the phenyl group and the methyl group have 30 Molar% phenyl hydrogen generation amount l4〇ml / g and viscosity 2〇mPaS organic hydrogen polyoxyalkylene 32 parts by mass, containing uranium uranium / 1,3 - diethylene tetramethyl dioxane The compound is uniformly mixed by mixing 0.5 parts by mass of a toluene solution of 1% by mass in terms of uranium atom content, 0.05 parts by mass of ethynylcyclohexanol, and 3 parts by mass of γ-glycidoxypropyltrimethoxy decane. Polyoxane composition (V). The polydecane composition (V) was heated at 150 ° C for 4 hours to harden it, and the hardness was 6 5 Torr in Shore D [Example 3] will have an average unit formula: (PhSiO^h.^) KCHpCH) -18- 201204786
MhSiOo.do.HPhzSiOh.^表示之液狀分枝結構之有機聚矽 氧烷[在25 °C時的黏度爲440mP as、經矽原子鍵結的乙烯基 之含有率=2 1.5莫耳％、經矽原子鍵結的有機基中之經矽原 子鍵結的苯基之含有率=3 5.6莫耳％、經標準苯乙烯換算後 的重量平均分子量=1〇〇〇]17質量份、具有由 (PhSi〇3/2)o.75[(CH2 = CH)Me2SiO〇.5]o.25表不之固體狀分枝 結構之有機聚矽氧烷[經矽原子鍵結的乙烯基之含有率=17 莫耳％、經矽原子鍵結的全部有機基中之經矽原子鍵結的 苯基之含有率=5 0莫耳％、經標準苯乙烯換算後的重量平均 分子量=1600]83 質量份、具有 HMediCKPhiSiOhSiMezH 的 結構且25 °C時的黏度爲4mP as之有機氫聚矽氧烷34.5質量 份、含有氯鉑酸/1，3 -二乙烯四甲基二矽氧烷錯合物以鉑原 子含量計爲1質量％之甲苯溶液0.5質量份、乙炔基環己醇 〇.〇5質量份、及γ-環氧丙氧基丙基三甲氧矽烷3質量份均一 地混合，而調製出聚矽氧烷組成物（W)。在150 °C下將 該聚矽氧烷組成物（W )加熱4小時使其硬化，硬度以 Shore D計爲 46。 [比較例1 ] 係使用主鏈僅由二苯基矽氧烷單位所構成，且黏度爲 0.4Pas之兩末端經甲基苯基乙烯基矽氧烷基封鎖的二苯基 矽氧烷共聚物50質量份，來取代具有由平均單位式： (PhSiO3/2)0.5[(CH2 = CH)Me2SiO0,5] 0 2 5 (Me3SiO〇.5)〇.25 表示 之液狀分枝結構之有機聚矽氧烷[黏度爲3 5 00mP as、經矽 •19- 201204786 原子鍵結的乙烯基之含有率=12.5莫耳％、經矽原子鍵結的 全部有機基中之經矽原子鍵結的苯基之含有率=25莫耳。/〇、 經標準苯乙烯換算後的重量平均分子量= 1 200]，並使用具 有HMejiCKPhzSiOhSiMhH的結構之有機氫聚矽氧烷29質 量份，除此之外，其他依循實施例1而調製出組成物（X) 。在1 50 °C下將該聚矽氧烷組成物（X )加熱4小時使其硬 化，硬度以Shore D計爲56。 [比較例2 ] 係使用主鏈僅由二苯基矽氧烷單位所構成，且黏度爲 0.4P as之兩末端經甲基苯基乙烯基矽氧烷基封鎖的二苯基 矽氧烷共聚物80質量份，來取代具有由平均單位式： (PhSi〇3/2)o.5[(CH2 = CH)Me2SiO〇.5]〇.25(Me3SiO〇.5)〇.25 表示 之液狀分枝結構之有機聚矽氧烷[黏度爲3 5 OOmPas、經矽 原子鍵結的乙烯基之含有率=12.5莫耳％、經矽原子鍵結的 全部有機基中之經矽原子鍵結的苯基之含有率=25莫耳％、 經標準苯乙烯換算後的重量平均分子量=1200]，並使用相 對於經矽原子鍵結的氫原子、苯基及甲基之合計具有30莫 耳％的苯基之氫氣產生量140ml/g且黏度20mPas之有機氫聚 矽氧烷31質量份，除此之外，其他依循實施例2而調製出 組成物（Y )。在1 50°C下將該聚矽氧烷組成物（Y )加熱 4小時使其硬化，硬度以Shore D計爲60。 [比較例3] -20- 201204786 係使用主鏈僅由二苯基矽氧烷單位所構成，且黏度爲 〇.4Pas之兩末端經甲基苯基乙烯基矽氧烷基封鎖的二苯基 矽氧烷共聚物26質量份，來取代具有由平均單位式： (?1^1〇3/2)0.17[((：112 = (：11)1^231〇0.5]0.5(?11231〇)0.33表示之液 狀分枝結構之有機聚矽氧烷[黏度爲4 4 OmP as、經矽原子鍵 結的乙烯基之含有率=21.5莫耳％、經矽原子鍵結的有機基 中之經矽原子鍵結的苯基之含有率=3 5.6莫耳％、經標準苯 乙烯換算後的重量平均分子量=1000]，並使用具有由 (PhSiOs/OmKCHfCHiMeiSiOo.sU.u表示之固體狀分枝 結構之有機聚矽氧烷[經矽原子鍵結的乙烯基之含有率=17 莫耳％、經矽原子鍵結的全部有機基中之經矽原子鍵結的 苯基之含有率=50莫耳％、經標準苯乙烯換算後的重量平均 分子量=1 600]74 質量份、具有 HMezSiCHPl^SiOhSiMezH 的 結構且25 °C時的黏度爲4mP as之有機氫聚矽氧烷31.6質量 份，除此之外，其他依循實施例3而調製出組成物（Z ) » 在1 5 0 °C下將該聚矽氧烷組成物（Z )加熱4小時使其硬化 ，硬度以Shore D計爲40。 以下列方式對上述實施例及比較例中所調製之聚矽氧 烷組成物（U ) ~ ( Z)進行評估。 [評估方法] 發光半導體封裝 發光元件係使用第1圖所示之發光半導體裝置8’其係 裝載具有由InGaN所構成之發光層，且主發光峰値爲 -21 - 201204786 470nm之LED晶片。密封樹脂7的硬化條件爲150°C、4小時 耐濕及紅外線回焊的試驗方法 將各10個製作出之發光半導體裝置放入於85 °C、85% 的恆溫恆濕室24小時後，通過紅外線回焊裝置（260°C ) 3 次，觀察其外觀的變化。結果如第1表所示。以確認到樹 脂的龜裂或從LED封裝之剝離者爲NG並計數。 [第1表] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 NG數/試驗數 0/10 0/10 0/10 6/10 8/10 3/10 如第1表所示，可得知實施例1~3中，其NG數均爲0， 在高溫/低溫的溫度循環條件下，耐龜裂性亦良好，未產 生剝離且取光效率高。此外，此般聚矽氧烷樹脂的透明性 亦佳。 另一方面’比較例1〜3中’半數以上均產生樹脂的龜 裂或從LED封裝之剝離。藉此可得知使用以往的材料作爲 密封材料者，LED的生產性惡化。 從以上內容中’可驗證到若是本發明之硬化性有機聚 矽氧烷組成物者，除了對熱衝擊具有高耐性而不易產生龜 裂之外’並具有高透明性，故有用於作爲光學裝置用或光 學零件用之材料或是各種領域中之封裝材料，尤其是有用 於作爲處在嚴苛的溫度循環下之發光元件用密封材料。 本發明並不限定於上述實施形態。上述實施形態僅爲 -22- 201204786 例示’只要與本發明之申請專利範圍所記載的技術性思想 實質上具有同一構成並可達同樣的作用效果者，均包含於 本發明之技術範圍內。 【圖式簡單說明】 第1圖係模式性顯示適合使用本發明之硬化性有機聚 矽氧烷組成物之發光半導體裝置的一例之剖面圖。 【主要元件符號說明】 1 :殼體 2 :發光元件 3、4 :引線電極 5 :焊晶材 6 :金線 7 :密封樹脂 8:半導體裝置（發光半導體裝置） -23-MhSiOo.do.HPhzSiOh.^ refers to the liquid branched structure of the organopolyoxyalkylene [the viscosity at 25 ° C is 440 mP as, the content of the vinyl group bonded by the ruthenium atom = 2 1.5 mol%, The content of the phenyl group bonded via the ruthenium atom in the organic group bonded by the ruthenium atom = 3 5.6 mol%, the weight average molecular weight after conversion by standard styrene = 1 〇〇〇] 17 parts by mass, (PhSi〇3/2)o.75[(CH2 = CH)Me2SiO〇.5]o.25 The solid polybutane of the solid branched structure [the content of vinyl groups bonded via a ruthenium atom =17 mole %, the content of the phenyl group bonded via the ruthenium atom in all the organic groups bonded via the ruthenium atom = 50% by mole, the weight average molecular weight after conversion by standard styrene = 1600] 83 A portion of organic hydrogen polyoxyalkylene having a structure of HMediCKPhiSiOhSiMezH and having a viscosity of 4 mP as at 45 ° C, 34.5 parts by mass, containing chloroplatinic acid/1,3-triethylenetetramethyldioxane complex as platinum The atomic content is 0.5 parts by mass of a toluene solution of 1% by mass, 5 parts by mass of ethynylcyclohexanol oxime, and 3 parts by mass of γ-glycidoxypropyltrimethoxy decane. The polysiloxane composition (W) was prepared by uniformly mixing. The polyoxyalkylene composition (W) was cured by heating at 150 ° C for 4 hours, and the hardness was 46 in terms of Shore D. [Comparative Example 1] A diphenyl sulfoxane copolymer in which the main chain was composed only of diphenyloxane units and the two ends of the viscosity of 0.4 Pas were blocked by methylphenylvinyl fluorenyloxy group. 50 parts by mass to replace the organic polymerization having a liquid branch structure represented by an average unit formula: (PhSiO3/2) 0.5 [(CH2 = CH)Me2SiO0, 5] 0 2 5 (Me3SiO〇.5) 〇.25 a siloxane having a viscosity of 3 5 00 mP as, a 矽 19-201204786 atomic bond, a vinyl content of =1 mol%, and a ruthenium atom bonded to a ruthenium atom bonded through a ruthenium atom Base content = 25 moles. /〇, weight average molecular weight after conversion by standard styrene = 1 200], and 29 parts by mass of organic hydrogen polyoxyalkylene having a structure of HMejiCKPhzSiOhSiMhH, except that the composition was prepared in accordance with Example 1. (X). The polyoxyalkylene composition (X) was hardened at 1, 50 °C for 4 hours to have a hardness of 56 in Shore D. [Comparative Example 2] The use of a diphenyl decane copolymer in which the main chain was composed only of diphenyloxane units and the two ends of which had a viscosity of 0.4 P as blocked by methylphenylvinyl decyloxyalkyl group 80 parts by mass of the substance, which has a liquid form represented by an average unit formula: (PhSi〇3/2)o.5[(CH2=CH)Me2SiO〇.5]〇.25(Me3SiO〇.5)〇.25 Branched structure of organopolyoxyalkylene [viscosity of 3 5 OOmPas, content of vinyl group bonded by ruthenium atom = 12.5 mol%, bonded by ruthenium atom in all organic groups bonded by ruthenium atom The content of the phenyl group = 25 mol%, the weight average molecular weight after conversion by standard styrene = 1200], and the use of the hydrogen atom bonded to the ruthenium atom, the total of the phenyl group and the methyl group has 30 mol% The composition (Y) was prepared in accordance with Example 2 except that the amount of the hydrogen generation of the phenyl group was 140 ml/g and the organic hydrogen polyoxyalkylene having a viscosity of 20 mPas was 31 parts by mass. The polyoxyalkylene composition (Y) was cured by heating at 50 ° C for 4 hours, and the hardness was 60 in Shore D. [Comparative Example 3] -20-201204786 A diphenyl group in which the main chain is composed only of diphenyloxane units and the viscosity is 〇.4 Pas blocked by methylphenylvinylphosphonyl group. 26 parts by mass of the decane copolymer, which has a unit of the average unit: (?1^1〇3/2) 0.17[((:112 = (:11)1^231〇0.5]0.5(?11231〇) The organic polyoxyalkylene of the liquid branched structure represented by 0.33 [viscosity is 4 4 OmP as, the content of the vinyl group bonded by the ruthenium atom = 21.5 mol%, and the organic group bonded via the ruthenium atom The content of the phenyl group bonded to the ruthenium atom = 3 5.6 mol%, the weight average molecular weight after conversion by standard styrene = 1000], and the solid branch structure represented by (PhSiOs/OmKCHfCHiMeiSiOo.sU.u) is used. The organic polyoxyalkylene [the content of the vinyl group bonded via the ruthenium atom = 17 mole%, the content of the phenyl group bonded via the ruthenium atom in the entire organic group bonded by the ruthenium atom = 50 moles %, the weight average molecular weight after conversion by standard styrene = 1 600] 74 parts by mass, having a structure of HMezSiCHPl^SiOhSiMezH and having a viscosity of 4 mP as at 25 °C The composition (Z) was prepared according to Example 3 except that the hydrogen polyoxyalkylene was 31.6 parts by mass. The polyoxane composition (Z) was heated at 150 ° C for 4 hours. It was hardened and the hardness was 40 in terms of Shore D. The polyoxane composition (U) ~ (Z) prepared in the above Examples and Comparative Examples was evaluated in the following manner. [Evaluation Method] Light-emitting semiconductor package light-emitting element The light-emitting semiconductor device 8' shown in Fig. 1 is used to mount an LED chip having a light-emitting layer composed of InGaN and having a main light-emitting peak of -21 - 201204786 470 nm. The curing condition of the sealing resin 7 is 150 °C. Test method for 4-hour moisture resistance and infrared reflow soldering. Each of the 10 fabricated light-emitting semiconductor devices was placed in a constant temperature and humidity chamber at 85 ° C for 8 hours, and then passed through an infrared reflow soldering device (260 ° C). Three times, the change in appearance was observed. The results are shown in Table 1. It was confirmed that the crack of the resin or the peeling from the LED package was NG and counted. [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 NG number/test number 0/10 0/10 0/10 6/10 8/1 0 3/10 As shown in Table 1, it can be seen that in Examples 1 to 3, the NG number is 0, and under high temperature/low temperature temperature cycling conditions, the crack resistance is also good, and no peeling occurs. Further, the transparency of the polyoxyalkylene resin is also good. On the other hand, in the comparative examples 1 to 3, cracks of the resin or peeling from the LED package occurred in more than half of the results. From this, it is known that the use of a conventional material as a sealing material deteriorates the productivity of the LED. From the above, it can be verified that the composition of the curable organopolyoxane of the present invention, in addition to being highly resistant to thermal shock and not susceptible to cracking, has high transparency and is therefore useful as an optical device. Materials for use with optical components or packaging materials in various fields, especially for sealing materials for light-emitting elements under severe temperature cycling. The present invention is not limited to the above embodiment. The above-described embodiment is only exemplified by the -22-201204786. As long as it has substantially the same configuration as the technical idea described in the patent application scope of the present invention and can achieve the same effects, it is included in the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a light-emitting semiconductor device in which a curable organopolysiloxane composition of the present invention is suitably used. [Description of main component symbols] 1 : Case 2 : Light-emitting element 3, 4 : Lead electrode 5 : Soldering crystal 6 : Gold wire 7 : Sealing resin 8 : Semiconductor device (light-emitting semiconductor device) -23-