200831613 九、發明說明 【發明所屬之技術領域】 本發明係關於熱傳導性聚砂氧組成物，及由該組成物 之硬化物所成之熱傳導性聚矽氧成形體，特別是用於發熱 性電子零件的冷卻用，作爲介裝於該電子零件與散熱裝置 (heat sink )、迴路基板等熱放散構件之間的熱傳達材料 之有效熱傳導性聚矽氧組成物，及由該組成物之硬化所成 之熱傳導性聚矽氧成形體。 【先前技術】 個人電腦、數位攝錄光碟、行動電話等電子機器所使 用之CPU、驅動1C、記憶體等LSI晶片，伴隨著高性能 化、高速化、小型化、高積體化，其本身成爲產生大量的 熱。藉由該熱使晶片的溫度上升而引起晶片的動作不良、 破壞。因此，已有多種提案爲了抑制動作中的晶片的溫度 上升的熱放散方法及使用於其之熱放散構件。 以往，於電子機器等中，爲了抑制動作中的晶片的溫 度上升，於所使用之散熱裝置中使用鋁或銅等熱傳導率高 的金屬板。該散熱裝置係傳導該晶片所產生的熱，藉由該 熱與外部氣體的溫度差而由表面放出。 此時，爲了將由晶片所產生的熱傳至散熱裝置，以具 有柔軟性之成形體或滑脂（grease )介裝於晶片與散熱裝 置之間，藉由該成形體或滑脂可提升由晶片對散熱裝置的 熱傳導效率。 -4 - 200831613 具有柔軟性之成形體相比於滑脂爲操作性優異，特別 是以熱傳導性聚矽氧等所形成之低硬度的熱傳導性成形體 (亦即，熱傳導性聚矽氧成形體）正使用於各種領域。成 形體爲柔軟的而越柔軟時，對晶片及散熱裝置的密著越佳 ，顯示更爲良好的放熱特性。成形體於多數的情況中，以 片（sheet)形狀提供。 製造此方式之片形狀的成形體的方法，可列舉使用鑄 模等冶具與加壓機，加熱硬化熱傳導性材料進行成形之加 壓成形法，以及於長形薄膜上吐出液狀的熱傳導性材料而 使用刮刀塗佈機或逗號塗佈機（comma coater)等塗佈成 一定厚度，藉由加熱硬化之連續成形法。 大量地成形比較薄的片狀形狀的成形體的情況中，相 較於批次處理所成之加壓成形法，藉由被覆之連續成形法 的效率佳。因此，成形成本爲以藉由被覆之連續成形法較 以加壓成形法之情況更爲有利。 所提供之片狀成形體，於使用時，可容易的由成形時 所使用之薄膜剝離爲必要者。爲使容易剝離的代表性手法 有於膜上塗佈界面活性劑等離型劑之方法，以及於組成物 中添加交聯地不倂入無官能的聚合物成分作爲內部添加離 型劑的方法。 於薄膜上塗佈界面活性劑等離型劑實施離型處理的情 況中’藉由於片形狀的成形體成形前，於薄膜上塗佈離型 劑的步驟爲必要，而造成成本提高。因此，較佳使用於組 成物中添加內部添加離型劑的手法。 -5- 200831613 作爲內部添加離型劑，較佳使用無官能的聚合物成分 。作爲無官能的聚合物成分，使用與基底聚合物之有機矽 氧烷完全相容的聚合物時，爲了獲得離型效果必須多量地 添加內部添加離型劑，此方式所得之片形狀成形體容易引 起油滲出的問題點。因此，爲了始添加量爲微量可得充分 的離型效果，較佳使用於基底聚合物之有機聚矽氧烷中不 溶解的無官能的聚合物。 ^ 微量添加有於基底聚合物之有機聚矽氧烷中不溶解的 無官能的聚合物的液狀組成物，於長形薄膜上吐出，連續 地被覆時，被覆開始時的片形狀成形體，與基材的長形薄 膜的剝離爲良好。然而，直接繼續被覆成形時，塗佈器前 的材料液貯存部分地長時間滯留的液狀材料於基材的長形 薄膜上被覆之方式，使所成形的片狀成形體與基材的長形 薄膜的剝離惡化，最後有片狀成形體貼著於長形薄膜的問 題點。 φ 〔專利文獻1〕曰本特開2005-035264號公報 〔專利文獻2〕日本特開2005-206733號公報 【發明內容】 〔發明欲解決之課題〕 本發明係有鑒於上述問題，以提供於基材的長形薄膜 上不施以離型處理而使用藉由被覆之連續成形方法成形時 ’與內部添加離型劑之含有量爲微量無關，就算在被覆開 始後經一段時間塗佈亦賦予剝離性不惡化之成形體之熱傳 -6 - 200831613 導性組成物以及由該組成物之硬化物所成之熱傳導性 氧成形體爲目的。 〔解決課題之手段〕 本發明者們，爲達成上述目的致力硏究的結果， 本發明。亦即，本發明提供含有下述之熱傳導性聚矽 成物： (a )具有鍵結於矽原子之烯基，鍵結於其他矽 之有機基全爲未取代烷基之有機聚矽氧烷：1 00質量f (b )熱傳導性塡充劑：200至5,000質量份； (c )具有鍵結於矽原子之氫原子之有機氫聚矽 :每1莫耳（a)成分中之烯基，使（C)成分中鍵結 原子之氫原子的量成爲0.1至5.0莫耳的量； (d )鉑族金屬系加成反應觸媒：有效量； (e) 以一定的改質率，具有未取代烷基以外之 於矽原子之未取代或經取代之一價烴基，且不具鍵結 原子之一價脂肪族不飽和烴基之有機聚砍氧院：〇 · 1 ^ 質量份；以及 (f) 以較（e)成分中之改質率更低之改質率， 未取代烷基以外之鍵結於矽原子之未取代或經取代之 烴基之與存在於（e)成分中者爲相同種類之一價烴 且不具鍵結於矽原子之一價脂肪族不飽和烴基之有機 氧{兀· 至2〇質量份。 再者，本發明提供由該組成物之硬化物所成之熱 聚矽 完成 氧組 原子 氧院 於矽 鍵結 於矽 5 20 具有 一價 基， 聚矽 傳導 -7- 200831613 性聚矽氧成形體。 本發明之熱傳導性聚砂氧組成物’於基材的長形薄膜 上不施以離型處理而使用藉由被覆之連續成形方法成形時 ，與內部添加離型劑之含有量爲微量無關’就算在被覆開 始後經一段時間塗佈亦賦予剝離性不惡化之成形體。 【實施方式】 以下，詳矽說明本發明。又，本發明中，黏度爲於 2 5 °C藉由迴轉黏度計所測定之値。 [(a)成分] (a )成分爲具有鍵結於矽原子之烯基，鍵結於其他 矽原子之有機基全爲未取代烷基之有機聚矽氧烷。（a) 成分之有機聚矽氧烷可爲直鏈狀或環狀，任一者之情況中 ，其分子內雖可含有分枝狀的構造，但由硬化物的機械強 度等物性的點而言，通常較佳爲實質上爲直鏈狀，具體而 言，主鏈爲主要的二有機聚矽氧烷單位所成之直鏈狀的二 有機聚矽氧烷爲較佳。上述烯基的位置並無特別限制。（ a)成分爲直鏈狀時，該烯基亦可存在於分子鏈的末端以 及僅存在非末端部分之任一方，亦可存在其兩方。又，直 鏈狀二聚矽氧烷的兩末端通常以三有機矽氧烷基封鎖。（ a)成分之有機聚砂氧院可單獨1種使用，亦可2種以上 倂用。倂用2種以上的有機聚矽氧烷時，其等之黏度亦可 互相有差異。 -8- 200831613 上述烷基，例如可列舉碳原子數較佳爲1至1 2、再較 佳爲1至10、更較佳爲1至6之未取代烷基。上述烷基可 全爲相同者，亦可爲不同者。上述烷基之具體例可列舉甲 基、乙基、丙基、異丙基、丁基、異丁基、第三·丁基、 戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷 基等未取代烷基。其等之中，較佳爲甲基、乙基、丙基等 碳原子數1至3之未取代烷基，特佳爲甲基。特別地，較 佳爲上述烷基全體的8 0莫耳％以上爲甲基。不限定要求所 製得組成物及成形體之耐溶劑性等特殊特性，由成本、取 得的容易性、化學安定性、環境負荷等理由，多數選擇上 述烷基全爲甲基。 上述烯基，例如可列舉碳原子數較佳爲2至8、再較 佳爲2至5之烯基。上述烯基可全爲相同者，亦可爲不同 者。上述烯基之具體例，可列舉乙烯基、烯丙基、·伸丙嫌 基、伸異丙烯基、丁烯基、己烯基、環己烯基等，其中較 佳爲乙烯基、烯丙基等低級烯基較佳，特佳爲乙烯基。 (a)成分之具體例可列舉下述一般式（1)至（3) 所表示之有機氫聚矽氧烷= X-Si(R1)2-[OSi(R1)2]a-[〇Si(R1)(X)]b-X (1) X.Si(R1)2-[〇Si(R1)2]a-[〇Si(R1)(X)]c.R1 (2) R1-Si(R1)2-[〇Si(Rl)2]a-[〇Si(R1)(X)]d.R1 (3) (式中，R1爲相同或不同之碳原子數較佳爲1至12 、再較佳爲1至1 〇、更較佳爲1至6的未取代烷基，X爲 相同或不同之碳原子數較佳爲2至8、再較佳爲2至5之 -9 - 200831613 烯基，a及b爲0或正數，c及d爲正數）。 上述R1，例如可列舉上述作爲（a )成分中作爲鍵結 於矽原子之未取代烷基之具體例示的未取代烷基。其等之 中，較佳爲甲基、乙基、丙基等碳原子數1至3之未取代 烷基，特佳爲甲基。特別地，較佳爲r 1的8 0莫耳％以上 爲甲基。再者，R1可全爲相同者，亦可爲不同者。不限定 要求所製得組成物及成形體之耐溶劑性等特殊特性，由成 本、取得的容易性、化學安定性、環境負荷等理由，多數 選擇全部的R1爲甲基。 上述X，例如可列舉上述作爲（a )成分中鍵結於矽 原子之烯基之具體例示的烯基，其中，較佳爲乙烯基、烯 丙基等低級烯基，特佳爲乙烯基。 上述a爲0或正數，較佳爲滿足10$aS10,000之正 數，再較爲滿足 50SaS 2,000之正數，更較佳爲滿足 10SaSl，00 0之正數。上述b爲0或正數，較佳爲滿足 〇$b/ ( a + b) S0.5 之數，更較佳爲滿足 0€b/ ( a + b) €0·1 之數。上述c爲正數，較佳爲滿足0<c/(a + c) $0.5之 正數，更較佳爲滿足〇<c/(a + c) €0.1之正數。上述d 爲正數，較佳爲滿足〇< d/ ( a + d) S0.5之正數，更較佳 爲滿足〇< d/ ( a + d) $0.1之正數。 [(b)成分] (b )成分爲熱傳導性塡充劑。（b )成分之平均粒徑 較佳爲〇·1至1〇〇 μπι、再較佳爲0.5至50 μιη、更較佳爲 -10- 200831613 0.5至3 Ομπι。又，本發明中，平均粒徑例如可藉由雷射繞 射法等作爲體積基準的累積平均徑而求得。（b )成分之 熱傳導性塡充劑可單獨1種使用，亦可混合2種以上使用 。混合2種以上的熱傳導性塡充劑使用時，其等之平均粒 徑亦可不同。 (b)成分可使用一般熱傳導性塡充劑所使用之物質 ，其具體例可列舉非磁性銅、鋁等金屬；氧化鋁、氧化矽 、氧化鎂、氧化鐵、氧化鋇、氧化鈦、氧化鉻等氧化物； 氮化鋁、氮化矽、氮化硼等氮化物；碳化矽等碳化物；人 工鑽石等。 (b )成分的使用量，相對於（a )成分1 00質量份， 通常爲200至5,000質量份，較佳爲300至1 500質量份 。該使用量過多時，所製得組成物爲作業性容易變差，容 易變爲成形困難。該使用量過少時，難以獲得具有期望的 熱傳導性之聚矽氧成形體。 [(c )成分] (C )成分爲具有鍵結於矽原子之氫原子（亦即Si-H 基）之有機氫聚矽氧烷，較佳爲分子內具有2個以上Si-H 基之有機氫聚矽氧烷，再較佳爲分子內具有3個以上Si-H 基之有機氫聚矽氧烷。（c)成分之有機氫聚矽氧烷，可 爲直鏈狀或環狀，任一情況中，其分子內可含有分枝狀構 造。上述Si-H基的位置並無特別限制。（c )成分爲直鏈 狀時，該Si-H基可存在於分子鏈的末端或僅存在於非末 -11 - 200831613 端部分之任一方，亦可存在於其兩方。（C )成分之有機 氫聚矽氧烷，可單獨1種使用，亦可2種以上倂用。 (c )成分之有機氫聚砂氧烷中，作爲矽原子鍵結有 機基，例如可列舉不含有脂肪族不飽和鍵之未取代或經取 代，碳原子數較佳爲1至12、再較佳爲1至1 〇、更較佳 爲1至6之1價烴基。上述矽原子鍵結有機基可全爲相同 者’亦可爲不同者。上述矽原子鍵結有機基之具體例，可 列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第三-丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、 十二烷基等烷基；環戊基、環己基、環庚基等環烷基；苯 基、甲苯基、二甲苯基、萘基、聯苯基等芳基；苄基、苯 基乙基、苯基丙基、甲基苄基等芳烷基；以及該等烴基之 一個以上的氯原子經以氣原子、氯原子、漠原子等鹵素原 子、氰基等經取代之基，例如氯甲基、2 -溴乙基、3 -氯丙 基、3,3,3 -三氟丙基、氯苯基、氟苯基、氰基乙基、 3,3,4,4,5,5,6,6,6-九氟己基等。其等之中，較佳爲甲基、 乙基、丙基、氯甲基、2-溴乙基、3，3,3-三氟丙基、氰基 乙基等未取代或經取代之碳原子數1至3之烷基以及苯基 、氯苯基、氟苯基等未取代或經取代之苯基。期望上述矽 原子鍵結有機基與（a )成分之鍵結於矽原子之未取代烷 基爲同一種類。 (c)成分之之具體例可列舉下述一般式至（6 )所表示之有機氫聚矽氧院： -12- 200831613 R2-Si(R2)2-[〇Si(R2)2]e.[〇Si(R2)(H)]f-OSi(R2)2.R2 (4) R2-Si(R2)2-[OSi(R2)2]e-[〇Si(R2)(H)]g-OSi(R2)2-H (5) H，Si(R2)2_[〇Si(R2)2]e-[〇Si(R2)(H)]h-OSi(R2)2-H (6) (式中’ R2爲不含有脂肪族不飽和鍵之相同或不同之 之未取代或經取代之碳原子數較佳爲1至1 2、再較佳爲1 至10、更較佳爲1至6的1價烴基，e、g及h爲0或正 數，f爲正數）。 上述R2，例如可列舉上述作爲（c)成分中矽原子鍵結 有機基之具體例示的1價烴基。其等之中，較佳爲甲基、 乙基、丙基、氯甲基、2 -溴乙基、3，3,3 -三氟丙基、氰基 乙基等未取代或經取代之碳原子數1至3的烷基以及苯基 、氯苯基、氟苯基等未取代或經取代之苯基。再者，R2可 全爲相同者，亦可爲不同者。期望R2與R1爲同一種類。 上述e爲〇或正數，較佳爲〇至5〇〇之數，再較佳爲 5至100之正數。上述f爲正數，較佳爲1至1〇〇之正數 ’再較佳爲2至50之正數。上述g爲〇或正數，較佳爲〇 至100之數，再較佳爲1至50之正數。上述h爲0或正 數，較佳爲0至100之數，再較佳爲〇至50之數。 (c)成分的使用量，相對於（a)成分中每1莫耳烯 基’ （c)成分中Si-H基的量通常成爲〇1至5 〇莫耳的 量’較佳使成爲0.3至3莫耳的量，再較佳使成爲〇.5至 2莫耳的量。（c)成分的使用量未達上述下限時，該組成 物的硬化容易成爲不充分，所製得硬化物作爲成形體時無 法操作；該使用量超過上述上限時，由該組成物的硬化物 -13- 200831613 所成之成形體，加熱成形時發泡可於成形體中造成空隙， 有熱傳導性惡化的情況。 [(d)成分] (d)成分爲鉬族金屬系加成反應觸媒，具有促進（a )成分中的烯基，與（c)成分中的Si-H基的加成反應的 作用。（d )成分可列舉作爲於羥矽烷基化反應所使用之 觸媒之周知的觸媒。其具體例，例如可列舉鉑（包含鉑黑 )、铑、鈀等鉑族金屬；H2PtCl4 · nH20、H2PtCl6 · ηΗ20 、NaHPtCU · nH20、KHPtCl6 · ιιΗ20、Na2PtCl6 · ηΗ20、 K2PtCl4 · nH20、PtCl4 · nH20、PtCl2、Na2HPtCl4 · nH20 ( 式中，n爲0至6之整數，較佳爲〇或6)等氯化鉑、氯 化鉑酸及氯化鉑酸鹽，醇改質氯化鈾酸（參照美國專利第 3,220,972號），氯化鉑酸與烯烴之複合體（參照美國專 利第 3，1 59,60 1 號、第 3，1 59,662 號、第 3,775,452 號）； 鉑黑、鈀等鉑族金屬担持於氧化鋁、氧化矽、碳等担體者 ;铑·烯烴複合體；氯三（三苯基膦）鍺（Wilkinson’s觸 媒）；氯化鉑、氯化鉑酸或氯化舶酸鹽與含有乙烯基之矽 氧烷之複合體等。（d)成分之鉑族金屬系加成反應觸媒 可1種單獨使用，亦可2種以上倂用。 (d)成分之使用量，雖可爲鉑族金屬系加成反應觸 媒之有效量，可根據期望的硬化速度而適宜增減。具體而 言，以相對於（a )成分換算爲鉛族金屬之質量基準，該 使用量較佳爲0.1至lOOOppm，再較佳爲0.5至200ppm， -14- 200831613 更較佳爲1 ·〇至1 OOppm。 [(e )成分] (e )成分爲以一定的改質率，具有未取代烷基以外 之鍵結於矽原子之未取代或經取代之一價烴基（以下有將 「未取代烷基以外之鍵結於矽原子之未取代或經取代之一 價烴基」稱爲「改質基」的情況），且不具鍵結於矽原子 之一價脂肪族不飽和烴基（例如烯基、炔基等）之有機聚 矽氧烷。（e)成分，與（f)成分一起，使用做爲內部添 加離型劑。（e )成分之有機聚矽氧烷，可爲直鏈狀或環 狀，任一情況中，其分子內可含有分枝狀構造。（e )成 分爲直鏈狀時，該改質基可存在於分子鏈的末端或僅存在 於非末端部分之任一方，亦可存在於其兩方。（e )成分 由於具有改質基，不易與（a)成分均一地相溶。（e)成 分之有機聚矽氧烷，可單獨1種使用，亦可2種以上倂用 。又，本說明書中，「改質率」爲有機聚矽氧烷中，相對 於鍵結矽原子之全有機基之改質基的比例。 (e)成分之有機聚矽氧烷中，作爲上述改質基，例 如可列舉未取代烷基以外之不含有脂肪族不飽和鍵結之未 取代或經取代之碳原子數較佳爲1至12、再較佳爲1至 10、更較佳爲1至6之1價烴基。上述改質基可全爲相同 者，亦可爲不同者。該改質基之具體例，可列舉環戊基、 環己基、環庚基等環烷基；苯基、甲苯基、二甲苯基、萘 基、聯苯基等芳基；苄基、苯基乙基、苯基丙基、甲基苄 -15- 200831613 基等芳院基；以及該等烴基之鍵結於碳原子之氫原子的部 份或全部經以氟原子、氯原子、溴原子等鹵素原子、氰基 等經取代之基，例如氯苯基、氟苯基；以及氯甲基、2-溴 乙基' 3-氯丙基、3,3,3_三氟丙基、氰基乙基' 3,3,4,4,5,5,6,6,6-九氟己基等經取代烷基等。其等之中， 較佳爲氯甲基、2-溴乙基、3，3,3-三氟丙基、氰基乙基等 碳原子數1至3之經取代烷基，以及苯基、氯苯基、氟苯 基等未取代或經取代之苯基。根據成本、化學安定性、環 境負荷等理由，較佳使用未取代或經取代之苯基作爲改質 基。（e)成分中之改質率，較佳爲5至100莫耳％，再較 佳爲7至5 0莫耳％，更較佳爲1 〇至2 5莫耳％。 (e )成分之有機聚矽氧烷中，作爲上述改質基以外 之矽原子鍵結有機基，例如可列舉碳原子數較佳爲1至12 、再較佳爲1至10、更較佳爲1至6之未取代烷基。上述 烷基可全爲相同者，亦可爲不同者。上述烷基之具體例可 列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第三-丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、 十二烷基等未取代烷基。其等之中，較佳爲甲基、乙基、 丙基等碳原子數1至3之未取代烷基。 (e )成分之具體例可列舉下述一般式（7 )所表示之 有機聚矽氧烷： R3.Si(R3)2-[〇Si(R3)2]i-R3 ( 7 ) (式中，R3爲不含有脂肪族不飽和鍵之相同或不同之 之未取代或經取代之碳原子數較佳爲1至1 2、再較佳爲1 -16 - 200831613 至10、更較佳爲1至6的1價烴基，i爲正數，惟，R3的 一部份或全部爲改質基）。該等有機聚矽氧烷可1種單獨 使用，亦可2種以上倂用。 上述R3，例如可列舉上述作爲（e )成分中改質基之 具體例示的1價烴基以及作爲（e )成分中未取代烷基之 具體例示的烷基。其等之中，作爲改質基，較佳爲氯甲基 、2-溴乙基、3，3,3-三氟丙基、氰基乙基等碳原子數1至3 之經取代烷基，以及苯基、氯苯基、氟苯基等未取代或經 取代苯基；作爲未取代烷基，較佳爲甲基、乙基、丙基等 碳原子數1至3之未取代烷基。作爲改質基，根據成本、 化學安定性、環境負荷等理由，較佳使用未取代苯基。全 R3中的改質基比例較佳爲5至1 0 0莫耳％，再較佳爲7至 50莫耳％，更較佳爲10至25莫耳％。 (e)成分的黏度，較佳爲1至100,000mPa· s，再較 佳爲10至10,000 mPa· S，再更較佳爲100至5,000mPa • s ° (e )成分之使用量，相對於（a )成分1 00質量份， 通常爲0.1至20質量份，較佳爲0.5至15質量份，再較 佳爲1至10質量份。該使用量比20質量份更多時，所製 得組成物之成形後容易產生大量的滲出。該使用量比0.1 質量份更少時，難以獲得期望的剝離性。 [(f)成分] (f )成分爲具有未取代烷基以外之鍵結於矽原子之 -17- 200831613 未取代或經取代之一價烴基之與存在於（e )成分中者爲 相同種類之一價烴基，亦即，存在於（e)成分中者爲相 同種類之改質基以較（e)成分中之改質率更低之改質率 ’且不具鍵結於矽原子之一價脂肪族不飽和烴基之有機聚 矽氧烷。（f)成分，與（e)成分一起使用做爲內部添加 離型劑。（f)成分之有機聚矽氧烷，可爲直鏈狀或環狀 ’任一情況中，其分子內可含有分枝狀構造。上述改質基 φ 的位置並無特別限制。（f)成分爲直鏈狀時，該改質基 可存在於分子鏈的末端或僅存在於非末端部分之任一方， 亦可存在於其兩方。（f)成分由於具有改質基，不易與 (a )成分均一地相溶。惟，由於（f)成分中之改質率比 (e )成分中之改質率更低，（f)成分相對於（a )成分 之相溶性，比（e )成分相對於（a )成分之相溶性更高。 (f)成分之有機聚矽氧烷，可單獨1種使用，亦可2種 以上倂用。 • (f)成分之有機聚矽氧烷中，作爲上述改質基，例 如可列舉未取代烷基以外之不含有脂肪族不飽和鍵結之未 取代或經取代之碳原子數較佳爲1至12、再較佳爲1至 10、更較佳爲〗至.6之1價烴基。上述改質基可全爲相同 者’亦可爲不同者。該改質基之具體例，可列舉上述作爲 (e)成分中改質基之具體例示之1價烴基。其等之中， 較佳爲氯甲基、2-溴乙基、3，3,3-三氟丙基、氰基乙基等 碳原子數1至3之經取代烷基，以及苯基、氯苯基、氟苯 基等未取代或經取代之苯基。根據成本、化學安定性、環 -18- 200831613 境負荷等理由，較佳使用未取代之苯基作爲改質基。(f )成分中之改質率，較佳爲1至20莫耳％，再較佳爲1至 1 〇莫耳％，更較佳爲1至5莫耳％，惟，（f)成分中之改 質率比（e)成分中之改質率更低。 (f )成分之有機聚矽氧烷中，作爲上述改質基以外 之矽原子鍵結有機基，例如可列舉碳原子數較佳爲1至1 2 、再較佳爲1至1 0、更較佳爲1至6之未取代烷基。上述 烷基可全爲相同者，亦可爲不同者。上述烷基之具體例可 列舉作爲（e )成分中未取代烷基之具體例示的烷基。其 等之中，較佳爲甲基、乙基、丙基等碳原子數1至3之未 取代烷基。 (f)成分之之具體例可列舉下述一般式（8)所表示 之有機聚矽氧烷： R4-Si(R4)2-[〇Si(R4)2]rR4 (8) (式中，R4爲不含有脂肪族不飽和鍵之相同或不同之 之未取代或經取代之碳原子數較佳爲1至1 2、再較佳爲1 至1 〇、更較佳爲1至6的1價烴基，j爲正數，惟，R4的 一部份爲與存在於（e )成分中者爲同一種類之改質基， 且（f)成分中之改質率比（e)成分中之改質率更低）。 該等有機聚矽氧烷可1種單獨使用，亦可2種以上倂用。 JL述R4，例如可列舉上述作爲（e )成分中改質基具 體例示之1價烴基以及作爲（e)成分中未取代烷基具體 例示之烷基。其等之中，作爲改質基，較佳爲氯甲基、2-溴乙基' 3,3,3-三氟丙基、氰基乙基等碳原子數1至3之 -19- 200831613 經取代烷基，以及苯基、氯苯基、氟苯基等未取 代苯基；作爲未取代烷基，較佳爲甲基、乙基、 原子數1至3之未取代烷基。作爲改質基，根據 學安定性、環境負荷等理由，較佳使用未取代苯 中的改質基比例較佳爲1至20莫耳％，再較佳怎 莫耳％，更較佳爲1至5莫耳％，惟，（f)成分 率比（e )成分中之改質率更低。 φ (Ο成分的黏度，較佳爲1至10〇,〇〇〇mPa 佳爲10至10, 〇〇〇 mPa· S，再更較佳爲1〇〇至 • s ° (f)成分之使用量，相對於（a)成分1〇〇 通常爲〇·1至20質量份，較佳爲〇·5至15質量 佳爲1至1 〇質量份。該使用量比2 0質量份多時 組成物之成形後容易產生大量的滲出。該使用量 量份更少時，難以獲得期望的剝離性。 [其他成分] 本發明之聚矽氧組成物，除了該等成分以外 ，可於不損及本發明目的之範圍內添加例如熱傳 劑的表面處理劑、用於調整硬化速度之反應抑制 乙炔環己醇）、用於著色之顏料•染料、難燃性 之用於提升本發明組成物及成形體機能之各種添 [組成物之製造方法] 代或經取 丙基等碳 成本、化 基。全R4 i 1 至 10 中之改質 • s，再較 5 3 0 0 0 m P a 質量份， 份，再較 ，所製得 比0.1質 ，必要時 導性塡充 劑（例如 賦予劑等 加劑。 •20- 200831613 本發明之熱傳導性聚砍氧組成物可藉由將上述成分根 據一般方法混合而製造。 [成形體之製造方法] 本發明之熱傳導性聚矽氧成形體，可將本發明之組成 物藉由習知的方法經硬化•成形而製造。該成形體的形狀 並無特別限制，可根據用途而適宜選擇，較佳爲片（sheet )狀。爲了使該組成物硬化•成形爲片狀，可採用使習知 的加成反應硬化型聚矽氧樹脂組成物硬化•成形爲片狀時 爲同樣的條件。該組成物於常溫雖可充分地硬化•成形爲 片狀，必要時亦可加熱。藉由上述方法製得作爲片之可操 作的彈性成形體。 本發明之聚矽氧組成物藉由連續成形法被覆於長形薄 膜上，之後藉由於常溫或加熱而硬化製得成形體，來自被 覆開始時所塗佈之組成物的部分與來自開始後經一段時間 塗佈之組成物的部份相比較，剝離性之差異小，顯示良好 的剝離性。 [用途] 本發明之熱傳導性聚矽氧成形體，例如可適合使用作 爲電子零件的熱傳達材料。藉由該熱傳導性聚矽氧成形體 ，該電子零件可有效地冷卻。此時，該成形體的形狀，如 上所述，可爲片狀。 -21 - 200831613 〔實施例〕 以下顯示實施例與比較例’更詳細說明本發明，但本 發明不以該等爲限。又，「Me」表示甲基。 [實施例1] 於品川式萬能攪拌機（品川工業所製）中置入兩端以 乙烯基封鎖、於25°C具有600mPa 的黏度的二甲基聚 矽氧院100g，與具有4#m平均粒徑之氧化錦（商品名： AL-24，昭和電工公司製）400g，混合60分鐘，獲得均一 的液狀基底500g。於該液狀基底5 0 0g中，添加甲基苯基 矽氧油KF54 (商品名，信越化學工業公司製，苯基含有 量：相對於全矽氧烷單位，25莫耳％爲二苯基矽氧烷單位 )2.0g與甲基苯基矽氧油KF5 0-300cs (商品名，信越化 學工業公司製，苯基含有量：相對於全矽氧烷單位，5莫 耳％爲二苯基矽氧烷單位）2.0g、氯化鉑酸2質量％2-乙基 己醇溶液O.lg、與乙炔基環己醇-50質量％甲苯溶液0.2g ，均一地混合。再添加下述一般式（9)所示之有機氫聚 矽氧烷16g :200831613 IX. OBJECTS OF THE INVENTION [Technical Field] The present invention relates to a thermally conductive polysilicate composition, and a thermally conductive polyoxynitride formed from a cured product of the composition, particularly for heat-generating electrons An effective heat conductive polyoxyl composition for heat transfer of a component as a heat transfer material interposed between the electronic component and a heat sink such as a heat sink or a circuit substrate, and a hardened material of the composition A thermally conductive polysiloxane molded body. [Prior Art] LSI chips such as CPUs, drives 1C, and memory used in electronic devices such as personal computers, digital camcorders, and mobile phones are high-performance, high-speed, miniaturized, and highly integrated. Become a lot of heat. The heat of the wafer is raised by the heat to cause malfunction or destruction of the wafer. Therefore, there have been various proposals for a heat dissipation method for suppressing an increase in temperature of a wafer during operation and a heat dissipation member used therefor. Conventionally, in an electronic device or the like, in order to suppress an increase in the temperature of a wafer during operation, a metal plate having a high thermal conductivity such as aluminum or copper is used for the heat sink used. The heat sink radiates heat generated by the wafer and is released from the surface by a temperature difference between the heat and the outside air. At this time, in order to transfer the heat generated by the wafer to the heat sink, a flexible molded body or grease is interposed between the wafer and the heat sink, and the molded body or the grease can be used to lift the wafer. Heat transfer efficiency to the heat sink. -4 - 200831613 The molded article having flexibility is excellent in handleability compared to grease, and is particularly a heat conductive molded body having low hardness formed by heat conductive polyfluorene or the like (that is, a thermally conductive polyoxynitride molded body) ) is being used in various fields. When the molded body is soft and soft, the adhesion to the wafer and the heat sink is better, and the heat release characteristics are more excellent. The molded body is provided in a sheet shape in most cases. The method of producing the molded article in the form of a sheet in this manner includes a press molding method in which a mold such as a mold and a press machine are used to heat-harden the thermally conductive material, and a liquid heat conductive material is discharged onto the elongated film. A continuous forming method in which a certain thickness is applied by heat treatment using a knife coater or a comma coater or the like is used. In the case where a relatively thin sheet-shaped formed body is formed in a large amount, the continuous forming method by coating is excellent in comparison with the press forming method by batch processing. Therefore, the forming cost is more advantageous in the case of the continuous forming method by coating than the press forming method. The sheet-like formed body to be provided can be easily peeled off from the film used at the time of molding, which is necessary. A representative method for easily peeling off is a method of applying a release agent such as a surfactant to a film, and a method of adding a cross-linking non-functional polymer component to the composition as an internally added release agent. . In the case where the release agent such as the surfactant is applied to the film to carry out the release treatment, the step of applying the release agent to the film before the formation of the formed body of the sheet shape is necessary, resulting in an increase in cost. Therefore, it is preferred to use a method of adding an internally added release agent to the composition. -5- 200831613 As a internally added release agent, a non-functional polymer component is preferably used. When a polymer which is completely compatible with the organic siloxane of the base polymer is used as the non-functional polymer component, it is necessary to add an internally added release agent in a large amount in order to obtain a release effect, and the sheet-shaped formed body obtained in this manner is easy. A problem that causes oil to seep out. Therefore, it is preferred to use a non-functional polymer which is insoluble in the organopolyoxane of the base polymer in order to obtain a sufficient release effect in a small amount. ^ A liquid composition in which a non-functional polymer which is insoluble in an organopolysiloxane of a base polymer is added in a small amount, and is discharged on an elongated film, and when continuously coated, the sheet-shaped formed body at the start of coating is covered. The peeling from the elongated film of the substrate was good. However, when the coating is directly continued to be formed, the liquid material stored in the material liquid before the applicator is partially covered on the elongated film of the substrate for a long time, so that the formed sheet-shaped formed body and the substrate are long. The peeling of the formed film deteriorates, and finally there is a problem that the sheet-shaped formed body is attached to the elongated film. φ 专利 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 When the long film of the substrate is not subjected to the release treatment and is formed by the continuous molding method by coating, the amount of the internally added release agent is not related to the amount of the internal addition agent, even after coating for a period of time after the start of coating. Heat transfer of a molded article which does not deteriorate in peelability -6 - 200831613 A conductive composition and a thermally conductive oxygen molded body formed from a cured product of the composition. [Means for Solving the Problem] The present inventors have made the present invention in an effort to achieve the above object. That is, the present invention provides a thermally conductive polyanthracene comprising: (a) an organopolyoxyalkylene group having an alkenyl group bonded to a ruthenium atom and an organic group bonded to another oxime which is an unsubstituted alkyl group; : 00 mass f (b) thermally conductive chelating agent: 200 to 5,000 parts by mass; (c) organic hydrogen condensed with a hydrogen atom bonded to a ruthenium atom: alkenyl group per 1 mole of (a) component , the amount of the hydrogen atom of the bonding atom in the component (C) is 0.1 to 5.0 moles; (d) the platinum group metal addition reaction catalyst: an effective amount; (e) with a certain degree of modification, An organic polyoxo compound having an unsubstituted or substituted one-valent hydrocarbon group other than an unsubstituted alkyl group and having no valent aliphatic unsaturated hydrocarbon group of a bonded atom: 〇·1 ^ parts by mass; f) a modification rate lower than the modification rate in the (e) component, and an unsubstituted or substituted hydrocarbon group bonded to the ruthenium atom other than the unsubstituted alkyl group is present in the component (e) One of the same kinds of valence hydrocarbons and no organic oxygen bonded to one of the hydrazine atoms of one of the hydrazine atoms is an organic oxygen {兀· to 2〇 parts by mass. Furthermore, the present invention provides a thermopolymerization of the cured material of the composition to complete the oxygen group atomization of the oxygen atom in the 矽5 20 having a monovalent group, the polyfluorene conduction -7-200831613 polyoxyl formation body. The thermally conductive polyaluminum composition of the present invention is formed on a long film of a substrate without being subjected to a release treatment, and is formed by a continuous molding method by coating, irrespective of the amount of the internally added release agent. Even if it is applied over a period of time after the start of coating, the molded body which does not deteriorate the peeling property is provided. [Embodiment] Hereinafter, the present invention will be described in detail. Further, in the present invention, the viscosity is enthalpy measured by a rotary viscometer at 25 °C. [(a) component] The component (a) is an organopolyoxyalkylene having an alkenyl group bonded to a ruthenium atom and an organic group bonded to another ruthenium atom being an unsubstituted alkyl group. (a) The organic polysiloxane of the component may be linear or cyclic, and in any case, although it may have a branched structure in its molecule, it may be a physical property such as mechanical strength of the cured product. In general, it is generally preferred to be substantially linear, and specifically, a linear diorganopolyoxyalkylene in which the main chain is a main diorganopolyoxyalkylene unit is preferable. The position of the above alkenyl group is not particularly limited. When the component (a) is linear, the alkenyl group may be present at one end of the molecular chain and only one of the non-terminal portions, or both of them may be present. Further, both ends of the linear dimercaptosiloxane are usually blocked with a triorganophosphonyl group. (a) The organic polysoda compound may be used alone or in combination of two or more. When two or more kinds of organopolyoxyalkylenes are used, the viscosity thereof may be different from each other. -8- 200831613 The above-mentioned alkyl group is, for example, an unsubstituted alkyl group having preferably 1 to 2 2, more preferably 1 to 10, still more preferably 1 to 6 carbon atoms. The above alkyl groups may all be the same or different. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a third butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. An unsubstituted alkyl group such as a thiol group, a decyl group or a dodecyl group Among them, an unsubstituted alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group is preferred, and a methyl group is particularly preferred. In particular, it is more preferred that 80% by mole or more of the entire alkyl group is a methyl group. The specific characteristics such as the solvent resistance of the composition and the molded article to be obtained are not limited, and the alkyl group is selected to be a methyl group in many cases for reasons such as cost, availability, chemical stability, and environmental load. The alkenyl group may, for example, be an alkenyl group having preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms. The above alkenyl groups may all be the same or different. Specific examples of the above alkenyl group include a vinyl group, an allyl group, a propylene group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group and the like. Among them, a vinyl group or an allylic group is preferred. A lower alkenyl group such as a group is preferred, and a vinyl group is particularly preferred. Specific examples of the component (a) include organic hydrogen polyoxane represented by the following general formulas (1) to (3) = X-Si(R1)2-[OSi(R1)2]a-[〇Si (R1)(X)]bX (1) X.Si(R1)2-[〇Si(R1)2]a-[〇Si(R1)(X)]c.R1 (2) R1-Si(R1 )2-[〇Si(Rl)2]a-[〇Si(R1)(X)]d.R1 (3) (wherein, R1 is the same or different, and the number of carbon atoms is preferably from 1 to 12, and then Preferably, it is 1 to 1 Torr, more preferably 1 to 6 unsubstituted alkyl groups, and X is the same or different carbon number is preferably 2 to 8, more preferably 2 to 5 -9 - 200831613 olefin Base, a and b are 0 or a positive number, and c and d are positive numbers). The above-mentioned R1 is, for example, a specific exemplified unsubstituted alkyl group as an unsubstituted alkyl group bonded to a ruthenium atom in the component (a). Among them, an unsubstituted alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group is preferred, and a methyl group is particularly preferred. In particular, it is preferred that 80% or more of r 1 is a methyl group. Furthermore, R1 may be the same or different. The specific characteristics such as the solvent resistance of the composition and the molded article to be obtained are not limited, and most of R1 is selected to be a methyl group for reasons such as cost, availability, chemical stability, and environmental load. The above-mentioned X is, for example, a specific exemplified alkenyl group which is an alkenyl group bonded to a ruthenium atom in the component (a). Among them, a lower alkenyl group such as a vinyl group or an allyl group is preferable, and a vinyl group is particularly preferable. The above a is 0 or a positive number, preferably a positive number of 10$aS10,000, and more preferably a positive number of 50 SaS 2,000, more preferably a positive number of 10 SaSl, 00 0. The above b is 0 or a positive number, preferably satisfies the number of 〇$b/( a + b) S0.5, and more preferably satisfies the number of 0€b/( a + b) €0·1. The above c is a positive number, preferably a positive number satisfying 0 <c/(a + c) $0.5, and more preferably a positive number satisfying 〇<c/(a + c) €0.1. The above d is a positive number, preferably a positive number satisfying 〇 < d / ( a + d) S0.5 , and more preferably a positive number satisfying 〇 < d / ( a + d) $0.1. [(b) component] The component (b) is a thermally conductive chelating agent. The average particle diameter of the component (b) is preferably 〇·1 to 1 〇〇 μπι, more preferably 0.5 to 50 μηη, still more preferably -10-200831613 0.5 to 3 Ομπι. Further, in the present invention, the average particle diameter can be obtained, for example, by a cumulative average diameter as a volume reference by a laser diffraction method or the like. (b) The thermally conductive chelating agent may be used alone or in combination of two or more. When two or more types of thermally conductive chelating agents are used, the average particle diameter of the materials may be different. As the component (b), a material which is generally used for a thermally conductive chelating agent can be used, and specific examples thereof include metals such as non-magnetic copper and aluminum; alumina, cerium oxide, magnesium oxide, iron oxide, cerium oxide, titanium oxide, and chromium oxide. Oxide; nitride such as aluminum nitride, tantalum nitride, boron nitride; carbide such as tantalum carbide; artificial diamond. The amount of the component (b) to be used is usually 200 to 5,000 parts by mass, preferably 300 to 1,500 parts by mass, per 100 parts by mass of the component (a). When the amount of use is too large, the composition obtained is likely to be deteriorated in workability, and it is easy to become difficult to form. When the amount used is too small, it is difficult to obtain a polyoxynitride molded body having desired thermal conductivity. [Component (c)] The component (C) is an organic hydrogen polyoxyalkylene having a hydrogen atom bonded to a halogen atom (i.e., a Si-H group), and preferably has two or more Si-H groups in the molecule. The organic hydrogen polyoxyalkylene is more preferably an organic hydrogen polyoxyalkylene having three or more Si-H groups in the molecule. The organic hydrogen polyoxyalkylene of the component (c) may be linear or cyclic, and in either case, it may have a branched structure in its molecule. The position of the above Si-H group is not particularly limited. When the component (c) is linear, the Si-H group may exist at the end of the molecular chain or may exist only at one of the terminal portions of the non-terminal -11 - 200831613, or may exist in both of them. The organic hydrogen polyoxyalkylene oxide of the component (C) may be used alone or in combination of two or more. In the organic hydrogen polyoxalate of the component (c), the organic group bonded to the ruthenium atom may, for example, be unsubstituted or substituted without an aliphatic unsaturated bond, and the number of carbon atoms is preferably from 1 to 12, and furthermore. It is preferably a monovalent hydrocarbon group of 1 to 1 Torr, more preferably 1 to 6. The above-mentioned ruthenium atom-bonded organic groups may all be the same or different. Specific examples of the above-mentioned ruthenium atom-bonded organic group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, and heptyl group. , an alkyl group such as an octyl group, a decyl group, a decyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, etc. An aryl group; an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group or a methylbenzyl group; and one or more chlorine atoms of the hydrocarbon group are a halogen atom such as a gas atom, a chlorine atom or a desert atom; A substituted group such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3, 3,4,4,5,5,6,6,6-nonafluorohexyl and the like. Among them, preferred are unsubstituted or substituted carbon such as methyl, ethyl, propyl, chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl or cyanoethyl. An alkyl group having 1 to 3 atomic atoms and an unsubstituted or substituted phenyl group such as a phenyl group, a chlorophenyl group or a fluorophenyl group. It is desirable that the above 矽 atom-bonded organic group is the same type as the unsubstituted alkyl group in which the component (a) is bonded to the ruthenium atom. Specific examples of the component (c) include organic hydrogen polyoxo represented by the following general formulas to (6): -12- 200831613 R2-Si(R2)2-[〇Si(R2)2]e. [〇Si(R2)(H)]f-OSi(R2)2.R2 (4) R2-Si(R2)2-[OSi(R2)2]e-[〇Si(R2)(H)]g -OSi(R2)2-H (5) H,Si(R2)2_[〇Si(R2)2]e-[〇Si(R2)(H)]h-OSi(R2)2-H (6) (wherein R2 is the same or different unsubstituted or substituted carbon atoms which do not contain an aliphatic unsaturated bond, preferably from 1 to 1, more preferably from 1 to 10, still more preferably 1 to A monovalent hydrocarbon group of 6 wherein e, g and h are 0 or a positive number, and f is a positive number). The above-mentioned R2 is, for example, a monovalent hydrocarbon group which is specifically exemplified as the ruthenium atom-bonded organic group in the component (c). Among them, preferred are unsubstituted or substituted carbon such as methyl, ethyl, propyl, chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl or cyanoethyl. An alkyl group having 1 to 3 atoms and an unsubstituted or substituted phenyl group such as a phenyl group, a chlorophenyl group or a fluorophenyl group. Furthermore, R2 may be the same or different. It is desirable that R2 and R1 are of the same kind. The above e is 〇 or a positive number, preferably 〇 to 5〇〇, and more preferably 5 to 100. The above f is a positive number, preferably a positive number of 1 to 1 ’ and more preferably a positive number of 2 to 50. The above g is 〇 or a positive number, preferably 〇 to 100, and more preferably a positive number of 1 to 50. The above h is 0 or a positive number, preferably 0 to 100, and more preferably 〇 to 50. The amount of the component (c) used is usually from 〇1 to 5 〇m to the amount of the Si-H group per 1 mole of the alkenyl group (c) in the component (a). The amount to 3 moles is more preferably an amount of 〇5 to 2 moles. When the amount of the component (c) is less than the lower limit, the curing of the composition is likely to be insufficient, and when the cured product is obtained as a molded body, the cured product cannot be handled. When the amount exceeds the upper limit, the cured product of the composition is cured. -13- 200831613 The molded body formed by foaming during heat molding may cause voids in the molded body and may deteriorate thermal conductivity. [Component (d)] The component (d) is a platinum group metal addition reaction catalyst, and has an action of promoting an addition reaction of an alkenyl group in the component (a) with a Si-H group in the component (c). The component (d) is a well-known catalyst which is used as a catalyst for the oxindole alkylation reaction. Specific examples thereof include platinum group metals including platinum (including platinum black), ruthenium, and palladium; H2PtCl4 · nH20, H2PtCl6 · ηΗ20, NaHPtCU · nH20, KHPtCl6 · ιιΗ 20, Na2PtCl6 · ηΗ20, K2PtCl4 · nH20, PtCl4 · nH20, PtCl2, Na2HPtCl4 · nH20 (where n is an integer from 0 to 6, preferably ruthenium or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate, alcohol modified uranium chloride (refer to the United States) Patent No. 3,220,972), a composite of chloroplatinic acid and an olefin (refer to U.S. Patent Nos. 3,1 59,60 1 , 3,1 59,662, 3,775,452); platinum group, palladium and other platinum group metals In the case of alumina, cerium oxide, carbon, etc.; cerium-olefin complex; chlorotris(triphenylphosphine) ruthenium (Wilkinson's catalyst); platinum chloride, chloroplatinic acid or chlorinated acid salt and a complex of vinyl oxirane, and the like. The platinum group metal addition reaction catalyst of the component (d) may be used alone or in combination of two or more. The amount of the component (d) used may be an effective amount of the platinum group metal addition reaction catalyst, and may be appropriately increased or decreased depending on the desired curing rate. Specifically, the amount of use is preferably from 0.1 to 1,000 ppm, more preferably from 0.5 to 200 ppm, more preferably from 1 to 10, based on the mass of the lead metal in terms of (a). 1 OOppm. [(e) component] The component (e) is an unsubstituted or substituted one-valent hydrocarbon group bonded to a ruthenium atom other than an unsubstituted alkyl group at a certain rate of modification (hereinafter, the "unsubstituted alkyl group" The case where the unsubstituted or substituted one-valent hydrocarbon group of the ruthenium atom is referred to as a "modified base", and is not bonded to one of the hydrazine atoms, such as an alkenyl group or an alkynyl group. Etc.) Organic polyoxane. The component (e) is used together with the component (f) as an internal release agent. The organopolyoxane of the component (e) may be linear or cyclic, and in either case, it may have a branched structure in its molecule. When the (e) is a linear form, the modified group may exist at the end of the molecular chain or may exist only in one of the non-terminal portions, or may exist in both of them. The component (e) has a modified base and is not easily compatible with the component (a). (e) The organic polyoxane of the component may be used alone or in combination of two or more. Further, in the present specification, the "modification rate" is a ratio of the modifying group of the organic group to the all-organic group of the bonded germanium atom in the organopolysiloxane. In the organopolyoxane of the component (e), examples of the modified group include, for example, an unsubstituted or substituted carbon atom having no aliphatic unsaturated bond other than the unsubstituted alkyl group. Further, it is more preferably from 1 to 10, more preferably from 1 to 6, of a monovalent hydrocarbon group. The above modified bases may all be the same or different. Specific examples of the modifying group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a biphenyl group; a benzyl group and a phenyl group; Ethyl, phenylpropyl, methylbenzyl-15-200831613, etc.; and some or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group are subjected to a fluorine atom, a chlorine atom, a bromine atom, etc. a substituted group such as a halogen atom or a cyano group, such as a chlorophenyl group or a fluorophenyl group; and a chloromethyl group, a 2-bromoethyl '3-chloropropyl group, a 3,3,3-trifluoropropyl group, and a cyano group. A substituted alkyl group such as an ethyl '3,3,4,4,5,5,6,6,6-nonafluorohexyl group. Among them, a substituted alkyl group having 1 to 3 carbon atoms such as a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group or a cyanoethyl group, and a phenyl group are preferable. An unsubstituted or substituted phenyl group such as chlorophenyl or fluorophenyl. The unsubstituted or substituted phenyl group is preferably used as a modifying group for reasons such as cost, chemical stability, environmental load and the like. The rate of reform in the component (e) is preferably from 5 to 100 mol%, more preferably from 7 to 50 mol%, still more preferably from 1 to 25 mol%. In the organopolyoxane of the component (e), the ruthenium atom-bonded organic group other than the above-mentioned modified group may, for example, preferably have 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably more preferably 1 to 10 carbon atoms. It is an unsubstituted alkyl group of 1 to 6. The above alkyl groups may all be the same or different. Specific examples of the above alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group and fluorene group. An unsubstituted alkyl group such as a thiol group, a decyl group or a dodecyl group. Among them, an unsubstituted alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group is preferred. Specific examples of the component (e) include an organopolyoxane represented by the following general formula (7): R3.Si(R3)2-[〇Si(R3)2]i-R3 ( 7 ) (wherein R3 is the same or different unsubstituted or substituted carbon atoms which do not contain an aliphatic unsaturated bond, preferably from 1 to 1, more preferably from 1 to 16 - 200831613 to 10, more preferably 1 To a monovalent hydrocarbon group of 6, i is a positive number, but a part or all of R3 is a modified group). These organic polyoxoxanes may be used alone or in combination of two or more. The above-mentioned R3 is, for example, a monovalent hydrocarbon group which is specifically exemplified as the modifying group in the component (e), and an alkyl group which is specifically exemplified as the unsubstituted alkyl group in the component (e). Among them, as the modifying group, a substituted alkyl group having 1 to 3 carbon atoms such as a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group or a cyanoethyl group is preferred. And an unsubstituted or substituted phenyl group such as a phenyl group, a chlorophenyl group or a fluorophenyl group; and an unsubstituted alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group as the unsubstituted alkyl group; . As the modifying group, an unsubstituted phenyl group is preferably used for reasons such as cost, chemical stability, environmental load and the like. The ratio of the modified base in the entire R3 is preferably from 5 to 100% by mole, more preferably from 7 to 50% by mole, still more preferably from 10 to 25% by mole. The viscosity of the component (e) is preferably from 1 to 100,000 mPa·s, more preferably from 10 to 10,000 mPa·s, still more preferably from 100 to 5,000 mPa • s ° (e), relative to (a) The component is 100 parts by mass, usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass. When the amount used is more than 20 parts by mass, a large amount of bleeding is likely to occur after the formation of the composition. When the amount used is less than 0.1 part by mass, it is difficult to obtain desired peelability. [(f) component] (f) component is a bond other than an unsubstituted alkyl group bonded to a ruthenium atom -17-200831613 Unsubstituted or substituted one-valent hydrocarbon group is the same as the one present in (e) component a one-valent hydrocarbon group, that is, a component having the same kind in the component (e) has a higher reforming rate than the (e) component, and is not bonded to one of the ruthenium atoms. An organic polyoxane having a valence of an aliphatic unsaturated hydrocarbon group. The component (f) is used together with the component (e) as an internal addition release agent. The organopolyoxane of the component (f) may be linear or cyclic. In either case, the molecule may have a branched structure. The position of the above modified base φ is not particularly limited. When the component (f) is linear, the modified group may exist at the end of the molecular chain or only in the non-terminal portion, or may exist in both of them. The component (f) has a modified base and is not easily compatible with the component (a). However, since the modification rate in the component (f) is lower than the modification rate in the component (e), the compatibility of the component (f) with respect to the component (a) is higher than the component (e) relative to the component (a). The compatibility is higher. The organopolyoxane of the component (f) may be used alone or in combination of two or more. In the organopolyoxane of the component (f), examples of the modified group include, for example, an unsubstituted or substituted carbon atom which does not contain an aliphatic unsaturated bond other than the unsubstituted alkyl group. The monovalent hydrocarbon group to 12, more preferably 1 to 10, more preferably 〗 〖 to 6. The above modified bases may all be the same or different. Specific examples of the modifying group include the above-exemplified monovalent hydrocarbon group as a modified group in the component (e). Among them, a substituted alkyl group having 1 to 3 carbon atoms such as a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group or a cyanoethyl group, and a phenyl group are preferable. An unsubstituted or substituted phenyl group such as chlorophenyl or fluorophenyl. The unsubstituted phenyl group is preferably used as a modifying group for reasons such as cost, chemical stability, and environmental load of -18-200831613. The modification rate in the component (f) is preferably from 1 to 20 mol%, more preferably from 1 to 1 mol%, still more preferably from 1 to 5 mol%, but in the component (f) The rate of improvement is lower than the rate of modification in component (e). In the organopolyoxane of the component (f), the organic group bonded to the ruthenium atom other than the above-mentioned modified group may, for example, preferably have 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and more preferably An unsubstituted alkyl group of 1 to 6 is preferred. The above alkyl groups may all be the same or different. Specific examples of the above alkyl group include a specific alkyl group as an unsubstituted alkyl group in the component (e). Among them, an unsubstituted alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group is preferred. Specific examples of the component (f) include an organopolyoxane represented by the following general formula (8): R4-Si(R4)2-[〇Si(R4)2]rR4 (8) (wherein R4 is the same or different unsubstituted or substituted carbon atoms which do not contain an aliphatic unsaturated bond, preferably 1 to 1, 2, more preferably 1 to 1 Torr, more preferably 1 to 6 a valence hydrocarbon group, j is a positive number, except that a part of R4 is the same type of modified group as that present in (e) component, and the modification rate in (f) component is changed in (e) component Lower quality). These organic polyoxoxanes may be used alone or in combination of two or more. For example, the above-mentioned monovalent hydrocarbon group exemplified as the modified base group in the component (e) and the alkyl group specifically exemplified as the unsubstituted alkyl group in the component (e) can be mentioned. Among them, as a modifying group, a chloromethyl group, a 2-bromoethyl '3,3,3-trifluoropropyl group, a cyanoethyl group or the like, and a carbon number of 1 to 3 are preferably -19-200831613 The substituted alkyl group and an unsubstituted phenyl group such as a phenyl group, a chlorophenyl group or a fluorophenyl group; and the unsubstituted alkyl group is preferably a methyl group, an ethyl group or an unsubstituted alkyl group having 1 to 3 atoms. As a modifying base, the ratio of the modifying group in the unsubstituted benzene is preferably from 1 to 20 mol%, more preferably from 0%, more preferably 1 based on the reasons of academic stability, environmental load, and the like. Up to 5 mol%, except that the (f) component ratio is lower than the (e) component. φ (the viscosity of the Ο component, preferably 1 to 10 〇, 〇〇〇mPa is preferably 10 to 10, 〇〇〇mPa· S, and more preferably 1 〇〇 to • s ° (f) composition The amount is usually from 1 to 20 parts by mass, preferably from 1 to 15 parts by mass, based on 1 part of the component (a), preferably from 1 to 1 part by mass. When the amount is more than 20 parts by mass, the composition is more than 20 parts by mass. A large amount of bleed is likely to occur after the formation of the article. When the amount is less, it is difficult to obtain a desired peeling property. [Other components] The polyfluorene oxide composition of the present invention can be used without being damaged. Within the scope of the object of the present invention, a surface treatment agent such as a heat transfer agent, a reaction for adjusting the curing rate to suppress acetylene cyclohexanol, a pigment for dyeing, a dye, and a flame retardant are used to enhance the composition of the present invention and Various additions of the functions of the molded body [manufacturing method of the composition] The carbon cost and the base of the propyl group are obtained by the generation or by taking. Modification of all R4 i 1 to 10 • s, then more than 5 3 0 0 m P a mass parts, parts, and then made 0.1 mass, if necessary, conductive agent (such as the agent, etc.) 20-200831613 The thermally conductive polyoxygenated composition of the present invention can be produced by mixing the above components according to a general method. [Method for Producing a Shaped Body] The thermally conductive poly(oxygen oxide formed article) of the present invention can be used. The composition of the present invention is produced by hardening and shaping by a conventional method. The shape of the molded body is not particularly limited, and may be appropriately selected depending on the application, and is preferably in the form of a sheet. In order to harden the composition. • It is formed into a sheet shape, and the same conditions can be employed in the case where the conventional addition reaction-curable polyoxynoxy resin composition is cured and formed into a sheet shape. The composition can be sufficiently cured at room temperature and formed into a sheet shape. And if necessary, heating. An elastic molded body which is operable as a sheet is obtained by the above method. The polyfluorene oxide composition of the present invention is coated on the elongated film by continuous molding, and then by normal temperature or heating. Hardening to form The portion derived from the composition applied at the start of coating was smaller than the portion from the composition which was applied after a period of time from the start, and the difference in peeling property was small, showing good peeling property. [Use] Heat conduction of the present invention The polyoxygenated oxide body can be suitably used, for example, as a heat transfer material for an electronic component. The electronic component can be effectively cooled by the thermally conductive polyoxynitride molded body. At this time, the shape of the molded body is as described above. [21] [Examples] The present invention will be described in more detail below with reference to the examples and comparative examples, but the present invention is not limited thereto. Further, "Me" means a methyl group. 1] In a ginseng-type universal mixer (manufactured by Shinagawa Kogyo Co., Ltd.), 100 g of a dimethyl polyxide chamber having a viscosity of 600 mPa at 25 ° C and a vinyl chloride block at both ends, and having an average particle diameter of 4 #m were placed. 400 g of oxidized bromine (trade name: AL-24, manufactured by Showa Denko KK) was mixed for 60 minutes to obtain a uniform liquid substrate of 500 g. To the liquid substrate 500 g, methyl phenyl sulfonium oil KF54 was added (product Name, Shin-Etsu Chemical Industry Company system, phenyl content: relative to the total oxane unit, 25 mol% is diphenyl siloxane unit) 2.0 g with methyl phenyl sulfonium oil KF5 0-300cs (trade name, Shin-Etsu Chemical Industry Company made, phenyl content: relative to the total oxane unit, 5 mole% is diphenyl siloxane unit) 2.0g, chloroplatinic acid 2% by mass 2-ethylhexanol solution O.lg, The mixture was uniformly mixed with 0.2 g of ethynylcyclohexanol-50% by mass toluene solution, and 16 g of the organic hydrogen polyoxyalkylene represented by the following general formula (9) was further added:
Me-Si(Me)2-[OSi(Me)2]27-[OSi(Me)(H)]2-OSi(Me)2-Me (9) 均一地混合，獲得組成物a。 使用HIRANO TECSEED公司製造之Multicoater將所 調製之組成物a，以成爲厚度〇.5mm之方式塗佈於PET薄 膜上。至全部的組成物a塗佈結束爲止，連續地進行組成 物a的塗佈。經塗佈之組成物a藉由於120 °C加熱1〇分鐘 -22- 200831613 而硬化，於PET薄膜上形成片狀成形體。 [比較例1] 於實施例1所製得之液狀基底500g中，添加氯化鉛 酸2質量％2-乙基己醇溶液O.lg與乙炔基環己醇-50質量 %甲苯溶液0.2g，均一地混合。再添加實施例1中所使用 之有機氫聚矽氧烷1 6g，均一地混合，製得組成物b。 所製得之組成物b，與實施例1同樣的方法，於PET 薄膜上硬化，於PET薄膜上形成片狀成形體。 [比較例2] 於實施例1所製得之液狀基底500g中，添加KF54 4.0g、氯化鉑酸2質量％2-乙基己醇溶液O.lg與乙炔基環 己醇-50質量％甲苯溶液0.2g，均一地混合。再添加實施 例1中所使用之有機氫聚矽氧烷1 6g，均一地混合，製得 組成物c。 所製得之組成物e，與實施例1同樣的方法，於PET 薄膜上硬化，於PET薄膜上形成片狀成形體。 [比較例3] 於實施例1所製得之液狀基底500g中，添加KF50-3 00cs 4.0g、氯化鉑酸2質量％2-乙基己醇溶液O.lg與乙 炔基環己醇-50質量％甲苯溶液〇.2g，均一地混合。再添 加實施例1中所使用之有機氫聚矽氧烷1 6g，均一地混合 -23- 200831613 ，製得組成物d。 所製得之組成物d，與實施例1同樣的方法’於PET 薄膜上硬化，於PET薄膜上形成片狀成形體。 [比較例4] 於實施例1所製得之液狀基底500g中’添加二甲基 矽氧油KF96-3 00cs (商品名，信越化學工業公司製） 4.0g、氯化鈾酸2質量％2-乙基己醇溶液0.丨§與乙炔基環 己醇-5 0質量％甲苯溶液 〇 . 2 g，均一地混合。再添加實施 例1中所使用之有機氫聚矽氧烷1 6g，均一地混合’製得 組成物e。 所製得之組成物e，與實施例1同樣的方法，於PET 薄膜上硬化，於PET薄膜上形成片狀成形體。 [比較例5] • 於實施例1所製得之液狀基底500g中，添加KF96- 300(^5(^、氯化鉛酸2質量％2-乙基己醇溶液〇.：^與乙炔 基環己醇-50質量％甲苯溶液0.2g，均一地混合。再添加 實施例1中所使用之有機氫聚矽氧烷1 6g，均一地混合， 製得組成物f。 所製得之組成物f，與實施例1同樣的方法，於PET 薄膜上硬化，於PET薄膜上形成片狀成形體。 [比較例6 ] -24- 200831613 準備表面塗佈有界面活性劑（商品名，mamalemon， 製造商名稱：LION公司，塗佈量30mg/m2)之PET薄膜。 使用使用HIRANO TECSEED公司製造之Multicoater將所 調製之比較例1所製得之組成物b，以成爲厚度0.5mm之 方式連續地塗佈於該PET薄膜上，藉由於120 °C加熱1〇 分鐘而硬化，於PET薄膜上形成片狀成形體。 組成物a至f中各成分之使用量示於表1。 〔表1〕 組成物 a b C d e f 例 實施例 1 比較例 卜6 比較例 2 比較例 3 比較例 4 比較例 5 液狀基底(g) 500 500 500 500 500 500 KF54(g) 2.0 4.0 KF50-300cs(g) 2.0 4.0 KF96-300cs(g) 4.0 50 白金觸媒*(g) 0.1 0.1 0.1 0.1 0.1 0.1 反應抑制劑**(g) 0.2 0.2 0.2 0.2 0.2 0.2 有機氫聚矽氧烷(g) 16 16 16 16 16 16Me-Si(Me)2-[OSi(Me)2]27-[OSi(Me)(H)]2-OSi(Me)2-Me (9) was uniformly mixed to obtain a composition a. The composition a prepared by using a Multicoater manufactured by HIRANO TECSEED Co., Ltd. was applied to a PET film so as to have a thickness of 55 mm. The coating of the composition a was continuously performed until the coating of all the compositions a was completed. The coated composition a was cured by heating at 120 ° C for 1 〇 -22 - 200831613 to form a sheet-like formed body on the PET film. [Comparative Example 1] In a liquid substrate 500g obtained in Example 1, 2% by mass of lead chloride acid 2-ethylhexanol solution O.lg and ethynylcyclohexanol-50% by mass toluene solution were added. g, uniformly mixed. Further, 16 g of the organohydrogenpolysiloxane used in Example 1 was added and uniformly mixed to obtain a composition b. The composition b thus obtained was cured on a PET film in the same manner as in Example 1 to form a sheet-like formed body on the PET film. [Comparative Example 2] In 500 g of the liquid substrate obtained in Example 1, 4.0 g of KF54, 2% by mass of chloroplatinic acid 2-ethylhexanol solution, O.lg and ethynylcyclohexanol-50 were added. 0.2 g of a toluene solution was uniformly mixed. Further, 16 g of an organohydrogenpolyoxyalkylene used in Example 1 was added and uniformly mixed to obtain a composition c. The obtained composition e was cured on a PET film in the same manner as in Example 1 to form a sheet-like formed body on the PET film. [Comparative Example 3] In 500 g of the liquid substrate obtained in Example 1, KF50-3 00cs 4.0 g, chloroplatinic acid 2% by mass 2-ethylhexanol solution O.lg and ethynylcyclohexanol were added. - 50 mass% toluene solution 〇. 2 g, uniformly mixed. Further, 16 g of the organohydrogenpolysiloxane used in Example 1 was added, and -23-200831613 was uniformly mixed to obtain a composition d. The obtained composition d was cured on a PET film in the same manner as in Example 1, and a sheet-like formed body was formed on the PET film. [Comparative Example 4] In the liquid substrate 500g obtained in Example 1, 'dimethyl oxime oil KF96-3 00cs (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 4.0 g, uranyl chloride 2% by mass 2-ethylhexanol solution 0. 丨§ with ethynylcyclohexanol-5 0% by mass toluene solution 2 2 g, uniformly mixed. Further, 16 g of an organohydrogenpolysiloxane used in Example 1 was added, and uniformly mixed to obtain a composition e. The obtained composition e was cured on a PET film in the same manner as in Example 1 to form a sheet-like formed body on the PET film. [Comparative Example 5] • KF96-300 (^5 (^, 2% by mass of lead chloride acid 2-ethylhexanol solution :.: ^ and acetylene) was added to 500 g of the liquid substrate obtained in Example 1. 0.2 g of a cyclohexanol-50 mass% toluene solution was uniformly mixed, and then 16 g of the organohydrogenpolysiloxane used in Example 1 was added, and uniformly mixed to obtain a composition f. The material f was cured on a PET film in the same manner as in Example 1 to form a sheet-like formed body on a PET film. [Comparative Example 6] -24- 200831613 Preparation of a surface-coated surfactant (trade name, mamalemon, Manufacturer's name: PET film of LION Co., Ltd., coating amount: 30 mg/m2) The composition b prepared in Comparative Example 1 prepared by using a Multicoater manufactured by HIRANO TECSEED Co., Ltd. was continuously formed to have a thickness of 0.5 mm. The film was applied to the PET film and cured by heating at 120 ° C for 1 minute to form a sheet-like formed body on the PET film. The amounts of the components used in the compositions a to f are shown in Table 1. [Table 1] Composition ab C def Example Example 1 Comparative Example 2 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 5 Liquid substrate (g) 500 500 500 500 500 500 KF54(g) 2.0 4.0 KF50-300cs(g) 2.0 4.0 KF96-300cs(g) 4.0 50 Platinum catalyst*(g) 0.1 0.1 0.1 0.1 0.1 0.1 Reaction Inhibitor**(g) 0.2 0.2 0.2 0.2 0.2 0.2 Organohydrogen polyoxyalkylene (g) 16 16 16 16 16 16
氯化鉑酸2質量％2-乙基己醇溶液 *乙炔基環己醇-50質量％甲苯溶液 [評估] 如下所述，觀察剝離性與滲出。結果示於表2。又， 表中，「基材薄膜的前處理」爲於比較例6所進行之對 PET薄膜表面的界面活性劑的塗佈。 -25- 200831613 <剝離性> 實施例1及比較例1至6所形成之片狀成形體由pet 薄膜剝離，觀察該片狀成形體的狀態。片狀成形體由PET 薄膜剝離時片狀成形體無變形，或變形小，於無張力狀態 回復片狀成形體的形狀時，評估爲剝離性良好（表2中顯 示爲「剝離良好」）。片狀成形體由PET薄膜剝離時片狀 成形體變形大，於無張力狀態亦無法回復片狀成形體的形 狀時，評估爲剝離性不佳（表2中顯示爲「剝離嚴重」） 。片狀成形體由PET薄膜剝離時片狀成形體的一部分或全 部仍然附著於PET薄膜而無法剝離時，評估爲剝離性非常 差（表2中顯示爲「貼附」）。 上述評估係於下述兩者進行，組成物連續塗佈的剛開 始後所塗佈組成物而來之片狀成形體以及組成物連續塗佈 的結束之前所塗佈組成物而來之片狀成形體。結果顯示於 表2中，見於分別設置之欄「剝離性（初期）」以及「剝 離性（結束之前）」。 <滲出> 確認片狀成形體之滲出的有無。具體而言，實施例1 以及比較例1至6所形成之片狀成形體，於室溫放置1 6 8 小時後，藉由目視觀察該片狀成形體表面，確認滲出的有 無。質量未增加時，評估爲無滲出（表2中顯示爲「無」 )。質量增加時，評估爲有滲出（表2中顯示爲「有」） -26- 200831613 〔表2〕 剝離性（初期） 剝離性（結束之前） 滲出 基材薄膜的前處理 實施例1 剝離良好 剝離良好 >fnT ΠΙΓ /\\\ 4vrr 1Ι1Γ j \ \\ 比較例1 貼附 貼附 4τττ ΊΙΗ! Μ、、 >frrr ΤΙΠ y \、、 比較例2 剝離良好 貼附 4nt Πιι y\\\ >fnrr ΤΓΤΓ J\\\ 比較例3 剝離嚴重 剝離嚴重 4πτ. ΙτΤΓ J\\\ ΜΠ J\\\ 比較例4 貼附 貼附 4rrr ΠΙΓ J\ w 4rrr ΙΙΠ7 J\ \\ 比較例5 剝離良好 剝離良好 有 dfrrr 1111: NN 比較例6 剝離良好 剝離良好 >frrp ΙΠΓ j\\\ 有Platinum Chloride 2% by mass 2-ethylhexanol solution * Ethynylcyclohexanol - 50% by mass toluene solution [Evaluation] Peelability and bleeding were observed as described below. The results are shown in Table 2. Further, in the table, "pretreatment of the base film" is the application of the surfactant to the surface of the PET film carried out in Comparative Example 6. -25-200831613 <Peelability> The sheet-like formed body formed in Example 1 and Comparative Examples 1 to 6 was peeled off from a pet film, and the state of the sheet-shaped formed body was observed. When the sheet-like formed body was peeled off from the PET film, the sheet-shaped formed body was not deformed or deformed little, and when the shape of the sheet-shaped formed body was restored in a state of no tension, it was evaluated that the peeling property was good (the peeling was good in Table 2). When the sheet-like formed body was peeled off from the PET film, the sheet-shaped formed body was greatly deformed, and when the shape of the sheet-shaped formed body could not be restored in the state of no tension, it was evaluated that the peeling property was poor (the peeling was severe in Table 2). When the sheet-like formed body was peeled off from the PET film, a part or the whole of the sheet-like formed body was still attached to the PET film and could not be peeled off, and the peeling property was evaluated to be extremely inferior (shown as "attachment" in Table 2). The above evaluation is carried out in the form of a sheet-like molded body obtained by applying the composition immediately after the composition is continuously applied, and a sheet formed by coating the composition before the continuous application of the composition. Shaped body. The results are shown in Table 2, and are shown in the respective columns "Removability (Initial)" and "Peeling (Before End)". <Exudation> The presence or absence of bleeding of the sheet-like formed body was confirmed. Specifically, the sheet-like molded body formed in Example 1 and Comparative Examples 1 to 6 was allowed to stand at room temperature for 168 hours, and the surface of the sheet-shaped formed body was visually observed to confirm the presence or absence of bleeding. When the quality did not increase, it was evaluated as no bleed (shown as "None" in Table 2). When the mass is increased, it is evaluated as bleeding (shown as "Yes" in Table 2). -26- 200831613 [Table 2] Peelability (initial) Peelability (before completion) Pretreatment of exuded base film Example 1 Peeling good peeling Good >fnT ΠΙΓ /\\\ 4vrr 1Ι1Γ j \ \\ Comparative Example 1 Attachment 4τττ ΊΙΗ! Μ,, >frrr ΤΙΠ y \,, Comparative Example 2 Peeling good attach 4nt Πιι y\\\ > ;fnrr ΤΓΤΓ J\\\ Comparative Example 3 Peeling severe peeling severe 4πτ. ΙτΤΓ J\\\ ΜΠ J\\\ Comparative example 4 Attachment attached 4rrr ΠΙΓ J\ w 4rrr ΙΙΠ7 J\ \\ Comparative Example 5 Peeling good peeling Good with dfrrr 1111: NN Comparative Example 6 Good peeling good peeling &fr; rp j\\\
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