200904857 九、發明說明 【發明所屬之技術領域】 本發明係關於一種籠蔽解離型矽氧烷樹脂及其製造方 法’詳而言之，係關於一種在矽原子上具有選自乙烯基、 烷基、苯基、（甲基）丙烯基、烯丙基或環氧乙烷環之一 種或2種以上的有機官能基，其中之至少2個係具有含不 飽和雙鍵之反應性有機官能基之籠蔽解離型矽氧烷樹脂及 其製造方法，而該不飽和雙鍵係選自乙烯基、（甲基）丙 稀基或嫌丙基者。 【先前技術】 聚苯基矽氧烷係耐熱性、電絕緣性等優，故可利用於 塗佈材、密封材、層間絕緣膜等之類。此聚苯基砂氧院之 製造方法的一例已知有：使苯基三氯矽烷於有機溶劑中水 解而形成苯基三羥基矽烷，使該水解物在無水之溶劑中使 用鹼性轉移及縮合觸媒而加熱，脫水縮聚合而得到籠蔽型 八苯基矽氧烷之方法（專利文獻1 ):使籠蔽型八苯基矽 氧烷分離，再度使用鹼性轉移及縮合觸媒而加熱聚合以得 到固有黏度低之苯基矽氧烷預聚物之方法（專利文獻2) ;其再進一步使用鹼性轉移及縮合觸媒而加熱聚合以製造 苯基矽氧烷聚合物之方法（非專利文獻1 )等。 又，形成籠蔽型之矽氧烷樹脂之一部分的矽氧烷鍵斷 裂，而籠蔽之一部分解離之籠蔽解離型矽氧烷樹脂的合成 法，係具有環己基之矽氧烷的合成法已被Feher.F.J.報告 200904857 (參照非專利文獻2 )，其以外，例如已報告具有苯基與 乙烯基之籠蔽解離型矽氧烷樹脂的製造方法（參照專利文 獻3 )。 又，在上述專利文獻3中係已記載使於不含有矽烷醇 基之籠蔽型聚苯基倍半矽氧烷的分子鏈末端之Si〇全部或 一部分具有反應性官能基之三有機甲矽烷基結合的聚矽氧 化合物，在有機溶劑中、鹼性移位及縮合觸媒之存在下進 行加熱，平衡反應而具有反應性官能基之苯基矽氧烷聚合 物的製造方法。 〔專利文獻1〕特公昭40- 1 5 98 900號公報 〔專利文獻2〕特開昭5 0- 1 3 9900號公報 〔專利文獻3〕特開平1 0-25 1 407號公報 〔非專利文獻 l〕J.P〇lymerSci.PartCNo.l，PP_83-97(1963) 〔非專利文獻 2〕J.Am.Chem_Soc.lll，1741 - 8 ( 1989 【發明內容】 (發明之揭示） (發明欲解決之問題） 如上述般，以往之籠蔽解離型矽氧烷樹脂的合成方法 ’係需要長的反應時間而不能以高效率得到目的物，或具 有硬化性之反應性官能基的數目很少，故不能得到充分的 彈性率或熱線膨脹率等的物性。另外，於全部之矽原子只 -6- 200904857 具有1種類具有硬化性之反應性官能基之籠蔽解離型砂氧 烷係分子構造之對稱性佳，故結晶性高。因此，與其他之 樹脂的相溶性差，要與其他之樹脂混合而製成已改質物性 之多樣的成形體乃很難。 本發明之目的係解決以往之缺點，在於提供一種與其 他之樹脂具有相溶性，分子量分布及分子構造可被控制之 具有乙烯基、烷基、苯基、（甲基）丙烯醯基、烯丙基或 環氧乙烷環之籠蔽解離型矽氧烷樹脂。又，在於提供一種 以高收率製造如此之籠蔽解離型矽氧烷樹脂的方法。 (用以解決問題之手段） 本發明人等係爲解決上述問題，經專心硏究之結果， 發現藉由特定之反應條件可解決此，終完成本發明。 亦即，本發明之籠蔽解離型矽氧烷樹脂，係以下述通 式（2 ) 〔R'R^SiOw〕m〔 R'SiOw〕n ( 2 ) (但，R1係乙烯基、烷基、苯基、（甲基）丙烯醯基、烯 丙基或具有環氧乙烷環之基，具有（m + n )個之R1之中的 至少2個係選自具有不飽和雙鍵之乙烯基、（甲基）丙烯 醯基或烯丙基之反應性有機官能基，R2係表示甲基；m係 1〜4之整數，n係8〜16之整數，m與η之和爲10~20)所 示。 200904857 又’本發明之籠蔽解離型矽氧烷樹脂，係藉由使以下 述通式（1 ) R'six3 ( 1 ) (但’R1係乙烯基、烷基、苯基、（甲基）丙烯醯基、烯 丙基或具有環氧乙烷環之基，X係表示選自烷氧基、鹵原 子或羥基之水解性基）所示之矽化合物的1種或2種以上 ，在鹼性觸媒存在下、非極性溶劑或極性溶劑之任一者或 兩者混合之溶劑中進行水解反應，同時並一部份縮合，使 所得到之聚縮合物進一步在非極性溶劑及鹼性觸媒的存在 下再縮合’再使二矽氧烷化合物對所得到之再縮合物進行 平衡化反應來得到。 又’本發明之籠蔽解離型矽氧烷樹脂之製造方法，其 特徵在於：藉由使以下述通式（1 ) R1 SiX3 ( 1 ) 〔但’R1係乙烯基、烷基、苯基、（甲基）丙烯醯基、烯 丙基或具有環氧乙烷環之基，X係表示選自烷氧基、鹵原 子或羥基之水解性基〕所示之矽化合物的1種或2種以上 ’在鹼性觸媒存在下、非極性溶劑或極性溶劑之任一者或 兩者混合之溶劑中進行水解反應，同時並一部份縮合，使 所得到之聚縮合物進一步在非極性溶劑及鹼性觸媒的存在 -8- 200904857 下再縮合’再使二矽氧烷化合物對所得到之再縮合物進行 平衡化反應。 使本發明中之籠蔽解離型矽氧烷樹脂的構造式之例表 示於下述式（4)〜（10)中。此處，構造式（4)係在通 式（2 )中爲m = 2及n = 8之情形，以下相同，（5 )係m = 3 、η = 9，（ ό)係 m = 2、η=ι〇 ’ （ 7)係 m = 3、η=11，（ 8) 係 m = 2 ’ π=12， （ 9)係 m = 3、n = 13， （ I〇)係 m = 2， n=l4°又’本發明之籠蔽解離型矽氧烷樹脂係亦有時採取 此等以外之m 數目’不限定於此等。又，構造式（4) (1 〇 )中之R1及R2係與通式（2 )之情形相同。 化1〕200904857 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a caged dissociation type decane resin and a method for producing the same, in detail, relating to a group selected from a vinyl group and an alkyl group on a ruthenium atom. One or two or more organic functional groups of a phenyl group, a (meth) propylene group, an allyl group or an oxirane ring, at least two of which have a reactive organic functional group containing an unsaturated double bond The caged dissociative siloxane resin and the method for producing the same, and the unsaturated double bond is selected from the group consisting of vinyl, (meth) propyl or propylene. [Prior Art] Polyphenyl siloxane is excellent in heat resistance and electrical insulation, and can be used for a coating material, a sealing material, an interlayer insulating film, and the like. An example of a method for producing the polyphenyl sulphate is to hydrolyze phenyltrichloromethane in an organic solvent to form phenyl trihydroxy decane, and to use the alkaline transfer and condensation in the anhydrous solvent. A method in which a catalyst is heated and dehydrated and polymerized to obtain a caged octadecyloxyalkylene (Patent Document 1): Separating the caged octaphenylphosphonane and heating it again using an alkali transfer and a condensation catalyst A method of obtaining a phenyl fluorene alkane prepolymer having a low inherent viscosity (Patent Document 2); and further heating a polymerization using a basic transfer and a condensation catalyst to produce a phenyl siloxane polymer (non- Patent Document 1) and the like. Further, a method for synthesizing a naphthenic bond in which a part of a caged naphthene resin is broken, and a caged dissociated deuterated alkane resin which is partially dissociated from a cage is a method for synthesizing a cyclohexyloxane In addition to the above, for example, a method of producing a cage-dissociated decane resin having a phenyl group and a vinyl group has been reported (see Patent Document 3). Further, in the above-mentioned Patent Document 3, a triorganomethane which has a reactive functional group in all or a part of Si 〇 at the end of the molecular chain of the caged polyphenylsesquioxane which does not contain a stanol group is described. A method for producing a phenyl siloxane polymer having a reactive functional group, which is heated in the presence of an organic solvent, a basic shift, and a condensation catalyst in an organic solvent to balance the reaction. [Patent Document 1] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. l] JP 〇 lymer Sci. Part C No. 1, PP _ 83-97 (1963) [Non-Patent Document 2] J. Am. Chem_Soc.lll, 1741 - 8 (1989) [Disclosure of the Invention] (Problem to be solved by the invention) As described above, the conventional method for synthesizing the caged dissociative deuterosiloxane resin requires a long reaction time and cannot obtain a target object with high efficiency, or the number of reactive functional groups having curability is small, so A physical property such as a sufficient modulus of elasticity or a coefficient of thermal linear expansion is obtained. In addition, the symmetry of the molecular structure of the caged dissociative lanthanane having one type of reactive functional group having a hardening property is good only for all of the ruthenium atoms -6-200904857. Therefore, the compatibility with other resins is inferior, and it is difficult to mix with other resins to form a molded body having various physical properties. The object of the present invention is to solve the conventional disadvantages in that Provide a kind of resin with other A caged dissociative oxirane resin having a compatibility of a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, an allyl group or an oxirane ring, which is compatible with a molecular weight distribution and a molecular structure. Further, it is to provide a method for producing such a caged dissociated siloxane resin in a high yield. (Means for Solving the Problem) The present inventors have found that the above problems have been solved by focusing on the above problems. The present invention can be finally solved by the specific reaction conditions. That is, the caged dissociative siloxane resin of the present invention is represented by the following formula (2) [R'R^SiOw]m [R'SiOw] n ( 2 ) (However, R 1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, an allyl group or a group having an oxirane ring, and has (m + n ) of R1 At least two are selected from the group consisting of a vinyl group having an unsaturated double bond, a reactive organic functional group of a (meth) acryl fluorenyl group or an allyl group, R 2 is a methyl group, and m is an integer of 1 to 4, and the n system is An integer of 8 to 16, the sum of m and η is 10 to 20). 200904857 Further, the caged dissociative siloxane resin of the present invention, By using the following general formula (1) R'six3 ( 1 ) (but 'R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring And X or more than two or more of the hydrazine compounds represented by the hydrolyzable group selected from the group consisting of an alkoxy group, a halogen atom or a hydroxyl group, and any one of a non-polar solvent or a polar solvent in the presence of a basic catalyst. Or a solvent in which the two are mixed, and simultaneously condensed, and the obtained polycondensate is further condensed in the presence of a non-polar solvent and a basic catalyst, and the dioxane compound is further condensed. The obtained recondensate is obtained by an equilibrium reaction. Further, the method for producing a caged dissociative siloxane resin according to the present invention is characterized in that R1 is a sulphuric acid, an alkyl group, a phenyl group, or a phenyl group, which is represented by the following formula (1): R1 (meth)acryloyl fluorenyl group, allyl group or group having an oxirane ring, and X system represents one or two kinds of hydrazine compounds represented by a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group. The above hydrolysis reaction is carried out in a solvent in which any one or both of a non-polar solvent or a polar solvent is present in a basic catalyst, and a part of the condensation is further condensed to further obtain a polycondensate in a non-polar solvent. And the presence of a basic catalyst -8- 200904857 under re-condensation 'the dioxane compound is subjected to an equilibrium reaction of the obtained recondensate. An example of the structural formula of the caged dissociative siloxane resin in the present invention is shown in the following formulas (4) to (10). Here, the structural formula (4) is the case where m = 2 and n = 8 in the general formula (2), the same applies hereinafter, (5) is m = 3, η = 9, (ό) is m = 2. η=ι〇' (7) is m = 3, η=11, (8) is m = 2 ' π=12, (9) is m = 3, n = 13, (I〇) is m = 2, n=l4° The 'm-number of the cage-dissociated siloxane-based resin of the present invention may be taken from the above, and is not limited thereto. Further, R1 and R2 in the structural formula (4) (1 〇 ) are the same as in the case of the general formula (2). 1]
〔化2〕〔化2〕
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R1 (9) 〔化7〕R1 (9) [Chem. 7]
ViR1^, R1 0 本發明之籠蔽解離型矽氧烷樹脂之製造方法中，係首 先使以通式（1 )所示之矽化合物，在鹼性觸媒存在下、 非極性溶劑或極性溶劑之任一者或兩者混合之溶劑中進行 水解反應。通式（1)中，R1係選自乙烯基、苯基、烷基 、（甲基）丙烯醯基、烯丙基或具有環氧乙烷環之基的有 機基，爲賦予硬化性，含有具不飽和雙鍵之基。 在通式（1 )中，X係水解性基，具體上係可舉例如 烷氧基、鹵原子或羥基，但宜爲烷氧基。烷氧基，可舉例 如甲氧基、乙氧基、正及異丙氧基、正-、異-、及第二丁 氧基等。其中，宜爲反應性商之甲氧基。 -11 - 200904857 有關以通式（1)所示之矽化合物，若顯示較佳之化 合物的具體例，可舉例如苯基三甲氧基矽烷、苯基三乙氧 基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三 甲氧基矽烷、乙基三乙氧基矽烷、正丙基三甲氧基矽烷、 正丙基三乙氧基矽烷、丁基三甲氧基矽烷、丁基三乙氧基 矽烷、戊基三甲氧基矽烷、戊基三乙氧基矽烷、辛基三甲 氧基矽烷、辛基三乙氧基矽烷、甲基丙烯氧基甲基三甲氧 基矽烷、甲基丙烯氧基甲基三乙氧基矽烷、3 -甲基丙烯 氧基丙基三甲氧基矽烷、3 -甲基丙烯氧基丙基三乙氧基 矽烷、3 -丙烯氧基丙基三甲氧基矽烷、3 -丙烯氧基丙基 三乙氧基矽烷、3 -環氧丙氧基丙基三甲氧基矽烷、3 -環 氧丙氧基丙基三乙氧基矽烷、2- (3,4 -環氧基環己基乙 基）三甲氧基矽烷、烯丙基三甲氧基矽烷、烯丙基三乙 氧基矽烷、對苯乙烯基三乙氧基矽烷、對苯乙烯基三甲氧 基矽烷、乙烯基三甲氧基矽烷、及乙烯基三乙氧基矽烷等 。其中，更宜爲原料取得容易之苯基三甲氧基矽烷、苯基 三乙氧基矽烷、3 -甲基丙烯氧基丙基三甲氧基矽烷、3- 環氧丙氧基丙基三甲氧基矽烷、及乙烯基三甲氧基矽烷等 〇 上述水解反應所使用之鹼性觸媒係可例示氫氧化鉀、 氫氧化鈉、氫氧化鉋等之鹼金屬氫氧化物之外，尙可例示 氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丁基銨、氫 氧化苯甲基三甲基錢、氨氧化苯甲基二乙基鞍寺之氮爭1化 銨鹽。此等之中’因觸媒活性高，較佳係可使用氫氧化四 -12- 200904857 甲基鏡。驗性觸媒一般係可使用來作爲水溶液。 有關水解反應條件係反應溫度宜爲0〜60 °c，更宜爲 20〜4〇°C。若反應溫度低於0°C，反應速度變慢，水解性基 以未反應的狀態殘存且耗費許多反應時間。另外，若高於 6〇°C ’反應速度太快’進行複雜之縮合反應，結果可促進 水解生成物之高分子量化。又，反應時間宜爲2小時以上 。若反應時間不足2小時’水解反應無法充分地進行，而 成爲水解性基以未反應的狀態殘存的狀態。 水解反應係必須有水的存在，但此亦可從鹼性觸媒之 水溶液供給。亦可另外加入水。水之量係宜足夠使水解性 基進行水解的量以上，較佳係理論量之1 _ 0〜1 . 5倍量。又 ’水解時係非極性溶劑或極性溶劑之中的一個或兩者合倂 而使用。較佳係可使用兩者，或只使用極性溶劑。極性溶 劑係可使用甲醇、乙醇、2 -丙醇等之醇類、或其他之極 性溶劑。較佳係與水具有溶解性之碳數丨〜6的低級醇類， 更宜使用2 -丙醇。若只使用非極性溶劑，反應系變成不 均一而反應中高分子體易析出。 水解反應終了後係使反應溶液以弱酸性溶液進行中和 ’形成中和或酸性之後，分離水或含有水之反應溶劑。水 或含有水之反應溶劑的分離，係可採用：以食鹽水等洗淨 此溶液，充分地除去水分或其他之雜質，其後，以無水硫 酸鎂等之乾燥劑乾燥等的手段。使用極性溶劑時，係可採 用減壓蒸發等之手段，除去極性溶劑之後，添加非極性溶 劑而使聚縮合物溶解而上述同樣地，進行洗淨、乾燥。有 -13- 200904857 關弱酸性溶液，係可使用硫酸稀釋溶液、鹽酸稀釋溶液、 檸檬酸溶液、醋酸、氯化銨水溶液、蘋果酸溶液、磷酸溶 液、草酸溶液等。非極性溶劑係只要以蒸發等的手段進行 分離，可回收水解反應生成物’但若非極性溶劑可使用來 作爲於如下之反應使用之非極性溶劑，並不須要分離此。 在本發明之水解反應中係與水解一起產生水解物的縮 合反應。伴隨水解物之縮合反應的聚縮合物，一般數目平 均分子量成爲5 00~7000的無色黏性液體。聚縮合物係依 反應條件而異，但數目平均分子量爲5 00〜3 000的樹脂（ 或寡物），於通式（1 )所示之水解性基X的大部分，較 佳係幾乎全部被OH基取代，進一步其OH基的大部分， 較佳係95%以上被縮合。 有關聚縮合物的構造係複數種之籠蔽型、梯型、隨機 型之矽氧烷，有關採取籠蔽型構造之化合物，完全之籠蔽 型構造的比率亦少，籠蔽之一部分開啓之不完全的籠蔽型 構造成爲主要。使此聚縮合物進一步在非極性溶劑及鹼性 觸媒的存在下進行加熱，藉由使矽氧烷鍵縮合（稱爲再縮 合），俾選擇性地製造再縮合物（籠蔽型構造的矽氧烷） 〇 得到再縮合物時係分離水或含有水之反應溶劑後，在 非極性溶劑及鹼性觸媒的存在下進行再縮合反應。有關再 縮合反應之反應條件係反應溫度宜爲90~200°C的範圍，更 宜爲100~140°C。若反應溫度太低，無法得到用以再縮合 反應之充分驅動力而不進行反應。若反應溫度太高，有可 • 14 - 200904857 能反應性有機官能基引起自己聚合反應，故必須抑制反應 溫度，或添加聚合抑制劑等。反應時間宜爲2〜1 2小時。 非極性溶劑之使用量係可爲滿足溶解水解反應生成物之量 ，鹼性觸媒之使用量相對於再縮合物，爲0.1〜5wt%的範 圍，更佳係0.5〜2.0wt%的範圍。 非極性溶劑係只要爲與水無溶解性或無乎無溶解性者 即可，但宜爲烴系溶劑。烴系溶劑係可舉例如甲苯、苯、 二甲苯等之沸點低的非極性溶劑，其中宜使用甲苯。另外 ，鹼性觸媒係可使用於水解反應所使用之鹼性觸媒，係可 舉例如氫氧化鉀、氫氧化鈉、氫氧化鉋等之鹼金屬氫氧化 物、或氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丁基 銨、氫氧化苯甲基三甲基銨、氫氧化苯甲基三乙基銨等之 氫氧化銨，但宜爲於四烷基銨等之非極性溶劑可溶性的觸 媒。又’使通式（1)之矽化合物在鹼性觸媒存在下水解 反應時使用非極性溶劑之情形，可使用如上述所例示者。 亦可使用與得到在水解反應使用之非極性溶劑與再縮合物 時所使用之非極性溶劑互相同樣者，亦可使用相異者，但 爲使合成順序等簡單較佳係可使用互相同樣者。 又’使用於再縮合之水解生成物係宜使用水洗、脫水 、濃縮者，但即使不進行水洗、脫水，亦可使用。此反應 之時’水亦可存在，但不須積極地加入，宜僅止於從驗性 觸媒溶液攜入之水分程度。又，聚縮合物之水解不充分進 行時’係必須爲使殘存之水解性基進行水解所需之理論量 以上的水分。再縮合反應後係水洗觸媒而除去，濃縮，可 -15- 200904857 得到再縮合物。 然後，於上述所得到之再縮合物加成二矽氧烷化合物 ，可得到籠蔽解離型矽氧烷樹脂。有關此二矽氧烷化合物 ，具體上可以下述通式（3)表示。又’於再縮合物加成 二矽氧烷化合物時之反應係宜在甲苯、苯、二甲苯等之非 極性溶劑、及氫氧化四甲基銨、氫氧化四乙基銨、氫氧化 四丁基銨等鹼性觸媒的存在下實施。 (R^^Si ) 2〇 ( 3 ) (但，R1係選自乙烯基、烷基、苯基、（甲基）丙烯醯基 、烯丙基或具有環氧乙烷環之基中一種或兩種之基’ R2係 表示甲基） 前述之再縮合物與以通式（3)所示之二矽氧烷化合 物之間的鹼性觸媒下之加成反應係平衡化反應’從氧原子 爲3/2個鍵結之矽原子單元（T單元）所構成的再縮合物 之解離、或以再縮合物單獨所產生的高分子量化之競爭反 應，故必須儘可能地優先進行前者（再縮合物之解離）。 又，本發明之反應係基本上爲平衡反應，故於目的物之末 端具有反應性官能基之籠蔽解離型矽氧烷樹脂的數目平均 分子量Μη、收率、及生成速度係依反應溫度、反應時間 、兩原料之添加量比、鹼觸媒量等而自己決定，故宜以如 下記載的條件下進行。 亦即，前述所得到之再縮合物係宜在非極性溶劑及鹼 -16- 200904857 性觸媒的存在下加成以通式（3 )所示之二矽氧烷化合物 。有關反應條件係反應溫度宜爲90〜200 °C之範圍，更宜爲 10 0〜140 °C。但，有關以通式（3 )所示之二矽氧烷化合物 之沸點低者係有可能反應溫度達到沸點以上而蒸發至反應 系外，故其情形係宜在沸點以下長時間反應。鹼性條件下 、形成再縮合物的籠蔽之矽氧烷鍵結係在於切斷與鍵結之 平衡反應，但若二矽氧烷化合物存在，被切斷之部分與二 矽氧烷化合物反應，故以籠蔽之一部分解璃之狀態安定， 可得到籠蔽解離型矽氧烷樹脂。此處所謂之籠蔽解離型矽 氧烷樹脂係表示形成籠蔽構造之矽氧烷鍵結之中至少一個 解璃以形成不完全的籠蔽構造之砂氧院分子構造。又，反 應時間宜爲1 ~ 5小時。 在再縮合物與二矽氧烷化合物之平衡化反應使用非極 性溶劑時，非極性溶劑之使用量係宜足夠溶解再縮合物之 量。另外，有關再縮合物與二矽氧烷化合物之反應比率係 對於以相當於再縮合物之T單元10個的〔VsiCh.s〕10所 示之構造單元1莫耳，宜二矽氧烷化合物爲0.5〜4.0莫耳 ，較佳係1 ·〇〜2.0莫耳之方式水解加成。若二矽氧烷化合 物少於此範圍，反應不會進行，而相反地若多，恐未反應 物對生成物之物性會造成不良影嚮，不佳。又，例如，使 用如六甲基二矽氧烷、1,3 -二乙烯基-1,1,3,3 -四甲基 二矽氧烷等揮發性高之二矽氧烷化合物時，係亦可考量反 應中進行揮發之量而稍多地設定添加量亦無妨。又，此處 所使用之非極性溶劑的例係可例示與得到再縮合物時所使 -17- 200904857 用者相同’亦可與得到再縮合物時所使用者相同，亦可使 用相異者。 又，於再縮合物與二矽氧烷化合物之平衡化反應用鹼 性觸媒時，有關鹼性觸媒之使用量係相對於以「R1 Si〇 1.5」ίο 所示之再縮合物的構造單元1莫耳’宜成爲0·05〜15莫 耳，較佳係0.06-0.1莫耳之方式加入驗性觸媒。 有關以通式（3)所示之二矽氧烷化合物，若顯示較 佳之化合物的具體例’可舉例如丨，3 —二苯基—l1，3,3 一 四甲基二砍氧院、六甲基一砂氧院、六乙基二砂氧院、六 苯基二砂氧院、五甲基一砂氧院、1，丨，3,3_四甲基二砂氧 院、m3 -四乙烯基二甲基二矽氧烷、1,3 -二乙基-1,1，3,3 -四甲基二砂氧院、-二正丙基—m3 -四 甲基二矽氧烷、丨，3 —二丁基—丨，1，3,3 -四甲基二矽氧烷 、1，3 -二戊基—丨，1，3,3 —四甲基二矽氧烷、1，3_二辛 基-1，1，3,3 -四甲基二砂氧院、丨，3 -二甲基甲烯氧基甲 基-1,1,3，3 -四甲基二砂氧院、丨，3 —二（3_甲基丙烯氧基 丙基）-1,1，3,3 -四甲基二矽氧烷、1，3 -二丙烯氧基甲 基-1,1,3，3 -四甲基一砂氧院、丨，3 -二（3_丙烯氧基丙基 )-1，1，3,3_四甲基二砂氧院、丨，3 -二（3 -環氧丙氧基 丙基）-1,1，3,3-四甲基二矽氧烷、雙-〔2- (3,4-環 氧基環己基）乙基〕-四甲基二砂氧院、丨，3 —二烯丙基-1，1,3,3-四甲基二砂氧院、U —二對苯乙烯基-1,1,3，3-四甲基二砂氧院、及丨，3_ —乙嫌基-丨，1，3,3 —四甲基二石夕 氧烷等。 -18- 200904857 依本發明所得到之籠蔽解離型矽氧烷樹脂係通式（2 )之m爲1〜4，η爲8〜16，m與η之和爲以10〜20所示之 構造式（4 )〜（1 〇 )所示之化合物的混合物所得到之情形 很多。又，所得到之籠蔽解離型矽氧烷樹脂的數目平均分 子量Mm—般爲600〜1 0000的範圍。 〔發明之效果〕 若使用本發明之籠蔽解離型矽氧烷樹脂的製造方法， 可以高收率製造分子量分散度低之構造被控制的籠蔽解離 型矽氧烷樹脂。所得到之籠蔽解離型矽氧烷樹脂係分子構 造的對稱性低且低黏度，具有可任意地與具有反應性官能 基之矽氧烷寡聚物調配之相溶性，且可廣泛地使用來作爲 硬化性樹脂組成物之原料。又，從類似於籠蔽構造之構造 的矽氧烷，使含有本發明之籠蔽解離型矽氧烷樹脂的硬化 性樹脂組成物硬化而得到之成形體係具備如無機玻璃之強 度、透明性、耐熱性、及尺寸安定性，且可賦予如塑膠之 高靭性、好加工性，而可適用於例如透鏡、光碟、光纖、 及平面顯示器基板等之光學用途，或各種輸送機械或住宅 等之窗材等，又，亦可適用於輕量性或高衝擊強度等所要 求之各種透明構件，利益、衝擊均大。 【實施方式】 〔用以實施發明之最佳形態〕 以下，依據實施例，更具體地說明本發明。 -19- 200904857 〔實施例1〕 於具備攪拌機、滴下漏斗及溫度計之反應容器中’置 入甲苯150ml與2 -丙醇（IPA) 85ml’置入5 %氫氧化四 甲基銨水溶液（TMAH水溶液）37.2g作爲鹼性觸媒。於 滴下漏斗中置入甲苯2 5 ml與三甲氧基乙烯基矽烷（信越 化學股份公司製KBM 1 003 ) 50.3 g，一邊攪拌反應容器， 一邊花3小時而在室溫下滴入三甲氧基乙烯基矽烷之甲苯 溶液。三甲氧基乙烯基矽烷滴下終了後，在室溫下攪拌2 小時。攪拌1小時後，停止攪拌而靜置1日。以1 〇%檸檬 酸水溶液23.0g中和反應溶液後，以飽和食鹽水洗淨，以 無水硫酸鎂脫水。過濾無水硫酸鎂，進行濃縮得到聚縮合 物2(K6g、收率77%。此聚縮合物係難溶於各種之有機溶 劑的白色固體。又，測定此聚縮合物之GPC的結果，數 目平均分子量爲 Mnll88，分子量分散度（Mw/Mn )爲 2.03。 然後，於具備攪拌機、Dean-Stark、冷卻管、及溫度 計之反應容器置入於上述所得到之聚縮合物15.0g與甲苯 3 80ml與5%TMAH水溶液1.72g，一邊以120°C餾去水， 一邊使甲苯迴流加熱而進行再縮合反應。甲苯回流後攪拌 3小時之後，返回至室溫，使反應終止。使反應溶液以 10%檸檬酸23.0g進行中和後，以飽和食鹽水進行洗淨， 以無水硫酸鎂脫水。過濾無水硫酸鎂，進行濃縮得到再縮 合物14.5g。所得到之再縮合物係白色固體，於各種之溶 -20- 200904857 劑顯示難溶性。測定此再縮合物之GPC的結果_ 中。以「tSiOu」n所示之再縮合物中，可得到 13以上之籠蔽型矽氧烷、梯型矽氧烷、及隨機型 譜峰1〔數目平均分子量Mnl979 (Mw/Mn2.〇3) η爲12以下之籠蔽型矽氧烷的譜峰2〔數目平 Μη 747 ( Mw/Mnl .02 )〕。 然後’於具備攪拌機、Dean-Stark及冷卻管 器置入於上述所得到之再縮合物14.5g、甲苯 5%TMAH 水溶液 3.0g 及 1,3 -二乙烯基-1，1，3，: 二矽氧烷（TMDVDS :信越化學工業股份公司製 )9.76g，一邊以120°C餾去水，一邊使甲苯迴流 行平衡化反應。甲苯回流後攪拌3小時之後，返 ，使反應終止。使反應溶液以1 0 %檸檬酸3.2 4 g 後，以飽和食鹽水進行洗淨，以無水硫酸鎂進行 濾無水硫酸鎂，進行濃縮以收率8 8 %得到目的之 型矽氧烷樹脂（混合物）1 6 · 9 g。所得到之籠蔽 氧烷樹脂係可溶於各種之有機溶劑的無色黏性液: 測定此籠蔽解離型矽氧烷樹脂之GPC的結 圖2中。籠蔽解離型矽氧烷樹脂之數目平均分 Mnl 049 (譜峰 3 : Mw/Mnl .17)得到。藉二矽氧 之平衡化反應，再縮合物之譜峰1( Μη 1 979 )朝 偏移，譜峰2 ( Μη747 )朝高分子側偏移（譜峰2 移之譜峰的數目平均分子量係與於再縮合物之譜 目平均分子量加成二矽氧烷化合物1分子之數値 I示於圖1 含有η爲 [矽氧烷的 〕與含有 均分子量 :之反應容 3 00ml ' ;-四甲基 LS - 725 0 加熱而進 回至室溫 進行中和 脫水。過 籠蔽解離 解離型矽 瞻 體。 果表示於 子量係以 烷化合物 低分子側 1 )。所偏 峰2的數 幾乎一致 -21 - 200904857 。又’有關譜峰1係〔WSiOu〕n的η爲13以上很大的 化合物，以平衡化反應中之加熱反覆矽氧烷鍵結之切斷與 鍵結而η變小，認爲此與二矽氧烷化合物反應。從此結果 ，籠蔽解離型矽氧烷樹脂係可藉由形成聚縮合物之籠蔽的 矽氧烷鍵結之一部分被切斷而與二矽氧烷化合物反應來得 到。 又，測定於上述所得到之籠蔽解離型矽氧烷樹脂的 1Η - NMR 後，以 6.2~5.7卩卩111之乙烯基所得到的 5.8〜6.2??111之多重譜峰與〇.17??111之甲基所得到的譜峰積 分比，係相對於乙烯基1 5.4爲甲基6。 進一步，使所得到之籠蔽解離型矽氧烷樹脂藉液體色 層分析大氣壓離子化分析計（LC/APCI - MS )進行質量分 析之結果示於圖3中。合倂，於表1中係使進行質量分析 所檢測出之主要的譜峰、與符合相當於其之化學式（2) 的m、η之數値歸納表示。所檢測出之譜峰 m / ζ係於下述 通式（2)(但，m爲1〜4，n爲8~16’m與η之和爲 10~20 )所示之籠蔽解離型矽氧烷樹脂的分子量’銨離子 加成之値。從此質量分析結果’可知籠蔽解離型砂氧院樹 脂係可藉由形成聚縮合物之籠蔽的矽氧烷鍵結之一部分被 切斷而與二矽氧烷化合物反應來得到。 (R'R22Si〇l/2 ] m C R1 Si〇3/2 ] n (2) -22- 200904857 〔表1〕 所檢測出之譜峰m/z m —-- n 882.1 1 9 836.2 2 ... 8 980.1 1 ----- 11 994.1 2 ----—_ 10 1152.1 2 -- 12 116.2 3 11 1324.1 3 13 1482.1 3 ------- 15 [R'R22SiO, /2 ] m [ R^iOs/a ) n (2) 〔實施例2〕 與實施例1同樣地，於具備攪拌機、滴下漏斗及溫度 計之反應容器中，使甲苯3 48ml、5%ΤΜΑΗ水溶液40.0g 、2 -丙醇（IPA) 192ml、三甲氧基乙烯基矽烷43.6g、三 甲氧基甲基矽烷47.4g、及IPA 128ml溶液花3小時滴下 後，在室溫（20〜25 °C )下攪拌3小時。使此反應溶液靜 置1日。反應溶液係以1 〇%檸檬酸水溶液進行中和後，以 飽和食鹽水進行洗淨，以無水硫酸鎂進行脫水。過濾無水 硫酸鎂，進行濃縮以收率80 %得到具有甲基與乙烯基之聚 縮合物46.6g。測定此聚縮合物之GPC的結果、數目平均 分子量係 Mnl447 ( Mw/Mn3 1 .5 )。 然後，於具備攪拌機、Dean-Stark、冷卻管、及溫度 計之反應容器中置入於上述所得到之聚縮合物15.0g與甲 苯3 8 0ml與5%TMAH水溶液1.72g，一邊以120°C餾去水 ，一邊使甲苯迴流加熱而進行再縮合反應。甲苯回流後擾 -23- 200904857 拌3小時之後，返回至室溫，使反應終止。使反應溶液以 1 0 %檸檬酸2 3.0 g進行中和後，以飽和食鹽水進行洗淨， 以無水硫酸鎂脫水。過濾無水硫酸鎂，進行濃縮得到再縮 合物1 4.5 g。所得到之再縮合物係可得到無色透明液體。 測定此再縮合物之GPC的結果表示於圖4中。以「 R 1 S i 0 i. 5」n所示之再縮合物之中，可得到含有η爲1 3以 上之籠蔽型矽氧烷、梯型矽氧烷、及隨機型矽氧烷的譜峰 4〔數目平均分子量Mnl676 (Mw/Mnl.27)〕與含有η爲 12以下之籠蔽型矽氧烷者之譜峰5〔數目平均分子量Μη 645 (Mw/Mnl.02)〕。但，再縮合物〔VSiOu〕η 中之 R!係含有只具有乙烯基者、只具有甲基者、具有乙烯基與 甲基之2種類者。 使於上述所得到之再縮合物l〇g、甲苯342ml、 5%TMAH水溶液3.0g及TMDVD 9.6g置入於具備攪拌機 ' Dean-Stark及冷卻管之反應容器中，一邊以120°C餾去 水，一邊使甲苯迴流加熱而進行水解加成反應。一邊進行 甲苯回流一邊攪拌3小時之後，返回至室溫，使反應終止 。使反應溶液以1 0%檸檬酸1.2g進行中和後，以蒸餾水 進行洗淨，以無水硫酸鎂脫水。過濾無水硫酸鎂，進行濃 縮以收率8 6%得到目的之籠蔽解離型矽氧烷樹脂1 1.4g。 所得到之籠蔽解離型矽氧烷樹脂係可溶於各種之有機溶劑 的無色黏性液體。測定此籠蔽解離型矽氧烷樹脂之GPC 的結果表示於圖5中。籠蔽解離型矽氧烷樹脂之數目平均 分子量係以Mn928 (譜峰6: Mw/Mnl.16)得到。 -24- 200904857 〔實施例3〕 與實施例1同樣地做法而得到再縮合物7.95§、六甲 基二矽氧烷1.41g、5%TMAH水溶液〇.47g及甲苯50ml置 入於具有攪拌機、Dean-Stark及冷卻管之反應容器中’以 8〇°C攪拌3小時後，昇溫至lOOt而攪拌1.5小時’進一 步昇溫至1 3 (TC而攪拌1 . 5小時。使反應溶液返回至室溫 而以檸檬酸、10%檸檬酸3.24g進行中和後，以飽和食鹽 水進行洗淨，以無水硫酸鎂脫水。過濾無水硫酸鎂，進行 濃縮以收率94%得到目的之籠蔽解離型矽氧烷樹脂9.45g 。所得到之籠蔽解離型矽氧烷係可溶於各種之有機溶劑的 無色黏性液體。測定此籠蔽解離型矽氧烷樹脂之GPC的 結果表示於圖6中。籠蔽解離型矽氧烷樹脂之數目平均分 子量係以Mn939 (譜峰7: Mw/Mnl.12)獲得。 〔實施例4〕 使與實施例1同樣地做法而得到再縮合物5.0 0 g、 1,3 -二（3 -環氧丙氧基丙基）-1,1,3,3 -四甲基二矽氧 烷（信越化學工業股份公司製 LS - 7970) 2.28g、 5%TMAH水溶液1.14g及甲苯63ml置入於具有攪拌機、 Dean-Stark及冷卻管之反應容器中，一邊以120 °C餾去水 ，一邊使甲苯迴流加熱而回流甲苯以進行再縮合反應。甲 苯回流後攪拌5小時之後’返回至室溫，使反應終止。使 反應溶液以飽和食鹽水進行洗淨，以無水硫酸鎂進行脫水 -25- 200904857 。過濾無水硫酸鎂，進行濃縮以收量89%得到目的 解離型矽氧烷樹脂、再縮合物、及1,3 -二（環氧 丙基）-1，1，3,3 -四甲基二矽氧烷的反應混合物< 在GPC中可確認出原料之二矽氧烷的譜峰（譜 Mn357)、與含有籠蔽解離型矽氧烷與再縮合物之 譜峰8: Μη 1 242 )。所得到之反應混合物係可溶於 有機溶劑的透明之黏性液體。測定此反應混合物： 的結果表不於圖7中。 〔實施例5〕 使與實施例1同樣做法而得到再縮合物4.00g 二（3 -甲基丙烯氧基丙基）-1，1,3,3 -四甲基二 2.2Ί g、5%TMAH水溶液1.07g及甲苯60ml置入於 拌機、Dean-Stark及冷卻管之反應容器中，一邊以 餾去水，一邊使甲苯迴流加熱而進行再縮合反應。 流後攪拌5小時之後，返回至室溫，使反應終止。 溶液以飽和食鹽水進行洗淨，以無水硫酸鎂進行脫 濾無水硫酸鎂，進行濃縮以收量9 1 %得到目的之籠 型矽氧烷樹脂、再縮合物、及1,3 -二（甲基丙烯 基）-1，1 , 3 , 3 -四甲基二矽氧烷的反應混合物5.5 G P C中可確認出原料之二矽氧烷的譜峰（譜峰1 1 : )、與含有籠蔽解離型矽氧烷樹脂與再縮合物之譜 峰1 0 : Μη 1 1 22 )。含有所得到之籠蔽解離型矽氧 的反應混合物係可溶於各種之有機溶劑的透明之黏ViR1^, R1 0 In the method for producing the caged dissociative siloxane resin of the present invention, the hydrazine compound represented by the formula (1) is first used in the presence of a basic catalyst, a nonpolar solvent or a polar solvent. The hydrolysis reaction is carried out in any one or a mixture of the two. In the formula (1), R1 is an organic group selected from the group consisting of a vinyl group, a phenyl group, an alkyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring, and is provided for imparting curability. A base with an unsaturated double bond. In the general formula (1), the X-based hydrolyzable group may, for example, be an alkoxy group, a halogen atom or a hydroxyl group, but is preferably an alkoxy group. The alkoxy group may, for example, be a methoxy group, an ethoxy group, a n-isopropoxy group, a n-, an iso-, a second butoxy group or the like. Among them, it is preferably a reactive methoxy group. -11 - 200904857 Regarding the hydrazine compound represented by the formula (1), specific examples of preferred compounds include phenyltrimethoxydecane, phenyltriethoxydecane, and methyltrimethoxydecane. , methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, butyl trimethoxy decane, butyl Triethoxy decane, pentyl trimethoxy decane, pentyl triethoxy decane, octyl trimethoxy decane, octyl triethoxy decane, methacryloxymethyl trimethoxy decane, methyl Propyleneoxymethyltriethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-methylpropoxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxy Decane, 3-propenyloxypropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4 -Epoxycyclohexylethyl)trimethoxydecane, allyltrimethoxydecane,allyltriethoxydecane,p-styrene Triethoxy decane, p-styryl trimethoxy decane, vinyl trimethoxy decane, and vinyl triethoxy decane. Among them, it is more preferable to obtain phenyltrimethoxydecane, phenyltriethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-glycidoxypropyltrimethoxy, which is easy to obtain as a raw material. The alkaline catalyst used in the above hydrolysis reaction, such as decane and vinyltrimethoxydecane, may be exemplified by an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or hydroxide. Tetramethylammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and nitrogen-sulphide sulphate of ampicillin. Among these, 'because of the high activity of the catalyst, it is preferred to use a tetrahydric hydroxide tetra-12-200904857 methyl mirror. An organic catalyst can generally be used as an aqueous solution. The hydrolysis reaction conditions are preferably from 0 to 60 ° C, more preferably from 20 to 4 ° C. When the reaction temperature is lower than 0 °C, the reaction rate becomes slow, and the hydrolyzable group remains in an unreacted state and takes a lot of reaction time. Further, if the reaction rate is too fast at a temperature higher than 6 ° C, a complicated condensation reaction is carried out, and as a result, the high molecular weight of the hydrolysis product can be promoted. Further, the reaction time is preferably 2 hours or more. When the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently, and the hydrolyzable group remains in an unreacted state. The hydrolysis reaction system must have water, but it can also be supplied from an aqueous solution of an alkaline catalyst. Water can also be added. The amount of water is preferably more than the amount of hydrolysis of the hydrolyzable group, preferably from 1 to 0 to 1. 5 times the theoretical amount. Further, in the case of hydrolysis, one or both of a nonpolar solvent or a polar solvent are used in combination. It is preferred to use both or only polar solvents. As the polar solvent, an alcohol such as methanol, ethanol or 2-propanol or other polar solvent can be used. Preferably, it is a lower alcohol having a carbon number of 丨 ≥ 6 which is soluble in water, and 2-propanol is more preferably used. When only a non-polar solvent is used, the reaction system becomes heterogeneous and the polymer is easily precipitated during the reaction. After the end of the hydrolysis reaction, the reaction solution is neutralized with a weakly acidic solution. After neutralization or acidification, water or a reaction solvent containing water is separated. The separation of water or a reaction solvent containing water may be carried out by washing the solution with salt water or the like, sufficiently removing water or other impurities, and then drying it with a drying agent such as anhydrous magnesium sulfate. When a polar solvent is used, the polar solvent is removed by a method such as evaporation under reduced pressure, and then the non-polar solvent is added to dissolve the polycondensate, and the mixture is washed and dried in the same manner as above. -13- 200904857 For weak acid solution, use sulfuric acid dilution solution, hydrochloric acid dilution solution, citric acid solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, phosphoric acid solution, oxalic acid solution, etc. The non-polar solvent is recovered by means of evaporation or the like, and the hydrolysis reaction product can be recovered. However, if the non-polar solvent can be used as a non-polar solvent for the following reaction, it is not necessary to separate it. In the hydrolysis reaction of the present invention, a condensation reaction of a hydrolyzate is produced together with hydrolysis. The polycondensate which is accompanied by the condensation reaction of the hydrolyzate generally has a colorless viscous liquid having an average molecular weight of 500 to 7000. The polycondensate varies depending on the reaction conditions, but the resin (or oligo) having a number average molecular weight of 500 to 3,000, and most of the hydrolyzable group X represented by the formula (1), preferably almost all It is substituted by an OH group, and further, most of the OH group, preferably 95% or more, is condensed. The structure of the polycondensate is a plurality of cage-type, ladder-type, and random type of decanes. The ratio of the cage-type structure to the cage-type structure is small, and one part of the cage is opened. Incomplete cage-type construction becomes the main. The polycondensate is further heated in the presence of a non-polar solvent and a basic catalyst, and the condensate is selectively produced by condensation of a siloxane coupling (referred to as recondensation) (caged structure) When the recondensate is obtained, the water or the reaction solvent containing water is separated, and then the recondensation reaction is carried out in the presence of a nonpolar solvent and a basic catalyst. The reaction conditions for the recondensation reaction are preferably in the range of from 90 to 200 ° C, more preferably from 100 to 140 ° C. If the reaction temperature is too low, a sufficient driving force for the recondensation reaction cannot be obtained without performing the reaction. If the reaction temperature is too high, it is possible that the reactive organic functional group causes its own polymerization reaction, so it is necessary to suppress the reaction temperature or add a polymerization inhibitor. The reaction time is preferably 2 to 12 hours. The amount of the non-polar solvent used may be such that the amount of the alkaline catalyst is from 0.1 to 5 wt%, more preferably from 0.5 to 2.0 wt%, based on the amount of the dissolved hydrolysis reaction product. The non-polar solvent is not particularly soluble in water or has no solubility, but is preferably a hydrocarbon solvent. The hydrocarbon solvent may, for example, be a nonpolar solvent having a low boiling point such as toluene, benzene or xylene, and toluene is preferably used. Further, the basic catalyst may be an alkali catalyst used for the hydrolysis reaction, and may, for example, be an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or hydroxide, or tetramethylammonium hydroxide. Ammonium hydroxide such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide, but preferably tetraalkylammonium or the like Non-polar solvent soluble catalyst. Further, in the case where a non-polar solvent is used in the hydrolysis reaction of the hydrazine compound of the formula (1) in the presence of a basic catalyst, the above-exemplified ones can be used. It is also possible to use the same non-polar solvent as that used in obtaining the non-polar solvent and the recondensate used in the hydrolysis reaction, and it is also possible to use a different one, but in order to make the synthesis sequence simple and preferable, the same can be used. . Further, the hydrolyzate used for recondensation is preferably washed with water, dehydrated or concentrated, but it can be used without washing or dehydrating. At the time of this reaction, water may also be present, but it is not necessary to actively add it, and it is preferable to stop only the moisture carried from the test catalyst solution. Further, when the hydrolysis of the polycondensate is insufficient, the amount of water required for the hydrolysis of the remaining hydrolyzable group is required. After the recondensation reaction, the catalyst is washed with water, and concentrated, and -15-200904857 can be obtained as a recondensate. Then, a dioxantane compound is added to the above-obtained recondensate to obtain a caged dissociated decane resin. The dioxantane compound can be specifically represented by the following formula (3). Further, the reaction in the case of adding a dioxane compound to the recondensate is preferably a nonpolar solvent such as toluene, benzene or xylene, and tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide. It is carried out in the presence of an alkaline catalyst such as a amide. (R^^Si ) 2〇( 3 ) (However, R 1 is selected from the group consisting of a vinyl group, an alkyl group, a phenyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring or The two kinds of radicals 'R2 are methyl groups> The addition reaction of the above-mentioned recondensate with the basic catalyst between the dioxane compounds represented by the general formula (3) is an equilibrium reaction 'from oxygen The atom is a dissociation of a recondensate composed of 3/2 bonded germanium atomic units (T units), or a competitive reaction of high molecular weight generated by the recondensate alone, so the former must be prioritized as much as possible ( Dissociation of the recondensate). Further, since the reaction system of the present invention is substantially an equilibrium reaction, the number average molecular weight Μη, yield, and rate of formation of the caged dissociative siloxane resin having a reactive functional group at the terminal of the target are dependent on the reaction temperature, The reaction time, the ratio of the addition amount of the two raw materials, the amount of the alkali catalyst, and the like are determined by themselves, and therefore it is preferably carried out under the conditions described below. That is, the above-mentioned recondensate is preferably added to the dioxane compound represented by the formula (3) in the presence of a nonpolar solvent and a base-16-200904857 catalyst. The reaction conditions are preferably in the range of from 90 to 200 ° C, more preferably from 10 0 to 140 ° C. However, in the case where the boiling point of the dioxane compound represented by the formula (3) is low, the reaction temperature may reach the boiling point or higher and evaporate outside the reaction system. Therefore, it is preferred to carry out the reaction for a long time below the boiling point. Under alkaline conditions, the caged heptane linkage forming the recondensate is in the equilibrium reaction between the cut and the bond, but if the dioxane compound is present, the cut portion reacts with the dioxane compound. Therefore, the caged dissociated siloxane resin can be obtained by setting a part of the cage to dissolve the glass. The caged dissociative siloxane resin referred to herein means a sand oxide molecular structure which forms at least one of the siloxane couplings of the cage structure to form an incomplete cage structure. Also, the reaction time should be 1 to 5 hours. When the non-polar solvent is used in the equilibrium reaction of the recondensate with the dioxane compound, the non-polar solvent is preferably used in an amount sufficient to dissolve the recondensate. Further, the reaction ratio of the recondensate to the dioxane compound is a structural unit of 1 volt, which is represented by [VsiCh.s] 10 of the T unit corresponding to the recondensate, and is preferably a dioxane compound. It is a hydrolyzed addition of 0.5 to 4.0 moles, preferably 1 to 2.0 2.0 moles. If the dioxane compound is less than this range, the reaction does not proceed, and conversely, if the amount is too large, the reactants may cause adverse effects on the physical properties of the product, which is not preferable. Further, for example, when a volatile dioxane compound such as hexamethyldioxane or 1,3-divinyl-1,1,3,3-tetramethyldioxane is used, It is also possible to measure the amount of volatilization in the reaction and set the amount of addition slightly. Further, examples of the non-polar solvent used herein may be the same as those used in the case of obtaining a recondensate, and may be the same as those of the user who obtains the recondensate, and may also use a different one. Further, when the alkaline catalyst is used for the equilibrium reaction between the recondensate and the dioxane compound, the amount of the basic catalyst used is relative to the structure of the recondensate represented by "R1 Si〇1.5". The unit 1 Moer' should be added to the 0. 05 to 15 moles, preferably 0.06-0.1 moles. With respect to the dioxantane compound represented by the formula (3), a specific example of a preferred compound can be mentioned, for example, hydrazine, 3-diphenyl-l,3,3-tetramethyl dioxin, Hexamethyl-sodium sulphate, hexa-ethyl sulphate, hexaphenyl shale, pentamethyl sulphate, 1, sputum, 3,3_tetramethyl shale, m3 - Tetravinyl dimethyl dioxane, 1,3 -diethyl-1,1,3,3 -tetramethyl oxalate, di-n-propyl-m3 -tetramethyldioxane , hydrazine, 3-dibutyl-hydrazine, 1,3,3-tetramethyldioxane, 1,3-dipentyl-hydrazine, 1,3,3-tetramethyldioxane, 1 ,3_dioctyl-1,1,3,3-tetramethyl oxalate, hydrazine, 3 -dimethylmethyloxymethyl-1,1,3,3-tetramethyl dimethyl sand Oxygen, bismuth, 3-bis(3-methacryloxypropyl)-1,1,3,3-tetramethyldioxane, 1,3-dipropenyloxymethyl-1,1 , 3,3 - tetramethyl-spinning institute, lanthanum, 3-bis(3-propenyloxypropyl)-1,1,3,3_tetramethyl oxalate, lanthanum, 3-two ( 3-glycidoxypropyl)-1,1,3,3-tetramethyldioxane, bis-[2-( 3,4-Epoxycyclohexyl)ethyl]-tetramethyl oxalate, oxime, 3-terenyl-1,1,3,3-tetramethyl oxalate, U-II P-styryl-1,1,3,3-tetramethyl oxalate, and hydrazine, 3 - ethyl sulphate, hydrazine, 1,3,3 - tetramethyl oxazepine, and the like. -18- 200904857 The caged dissociative azepine resin obtained according to the invention has the formula (2) m of 1 to 4, η of 8 to 16, and the sum of m and η is 10 to 20 A mixture of the compounds of the formula (4) to (1 〇) is obtained in many cases. Further, the number average molecular weight Mm of the obtained caged dissociative azepine resin is generally in the range of 600 to 1 0000. [Effects of the Invention] When the method for producing a caged dissociative azepine resin of the present invention is used, a cage-dissociated decane resin having a structure whose molecular weight dispersion is low can be produced in a high yield. The obtained caged dissociative siloxane oxide-based molecular structure has low symmetry and low viscosity, and has compatibility with arsonane oligomers having reactive functional groups, and can be widely used. It is used as a raw material of a curable resin composition. In addition, the molding system obtained by curing the curable resin composition containing the cage-dissociated siloxane resin of the present invention from a siloxane having a structure similar to a cage structure has strength and transparency such as inorganic glass. Heat resistance and dimensional stability, and can impart high toughness and good processability, such as plastics, and can be applied to optical applications such as lenses, optical disks, optical fibers, and flat panel display substrates, or various transportation machinery or residential windows. Materials, etc., can also be applied to various transparent components required for light weight or high impact strength, and the benefits and impacts are large. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be more specifically described based on examples. -19- 200904857 [Example 1] Into a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, '150 ml of toluene and 85 ml of 2-propanol (IPA) were placed in a 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution). ) 37.2 g as an alkaline catalyst. 5 5 g of toluene and 50.3 g of trimethoxyvinyl decane (KBM 1 003, manufactured by Shin-Etsu Chemical Co., Ltd.) were placed in a dropping funnel, and the reaction vessel was stirred, and trimethoxyethylene was added dropwise at room temperature for 3 hours. A solution of toluene in toluene. After the dropwise addition of trimethoxyvinyl decane, it was stirred at room temperature for 2 hours. After stirring for 1 hour, the stirring was stopped and allowed to stand for 1 day. The reaction solution was neutralized with 23.0 g of a 1% aqueous solution of citric acid, and then washed with saturated brine and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain a polycondensate 2 (K6 g, yield 77%. This polycondensate was a white solid which was hardly soluble in various organic solvents. Further, the results of the GPC of the polycondensate were measured, and the number averaged. The molecular weight is Mnll88, and the molecular weight dispersion degree (Mw/Mn) is 2.03. Then, in a reaction vessel equipped with a stirrer, a Dean-Stark, a cooling tube, and a thermometer, 15.0 g of the above-mentioned polycondensate and 3 80 ml of toluene are placed. 1.72 g of a 5% TMAH aqueous solution, water was distilled off at 120 ° C, and re-condensation reaction was carried out while refluxing toluene. The toluene was refluxed, stirred for 3 hours, and then returned to room temperature to terminate the reaction. 23.0 g of citric acid was neutralized, and the mixture was washed with saturated brine and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 14.5 g of a recondensate. The obtained recondensate was white solid.溶-20-200904857 The agent shows poor solubility. The result of measuring the GPC of the recondensate is _. In the recondensate represented by "tSiOu" n, more than 13 caged siloxanes and ladder ruthenium can be obtained. oxygen And random type peak 1 [number average molecular weight Mnl979 (Mw / Mn2. 〇 3) η is 12 or less of the caged oxirane peak 2 [number Μ η 747 ( Mw / Mnl .02 )]. Then 'With a blender, Dean-Stark and a cooling tube, 14.5 g of the recondensate obtained above, 3.0 g of toluene 5% TMAH aqueous solution and 1,3 -divinyl-1,1,3,: 9.76 g of oxane (TMDVDS: manufactured by Shin-Etsu Chemical Co., Ltd.), and the toluene was returned to the epidemic equilibrium reaction while distilling off water at 120 ° C. The toluene was refluxed, stirred for 3 hours, and then returned to terminate the reaction. After washing with 3.2 g of 10% citric acid, the mixture was washed with saturated brine, and anhydrous magnesium sulfate was filtered over anhydrous magnesium sulfate, and concentrated to give a yield of 8 8 % to obtain a desired type of oxirane resin (mixture) 1 6 · 9 g. The obtained caged oxyalkylene resin is a colorless viscous solution soluble in various organic solvents: Determination of the GPC of the caged dissociated siloxane resin. Figure 2: Cage dissociation type 矽 oxygen The number of alkane resins is averaged by Mnl 049 (peak 3: Mw/Mnl.17). , the peak of the recondensate 1 ( Μη 1 979 ) is shifted, and the peak 2 ( Μη747 ) is shifted toward the polymer side (the number average peak molecular weight of the peak of the peak shift 2 is the spectrum of the recondensate) The average molecular weight addition dioxane compound 1 molecule number 値I is shown in Figure 1 containing η [矽 oxane] and containing the average molecular weight: the reaction volume of 300 rpm '; - tetramethyl LS - 725 0 heating Return to room temperature for neutralization and dehydration. The cage dissociated dissociated form. The fruit is expressed as a sub-component of the alkane compound on the low molecular side 1). The number of peaks 2 is almost the same -21 - 200904857. Further, the compound η of the peak 1 system [WSiOu]n is a compound having a large size of 13 or more, and the θ is reduced by the cleavage and bonding of the heating in the equilibrium reaction, and the η is reduced. The oxirane compound is reacted. From this result, the caged dissociative siloxane resin can be obtained by reacting a part of the caged siloxane coupling forming the polycondensate with a dioxane compound. Further, after the 1 Η-NMR of the caged dissociated azepine resin obtained above, the multiple peaks of 5.8 to 6.2?? 111 obtained by the vinyl group of 6.2 to 5.7 卩卩 111 and 〇.17? The peak integration ratio obtained by the methyl group of 111 is methyl 6 with respect to vinyl group 5.4. Further, the results of mass analysis of the obtained cage-dissociated deuterated alkane resin by liquid chromatography analysis atmospheric pressure ionization analyzer (LC/APCI-MS) are shown in Fig. 3. In the case of the combination, in Table 1, the main peak detected by the mass spectrometry and the number of m and η corresponding to the chemical formula (2) corresponding thereto are summarized. The detected peak m / ζ is in the cage dissociation type represented by the following general formula (2) (however, m is 1 to 4, n is 8 to 16'm and the sum of η is 10 to 20) The molecular weight of the decane resin is the addition of ammonium ion. From the results of the mass analysis, it is understood that the caged dissociated oxalate resin can be obtained by reacting one of the caged siloxane couplings forming the polycondensate with a dioxane compound. (R'R22Si〇l/2 ] m C R1 Si〇3/2 ] n (2) -22- 200904857 [Table 1] The detected peak m/zm —- n 882.1 1 9 836.2 2 .. 8 980.1 1 ----- 11 994.1 2 -----_ 10 1152.1 2 -- 12 116.2 3 11 1324.1 3 13 1482.1 3 ------- 15 [R'R22SiO, /2 ] m [ R^iOs/a) n (2) [Example 2] In the same reaction container as in Example 1, toluene 3 48 ml, 5% hydrazine aqueous solution 40.0 g, 2-propane in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer The alcohol (IPA) 192 ml, trimethoxyvinyl decane 43.6 g, trimethoxymethyl decane 47.4 g, and IPA 128 ml solution were dropped for 3 hours, and then stirred at room temperature (20 to 25 ° C) for 3 hours. The reaction solution was allowed to stand for 1 day. The reaction solution was neutralized with a 1% by weight aqueous citric acid solution, washed with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered, and concentrated to give a condensate of 46.6 g of a methyl group and a vinyl group in a yield of 80%. The GPC of this polycondensate was measured and the number average molecular weight was Mnl447 (Mw/Mn3 1.5). Then, 15.0 g of the above-mentioned polycondensate and 1.72 g of a toluene solution of 5% TMAH were placed in a reaction vessel equipped with a stirrer, a Dean-Stark, a cooling tube, and a thermometer, and distilled at 120 ° C. The water was dehydrated, and the toluene was refluxed while heating to carry out a recondensation reaction. Toluene after refluxing -23-200904857 After mixing for 3 hours, return to room temperature to terminate the reaction. The reaction solution was neutralized with 10% citric acid 23.0 g, washed with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to give a recondensed product of 14.5 g. The resulting recondensate is obtained as a colorless transparent liquid. The results of measuring the GPC of this recondensate are shown in Fig. 4. Among the recondensates represented by "R 1 S i 0 i. 5" n, a caged siloxane having a η of 13 or more, a ladder siloxane, and a random siloxane can be obtained. Peak 4 (number average molecular weight Mnl 676 (Mw/Mnl. 27)) and peak 5 (number average molecular weight Μ 645 (Mw/Mnl. 02)) of a caged siloxane having a η of 12 or less. However, the R! in the recondensate [VSiOu] η contains those having only a vinyl group, a methyl group alone, and a vinyl group and a methyl group. The recondensate l〇g obtained in the above, 342 ml of toluene, 3.0 g of a 5% TMAH aqueous solution, and 9.6 g of TMDVD were placed in a reaction vessel equipped with a stirrer 'Dean-Stark and a cooling tube, and distilled at 120 ° C. The water is subjected to a hydrolysis addition reaction while heating the toluene under reflux. The mixture was stirred for 3 hours while refluxing with toluene, and then returned to room temperature to terminate the reaction. The reaction solution was neutralized with 1.2 g of 10% citric acid, washed with distilled water, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered, and concentrated to give a desired yield of 81.4 g of a caged dissociated decane resin. The resulting caged dissociative decane resin is a colorless viscous liquid which is soluble in various organic solvents. The results of measuring the GPC of the caged dissociated azepine resin are shown in Fig. 5. The number average molecular weight of the caged dissociated siloxane resin was obtained by Mn928 (peak 6: Mw/Mnl. 16). -24-200904857 [Example 3] In the same manner as in Example 1, a recondensate of 7.95 §, hexamethyldioxane 1.41 g, a 5% TMAH aqueous solution of 47.47 g, and toluene of 50 ml were placed in a mixer. In a reaction vessel of Dean-Stark and a cooling tube, after stirring at 8 ° C for 3 hours, the temperature was raised to 100 t and stirred for 1.5 hours. The temperature was further raised to 13 (TC and stirred for 1.5 hours. The reaction solution was returned to room temperature. After neutralizing with citric acid and 10% citric acid 3.24 g, it was washed with saturated brine and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to give a desired yield of 94%. The oxane resin was 9.45 g. The obtained caged dissociative siloxane was a colorless viscous liquid which was soluble in various organic solvents. The results of measuring the GPC of the caged dissociated siloxane resin are shown in Fig. 6. The number average molecular weight of the caged dissociated siloxane resin was obtained by Mn939 (peak peak 7: Mw/Mnl.12). [Example 4] A recondensate of 5.00 g was obtained in the same manner as in Example 1. 1,3 -bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldioxine (LS-7970, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.28 g, 1.14 g of 5% TMAH aqueous solution and 63 ml of toluene were placed in a reaction vessel equipped with a stirrer, Dean-Stark and a cooling tube, while distilling off water at 120 °C. The toluene was heated under reflux to reflux the toluene to carry out a recondensation reaction. After the toluene was refluxed, the mixture was stirred for 5 hours, and then returned to room temperature to terminate the reaction. The reaction solution was washed with saturated brine and dehydrated with anhydrous magnesium sulfate - 25 - 200904857. Filtered anhydrous magnesium sulfate, concentrated to obtain 89% yield of the desired dissociated azide resin, recondensate, and 1,3 -di(epoxypropyl)-1,1,3,3 -tetra Reaction mixture of quinonedioxane < The peak of the dioxane of the starting material (spectrum Mn 357) and the peak of the caged dissociated oxime and recondensate 8: Μη 1 were confirmed in GPC. 242). The resulting reaction mixture is a transparent viscous liquid which is soluble in an organic solvent. The results of the determination of this reaction mixture are shown in Figure 7. [Example 5] A recondensate of 4.00 g of bis(3-methylpropenyloxypropyl)-1,1,3,3-tetramethyldi2.2 g, 5% was obtained in the same manner as in Example 1. 1.07 g of a TMAH aqueous solution and 60 ml of toluene were placed in a reaction vessel of a mixer, a Dean-Stark, and a cooling tube, and the water was distilled off, and toluene was reflux-heated to carry out a recondensation reaction. After stirring for 5 hours, the mixture was returned to room temperature to terminate the reaction. The solution was washed with saturated brine, and anhydrous magnesium sulfate was filtered off over anhydrous magnesium sulfate, and concentrated to obtain 9 1 % to obtain the desired cage-type oxirane resin, recondensate, and 1,3 -di (A) Reaction mixture of 1,1,3,3-tetramethyldioxane in 5.5 GPC The peak of the dioxane of the starting material (peak 1 1 : ) can be confirmed in the GPC, and the cage is contained. The peak of the dissociated decane resin and the recondensate 1 0 : Μη 1 1 22 ). The reaction mixture containing the obtained caged dissociated helium oxygen is transparent and soluble in various organic solvents.
之籠蔽 丙氧基 ;.48g ° 峰 9 : 譜峰（ 各種之 > GPC ' 1,3 - 矽氧烷 具備攪 1 20°C 甲苯回 使反應 水。過 蔽解離 氧基丙 1 g。在 Mn422 峰（譜 烷樹脂 性液體 -26- 200904857 。測定此反應混合物之GPC的結果表示於圖8中。 在上述實施例1~5中’使於再縮合物中使二矽氧烷化 合物平衡化反應之反應時的饋入量歸納表示於以下之表2 中〇 〔表2〕 二矽氧烷化合物之平衡化反應的饋入量 再縮合物 J TM AH 二矽氧烷化合物 [R'SiOislio 理論分子量 mmol mmol 相對於 [R'SiOi.^.o 之莫耳比 mmol 相對於 [^SiO.sJio 之莫耳比 實施例1 791.3 18.3 1.65 0.09 52.4 2.9 實施例2 731.3 13.7 1.65 0.12 51.5 3.8 實施例3 791.3 10.0 0.25 0.03 8.68 0.9 實施例4 791.3 6.32 0.63 0.10 6.29 1.0 實施例5 791.3 5.05 0.59 0.12 5.87 1.2 又’於下述表3中係歸納表示於上述實施例1〜5中所 得到之籠蔽解離型矽氧烷樹脂的GPC計算結果。藉二矽 氧烷化合物之平衡化反應，再縮合物之譜峰1( Μη 1 979 ) 係朝低分子側偏移，譜峰2 ( Μη747 )朝高分子側偏移。 所偏移之譜峰的數目平均分子量係與於再縮合物之譜峰2 的數目平均分子量加成二矽氧烷化合物1分子之數値幾乎 —致。又’有關譜峰1係〔R1 S i 〇! 5〕η的η爲1 3以上很 大的化合物’以平衡化反應中之加熱反覆矽氧烷鍵結之切 斷與鍵結而η變小’認爲此與二矽氧烷化合物加成。從此 等之結果’於實施例1〜5所得到之籠蔽解離型矽氧烷樹脂 -27- 200904857 係可藉由形成聚縮合物之籠蔽的矽氧烷鍵結之一部分被切 斷而與二矽氧烷化合物反應來得到。 〔表3〕 實施例1至實施例5之籠蔽解離型矽氧烷樹脂的Gpc計算結果 R' R2 譜峰數目平均分子量 實施例 1 CHZ*CH- CH3— 3 Mn1049(Uw/Mn1. 17) 實施例 2 CH3- ： CH2 = CH- =5:7 CH广 6 Mn928 (Mw/Mn1. 16) 實施例 3 CH3- ： CHr = CH-= 2 : 10 CHa- 7 Mn939 (Mw/Mn)1.1Z 實施例 4 歐:吼=ch一 =2 : 10 ch3— 8 Mn1242 (Mw/Mn1. 98) 9 二矽氧烷 Mn357 (M*/Mn1_00) 實施例 5 CH2 = C(CH3)-C00-(CH2) 3-: ch2=ch-=2 ： 10 CH广 10 Mn1122 (Mw/Mn3. 31) 11 二较氧烷Mn422.(M*/Mn1. 00> 進一步，確認於上述實施例1 ~5所得到之籠蔽解離型 矽氧烷樹脂與其他之矽氧烷樹脂（11 )〜（1 4 )的相溶性 。結果表示於表4中。從此結果，再縮合物之籠蔽狀矽氧 烷係結晶性高，與其他之矽氧烷樹脂之相溶性幾乎沒有’ 但藉平衡化反應使籠蔽構造的一部份的矽氧烷鍵結解離之 籠蔽解離型矽氧烷樹脂中係可知與其他之矽氧烷樹脂之相 溶性大大地提高。又，在表4中之記號係「〇：具有相溶 性，X :無相溶性」。又，確認出相溶性之矽氧烷樹脂（ 11) 、（12) 、（13) 、（14)係以下述所示之通式表示 的化合物。 -28- 200904857 化 8 Η» ο MIsiThe caged propoxy group; 48g ° peak 9 : peak (various > GPC ' 1,3 - decane has a stirring of 20 ° C toluene back to the reaction water. In the Mn422 peak (Alkane Resin Liquid -26-200904857. The results of measuring the GPC of this reaction mixture are shown in Fig. 8. In the above Examples 1 to 5, 'the dioxane compound was equilibrated in the recondensate. The feed amount in the reaction of the reaction is summarized in Table 2 below. [Table 2] Feeding amount of the dioxane compound. Feed amount Recondensate J TM AH Dioxane compound [R'SiOislio Theoretical molecular weight mmol mmol relative to [R'SiOi.^.o molar ratio of mmol relative to [^SiO.sJio molar ratio Example 1 791.3 18.3 1.65 0.09 52.4 2.9 Example 2 731.3 13.7 1.65 0.12 51.5 3.8 Example 3 791.3 10.0 0.25 0.03 8.68 0.9 Example 4 791.3 6.32 0.63 0.10 6.29 1.0 Example 5 791.3 5.05 0.59 0.12 5.87 1.2 Again, the cage dissociation obtained in the above Examples 1 to 5 is summarized in Table 3 below. GPC calculation results for a type of decane resin. In the equilibrium reaction of the substance, the peak 1 ( Μη 1 979 ) of the recondensate shifts toward the low molecular side, and the peak 2 ( Μη747 ) shifts toward the polymer side. The number average molecular weight of the shifted peak The number average molecular weight of the peak 2 of the recondensate is almost the same as the number of molecules of the dioxane compound. The η of the related peak 1 system [R1 S i 〇! 5] η is 1 3 . The above-mentioned large compound 'is considered to be added to the dioxane compound by the cleavage and bonding of the oxirane bond by the heating in the equilibrium reaction, and the addition of the dioxane compound is considered. The caged dissociated siloxane oxide obtained in 1 to 5, -27-200904857, can be obtained by reacting a dioxane compound by cleaving one of the caged siloxane couplings forming the polycondensate [Table 3] Gpc calculation results of the caged dissociated azide resin of Examples 1 to 5 R' R2 Peak number average molecular weight Example 1 CHZ*CH-CH3-3 Mn1049 (Uw/Mn1. 17 Example 2 CH3-: CH2=CH-=5:7 CH6 6 Mn928 (Mw/Mn1. 16) Example 3 CH3- : CHr = CH-= 2 : 10 CHa- 7 Mn939 (Mw/Mn) 1.1Z Example 4 Ou: 吼 = ch = 2 : 10 ch3 - 8 Mn1242 (Mw / Mn1. 98) 9 Dioxane Mn357 (M* / Mn1_00) Example 5 CH2 = C (CH3)-C00-(CH2) 3-: ch2=ch-=2: 10 CH widely 10 Mn1122 (Mw/Mn3. 31) 11 dioxane Mn422. (M*/Mn1. 00> Further, confirmed The compatibility of the caged dissociated siloxane resin obtained in the above Examples 1 to 5 with other oxirane resins (11) to (14). The results are shown in Table 4. As a result, the caged siloxane of the recondensate has high crystallinity and has little compatibility with other oxirane resins. However, a part of the cage structure is supported by a balance reaction. In the dissociated cage-dissociated siloxane resin, it is known that the compatibility with other decane resins is greatly improved. Further, the symbols in Table 4 are "〇: compatible, X: incompatible". Further, it has been confirmed that the compatible naphthenic resins (11), (12), (13), and (14) are compounds represented by the following general formula. -28- 200904857 化 8 Η» ο MIsi
Me •I»s-ο 二 \ Η 、si/x\Me Η si \ e Μ .Η 化 9Me •I»s-ο 二 \ Η , si/x\Me Η si \ e Μ .Η 9
-29- 200904857 〔表4〕 籠蔽解離型矽氧烷樹脂與其他之矽氧烷樹脂之相溶性的確認 (11) (12) (13) (14) 實施例1之再縮 合物 X X X X 實施例1之籠蔽 解離型矽氧烷 〇 〇 〇 〇 實施例2之籠蔽 解離型矽氧烷 〇 〇 〇 〇 實施例3之籠蔽 解離型矽氧烷 〇 〇 〇 〇 實施例4之籠蔽 解離型矽氧烷 〇 〇 〇 〇 實施例5之籠蔽 解離型矽氧烷 〇 〇 〇 〇 又’在下述之表5中係表示於上述實施例丨〜5中所得 到之籠蔽解離型砂氧烷樹脂的GPC圖中，除去原料之二 矽氧烷化合物的譜峰3、6、7、8、1 0以谷譜峰進行分割 ’再進行計算’相當於通式（2 ) [RlR22Si〇l/2 ) m ( R>Si〇3/2 ] η ( 2 ) (但，m係1-4之整數’ η係8〜16之整數’ m與η之和爲 10〜20)之分孑量範圍的數目平均分子量與其面積比率歸 納之結果。 -30- 200904857 〔表5〕 R1 RJ 數目平均分子量湎積％) 實施例1 (譜峰3) ch2=ch- ch3- Μπ954 (72. 7%) 實施例2 (譜峰6) CH3- : CH2 = CH- =5:7 ch3- Μη817(7Ζ. 7%) 實施例3 (譜峰7) CH3- ： CH2 = CH-= 2 : 10 ch3- Μη870 (82%) 實施例4 (譜峰8) A H, /\/c\ CHa—5 〇-(叫-:CHZ = CH_ =2 : 10 CH3- Μη851 (52. U) 實施例5 (譜峰10) CH2 = C(CH3)-COO-(CH2) 3-: ch2 = ch-=2 : Iff ch3- Μη790 (52. 6%) 【圖式簡單說明】 圖1係R1爲CH2 = CH -之再縮合物的GPC圖。 圖2係R1爲CH2 = CH - 、R2爲CH3 -之籠蔽解離型矽 氧烷樹脂混合物的GPC圖。 圖3係R1爲CH2 = CH -、R2爲CH3 -之籠蔽解離型矽 氧烷樹脂混合物的MS光譜。 圖4係R1爲（CH3- ： CH2 = CH - =5 ： 5)之再縮合物 的GPC圖。 圖 5 係 R1 爲（CH3 - : CH2 = CH - =5 : 7 ) 、R2 爲 CH3 -之籠蔽解離型矽氧烷樹脂的GPC圖。 圖 6 係 R1 爲（CH3- ： CH2 = CH - =2 ： 10) 、R2 爲 CH3 -之籠蔽解離型矽氧烷樹脂混合物的GPC圖。 圖7係R1爲 -31 - 200904857 〔化 1 2〕 八 h2 / \ /c\ ch2—CH 〇-(CH2)3— ： CH2 = CH- = 2 : 10 ，R2爲CH3 -之籠蔽解離型矽氧烷樹脂混合物的 〇 圖 8 係 - COO - ( CH2 CH2 = CH - =2 ： 10 ) 、R2 = CH3 -之籠蔽解離型矽 _ 混合物的G P C圖。 GPC圖 )3 -: 烷樹脂 -32--29- 200904857 [Table 4] Confirmation of compatibility of caged dissociated siloxane resin with other decane resin (11) (12) (13) (14) Recondensate XXXX of Example 1 Example 1 caged dissociated oxane oxime, caged dissociated oxoxane of Example 2, caged dissociated oxoxane of Example 3, caged dissociation of Example 4 The oxime-type oxime oxime of Example 5 is shown in Table 5 below as the caged dissociated sand oxymethane obtained in the above Examples 丨~5. In the GPC chart of the resin, the peaks 3, 6, 7, 8, and 10 of the dioxane compound from which the raw material is removed are divided by the peak of the peak spectrum and then calculated. The equivalent of the formula (2) [RlR22Si〇l/ 2) m ( R > Si 〇 3 / 2 ] η ( 2 ) (however, the integer number of m is 1-4 ' η is an integer of 8 to 16 'the sum of m and η is 10 to 20) The number average molecular weight and its area ratio are summarized as follows. -30- 200904857 [Table 5] R1 RJ number average molecular weight accumulation %) Example 1 (Spectrum peak 3) ch2=ch-ch3- Μπ95 4 (72.7%) Example 2 (Spectrum 6) CH3-: CH2 = CH- = 5:7 ch3- Μη817 (7 Ζ. 7%) Example 3 (Spectrum 7) CH3-: CH2 = CH- = 2 : 10 ch3- Μη870 (82%) Example 4 (Spectrum 8) AH, /\/c\ CHa—5 〇-(called-:CHZ = CH_ =2 : 10 CH3- Μη851 (52. U) Example 5 (Spectrum peak 10) CH2 = C(CH3)-COO-(CH2) 3-: ch2 = ch-=2 : Iff ch3- Μη790 (52.6%) [Simple description of the diagram] Figure 1 is R1 GPC diagram of the recondensate of CH2 = CH - Figure 2 is a GPC diagram of a mixture of caged dissociated helioxane resins with R1 being CH2 = CH - and R2 being CH3 - Figure 3 is where R1 is CH2 = CH - , R2 is the MS spectrum of the caged dissociated decane resin mixture of CH3 - Fig. 4 is a GPC diagram of the recondensate of R1 (CH3-: CH2 = CH - = 5: 5). (CH3 - : CH2 = CH - =5 : 7 ) , and R2 is the GPC diagram of the caged dissociated azepine resin of CH3 - Figure 6 is R1 is (CH3- : CH2 = CH - = 2 : 10), R2 is a GPC chart of a caged dissociated oxirane resin mixture of CH3. Figure 7 is a R1 of -31 - 200904857 [Chemical 1 2] 八h2 / \ /c\ ch2—CH 〇-(CH2)3— : CH2 = CH- = 2 : 10 , R2 is CH3 - cage dissociation type Figure 8 shows the GPC pattern of the caged dissociated 矽_ mixture of COO - ( CH2 CH2 = CH - = 2 : 10 ) and R2 = CH3 -. GPC chart) 3 -: Alkane resin -32-