TW200911887A - Silicon-containing compound, curable composition, and cured material - Google Patents

Abstract

To provide a curable composition excellent in a handling property and a curing property in which an obtained cured article is excellent in transparency and flexibility. The curable composition comprises a silicon-containing compound represented by general formula (1), the compound in which Z is a hydrogen atom in general formula (1), the compound in which Z is a 2-4C alkenyl group or an alkynyl group, and a hydrosilylated reaction catalyst. In the formula, R<SP>a</SP>-R<SP>d</SP>are a 1-12C saturated aliphatic hydrocarbon group, R<SP>e</SP>is a 1-12C saturated aliphatic hydrocarbon group or a 6-12C aromatic hydrocarbon group, Y is a 2-4C alkylene group, Z is a hydrogen atom or a 2-4C alkenyl group or an alkynyl group, K is an integer of 2-7, T is an integer of 1-7, P is an integer of 0-3, and M is the number in which the mass average molecular weight of the silicon-containing compound is made to 3,000-1,000,000.

Description

200911887 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有特定結構之新穎的含有矽之化合 物、含有該化合物而形成之硬化性組合物、及使該組合物 熱硬化而形成之硬化物，詳細而言，本發明係關於一種提 供硬化性組合物的含有矽之化合物、含有此含有矽之化合 物的硬化性組合物、以及透明性及可撓性優異之硬化物，200911887 IX. Description of the Invention: [Technical Field] The present invention relates to a novel bismuth-containing compound having a specific structure, a curable composition formed by containing the compound, and a heat-cured composition of the composition. In particular, the present invention relates to a cerium-containing compound which provides a curable composition, a curable composition containing the cerium-containing compound, and a cured product excellent in transparency and flexibility.

上述硬化性組合物之操作性及硬化性優異，形成透明性及 可撓性優異之硬化物。 【先前技術】 對於將有機原材料及無機原材料組合而成之複合材料， 業者-直在進行各種研究，在工業上，亦利用使無機填充 劑與有機高分子複合之方法、或以有機高分子對金屬表面 加以修飾之塗佈的方法等。對於該等有機/無機複合材料 而言，由於構成該等複合材料之原材料具有微米級以上之 大小，故雖然可將-部分物性提高至預想值以上，但其他 多數性能或物性僅表現出根據有機原材料及無機原材料各 自之性能或物性之加成規則所預料的值。 :方面’近年來’對以下有機/無機複合材料之研究 ,為盛行：有機原材料及無機原材料各原材 (domain)之大小為奈米級， ' levpn. ^ 而以刀子水平（molecular 成為°而成之有機/無機複合材料。業者期望此類材料 :為如下材料：不僅兼具各原材料之特 材料之優點，進而具有加成規則 U原 d热法預科的與各原材料自 130805.doc 200911887 身完全不同之新功能性。 此種有機/無機複合材料中，存為一 + 廿仕一方之原材料及另一The curable composition is excellent in workability and curability, and forms a cured product excellent in transparency and flexibility. [Prior Art] For a composite material in which an organic raw material and an inorganic raw material are combined, the industry directly conducts various studies, and industrially, a method of compounding an inorganic filler with an organic polymer or an organic polymer pair is also used. A method of coating a metal surface to be modified, and the like. For these organic/inorganic composite materials, since the raw materials constituting the composite materials have a size of a micron or more, although the -partial physical properties can be increased to a predetermined value or more, most other properties or physical properties are only expressed according to organic The value expected by the addition rule of the performance or physical properties of the raw materials and inorganic raw materials. : The aspect of 'in recent years' research on the following organic/inorganic composite materials is prevalent: the size of each raw material of organic raw materials and inorganic raw materials is nanometer, 'levpn. ^ and the level of knife is (molecular becomes ° Into organic/inorganic composite materials. The industry expects such materials: the following materials: not only the advantages of the special materials of each raw material, but also the addition rules U original d thermal prep and the raw materials from 130805.doc 200911887 A completely different new functionality. In this organic/inorganic composite material, it is one of the raw materials of the + one side and the other

方之原材料以分子水平經由共價鍵而鍵結之化學鍵Μ、 収以-方之原材料作為基質並使另—方之原材料細微地 y於此基質中並複合化的混合型。至於合成該等有機/ :機複合㈣中所使用之無機原㈣的方法，係使用溶 膠-凝膠法’所謂該溶膠-凝膠法，係指藉由前驅物分子之 水解及其後所進行之聚縮合反應，而在低溫下獲得交聯之 無機氧化物的反應。由該溶膠-凝膠法所獲得之益機原材 料，有在短期間内膠化等保存穩定性差之問題。 ” 非專利文獻！中，藉由下述方法來嘗試改良保存穩定 性：著眼於烷基三烷氧基矽烷之由烷基鏈長所致的縮合速 度之差異’在甲基三甲氧基矽烷之聚縮合後，添加聚縮合 速度較慢之長鏈烧基三院氧基錢，對聚石夕氧貌中之石夕醇 基進行封端；進而，使用鋁觸媒進行甲基三甲氧基矽烷之 聚縮合反應，在達到特定分子量時添加乙醯丙酮，在反應 系中進行配位基交換。然而，該等方法對保存穩定性之改 善並不充分。又，由溶膠-凝膠法所獲得之無機原材料存 在可撓性之問題。 相對於此，作為化學鍵結型之有機/無機複合材料，提 出有含有特定的含有矽之聚合物的硬化性組合物。例如， 於專利文獻1中揭示有如下含有矽之硬化性組合物：含有 具有交聯結構且具有烯基及炔基的含有矽之聚合物（a)、 具有交聯結構且具有矽烷基的含有矽之聚合物…卜及鉑 130805.doc 200911887 系觸媒（D)，且操作性及硬化性優異，所獲得之硬化物之 耐熱性亦優異。然而，該含有矽之硬化性組合物有如下問 題：硬化特性未必充分，無法在低溫下、在短時間内獲得 具有充分之性能的硬化物。 [非專利文獻1]曰本化學會雜誌，No. 9，571(1998) [專利文獻1]曰本專利特開2005-325174號公報 【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供一種操作性及硬化性優異、所獲 得之硬化物的透明性及可撓性優異之硬化性組合物。 [解決問題之技術手段] 本發明者等人為解決上述課題而進行研究，結果發現， 具有特定結構的含有矽之化合物及含有該含有矽之化合物 的硬化性組合物可解決上述課題，從而完成本發明。° 本發明提供一種以下述通式⑴表示之含有石夕 物： σ [化1]A raw material in which a raw material of a square is bonded at a molecular level via a covalent bond, and a raw material of the raw material is used as a substrate, and another raw material is finely mixed in the matrix and composited. As for the method of synthesizing the inorganic raw materials (IV) used in the organic/combination (4), the sol-gel method is used, which means that the sol-gel method is carried out by hydrolysis of precursor molecules and thereafter. The polycondensation reaction is carried out, and the reaction of the crosslinked inorganic oxide is obtained at a low temperature. The raw material of the machine obtained by the sol-gel method has a problem of poor storage stability such as gelation in a short period of time. In the non-patent literature!, attempts have been made to improve the storage stability by focusing on the difference in the condensation rate due to the alkyl chain length of the alkyltrialkoxydecane in the methyltrimethoxydecane. After the polycondensation, a long-chain polyoxyalkylene group having a slower polycondensation rate is added to cap the phenolic alcohol group in the polyoxan oxy-morphology; and further, an aluminum catalyst is used for methyltrimethoxydecane. The polycondensation reaction is carried out by adding acetamidine acetone to a specific molecular weight, and performing ligand exchange in the reaction system. However, these methods are insufficient for improving storage stability. Further, obtained by a sol-gel method In the case of the chemical bonding type organic/inorganic composite material, a curable composition containing a specific polymer containing ruthenium has been proposed. For example, Patent Document 1 discloses A curable composition containing ruthenium containing a ruthenium-containing polymer (a) having a crosslinked structure and having an alkenyl group and an alkynyl group, a ruthenium-containing polymer having a crosslinked structure and having a decyl group, and platinum 130805.doc 200911887 is a catalyst (D), and is excellent in workability and hardenability, and is excellent in heat resistance of the obtained cured product. However, the curable composition containing bismuth has the following problems: the hardening property is not necessarily sufficient A cured product having sufficient performance is obtained in a short time at a low temperature. [Non-Patent Document 1] Sakamoto Chemical Society, No. 9,571 (1998) [Patent Document 1] Japanese Patent Laid-Open No. 2005-325174 [Explanation of the Invention] [Problems to be Solved by the Invention] An object of the present invention is to provide a curable composition which is excellent in workability and curability, and which is excellent in transparency and flexibility of a cured product obtained. In order to solve the above problems, the present inventors have found that a compound containing ruthenium having a specific structure and a curable composition containing the ruthenium-containing compound can solve the above problems, and the present invention has been completed. The present invention provides a stone-like object represented by the following general formula (1): σ [Chemical Formula 1]

⑴ (式中，Ra〜Rd為既可相同亦可不同之 二 和脂肪族烴基；R6為碳原子數為 為&quot;2之飽 或可由飽和脂肪族烴基取代 曰肪族烴基、 原子數為6〜12之芳香族烴 130805.doc 200911887 基，當存在複數個Re時，該等Re既可相同亦可不同；γ為 碳原子數為2〜4之伸烷基，2為氫原子或碳原子數為2〜4之 烯基或炔基，Κ為2〜7之數，τ為1〜7之數，Ρ為〇〜3之數；Μ 為使以通式（1)表示之含有矽之化合物的質量平均分子量為 3000〜1〇〇萬之數）。 又，本發明提供一種硬化性組合物，其係含有（八1)上述 通式（1)中之Ζ為氫原子的上述含有矽之化合物、（Η〗）上述 通式0)中之Ζ為碳原子數為2〜4之烯基或炔基的上述含有 矽之化合物、及（c)矽氫化反應觸媒而形成者。 又本發明提供一種使上述硬化性組合物硬化而形成之 含有矽之硬化物。 [發明之效果] 根據本發明’可提供一種操作性及硬化性優異之硬化性 、且^物，耐熱性、透明性及柔軟性優異之硬化物，以及提 供該專硬化性組合物及硬化物的含有石夕之化合物。 【實施方式】 對以上述通式（1)表示之本發明的含有石夕之化合 物加以說明。 、通式（1 )中，作為以Ra〜Re表示之碳原子數為1〜I〗之 飽和脂肪族煙基’可列舉：甲基、乙基、丙基、異丙基、 :基丁基、第三丁基、異丁基、戊基、異戊基、第 戊基&amp;基、2-己基、3•己基、環己基、i甲基環己 ^庚基2_庚基、3-庚基、異庚基、第三庚基、正辛 基、異辛基、第三辛基、2_乙基己基、壬基、異壬基、癸 130805.doc 200911887 基、十二烷基等。 6 12之“永$之可由飽和脂肪族烴基取代的碳原子數為 的整二包括取代基㈣和脂妨族烴基(1) (wherein, Ra to Rd are two or more aliphatic hydrocarbon groups which may be the same or different; R6 is a saturated carbon group having a carbon atom number of &quot;2 or may be substituted by a saturated aliphatic hydrocarbon group, and the number of atoms is 6 ~12 of aromatic hydrocarbon 130805.doc 200911887 base, when there are multiple Re, the Re can be the same or different; γ is a 2 to 4 carbon alkyl group, 2 is a hydrogen atom or a carbon atom The number is 2 to 4 alkenyl or alkynyl groups, Κ is a number from 2 to 7, τ is a number from 1 to 7, and Ρ is a number from 〇 to 3; Μ is a compound represented by the formula (1) The mass average molecular weight of the compound is from 3,000 to 1,000,000. Further, the present invention provides a curable composition comprising (a) a compound containing ruthenium wherein ruthenium in the above formula (1) is a hydrogen atom, (Η), and a ruthenium in the above formula 0) The ruthenium-containing compound having an alkenyl group or an alkynyl group having 2 to 4 carbon atoms and (c) a hydrogenation-reactive catalyst are formed. Further, the present invention provides a cured product containing ruthenium formed by curing the curable composition. [Effects of the Invention] According to the present invention, it is possible to provide a cured product which is excellent in workability and curability, and which is excellent in heat resistance, transparency, and flexibility, and provides the hardenable composition and cured product. Contains the compound of Shi Xi. [Embodiment] The compound containing the compound of the present invention represented by the above formula (1) will be described. In the general formula (1), the saturated aliphatic nicotyl group having a carbon number of 1 to I represented by Ra to Re may be exemplified by methyl, ethyl, propyl, isopropyl, or butyl. , tert-butyl, isobutyl, pentyl, isopentyl, pentyl &amp; yl, 2-hexyl, 3 hexyl, cyclohexyl, i methylcyclohexylheptyl 2 -heptyl, 3- Heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, hydrazine 130805.doc 200911887, dodecyl, etc. . 6 12 "The last two carbon atoms substituted by a saturated aliphatic hydrocarbon group, including the substituent (4) and the aliphatic hydrocarbon group

Am 為12者。作為取代基即飽和脂肪族煙 土歹1 ，可採用以上所例示之飽和脂肪族烴 =碳原子數者。因此，作為^表示之可由飽和脂^ 包基取代㈣科數為6〜12之芳㈣烴基，可列舉：苯Am is 12 people. As the substituent, i.e., saturated aliphatic tobacco 歹1, the above-exemplified saturated aliphatic hydrocarbon = carbon atom number can be used. Therefore, the aryl (tetra) hydrocarbon group which may be substituted by a saturated aliphatic group as a ^ (4) is 6 to 12, and may be exemplified by benzene.

土 =基2-甲基苯基、3_甲基苯基、4·甲基苯基、^異 丙基：基、4_異丙基苯基、4_丁基苯基、4—異丁基苯基、 :一丁基苯基、4-己基苯基、4_環己基苯基、2 3·二甲 基本基、2,4-二曱基苯基、2,5_二甲基苯基、a二甲基苯 ，、3,4-二甲基苯基、3,5_二甲基苯基、環己基苯基、聯 苯基、2,4,5_三甲基苯基等。 又，作為以Y表示之碳原子數為2〜4之伸烷基，可列舉 CH2CH2- ^ -CH2CH2CH2- &gt; -CH2CH2CH2CH2- ' -CH(CH3)CH2- 、-ch2ch(ch3)_ 等。 作為以Z表示之碳原子數為2〜4之烯基，可列舉ch2=ch_ 、ch2-ch-ch2-、CH2=CH-CH2-CH2-、ch2=c(ch3)_、 CH2-C(CH3)-CH2-、CH2=CH-CH(CH3)_等，作為以z表示之 石厌原子數為2〜4之炔基，例如可列舉下述基。 [化2] CH~C —' CH^C—CH2—, CH=C_CH_ 以上述通式（1)表示之本發明的含有石夕之化合物之較好 130805.doc -10· 200911887 形態為以下述通式（2)表示之含有矽之化合物。以下述通式 (2)表示之含有矽之化合物，係以上述通式（1)表示之含有 矽之化合物中T=K者。利用通常之合成方法所獲得者，係 以下述通式（2)表示之含有石夕之化合物、或複數種以上述通 式⑴表示之含有矽之化合物的混合物，其係將以下述通式 (2)表示之含有矽之化合物作為主成分者。例如，即便在使 用多官能之以（RaSiHO)K表示之環聚矽氧烷作為導入環聚 矽氧烷環之化合物時，上述通式（1)之1了為大於丨之數的 化合物的生成量亦極少。其原因在於，非環狀之聚矽氧烧 經由Y而與環聚石夕氧烧的2個以上之_鍵結而成的化合物 之生成在能量方面非常不利。 [化3]Soil = 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, isopropyl:yl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutyl Phenylphenyl, :-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 2 3 -dimethyl basic, 2,4-didecylphenyl, 2,5-dimethylbenzene Base, a dimethylbenzene, 3,4-dimethylphenyl, 3,5-dimethylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, etc. . Further, examples of the alkylene group having 2 to 4 carbon atoms represented by Y include CH2CH2-^-CH2CH2CH2-&gt;-CH2CH2CH2CH2-'-CH(CH3)CH2-, -ch2ch(ch3)_ and the like. Examples of the alkenyl group having 2 to 4 carbon atoms represented by Z include ch2=ch_, ch2-ch-ch2-, CH2=CH-CH2-CH2-, ch2=c(ch3)_, and CH2-C ( CH3)-CH2-, CH2=CH-CH(CH3)_, etc., and the alkynyl group represented by z, wherein the number of the anaerobic atoms is 2 to 4, for example, the following group can be mentioned. [Chem. 2] CH~C — 'CH^C—CH 2 —, CH=C_CH_ The preferred embodiment of the present invention containing the compound of the invention represented by the above formula (1) is 130805.doc -10· 200911887. A compound containing hydrazine represented by the formula (2). The compound containing ruthenium represented by the following formula (2) is T=K in the compound containing ruthenium represented by the above formula (1). The compound obtained by the usual synthesis method is a mixture containing a compound of the compound represented by the following formula (2) or a plurality of compounds containing a ruthenium represented by the above formula (1), which is based on the following formula ( 2) A compound containing ruthenium as a main component. For example, even when a polyfunctional cyclic polyoxyalkylene represented by (RaSiHO)K is used as a compound into which a cyclic polyoxyalkylene ring is introduced, the compound of the above formula (1) is a compound larger than the number of ruthenium. The amount is also very small. The reason for this is that the formation of a compound in which acyclic polypyroxene is bonded to two or more of the cyclomethoxazole by Y is very disadvantageous in terms of energy. [Chemical 3]

(式中，Ra〜Rd為既可相同亦可不同 』之妷原子數為1〜12之 和脂肪族烴基，V為碳原子數為丨 12之飽和脂肪族烴基 或可由飽和脂肪族烴基取代之碳原子數為6〜12之芳香族 基’當存在複數個Re時，該等Re既可相同亦可不同。' 碳原子數為2〜4之伸烷基’ Z為氫E ; * ^ ^ η轧原子或碳原子數為2心 烯基或炔基，k為2~7之數，ρ為i〜4 之數。m為使以通式 表示之含有矽之化合物的質量平均 J刀十I為3000〜1〇〇萬 130805.doc -11 · 200911887 數）。 上述通式⑴或通式（2)中之Ra〜Rd較好的是甲基，其原因 在於，所獲得之硬化物之对熱性良好。 又，上述通式（1)或通式（2)中之Re較好的是碳原子數為 1〜12之飽和脂肪族烴基，其原因在於所獲得之硬化物之耐 光性良好，上述通式（1)或通式（2)中之以更好的是甲基， 其原因在於所獲得之硬化物之耐熱性亦良好。 又，上述通式（2)中之k為2〜7。若k大於7，則官能基數 過多，無法獲得所得硬化物所需之可撓性。1^為2〜5者在工 業上可容易地獲取原料、且官能基數適當，故較好，最好 的是k為3。 本發明之含有矽之化合物的質量平均分子量為3〇〇〇〜ι〇〇 萬。若質量平均分子量小於3000，則所獲得之硬化物之耐 熱！生不充分，若質量平均分子量大於丨〇〇萬則黏度會變 大而妨礙操作。質量平均分子量較好的是5〇〇〇〜50萬， 更好的是1萬〜1〇萬。 本發明之含有矽之化合物視其製造方法而不同，並無特 J P『制 了應用眾所周知之反應來製造。以下製造方法 中以本發明之含有矽之化合物的以上述通式（2)表示者作 為代表，對上述通式（2)中之z為氫原子者、z為碳原子數 為2〜4之稀基或炔基者依序加以說明。 又’以下，將上述通式（1)或（2)中之Z為氫原子者分別表 述為3有矽之化合物（A1)或（A2)，將上述通式（1)或〇中 之Z為碳原子數為2〜4之烯基或炔基者分別表述為含有矽之 130805.doc 200911887 化合物（B1)或（B2)。 以下，對上述通式（2)中之Z為氫原子的含有矽之化合物 (A2)之製造方法加以說明。 含有矽之化合物（A2)，例如，可藉由將具有不飽和鍵之 非環狀聚矽氧烷化合物（al)作為前驅物並使之與環狀聚矽 氧烷化合物（a2)反應而獲得。 上述具有不飽和鍵之非環狀聚矽氧烷化合物（al)可藉由 如下方式獲得：使1種或2種以上之二官能矽烷化合物利用 水解進行縮合反應後，當{)為1時與單官能單矽烷化合物反 應，當p為3時與三官能單矽烷化合物反應，當0為4時與四 官能單矽烷化合物反應，進而與具有不飽和基之單官能矽 烷化合物反應而獲得。當1)為2時，可在縮合反應之後與具 有不飽和基之單官能找化合物反應而獲得。作為該等石夕 烷化合物之官能基，代表性者為烷氧基、鹵基或羥基。具 有不飽和鍵之非隸聚錢Μ合物㈣與環狀聚石夕氧烧 化合物⑻）係藉由（al)之不飽和鍵結碳與⑷）之基的反 應而鍵結。 作為上述具有不飽和鍵之非環狀聚矽氧烷化合物之 製造中所使用的上述二官能矽烷化合物之例，可列舉：二 甲基二甲氧基㈣、二曱基二乙氧基錢、二乙基二甲氧 基矽烷、一乙基二乙氧基矽烷、二丁基二甲氧基矽烷、二 丁基二乙氧基矽烷、二辛基二曱氧基矽烷、二辛基二乙氧 土夕烧等氧基單#烧化合物；將該等二烧氧基單石夕烧 化口物之1個或2個烷氧基取代為選自由氟、氯、溴及碘所 130805.doc 200911887 、且成之群中的_素原子或羥基之單矽燒化合物；由2個以 上之該等單矽烷化合物縮合而成的二矽氧烷化合物及低聚 矽氧烷化合物。(wherein, Ra to Rd are the same or different, and the number of ruthenium atoms is from 1 to 12 and the aliphatic hydrocarbon group, and V is a saturated aliphatic hydrocarbon group having a carbon number of 丨12 or may be substituted by a saturated aliphatic hydrocarbon group. An aromatic group having 6 to 12 carbon atoms. When a plurality of Re are present, the Re may be the same or different. 'Alkyl group having 2 to 4 carbon atoms' Z is hydrogen E; * ^ ^ The number of atoms or carbon atoms of η is 2 alkenyl or alkynyl groups, k is the number of 2 to 7, and ρ is the number of i to 4. m is the mass average J-knife of the compound containing ruthenium represented by the general formula. I is 3000~1 million 130805.doc -11 · 200911887 number). In the above formula (1) or in the formula (2), Ra to Rd are preferably a methyl group because the obtained cured product is excellent in heat resistance. Further, Re in the above formula (1) or formula (2) is preferably a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, because the cured product obtained has good light resistance, and the above formula The methyl group in (1) or (2) is more preferably a methyl group because the heat resistance of the obtained cured product is also good. Further, k in the above formula (2) is 2 to 7. If k is more than 7, the number of functional groups is too large, and the flexibility required for the obtained cured product cannot be obtained. When 1^ is 2 to 5, it is industrially easy to obtain a raw material, and the number of functional groups is appropriate, so it is preferable that k is 3. The ruthenium-containing compound of the present invention has a mass average molecular weight of from 3 Å to 1,000,000. If the mass average molecular weight is less than 3,000, the hardened material obtained is resistant to heat! If the mass average molecular weight is more than 10,000, the viscosity will become large and hinder the operation. The mass average molecular weight is preferably from 5 〇〇〇 to 500,000, and more preferably from 10,000 to 10,000. The ruthenium-containing compound of the present invention differs depending on the method of production, and is not produced by a known reaction. In the following production method, the compound containing ruthenium of the present invention is represented by the above formula (2), and when z in the above formula (2) is a hydrogen atom, z is a carbon atom number of 2 to 4. The dilute or alkynyl groups are described in order. Further, in the following, the Z in the above formula (1) or (2) is a hydrogen atom, and is represented as a compound having a ruthenium (A1) or (A2), respectively, and the Z in the above formula (1) or oxime The alkenyl or alkynyl group having 2 to 4 carbon atoms is represented as a compound (B1) or (B2) containing oxime 130805.doc 200911887, respectively. Hereinafter, a method for producing the ruthenium-containing compound (A2) in which Z in the above formula (2) is a hydrogen atom will be described. The ruthenium-containing compound (A2) can be obtained, for example, by reacting an acyclic polyoxy siloxane compound (al) having an unsaturated bond as a precursor and reacting it with a cyclic polyoxy siloxane compound (a2). . The acyclic polysiloxane compound (al) having an unsaturated bond can be obtained by subjecting one or two or more difunctional decane compounds to a condensation reaction by hydrolysis, and when {) is 1, The monofunctional monodecane compound is reacted, reacted with a trifunctional monodecane compound when p is 3, reacted with a tetrafunctional monodecane compound when 0 is 4, and further reacted with a monofunctional decane compound having an unsaturated group. When 1) is 2, it can be obtained by reacting with a monofunctional compound having an unsaturated group after the condensation reaction. The functional group of the alkane compound is typically an alkoxy group, a halogen group or a hydroxyl group. The non-accumulated ruthenium complex (4) having an unsaturated bond and the cyclic polyoxo-oxygen compound (8) are bonded by a reaction of (a) unsaturated bond carbon with a group of (4)). Examples of the above-mentioned difunctional decane compound used in the production of the above-mentioned acyclic polysiloxane compound having an unsaturated bond include dimethyldimethoxy (tetra), dimercaptodiethoxy, and Diethyldimethoxydecane, monoethyldiethoxydecane, dibutyldimethoxydecane, dibutyldiethoxydecane,dioctyldimethoxyoxydecane,dioctyldiethyl Oxygen-sintering isotope-like compound; one or two alkoxy groups of the above-mentioned two alkoxylated monolithic sulphonate are substituted with fluorine, chlorine, bromine and iodine selected from 130805.doc 200911887 And a mono-sintering compound of a _ atom or a hydroxy group in the group; a dioxane compound and an oligomethoxy alkane compound obtained by condensing two or more of the monodecane compounds.

作為上述單g能單石夕烧化合物，例如可列舉：三曱基乙 氧基矽烷、三曱基甲氧基矽烷、2乙基乙氧基矽烷、三乙 基甲氧基矽烷、三丁基曱氧基矽烷、三丁基乙氧基矽烷、 二辛基甲氧基矽烷、三辛基乙氧基矽烷、三苯基乙氧基矽 貌、三苯基甲氧基碎烧、甲基二笨基乙氧基料、二甲基 苯基乙氧基矽烷等單烷氧基矽烷化合物；將該等單烷氧基 夕烷化σ物之烷氧基取代為選自由氟、氯、溴及碘所組成 之群中的齒素原子或羥基之單矽烷化合物。 作為上述二官能單矽烷化合物，可列舉：三乙氧基曱基 石夕院、三甲氧基甲基料、=乙氧基乙基魏、三甲氧基 二基矽烷、三乙氧基丁基矽烷、〗曱氧基丁基矽烷、三乙 氧基辛基石夕烧、三甲氧基辛基石夕燒、三乙氧基苯基石夕炫、 三甲氧基苯基錢等三絲基料化合物；將該等三院氧 基矽烷化合物之1〜3個烷氧基取代為選自由氟、氯、漠及 碘所、’且成之群中的鹵素原子或羥基之單矽烷化合物。 作為上述四官能單矽烷化合物，可列舉：四乙氧基矽 烧、四甲氧基㈣等吨氧基㈣化合物；將該等四貌氧 基石夕烧化合物之1〜4個燒氧基取代為選自由氣、氯、漠及 磁所、，且成之群+的自素原子或經基之單⑦烧化合物。 作為上述具有不飽和基之單官能料化合物，可列舉： 甲基乙稀基氯發燒、二甲基乙烯基甲氧基石夕烧、二甲基 130805.doc 200911887 乙烯基乙氧基矽烷、二苯基乙烯基氣矽烷、二苯基乙烯基 乙氧基矽烷、二苯基乙烯基甲氧基矽烷、甲基苯基乙烯基 氣矽烷、甲基苯基乙氧基矽烷、甲基苯基曱氧基矽烷等。 作為上述環狀聚矽氧炫化合物（a2)，可列舉：丨，3，5_三甲 基環三矽氧烷、1，3,5,7-四甲基環四矽氧烷、五 甲基環五矽氧烷、六曱基環六矽氧烷、 1，3,5,7,9，11，13-七甲基環七石夕氧炫、U3,15_ 八Examples of the mono g-energy monolithic compound include trimethyl ethoxy decane, trimethyl methoxy decane, 2 ethyl ethoxy decane, triethyl methoxy decane, and tributyl.曱 decyl decane, tributyl ethoxy decane, dioctyl methoxy decane, trioctyl ethoxy decane, triphenyl ethoxy fluorene, triphenyl methoxy calcination, methyl two a monoalkoxydecane compound such as a benzyl ethoxylate or a dimethylphenyl ethoxy decane; and the alkoxy group of the monoalkoxy sulfonated sigma is substituted with fluorine, chlorine, bromine and A dentate atom or a monodecane compound of a hydroxyl group in a group consisting of iodine. Examples of the difunctional monodecane compound include triethoxysulfonyl Shichi, trimethoxymethyl, ethoxyethyl, trimethoxy decyl, and triethoxybutyl decane. a three-filament base compound such as methoxy butyl decane, triethoxy octyl sulphate, trimethoxy octyl sulphur, triethoxy phenyl sulphate, trimethoxy phenyl hydrazine; The one to three alkoxy groups of the tri-yard oxydecane compound are substituted with a monodecane compound selected from a halogen atom or a hydroxyl group in a group of fluorine, chlorine, and iodine. Examples of the tetrafunctional monodecane compound include a tonoxy (tetra) compound such as tetraethoxy oxime or tetramethoxy (tetra); and 1 to 4 alkoxy groups of the tetramorphous oxy-stone compound are substituted. Choose free gas, chlorine, indifferent to magnetic, and into a group of + self-priming atoms or a single 7-burning compound. The monofunctional compound having an unsaturated group may, for example, be a methyl ethyl chloride-based calcination, a dimethylvinyl methoxy group, a dimethyl 130805.doc 200911887 vinyl ethoxy decane, a diphenyl group. Vinyl decane, diphenylvinyl ethoxy decane, diphenylvinyl methoxy decane, methyl phenyl vinyl decane, methyl phenyl ethoxy decane, methyl phenyl oxime Base decane and the like. Examples of the cyclic polyfluorene oxide compound (a2) include anthracene, 3,5-trimethylcyclotrioxane, 1,3,5,7-tetramethylcyclotetraoxane, and five Base ring pentaoxane, hexakisylcyclohexaoxane, 1,3,5,7,9,11,13-heptamethylcyclo-seven oxime, U3,15_8

甲基環八矽氧烷、U5-三乙基環三矽氧烷、A”四乙 基％四矽氧烷、五乙基環五矽氧烷、 1’3,5,7’9,11-六乙基環六矽氧烷、1&gt;3,5_三苯基環三矽氧 烷、1，3,5,7-四苯基環四矽氧烷、丨，3,5,7,9_五苯基環五石夕 氧烷、1，3,5,7,9，11-六苯基環六矽氧烷等。 又，作為上述二官能矽烷化合物、單官能單矽烷化合 物、三官能單矽烷化合物、四官能單矽烷化合物、具有不 飽和基之單官能石夕烧化合物、或環狀聚石夕氧烧化合物 ㈣，若使用將各化合物所具有之一部分或全部氫原子取 代為氖及/或氟者，則可獲得後述之將本發明之含有石夕之 化合物的一部分或全部氫原子取代為氣及/或氟者。 用Μ摱得含有 V / w別‘姆物即具有不飽和鍵 之非環狀Μ減化合物㈣之利用水解所進行之縮合反 應，可藉由所謂之溶膠_凝膝反應而進行。二官能截 ^之水解·縮合反應係藉由如下方式進行：絲基或函 基藉由水進行水㈣生成料基⑻.基），該生成之石夕 醇基彼此、料基料氧基、切醇基與自基縮合。為使 130805.doc -15· 200911887 該水解反應迅速地進行， 入觸媒。又，該縮人反應亦二 適…，亦可加 之溶劑中所含的微= 空氣中之水分、或水以外 、、容南1 If I ϋ 里7而進行。該反應中亦可使用溶劑， 特別限定，具體而言，例如可列舉：水，或甲 紅乙知、正丙τ 基乙基嗣、二二異：；、正丁醇、異丁醇、丙酮1 劑可使用戰:二:二等親水_ 列舉:St::媒’用酸或驗，具體而言’例如可 酸化：酸單異丙赌等有機酸類；氯氧化納、氯氧化二 ―、氨等無機鹼類，·三〒胺、三乙胺、單乙醇胺、： ^胺4胺化合物（有機驗）類；鈦酸四異丙醋，鈦酸四丁 =等鈦化合物類；月桂酸二丁基錫、辛基錫酸等錫化合物 1 ’二化合物類；三乙醯丙_料銘化合物 類’鐵、始、I孟、辞等金屬之氣化物，及該等金屬之環院 酉夂鹽及辛酸鹽等金屬幾酸鹽類等；該等觸媒可 併用2種以上。又，由2種以上之二官能㈣化合物進2 解-縮合反應時’既可於分別單獨進行某種程度之水解後 者此α而進一步進行水解縮合反應，亦可將所有二官 能石夕院化合物混合而—起進行水解·縮合反應。 一 如上所述’前驅物即具有不飽和鍵之非環狀聚石夕氧烧化 合物（al)可藉由如下方式而獲得：在上述水解-縮合反應之 後’當“1時進一步與單官能單石夕炫化合物反應，當P為3 時進丨與二官能單石夕烧化合物反應，當p為4時進一步與 130805.doc -16- 200911887 四官能單矽烷化合物反應，繼而與具有不飽和基之單官能 矽烷化合物反應而獲得；當P為2時可與具有不飽和基之I 官能矽烷化合物反應而獲得。 前驅物即具有不飽和鍵之非環狀聚矽氧烷化合物（a”與 環狀聚矽氧烷化合物（a2)的反應，可使用利用矽氫化反應 之方法。例如，含有矽之化合物（A2)可藉由如下方式而獲 知·將非環狀聚矽氧烷化合物（al)與環狀聚矽氧烷化合物 (a2)混合’添加任意量之鉑觸媒之後進行加熱。 以下，對上述通式（2)中之Z為碳原子數為2〜4之烯基或 炔基的含有矽之化合物（B2)之製造方法加以說明。 含有矽之化合物（B2)，例如，可藉由將非環狀聚矽氧烷 化合物（bl)作為前驅物，並使之與具有不飽和鍵的環狀聚 矽氧烷化合物（b2)反應而獲得。非環狀聚矽氧烷化合物 (bl)可藉由如下方式而獲得：使1種或2種以上之二官能矽 烷化合物利用水解進行縮合反應後，當1)為1時與單官能單 矽烷化合物反應，當p為3時與三官能單矽烷化合物反應， 當p為4時與四官能單矽烷化合物反應，進而與導入以_^基 之化合物反應。非環狀聚矽氧烷化合物（bl)與具有不飽和 鍵之環狀聚矽氧烷化合物（b2)係藉由（bl)之Si H基與（b2)之 不飽和基的反應而鍵結。上述二官能矽烷化合物之代表性 B能基為烧氧基、_基或經基。 作為上述非環狀聚矽氧烷化合物（bl)之製造中所使用的 上述二官能矽烷化合物之例，可列舉：二甲基二甲氧基矽 烷、二甲基二乙氧基矽烷、二乙基二甲氧基矽烷、二乙基 130805.doc 200911887 二乙氧基矽烷、二丁基二甲氧基矽烷、二丁基二乙氧基矽 烷、一辛基二甲氧基矽烷、二辛基二乙氧基矽烷等二烷氧 基單矽烷化合物；將該等二烷氧基單矽烷化合物之丨個或2 個烷氧基取代為選自由氟、氯、溴及碘所組成之群中的鹵 素原子或羥基的單矽烷化合物；2個以上之該等單矽烷化 合物縮合而成的二矽氧烷化合物及低聚矽氧烷化合物。 作為上述單官能單矽烷化合物，例如可列舉：三甲基乙 氧基石夕烧、三甲基甲氧基石夕燒、三乙基乙氧基石夕貌、三乙 基甲氧基矽烷、三丁基甲氧基矽烷、三丁基乙氧基矽烷、 三辛基甲氧基石夕院、三辛基乙氧基石夕烧 '三苯基乙氧基石夕 三苯基甲氧基矽烷、曱基二苯基乙氧基矽烷、二曱基 本基乙氧基石夕烧等單燒氧基石夕烧化合物；將該等單烧氧基 矽貌化合物之烧氧基取代為選自由敦、氯、漠及砍所組成 之群中的i素原子或羥基之單矽烷化合物。 作為上述三官能單石夕貌化合物，例如可列舉：三 Γ基石夕烧、三甲氧基甲基錢、三乙氧基乙基㈣、三ΐ 乳基乙基魏、：乙氧基丁基㈣、三甲氧基丁基石夕院、 二乙，基憾料、三甲氧基辛基石夕貌'三乙氧基苯基石夕 、元-h基本基錢等三絲基料化合物；將該等二 =基#化合物之1〜3個院氧基取代為選自由氣、氯了 所組成之群中的自素原子或羥基之單矽烷化合物。 乍為上相官能單石夕燒化合物，例如可列舉：四乙氧基 :、四f乳基石夕炫等四炫氧基石夕貌化合物·將該等四烷 院化合物之1〜4個院氧基取代為選自由氣、氯、漠 130805.doc -18- 200911887 及埃所組成之群中的_素原子或㈣之單找化合物。 作為上述具有不飽和鍵之環狀聚矽氧烷化合物（b2)，可 列舉.1，3,5-二甲基_1，3,5_三乙烯基環三矽氧烷、 四甲基-1，3,5,7-四乙烯基環四矽氧烷、my·五甲基_ ι，3,5,7,9-五乙烯基環五矽氧烷、_六甲基_ 1，3,5,7,9，11-六乙烯基環六矽氧烷、1，3,5,7,9，11，13_七甲 基·1’3,5,7,9，11，13-七乙烯基環七矽氧烷、 1，3,5,7,9，11，13’15-八甲基_1，3,5,7911，13，15_八乙烯基環八 矽乳烷、1，3,5-三苯基三乙烯基環三矽氧烷、 1，3,5’7-四苯基_1，3,5,7_四乙烯基環四矽氧烷、五 本基-1，3,5,7,9-五乙婦基環五石夕氧烧等。 作為上述導入Si-H基之化合物，可列舉：二甲基氣矽 烧、二甲基甲氧基石夕烧' 三甲基乙氧基石夕烧、二苯基氣矽 烧、二苯基甲氧基石夕烧、二苯基乙氧基石夕烧、苯基甲基氣 石夕烧、苯基甲基甲氧基石夕烧、苯基甲基乙氧基石夕燒、經基 二甲基矽烷、羥基二苯基矽烷、羥基苯基甲基矽烷等。 又，作為上述二官能矽烷化合物、單官能單矽烷化合 物、三官能單矽烷化合物、四官能單矽烷化合物、導入Μη基之化合物 、或具有不飽和鍵之環狀聚矽氧烷化合物 (b2)，若使用將各化合物所具有的_部分或全部氫原子取 代為氘及/或氟者，則可獲得後述之將本發明的含有矽之 化合物的一部分或全部氫原子取代為氘及/或氟之化合 物。 用以獲得含有矽之化合物（B 2)之前驅物即非環狀聚矽氧 130805.doc -19- 200911887 烷化合物⑽的利用水解所進行之縮合反應，可藉由所謂 之岭膠-凝膠反應來進行，其與上述具有不飽和鍵之非環 狀聚夕氧烷化合物(al)中所說明之溶膠-凝膠反應相同。 Ά物即非環狀聚⑦氧烧化合物（b ^)與具有不飽和鍵之 %狀聚梦氧院化合物（b2)的反應’可使用利时氫化反應 之方法例如，將非環狀聚矽氧烷化合物（bl)與具有不飽 和鍵之環狀聚石夕氧燒化合物（b2)混纟，添加任意量之翻觸 媒之後進行加熱’藉此可獲得含有矽之化合物（B2)。 本發明之含有矽之化合物，除如下所述可用作硬化性組 t物之主成分以外，亦可與其他高分子化合物或高分子組 合物混合而用於樹脂、塑膠改質劑等用途。 再者，雖然在本發明之含有矽之化合物的範圍之外，但 上述通式（1)或（2)中之非環狀矽氧烷鏈中，可導入硼、 鎂、紹、磷、鈦、鉛、铪、鐵、鋅、鈮、鈕、錫、碲等矽 以外之元素。作為其方法，例如可列舉如下方法：併用供 給該等其他元素之衍生物並進行水解_縮合反應，於矽氧 烷鏈中組入矽以外之元素。又，亦可存在將上述含有矽之 化合物的一部分或全部氫原子取代為氘及/或氟者。 其次’就本發明之硬化性組合物加以說明。 本發明之硬化性組合物，係含有上述通式（1)中之z為氫 原子的含有矽之化合物（A1)、上述通式（1)中之Z為碳原子 數為2〜4之烯基或炔基的含有矽之化合物（B1)、及梦氫化 反應觸媒（C)作為必需成分之組合物。本發明之硬化性組 合物，係藉由熱及矽氫化反應觸媒（c)之作用而使含有矽 130805.doc -20- 200911887 之化合物（A 1)之Z基與含有矽之化合物（B1)之Z基反應而硬 化。本發明之硬化性組合物所含有的含有矽之化合物（A i) 及含有矽之化合物（B1)各自之較好形態為上述含有矽之化 合物（A2)及含有矽之化合物（B2)。 f 本發明之硬化性組合物中，相對於i 〇〇質量份的含有矽 之化合物（A1)，較好的是含有5〜5〇〇〇質量份的含有矽之化 口物（B1 )，更好的是10〜1 〇〇〇質量份。又，就硬化性及保 存穩定性之觀點而言，在本發明之硬化性組合物中，矽氫 化反應觸媒（C)之含量較好的是5質量％以下，更好的是 0_0001〜1,〇質量％。若矽氫化反應觸媒（C)之含量多於5質 量％，則有時會影響硬化性組合物之穩定性。 本發明之石夕氫化反應觸媒（〇,係含有選自由促進石夕氯 化反應之翻、把及錢所組成之群中的一種以上金屬之取所 周知之觸媒。例如，作為 烯基甲基錯合物、始二乙^其觸媒’可列舉：翻-叛基乙 鉑产 —乙烯基四甲基二矽氧烷錯合物、 ^魅甲基發氧燒錯合物、I辛㈣合物等。作為 把系觸媒及錯系觸據 加 你…如可列舉：於該㈣觸媒中代替 銘而含有同為銘系金屬之 料Τ代替 反應觸媒既可使用!種，亦可併用：化5物。該等錢化 之觀點而言，較好的是含有^種以上。尤其就硬化性 箱-幾基乙埽基甲基錯合物。又具體而言’較好的是 等含有上述㈣金屬的所謂之—（二本基膦）氯化姥⑴ 化反應觸媒（c)中。 mson觸媒亦包含在矽氬 本發明之硬化性組合物 視需要亦可含有可與含有矽 I30805.doc 200911887 之化合物（A1)或含有矽之化合物（B1)反應之化合物（D)。 該化合物（D)例如可為了提高密著性而使用。該化合物 (D)係與上述含有矽之化合物（A1)中之以汨基反應之化合 物、或與上述含有矽之化合物（B1)中之烯基或炔基反應之 化合物，可使用1種或混合使用2種以上。化合物種類並無 特別限定，就硬化物之耐熱性之觀點而言較好的是聚石夕氧 烷化合物。作為該聚矽氧烷化合物，例如可列舉：於具有 直鏈或支鏈之聚二甲基矽氧烷的兩末端具有乙烯基、乙炔 基、Si-H基等基的聚石夕氧；於具有直鍵或支鍵之二甲基石夕 氧烷與二苯基矽氧烷的無規及/或嵌段物之兩末端，具有 乙烯基、乙快基、Si_H基等基的聚石夕氧；將具有直鍵或支 鍵之聚二甲基石夕氧烧的一部分甲基取代為選自乙婦基、乙 炔基及Si-H基中之基的聚石夕氧；將具有直鍵或支鍵之二甲 基石夕氧烧與二苯基石夕氧院的無規及/或嵌段物的一部分甲 基或f基，取代為選自乙稀基、乙块基及Si-H基中之基的 聚矽氧；具有乙烯基、乙炔基、Si-H基等基之樹脂等。 相對於反應對象即含有石夕之化合物⑷）及含有石夕之化合 物=1)之總量，使用該化合物⑼時之使用量較好的是^ 質以下。若化合物(D)之使用量多於％質量％，則有時 所獲得之硬化物之柔軟性及耐光性會下降。 料本化性組合物中，亦可進-步調配無機填充 枓、耐候性賦予劑等成分作為任意成分。 ^上述無機填充料’例如可列舉：所謂之填充劑、礦 …機材科’或藉由有機改性處理等對該等加以改質而 130805.doc -22- 200911887 成者。具體而言，仓丨 填充料、二氧化砂凝體二氧化梦、二氧切 氧化鈦等金屬氧化物;雲:蒙=;氧化銘、氧化鋅、 絹雲母、高嶺石、璲 ^ ^桑土類、 石、鐵、# $ ^ 、長石粉、蛭石、厄帖浦石、滑 石、鐵滑石、葉臘石等 ^ 等加以改質而成者。類’4由有機改性處理等對該 ^尤耐熱性之觀點而言，上述無機填充料之粒 ΓμΠ1以下’更好的是〜以下。又，當硬化物之二 重視透明性時，較好的曰你m θ 初《用途 的疋使用篁較少而效果較高之1 μηι以 下之微粒子。本發明夕施/ α &quot;、 之硬化性組合物中之無機填充料之含 θ ’當重視透明性時較好的是儘可能少地使用，故較好的 疋0〜10質量％，每田+A1 田用於k向耐熱性、增黏、賦予觸變性 時，較好的是1 〇〜90質量％。 作為亡述耐候性賦予劑，可使用光穩定劑、紫外線吸收 d I系抗氧化劑、硫系抗氧化劑、磷系抗氧化劑等眾所 周知之通常所使用者。例如，光穩定劑可列舉受阻胺類， 备、外線吸收劑可列舉2·經基二苯甲_類、2_(2_經基苯基） j开三°坐類、2-(2_經基苯基M，6-二芳基^3,5-三嗪類、 笨曱I自曰類、氰基丙烯酸酯類，酚系抗氧化劑可列舉三乙 醇雙[3-(3-第二丁基·5_曱基_4_羥基苯基）丙酸酯]、二丁 基經基曱苯（ΒΗΤ)、2,6-二第三丁基-對甲酚（DBpc)等，硫 系抗氧化劑可列舉二燒硫基二丙酸酯類、烧基疏基丙酸 酿類’碟系抗氧化劑可列舉有機亞磷酸酯類。 使用上述耐候性賦予劑時，就耐熱性、電氣特性、硬化 130805.doc •23- 200911887 性、力學特性、保存穩定性、操作性之觀點而言，在本發 明之硬化餘合物巾其含量較好的是〇._1〜50質#%，更 好的是0.001〜〗〇質量0/〇。 本發明之硬化性組合物中，可於不損及本發明之目標性 能的範圍内，調配其他眾所周知之各種樹脂、添加劑、填 充劑等。作為可任意調配的各種樹脂之例，可列舉··聚醯 ^胺樹脂、聚乙二醇或聚丙二醇等聚醚樹脂、聚胺基甲酸 s曰树月曰、氧樹脂、酚樹脂、聚酯樹脂、三聚氰胺樹脂、 聚醯胺樹脂、聚苯硫騎脂等，作為可任意調配的添加劑 之例，可列舉抗靜電劑等。 為了不彳貝及本發明之目標性能，含有矽之化合物（A1)、 含有矽之化合物（B1)及矽氫化反應觸媒（c)以外之任意成分 之使用*，㈣於含有矽之化合物(A1)與纟有矽之化合物 (B1)的總量100質量份，較好的是合計量為1〇質量份以 下。 本發明之硬化性組合物在室溫（25〇c)下具有良好之流動 性，因而操作性優異。關於流動性，在不含無機填充料之 狀態下、於室溫（25。〇下用E型黏度計測定之黏度較好的是 50 Pa，S以下，更好的是10 Pa.s以下。 又’本發明之硬化性組合物之硬化物，财熱性、对龜裂 性、透明性、耐光性等優異。詳細而言，由本發明之硬化 性組合物’可較好地獲得引起硬化物之5質量。/。之質量減 少的溫度為300°C以上、更好的是400°C以上的硬化物。 又’可較好地獲得龜裂之產生較少的硬化物。 130805.doc -24- 200911887 本發明之硬化物係使本發明之硬化性組合物硬化而形成 者。硬化時之加熱溫度較好的是〇〜3〇(rc，更好的是 100〜200°c。硬化時間較好的是〇丨〜10小時，更好的是 0.5〜6小時。藉由在該等硬化反應條件下進行硬化反應疋 可由本發明之硬化性組合物獲得具有耐熱性、耐龜裂性等 優異之性能的硬化物。 本發明之硬化物係具有優異之物性，尤其係m耐 (' 熱性、财龜裂性、财光性、耐溶劑性、耐驗性、耐候性、 耐污染性、阻燃性、耐濕性、阻氣性、可撓性、伸長率或 強度、電氣絕緣性、低介電常數性等力學特性、光學特 性、電氣特性等優異之材料。 含有本發明之含有⑦之化合物㈣成的本發明之硬化性 組合物，穩定性、硬化性等優異，進而其硬化物之耐龜裂 性、耐熱性、収劑性、耐鹼性、耐候性、光學特性、電 氣特性等各物性優異。本發明之硬化性组合物可應用於電 氣/電子材料領域之顯示材料/光材料/記錄材料/半導體等 之密封材料、高電壓絕緣材料、以絕緣/抗振/防水/防渴為 目的之灌注/密封材料、塑膠零件之試製母模、塗佈材 料、層間絕緣膜、絕緣用封裝、熱收縮橡膠管、〇严顧 示裝置用密封劑/保護材料、光波導管、光纖保護：料： 光學透鏡、光學設備用接著劑、高耐熱性接著劑、高散妖 性材料、高耐熱密封材料、太陽電池/燃料電池用構件、 電池用固態電解質、絕緣包覆材料1印機用感光鼓、氣 體分離膜等。又’亦可應用於土木/建材領域之混凝平 130805.doc -25- 200911887 護材料、襯砌、土壤注入劑、密封劑、蓄冷蓄熱材料、玻 璃鍍膜等’進而在醫療用材料領域中亦可應用於試管、密 封材料、塗佈材料、滅菌處理裝置用密封材料、隱形眼 鏡、富氧膜等。 u [實施例] 以下，藉由實施例等進一步說明本發明，但I發明並不 • 因該等實施例等而受到限定。又，實施例中之「份」或 「％」係以質量為基準。 Ο [合成例1] 將100份之二氯二甲基矽烷滴加至丨〇〇份之離子交換水、 5〇份之甲苯及450份之48〇/〇氫氧化鈉水溶液的混合物中， 使之於105°C下聚合5小時。用500份之離子交換水對所獲 得之反應溶液進行水洗，然後使該甲苯溶液脫水，加入2〇 份之吡啶，於其中進一步加入20份之二曱基乙烯基氣矽烷 並在70C下授拌30分鐘。其後，用1〇〇份之離子交換水進 t 行水洗之後，於bOt下減壓餾去溶劑。繼而以1〇〇份之乙 腈進行清洗’然後於70°C下減壓餾去溶劑，獲得具有不飽 和鍵之非環狀聚紗氧烧化合物（a 1 -1) ^於下述條件下藉由 GpC(gel permeation chromatography，凝膠渗透層析法）進 行分析之結果為非環狀聚矽氧烷化合物（aU)之分子量為 Mw=20,000。再者，以下之GPC均係在該條件下進行。 (GPC之測定條件） 管柱：TOSOH股份有限公司製造之TSK-GEL MULTIPORE HXL Μ，7.8 mm&gt;&lt;300 mm 130805.doc -26- 200911887 展開溶劑：四氫咬喃 [實施例1 ] 將100份之合成例1中獲得之非環狀聚矽氧烷化合物（Μι)溶解於 200份之 曱苯中 ，加入 〇_〇〇3份之 鉑觸媒 、及 1〇份 之作為環狀聚石夕氧院化合物的1,3,5,7-四甲基環四石夕氧 烧’使之於105t下反應2小時。於7(TC下減壓餾去溶劑之 後以100份之乙腈進行清洗。其後，於70。〇下減壓館去溶 劑’獲得含有矽之化合物（A-1)。GPC之分析結果為含有石夕 之化合物（A-1)之分子量為Mw=22,000。 [合成例2] 將100份之二氣二曱基矽烷滴加於1〇〇份之離子交換水、 50份之甲苯及450份之48%氫氧化鈉水溶液的混合物中， 使之於1 05°C下聚合5小時。用500份之離子交換水對所獲 得之反應溶液進行水洗’其後使該甲苯溶液脫水，加入2〇 份之吼咬，於其中進一步加入20份之二甲基氯矽烷並於 7〇°C下攪拌30分鐘。其後’以1〇〇份之離子交換水進行水 洗之後，於150°C下減壓餾去溶劑。繼而以100份之乙猜進 行清洗’其後於70°C下減壓餾去溶劑，獲得非環狀聚妙氧 烷化合物（bl-1)。GPC之分析結果為非環狀聚矽氧烷化合 物（b卜1)之分子量為Mw=20,000。 [實施例2] 將100份之合成例2中所獲得之非環狀聚矽氧烷化合物 (bl-Ι)溶解於200份之甲苯中，加入〇.〇〇3份之鉑觸媒、及 10份之作為具有不飽和鍵之環狀聚矽氧烷化合物的 130805.doc -27- 200911887 1,3,5,7-四曱基-1，3,5,7-四乙烯基環四矽氧烷，使之於 105°C下反應2小時。於70°C下減壓顧去溶劑之後以1〇〇份 之乙腈進行清洗。其後於70°C下減壓餾去溶劑，獲得含有 石夕之化合物（B-1)。GPC之分析結果為含有石夕之化合物（B-1)之分子量為Mw=22,000。 [合成例3] 將100份之二氯二曱基矽烷滴加於1 〇〇份之離子交換水、 50份之甲苯及450份之48%氫氧化鈉水溶液的混合物中， 使之於105°C下聚合5小時。用500份之離子交換水對所獲 得之反應溶液進行水洗，其後使該甲苯溶液脫水。加入2〇 份之°比啶’進而加入0.5份之甲基三氯矽烧，於室溫下攪 拌30分鐘’進而於7〇°C下攪拌30分鐘，然後將該溶液分為 兩等份。 於其中一份溶液中，添加2.5份之作為具有不飽和鍵之 單g能石夕烧化合物的二甲基乙烯基氣石夕烧，於室溫下搜拌 30分鐘’進而於70°C下攪拌30分鐘，然後以離子交換水進 行水洗，由此去除吡啶鹽酸鹽，獲得具有不飽和鍵之非環 狀聚矽氧烷化合物（al-2)。 於另一份溶液中，加入2.5份之作為導入Si-H基之化合物 的二甲基氣矽烷，於室溫下攪拌3〇分鐘，進而於7〇。〇下攪 拌30分鐘，然後以離子交換水進行水洗，由此去除吡啶鹽 酸鹽，獲得非環狀聚矽氧烷化合物（bl_2)。 [實施例3] 將100份之合成例3中所獲得之具有不飽和鍵之非環狀聚 130805.doc -28- 200911887 矽氧烷化合物（al-2)溶解於2〇〇份之曱苯中加入〇 〇〇3份 之鉑觸媒、及ίο份之作為環狀聚矽氧烷化合物的 四甲基環四矽氧烷，使之K1〇5〇c下反應2小時。於7〇。〇下 減壓餾去溶劑之後以1〇〇份之乙腈進行清洗。其後於7〇Cc 下減壓餾去溶劑，獲得含有矽之化合物（A_2)。Gpc之分析 結果為含有矽之化合物（A_2)之分子量為Mw=42,〇〇〇。 [實施例4 ] 將100份之合成例3中所獲得之非環狀聚矽氧烷化合物 (bl-2)溶解於200份之甲苯中’加入〇 〇〇3份之鉑觸媒、及 1 〇份之作為具有不飽和鍵之環狀聚矽氧烷化合物的 1,3,5,7-四曱基-1,3,5,7-四乙稀基環四石夕氧烧，使之於 105 C下反應2小時。於70°C下減壓鶴去溶劑之後以1 〇〇份 之乙腈進行清洗。其後於7 0 °C下減壓顧去溶劑，獲得含有 石夕之化合物（B-2)。GPC之分析結果為含有石夕之化合物（b_ 2)之分子量為Mw=42,000。 [合成例4] 將100份之二氯二曱基矽烷滴加於100份之離子交換水、 50份之甲苯及450份之48%氫氧化鈉水溶液的混合物中， 使之於105°C下反應5小時。用500份之離子交換水對所獲 得之反應溶液進行水洗’其後使該甲苯溶液脫水。加入2〇 份之吡啶，進而加入0.5份之四氯矽烷，於室溫下授掉3〇 分鐘’進而於70。(：下攪拌3〇分鐘，然後將該溶液分為兩等 份。 於其中一份溶液中，加入2.5份之作為具有不飽和鍵之 130805.doc -29- 200911887 單官能矽烧化合物的二甲基乙稀基氣矽烷，於室溫下授拌 30分鐘’進而於7〇。(：下攪拌30分鐘，然後以離子交換水進 行水洗，由此去除吡啶鹽酸鹽，獲得具有不飽和鍵之非環 狀聚矽氧烷化合物（al_3)。 於另一份溶液中’加入2.5份之作為導入Si-H基之化合物 的二甲基氯矽烷，於室溫下攪拌30分鐘，進而於7(rc下攪 拌30分鐘，然後以離子交換水進行水洗，由此去除吡啶鹽 酸鹽’獲得非環狀聚矽氧烷化合物（b 1 _3)。 [實施例5] 將100伤之合成例4中所獲得之具有不飽和鍵之非環狀聚 矽氧烷化合物（al-3)溶解於200份之甲苯中，加入〇〇〇3份 之鉑觸媒、及10份之作為具有不飽和鍵之環狀聚矽氧烷化 合物的1，3,5,7-四曱基環四矽氧烷，使之κ1〇Γ(：下反應2小 時。於70°C下減壓餾去溶劑之後以1〇〇份之乙腈進行清 洗。其後於70。(：下減壓餾去溶劑，獲得含有矽之化合物 (A-3)。GPC之分析結果為含有矽之化合物（A_3)之分子量 為 Mw=52,000。 [實施例6] 將100份之合成例4中所獲得之非環狀聚矽氧烷化合物 (bi-3)溶解於200份之甲苯中，加入〇〇〇3份之翻觸媒、及 10份之作為具有不飽和鍵之環狀聚矽氧烷化合物的 1，3,5,7-四甲基-1，3,5,7-乙烯基環四矽氧烷，使之於1〇5〇C 下反應2小時。於70。(：下減壓餾去溶劑之後以1〇〇份之乙腈 進行清洗。其後於70°C下減壓餾去溶劑，獲得含有矽之化 130805.doc -30- 200911887 合物（B-3)。GPC之分析結果為含有矽之化合物（B_3)之分 子量為 Mw=52,000。 [實施例7] 於將50份之實施例1中所獲得的含有矽之化合物（n)與 5〇份之實施例2中所獲得的含有矽之化合物混合而成 者中，混合〇_〇〇5份之作為矽氫化反應觸媒（c)的鉑-羧基乙 稀基甲基錯合物’獲得硬化性組合物N 〇. 1。 [實施例8] 於將50份之實施例3中所獲得的含有矽之化合物（A_2)與 5 〇份之實施例4中所獲得的含有矽之化合物（B _ 2)混合而成 者中，混合0.005份之作為矽氫化反應觸媒（c)的鉑-羧基乙 烯基甲基錯合物’獲得硬化性組合物N〇. 2。 [實施例9] 於將50份之實施例5中所獲得的含有石夕之化合物（A_3)與 5〇份之實施例6中所獲得的含有矽之化合物（B_3)混合而成 者中，混合0.005份之作為矽氫化反應觸媒（c)的鉑-羧基乙 烯基甲基錯合物’獲得硬化性組合物N〇. 3。 [比較例1 ] 於將50份之上述合成例丨中所獲得的具有不飽和鍵之非 %狀聚矽氧烷（al_l)與50份之上述合成例2中所獲得的非環 狀聚矽氧烷化合物（bl-i)混合而成者中，混合〇 〇〇5份之作 為硬化觸媒的鉑-羧基乙烯基甲基錯合物，獲得比較用之 硬化性組合物（比_丨）。 [比較例2] J30805.doc 31 200911887 於將50份之以二曱基二甲氧基矽烷及乙烯基曱基二甲氧 基矽烷作為單體使之無規縮合而成之聚矽氧烷（Mw : 3 〇,000，乙烯基量：3.5 mmol/g)、與50份之以二曱基二曱 氧基矽烷及甲基二甲氧基矽烷作為單體使之無規縮合而成 之聚石夕氧烧（Mw=30,〇〇〇，Si_H基量：3·5 mm〇1/g)混合而成 者中，混合0.005份之作為硬化觸媒的鉑_羧基乙烯基甲基 錯合物，獲得比較用之硬化性組合物（比_2)。 [比較例3] 於將50份之以乙烯基三曱氧基矽烷、曱基三甲氧基矽烷 及二曱基二甲氧基矽烷作為單體並以莫耳比為丨：4: 5之 比例無規縮合而成之聚矽氧烷樹脂（Mw : 3〇,〇〇〇，乙烯基 量·’ 3.5 mmol/g)、與50份之以三甲氧基矽烷、曱基三曱氧 基矽烷及—曱基二甲氧基矽烷作為單體並以莫耳比為&quot; 4 . 5之比例無規縮合而成之聚矽氧烷樹脂: ⑻〇， S!-H基量：3.5 mm〇1/g)混合而成者中，混合〇 〇〇5份之作 為硬化觸媒的1白叛基乙烯基曱基錯合物，獲得比較用之 硬化性組合物（比。 [比較例4] 於將50伤之實施例}中所獲得的含有矽之化合物（八_1)與 伤之兩末鸲為乙烯基的聚二甲基矽氧烷（Mw : 2〇,〇〇〇)混 口而成者中，混合G GG5份之作為硬化觸媒㈣基乙婦 基甲基錯合物，獲得比較用之硬化性組合物（比十。 [比較例5] 知之實知例2中所獲得的含有石夕之化合物（B_ 1)與 130805.doc •32· 200911887 5 0伤之兩末端為以_11基的聚二曱基矽氧烷（1^冒：2〇,〇〇〇)混 合而成者中，混合〇.〇〇5份之作為硬化觸媒的鉑-羧基乙烯 基甲基錯合物’獲得比較用之硬化性組合物（比-5)。 [比較例6] 混合90份之二氯二曱基矽烷與9份之二氯二苯基矽烷， 滴加於1〇〇份之離子交換水、5〇份之甲苯及45〇份之48%氫 氧化納水溶液的混合物中’使之於1 05 °C下聚合5小時。用 500伤之離子交換水對所獲得之反應溶液進行水洗，其後 使該甲本/谷液脫水，加入2〇份之„比咬，於其中進一步加入 20份之二曱基乙烯基氣矽烷，於701下攪拌30分鐘。然 後’以1 00份之離子交換水進行水洗之後，於15〇。〇下減壓 餾去溶劑。繼而以100份之乙腈進行清洗，其後於7〇〇c下 減壓餾去溶劑，獲得具有不飽和鍵之非環狀聚矽氧烷化合 物（比 al-Ι)。 將100份之所獲得的具有不飽和鍵之非環狀聚矽氧烷化 合物（比al-Ι)溶解於2〇〇份之曱苯中，加入〇〇〇3份之鉑觸 媒、及ίο份之作為環狀聚矽氧烷化合物的i,3,5 7四甲基 環四矽氧烷，使之於105°C下反應2小時。於70°C下減壓餾 去溶劑之後以1〇〇份之乙腈進行清洗。其後於7crc下減壓 館去溶劑’獲得含有矽之化合物（比A_ 1)。GPC之分析結果 為含有矽之化合物（比A-1)之分子量為Mw=22,000。 另一方面’混合90份之二氯二甲基矽烷與1〇份之二氯二 苯基矽烷’滴加於1 〇〇份之離子交換水、5〇份之曱苯及450 份之48°/。氫氧化鈉水溶液的混合物中，使之於1 〇5。〇下聚合 130805.doc -33- 200911887 5小時。用500份之離子交換水對所獲得之反應溶液進行水 洗，其後使該曱苯溶液脫水，加入2 〇份之D比〇定，於其中進 一步加入20份之二曱基氯矽烷並於7(rc下攪拌3〇分鐘。然 後’以100份之離子交換水進行水洗之後，於1 5〇t&gt;c下減壓 顧去溶劑。繼而以1 〇〇份之乙腈進行清洗，其後於7(rc下 減壓餾去溶劑’獲得非環狀聚矽氧烷化合物（比。 將1〇〇份之所獲得的非環狀聚矽氧烷化合物（比bl_1}溶解 於200份之甲苯中，加入0.003份之鉑觸媒、及1〇份之作為 具有不飽和鍵之環狀聚矽氧烷化合物的US,'四甲基_ 1，3,5,7-四乙烯基環四矽氧烷，使之於1〇5。〇下反應2小時。 於70°C下減壓餾去溶劑之後以1 00份之乙腈進行清洗。其 後於70 C下減壓餾去溶劑，獲得含有矽之化合物（比&amp;丨）。 GPC之分析結果為含有石夕之化合物（比丨）之分子量為 Mw=22,000。 於將50份之上述含有矽之化合物（比八_丨）與5〇份之上述 含有矽之化合物（比B-丨）混合而成者中，混合〇 〇〇5份之作 為硬化觸媒的鉑-羧基乙烯基甲基錯合物，獲得比較用之 硬化性組合物（比_6)。 [比較例7] 混合75份之二氣二甲基矽烷與24份之二氯二苯基矽烷， 滴加於100份之離子交換水、5〇份之曱笨及45〇份之48%氫 氧化鈉水溶液的混合物中，使之於1〇5它下聚合5小時。用 500份之離子交換水對所獲得之反應溶液進行水洗，其後 使5亥甲苯溶液脫水，加入2〇份之吡啶，於其中進一步加入 130805.doc -34- 200911887 20份之二甲基乙烯基氯矽烷，於7(rc下攪拌3〇分鐘。然 後，以1〇〇份之離子交換水進行水洗之後，於15〇t&gt;c下減壓 餾去溶劑。繼而以100份之乙腈進行清洗，其後於7(rc下 減壓餾去溶劑，獲得具有不飽和鍵之非環狀聚矽氧烷化合 物（比 al-2)。 將100份之所獲得的具有不飽和鍵之非環狀聚矽氧烷化 合物（比al-2)溶解於200份之甲苯中，加入〇〇〇3份之鉑觸 媒、及ίο份之作為環狀聚矽氧烷化合物的四曱基 ί衣四矽氧烷，使之K105〇c下反應2小時。於7〇它下減壓餾 去溶劑之後以100份之乙腈進行清洗。其後K7(rc下減壓 餾去溶劑，獲得含有矽之化合物（比A_2)。GPC之分析結果 為含有矽之化合物（比A-2)之分子量為Mw=22,〇〇〇。 另一方面，混合75份之二氣二曱基矽烷與24份之二氣二 笨基矽烧，滴加於100份之離子交換水、5〇份之甲苯及45〇 伤之48 /。氫氧化鈉水溶液的混合物中，使之於1 。〇下聚合 5小時份之離子交換水對所獲得之反應溶液進行水 洗，其後使該曱苯溶液脫水，加入2〇份之吡啶，於其中進 步加入20份之二甲基氣矽烷，於7〇。〇下攪拌3〇分鐘。然 後，以1〇〇伤之離子交換水進行水洗之後，於下減壓 餾去溶劑。繼而以100份之乙腈進行清洗，其後於冗^下 減壓餾去溶劑’獲得非環狀聚石夕氧烧化合物（比bi_2)。 將1〇〇份之所獲得的非環狀聚矽氡烷化合物（比bl_2)溶解 於200伤之甲苯中，加入〇 〇〇3份之鉑觸媒、及份之作為 具有不飽和鍵之環狀聚石夕氧垸化合物的以^四甲基· 130805.doc -35- 200911887 1，3,5,7-四乙烯基環四矽氧烷，使之於1〇5。(：下反應2小時。 於70°C下減壓館去溶劑之後以100份之乙腈進行清洗。其 後於70°C下減壓館去溶劑，獲得含有石夕之化合物（比b-2)。 GPC之分析結果為含有矽之化合物（比b-2)之分子量為 Mw=22,000 ° 於將50份之上述含有矽之化合物（比A_2)與5〇份之上述 含有矽之化合物（比B-2)混合而成者中，混合〇.005份之作 為硬化觸媒的鉑·羧基乙烯基曱基錯合物，獲得比較用之 硬化性組合物（比-7)。 [實施例10-12、比較例8〜12] 於紹板上將上述實施例7〜9中所獲得之硬化性組合物N〇 1〜3及比較例1〜5中所獲得之比較用硬化性組合物（比_ 1)〜（比-5)分別製成膜厚約為1 mm之膜，於150°C下加熱30 分鐘使之硬化’獲得硬化物No. 1〜3及硬化物比1〜5。又， 所使用之硬化性組合物之編號與所獲得之硬化物之編號分 別相對應。以如下方式對該等硬化物進行硬化狀態之評價 及180度彎曲試驗。 硬化狀態係根據特定硬化時間後硬化膜有無黏著感來判 斷將具有机動性之狀態評價為χ，並無流動性但有黏著 感者視其程度而評價為△〜。’無黏著感時評價為◎。 180度彎曲試驗中，對在銘板上製作膜厚約為1 mm之膜 而獲侍的硬化膜觀察彎曲1 8〇度時的膜之狀態。將彎折1 80 度時❹無龜裂及剝離之樣品評價為。’將f折1 80度時產 裂而4折90度時未產生龜裂及剝離之樣品評價為△, 130805.doc -36· 200911887 將彎折90度時產生龜裂之樣品評價為 將結果示於表1中。 [表1] 硬化物 硬化狀態 實施例10 實施例11 No. 1 No. 2 ΐδυ度臂曲誠給 實施例12 No. 3 _ ◎ δ~~'~ + X --- 比較例8 比1 X 比較例9 比較例10 1 tb2 未评價 X 比較例11 比較例12 比4 比5 ◎ 〇 Δ ~ Δ~~' 〇 •~~… 」 如表1所明示，實施例10〜12之硬化物N〇^與比較例 9〜12之硬化物比2〜5相比，硬化狀態為同等程度或有所提 高，180度彎曲試驗之評價結果均有所提高。又，由硬化 性組合物（比-1)無法獲得充分之固體硬化物。由此可確 認，藉由採用本發明之構成，硬化狀態及柔軟性會提高。 [實施例13〜15、比較例13及14] 將上述實施例7〜9中所獲得之硬化性組合物N〇 . ^及上 t, 述比較例6、7中所獲得之硬化性組合物（比_6)、（比_7)分別 注入至20 mmx20 mmx3 mm之模具中’於15〇。〇下加熱1 hr ’獲得厚度為3 mm之硬化物No. 4~6及比6、比7。針對 該等硬化物，使用高壓水銀燈進行光劣化試驗，該光劣化 ' 試驗係利用365 nm之輸出為9.96 W/cm之放射線照射2小時 而實施。將光劣化試驗前後之400 nm之透射率示於表2 中。 130805.doc -37- 200911887 [表2] 硬化性組合物 硬化物 照射前透射率 照射後透射率 實施例13 No. 1 No. 4 92 92 實施例14 No. 2 No. 5 92 92 實施例15 No. 3 No. 6 92 92 比較例11 比·6 比6 91 86 比較例12 比-7 比7 90 80 如表2所明示，實施例1 3~ 1 5之硬化物No. 4~6與比較例 11、12之硬化物比6、比7相比，财光性均有所提高。由此 可確認，使Ra〜Re僅由脂肪族組成的硬化性組合物硬化而 成之硬化物，耐光性良好。 130805.doc •38-Methylcyclooctadecane, U5-triethylcyclotrioxane, A"tetraethylcyclotetraoxane, pentaethylcyclopentaoxane, 1'3,5,7'9,11 -hexaethylcyclohexaoxane, 1&gt;3,5-triphenylcyclotrioxane, 1,3,5,7-tetraphenylcyclotetraoxane, hydrazine, 3,5,7, 9_pentaphenylcyclopentaoxane, 1,3,5,7,9,11-hexaphenylcyclohexaoxane, etc. Further, as the above difunctional decane compound, monofunctional monodecane compound, three a functional monodecane compound, a tetrafunctional monodecane compound, a monofunctional rock-burning compound having an unsaturated group, or a cyclic polyoxo-oxygen compound (IV), if a part or all of a hydrogen atom of each compound is substituted with hydrazine And/or fluorine, it is possible to obtain a part or all of the hydrogen atoms of the compound containing the invention of the present invention, which are described later, and which are substituted with gas and/or fluorine. The condensation reaction of the acyclic reduced compound (4) of the saturated bond by hydrolysis can be carried out by a so-called sol-knee reaction. The hydrolysis and condensation reaction of the difunctional moiety is as follows. Carrying out: the silk or the functional group is made of water (4) to form a base (8). The base is formed by condensing the base group, the base oxy group, the cut alcohol group and the self group, for the purpose of making 130805.doc - 15· 200911887 The hydrolysis reaction proceeds rapidly and enters the catalyst. In addition, the condensation reaction is also suitable..., or the micro-containing water contained in the solvent, or water, or Rongnan 1 If I The solvent may be used in the reaction, and is particularly limited, and specific examples thereof include water, or erythroacetate, n-propenyl s-ethyl hydrazine, di-iso-di:, n-butanol, Isobutanol, acetone 1 can be used in war: 2: second-class hydrophilic _ List: St:: medium 'use acid or test, specifically 'for acidification: acid mono-isopropyl gambling and other organic acids; Chlorine Oxidation, inorganic bases such as ammonia, triterpeneamine, triethylamine, monoethanolamine, amine amine compound (organic test); tetraisopropyl vinegar, tetrabutyl titanate, etc. Class; tin compounds such as dibutyltin laurate and octylstannic acid 1 'di-compounds; triethyl hydrazine propylene _ material compound 'iron, a vapor of a metal such as the first, I, and the singer, and a metal acid salt such as a sulphate salt or an octanoate of the metal; the catalyst may be used in combination of two or more kinds. When the difunctional (four) compound is subjected to the 2nd solution-condensation reaction, the hydrolysis reaction can be further carried out by separately hydrolyzing the latter α to a certain extent, and all the difunctional stone compound compounds can be mixed and hydrolyzed. The condensation reaction. As described above, the precursor, that is, the acyclic polyoxo-oxygen compound (al) having an unsaturated bond, can be obtained by: following the above hydrolysis-condensation reaction, 'when a monofunctional monolithic compound, when P is 3, the ruthenium is reacted with a difunctional monolithic compound, and when p is 4, it is further reacted with a 130805.doc -16-200911887 tetrafunctional monodecane compound, and then It is obtained by reacting an unsaturated group of a monofunctional decane compound; when P is 2, it can be obtained by reacting with an I functional decane compound having an unsaturated group. The precursor, that is, the reaction of the acyclic polyoxy siloxane compound (a" having an unsaturated bond with the cyclic polyoxy siloxane compound (a2), a method using a hydrazine hydrogenation reaction, for example, a compound containing hydrazine (A2) can be used. It can be known that the acyclic polyoxy siloxane compound (al) and the cyclic polyoxy siloxane compound (a2) are mixed, and heating is carried out by adding an arbitrary amount of a platinum catalyst. A method for producing a ruthenium-containing compound (B2) wherein Z in the formula (2) is an alkenyl group or an alkynyl group having 2 to 4 carbon atoms. The compound (B2) containing ruthenium, for example, may be The cyclic polyoxyalkylene compound (b1) is used as a precursor and is obtained by reacting with a cyclic polyoxyalkylene compound (b2) having an unsaturated bond. The acyclic polyoxyalkylene compound (bl) can be borrowed. It is obtained by reacting one or two or more difunctional decane compounds with a hydrolysis reaction, and reacting with a monofunctional monodecane compound when 1) is 1, and a trifunctional monodecane compound when p is 3. Reaction, when p is 4, reacts with a tetrafunctional monodecane compound, And reacting with a compound introduced into a group. The acyclic polyoxyalkylene compound (b1) and the cyclic polyoxyalkylene compound (b2) having an unsaturated bond are based on the Si H group of (bl) B2) The bond of the unsaturated group is bonded. The representative B-energy group of the above-mentioned difunctional decane compound is an alkoxy group, a methic group or a thiol group. In the production of the above non-cyclic polyoxy siloxane compound (bl) Examples of the above-mentioned difunctional decane compound to be used include dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl dimethoxy decane, and diethyl 130805.doc 200911887 a dialkoxy monodecane compound such as oxydecane, dibutyldimethoxydecane, dibutyldiethoxydecane, monooctyldimethoxydecane or dioctyldiethoxydecane; The monodecane compound in which one or two alkoxy groups of the dialkoxymonodecane compound are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine; and more than two of these a dioxane compound and an oligomeric alkoxylate compound obtained by condensing a decane compound. Examples of the monofunctional monodecane compound include trimethylethoxy zephyr, trimethyl methoxy sinter, triethyl ethoxy oxime, triethyl methoxy decane, and tributyl methoxy decane. , tributyl ethoxy decane, trioctyl methoxy shixi, trioctyl ethoxy oxime, triphenyl ethoxy oxalate methoxy decane, decyl diphenyl ethoxy a single alkoxylate compound such as decane or a ruthenium base ethoxylate; and the alkoxy group of the monoalkoxy quinone compound is substituted with a group selected from the group consisting of Dun, Chlorine, Mohe and Chopping Examples of the above-mentioned trifunctional monolithic compound include triterpene sulphate, trimethoxymethyl ketone, triethoxyethyl (tetra), and triterpenoid. Ethyl Wei,: Ethoxybutyl (tetra), Trimethoxybutyl Shi Xiyuan, Diethyl, Kefu, Trimethoxyoctyl Shiki, 'Triethoxyphenyl Shi Xi, Yuan-h basic base money, etc. a three-filament base compound; one to three of the oxy groups of the two compounds are selected from the group consisting of gas and chlorine. A mono-decane compound of a self-priming atom or a hydroxyl group in the group formed. The oxime is an upper phase functional monolithic smoldering compound, and examples thereof include tetraethoxy: tetracyloxycarb sulphate, and the like. The base substitution is a single-finger compound selected from the group consisting of gas, chlorine, desert 130805.doc -18-200911887 and angstrom, or (d). The cyclic polyoxy siloxane compound (b2) having an unsaturated bond may, for example, be 1,1,3,5-dimethyl-1,3,5-trivinylcyclotrioxane or tetramethyl- 1,3,5,7-tetravinylcyclotetraoxane, my·pentamethyl_ι,3,5,7,9-pentavinylcyclopentaoxane, _hexamethyl_ 1,3 ,5,7,9,11-hexavinylcyclohexaoxane, 1,3,5,7,9,11,13-heptamethyl·1'3,5,7,9,11,13- Heptavinylcyclopentaoxane, 1,3,5,7,9,11,13'15-octamethyl-1,3,5,7911,13,15-octavinylcyclooctadecane, 1,3,5-triphenyltrivinylcyclotrioxane, 1,3,5'7-tetraphenyl-1,3,5,7-tetravinylcyclotetraoxane, pentabase -1,3,5,7,9-five-female ring-based five-stone oxygen burning. Examples of the compound into which the Si-H group is introduced include dimethyl ketone, dimethyl methoxy sinter, trimethyl ethoxy sinter, diphenyl sulphur, and diphenyl methoxy. Base stone kiln, diphenylethoxy zephyr, phenylmethyl gas smelting, phenylmethyl methoxy sinter, phenylmethyl ethoxy sinter, dimethyl decane, hydroxyl Diphenyl decane, hydroxyphenyl methyl decane, and the like. Further, the difunctional decane compound, the monofunctional monodecane compound, the trifunctional monodecane compound, the tetrafunctional monodecane compound, the compound introduced into the Μn group, or the cyclic polyoxy siloxane compound (b2) having an unsaturated bond, When one or all of the hydrogen atoms of the respective compounds are substituted with hydrazine and/or fluorine, a part or all of the hydrogen atoms of the hydrazine-containing compound of the present invention may be substituted with hydrazine and/or fluorine as described later. Compound. The condensation reaction by hydrolysis to obtain the precursor of the compound (B 2 ) containing a ruthenium (B 2 ), that is, a non-cyclic polyoxo 130805.doc -19-200911887 alkyl compound (10), which can be obtained by a so-called gel-gel The reaction is carried out in the same manner as the sol-gel reaction described in the above-mentioned acyclic polyoxosiloxane compound (al) having an unsaturated bond. The reaction of a non-cyclic poly 7 Oxygen-sintering compound (b ^) with a polymorphic compound (b2) having an unsaturated bond can be carried out by a method of hydrogenation reaction, for example, acyclic polycondensation The oxane compound (b1) is mixed with a cyclic polyoxo-oxygen compound (b2) having an unsaturated bond, and is heated by adding an arbitrary amount of a catalyst, and thereby a compound (B2) containing ruthenium can be obtained. The ruthenium-containing compound of the present invention can be used as a main component of the curable group as described below, and can be used in combination with other polymer compounds or polymer compositions for use in resins and plastic modifiers. Further, in addition to the range of the ruthenium-containing compound of the present invention, boron, magnesium, samarium, phosphorus, and titanium may be introduced into the acyclic siloxane chain in the above formula (1) or (2). , lead, antimony, iron, zinc, antimony, button, tin, antimony and other elements. As the method, for example, a method in which a derivative other than the other element is supplied and a hydrolysis-condensation reaction is carried out, and an element other than ruthenium is incorporated in the siloxane chain. Further, some or all of the hydrogen atoms of the above-mentioned compound containing ruthenium may be substituted with ruthenium and/or fluorine. Next, the curable composition of the present invention will be described. The curable composition of the present invention contains a ruthenium-containing compound (A1) in which z in the above formula (1) is a hydrogen atom, and Z in the above formula (1) is an alkene having 2 to 4 carbon atoms. A composition containing a ruthenium-based compound (B1) or an azide hydrogenation reaction catalyst (C) as an essential component. The curable composition of the present invention is a Z group containing a compound (A 1) of 矽130805.doc -20- 200911887 and a compound containing ruthenium (B1) by the action of heat and hydrogenation reaction catalyst (c). The Z-based reaction hardens. The preferred form of each of the ruthenium-containing compound (A i) and the ruthenium-containing compound (B1) contained in the curable composition of the present invention is the above-mentioned ruthenium-containing compound (A2) and ruthenium-containing compound (B2). In the curable composition of the present invention, it is preferred to contain 5 to 5 parts by mass of the hydrazine-containing chemical substance (B1) based on the yttrium-containing compound (A1). More preferably, it is 10 to 1 part by mass. In the curable composition of the present invention, the content of the rhodium hydrogenation catalyst (C) is preferably 5% by mass or less, more preferably 0-0001 to 1 in terms of hardenability and storage stability. , 〇 quality%. If the content of the hydrogenation catalyst (C) is more than 5% by mass, the stability of the curable composition may be affected. The catalyst for the hydrogenation reaction of the present invention is a catalyst containing at least one metal selected from the group consisting of a group of fluorination reactions and a chlorination reaction, for example, as an alkenyl group. The methyl complex compound, the first two ethyl esters, and the catalyst thereof can be exemplified by the product of the thiophene-platinum-vinyl tetramethyldioxane complex, the melamine methyloxy oxymethane complex, and the I. The symplectic (tetra) compound, etc. is added as a catalyst and a wrong system. For example, in the (four) catalyst, instead of the inscription, the material of the same type of metal is used instead of the reaction catalyst. It can also be used in combination: it is preferable to contain more than one kind, especially in the case of a hardenable box-succinylmethyl group complex. It is preferred to wait for the so-called (di-based phosphine) ruthenium chloride (1) reaction catalyst (c) containing the above-mentioned (IV) metal. The mson catalyst is also contained in the argon-argon composition of the present invention. Containing a compound (D) which can react with a compound (A1) containing hydrazine I30805.doc 200911887 or a compound (B1) containing hydrazine. (D) It can be used, for example, in order to improve adhesion. The compound (D) is a compound which reacts with a mercapto group in the above-mentioned compound (A1) containing ruthenium or an alkene compound (B1) The compound to be reacted with the alkynyl group or the alkynyl group may be used singly or in combination of two or more. The type of the compound is not particularly limited, and from the viewpoint of heat resistance of the cured product, a polyoxanthene compound is preferred. The oxoxane compound may, for example, be a polyoxan having a vinyl group, an ethynyl group, a Si-H group or the like at both ends of a linear or branched polydimethyl siloxane having a direct bond; Or a carboxy oxaxoxane and a diphenyl fluorene oxide at both ends of the random and / or block, having a group of vinyl, ethyl fast, Si_H groups, etc.; a part of the methyl group of the polydimethyl oxalate having a direct bond or a bond is substituted with a group selected from the group consisting of an ethyl group, an ethynyl group and a Si-H group; it will have a direct bond or a bond a part of the methyl or f group of the random and/or block of dimethyl oxalate and diphenyl oxalate a polyfluorene oxide selected from the group consisting of an ethylene group, an ethyl group, and a Si-H group; a resin having a group such as a vinyl group, an ethynyl group, or a Si-H group; and the like (4)) and the total amount of the compound containing the compound of Shixi; = 1), when the compound (9) is used, the amount used is preferably less than or equal to the following. When the amount of the compound (D) used is more than % by mass, the softness and light resistance of the obtained cured product may be lowered. In the present composition, a component such as an inorganic filler or a weather resistance imparting agent may be further added as an optional component. The above-mentioned inorganic filler ′ is exemplified by a so-called filler, a mineral material, or an organic modification treatment, etc., 130805.doc -22-200911887. Specifically, metal oxides such as Cangjie filler, dioxide dioxide dioxide dioxide dioxide dioxide, and dioxygenated titanium oxide; cloud: Meng =; oxidation Ming, zinc oxide, sericite, kaolinite, 璲^^ mulberry Class, stone, iron, # $ ^, feldspar powder, vermiculite, erbium, talc, iron talc, pyrophyllite, etc. The term '4' is preferably from the viewpoint of the heat resistance of the inorganic filler, etc., to the above-mentioned inorganic filler. In addition, when the second of the cured product emphasizes transparency, it is better to use the microparticles below 1 μηι with less effect and less effect. In the present invention, the θ' of the inorganic filler in the curable composition of the present invention is preferably used as little as possible when the transparency is emphasized, so that it is preferably 0 to 10% by mass per When the field +A1 field is used for heat resistance, viscosity increase, and thixotropy, it is preferably from 1 90 to 90% by mass. As the endurance-imparting agent, a conventionally known user such as a light stabilizer, an ultraviolet absorbing antioxidant, a sulfur-based antioxidant, or a phosphorus-based antioxidant can be used. For example, the light stabilizer may be a hindered amine, and the external absorbent may be exemplified by 2, thiophene benzoate, 2 _(2 _ phenylphenyl) j open tris, 2 (2_ Phenylphenyl M,6-diaryl^3,5-triazines, awkward I self-quinones, cyanoacrylates, phenolic antioxidants can be cited as triethanol bis [3-(3-second butyl) ··5 — fluorenyl _ 4 — hydroxyphenyl) propionate], dibutyl benzyl hydrazine (ΒΗΤ), 2,6-di-t-butyl-p-cresol (DBpc), etc. Examples of the oxidizing agent include dithio-sodium dipropionate and sulphur-based propionic acid. The dish-based antioxidants include organic phosphites. When the weather resistance-imparting agent is used, heat resistance, electrical properties, and hardening are used. 130805.doc •23- 200911887 In terms of properties, mechanical properties, storage stability, and operability, the content of the hardened residual towel of the present invention is preferably 〇._1~50##, better 0.001 to 〖mass 0/〇. In the curable composition of the present invention, various well-known various resins, additives, fillers, and the like can be blended in a range that does not impair the target performance of the present invention. Examples of various resins to be arbitrarily formulated include polyether resins such as polyfluorene-amine resins, polyethylene glycol or polypropylene glycol, polyaminocarbamic acid samarium, oxygen resins, phenol resins, polyester resins, and the like. Examples of the melamine resin, the polyamide resin, the polyphenylene sulfide, and the like, as an additive which can be optionally formulated, an antistatic agent, etc., in order to prevent the mussels and the target properties of the present invention, the compound (A1) containing ruthenium, The use of any component other than the ruthenium-containing compound (B1) and the ruthenium hydrogenation catalyst (c)*, (iv) 100 parts by mass of the total amount of the compound (A1) containing ruthenium and the ruthenium-containing compound (B1) It is preferable that the total amount is 1 part by mass or less. The curable composition of the present invention has good fluidity at room temperature (25 〇c), and thus is excellent in handleability. Regarding fluidity, it is free from inorganic fillers. In the state, the viscosity measured by an E-type viscometer at room temperature (25. 〇 is preferably 50 Pa, S or less, more preferably 10 Pa.s or less. Further, the cured product of the curable composition of the present invention) , financial efficiency, cracking, transparency, light resistance, etc. In detail, the curable composition of the present invention can preferably obtain a cured product having a temperature at which the mass of the cured product is reduced by 500 ° C or higher, more preferably 400 ° C or higher. Further, it is possible to obtain a cured product having less cracking. 130805.doc -24- 200911887 The cured product of the present invention is formed by hardening the curable composition of the present invention. The heating temperature at the time of hardening is good. It is 〇~3〇(rc, more preferably 100~200°c. The hardening time is preferably 〇丨10 hours, more preferably 0.5~6 hours. By the hardening reaction conditions The hardening reaction can obtain a cured product having excellent properties such as heat resistance and crack resistance by the curable composition of the present invention. The cured product of the present invention has excellent physical properties, in particular, m resistance ('heat, cracking, fortune, solvent resistance, durability, weather resistance, stain resistance, flame retardancy, moisture resistance) A material excellent in mechanical properties such as gas barrier properties, flexibility, elongation, strength, electrical insulating properties, low dielectric constant, optical properties, electrical properties, etc. The present invention containing the compound (4) of the present invention The curable composition is excellent in stability, hardenability, and the like, and is excellent in physical properties such as crack resistance, heat resistance, collectability, alkali resistance, weather resistance, optical properties, and electrical properties of the cured product. The curable composition can be applied to display materials in the field of electrical/electronic materials/sealing materials such as light materials/recording materials/semiconductors, high-voltage insulating materials, perfusion/sealing for insulation/anti-vibration/waterproof/anti-thirst purposes Prototype of materials, plastic parts, coating materials, interlayer insulation film, insulation package, heat shrinkable rubber tube, sealant/protective material for sturdy inspection device, optical waveguide, fiber protection: material: optical Adhesive for mirror and optical equipment, high heat-resistant adhesive, high-floating material, high heat-resistant sealing material, solar cell/fuel cell member, solid electrolyte for battery, insulating coating material, photosensitive drum for printing machine, gas Separation membrane, etc. It can also be used in the field of civil engineering/building materials. 130805.doc -25- 200911887 Materials, linings, soil injections, sealants, cold storage materials, glass coatings, etc. The present invention can also be applied to test tubes, sealing materials, coating materials, sealing materials for sterilization treatment devices, contact lenses, oxygen-rich films, etc. [Examples] Hereinafter, the present invention will be further described by way of Examples, etc. It is not limited to these examples, etc. Further, the "parts" or "%" in the examples are based on mass. Ο [Synthesis Example 1] 100 parts of dichlorodimethyl decane was added dropwise. To a mixture of ion-exchanged water, 5 parts of toluene and 450 parts of 48 〇/〇 sodium hydroxide aqueous solution, and polymerized at 105 ° C for 5 hours. 500 parts of ion-exchanged water was used. Obtained The reaction solution was washed with water, then the toluene solution was dehydrated, 2 parts of pyridine was added, 20 parts of decylvinyl gas decane was further added thereto, and the mixture was stirred at 70 C for 30 minutes. Thereafter, 1 part was used. After the ion-exchanged water was washed with water, the solvent was distilled off under reduced pressure at bOt, followed by washing with 1 part of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain an acyclic group having an unsaturated bond. The poly-glow-oxygen compound (a 1 -1) is analyzed by GpC (gel permeation chromatography) under the following conditions, and the result is an acyclic polyoxane compound (aU). The molecular weight was Mw = 20,000. Further, the following GPC was carried out under the conditions. (Measurement conditions of GPC) Column: TSK-GEL MULTIPORE HXL manufactured by TOSOH Co., Ltd., 7.8 mm&gt;&lt;300 mm 130805.doc -26- 200911887 Developing solvent: tetrahydroanthracene [Example 1] 100 parts of the acyclic polyoxy siloxane compound (Μι) obtained in Synthesis Example 1 was dissolved in 200 parts In benzene, 3 parts of platinum catalyst is added, and 1 part of 1,3,5,7-tetramethylcyclotetrazepine oxygenate as a cyclic polyoxo compound is added. The reaction was carried out at 105 t for 2 hours. The solvent was distilled off under reduced pressure of 7 (TC), and then washed with 100 parts of acetonitrile. Thereafter, the compound (A-1) containing ruthenium was obtained at 70% under reduced pressure in a vacuum chamber. The analysis result of GPC was contained. The molecular weight of the compound (A-1) of Shixi is Mw=22,000. [Synthesis Example 2] 100 parts of dioxane-decane is added dropwise to 1 part of ion-exchanged water, 50 parts of toluene and 450 parts. The mixture was polymerized at 50 ° C for 5 hours in a mixture of 48% aqueous sodium hydroxide solution. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated and added to 2 Torr. Part of the bite, further adding 20 parts of dimethylchloromethane and stirring at 7 ° C for 30 minutes. Thereafter, after washing with 1 part of ion-exchanged water, it was reduced at 150 ° C. The solvent was distilled off, and the solvent was washed with 100 parts of B. Then, the solvent was distilled off under reduced pressure at 70 ° C to obtain a non-cyclic polyoxane compound (bl-1). The analysis result of GPC was acyclic. The molecular weight of the polyoxyalkylene compound (b) is Mw = 20,000. [Example 2] 100 parts of the non-synthesis obtained in Synthesis Example 2 The polyoxyalkylene compound (bl-Ι) was dissolved in 200 parts of toluene, and 3 parts of platinum catalyst was added, and 10 parts of a cyclic polysiloxane compound having an unsaturated bond was used. .doc -27- 200911887 1,3,5,7-tetradecyl-1,3,5,7-tetravinylcyclotetraoxane, allowed to react at 105 ° C for 2 hours. At 70 ° C After the solvent was removed, the solvent was washed with 1 part of acetonitrile, and then the solvent was evaporated under reduced pressure at 70 ° C to obtain the compound (B-1) containing the compound. The analysis result of GPC was The molecular weight of the compound (B-1) was Mw = 22,000. [Synthesis Example 3] 100 parts of dichlorodioxane was added dropwise to 1 part of ion-exchanged water, 50 parts of toluene and 450 parts of 48 The mixture of the aqueous sodium hydroxide solution was polymerized at 105 ° C for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated. The mixture was further added with 0.5 part of methyltrichloropyrene, stirred at room temperature for 30 minutes' and further stirred at 7 ° C for 30 minutes, and then the solution was divided into two equal portions. To the solution, 2.5 parts of dimethylvinyl ash as a single g-energy compound having an unsaturated bond was added, and the mixture was stirred at room temperature for 30 minutes', and further stirred at 70 ° C for 30 minutes. Then, the mixture was washed with ion-exchanged water to thereby remove the pyridine hydrochloride to obtain an acyclic polysiloxane compound (al-2) having an unsaturated bond. In another solution, 2.5 parts of the solution was introduced as Si. The dimethyl decane of the -H group compound was stirred at room temperature for 3 minutes and further at 7 Torr. The mixture was stirred for 30 minutes under the arm, and then washed with ion-exchanged water to thereby remove the pyridine hydrochloride to obtain a non-cyclic polyoxane compound (bl_2). [Example 3] 100 parts of the non-cyclic poly 130805.doc -28- 200911887 oxane compound (al-2) having an unsaturated bond obtained in Synthesis Example 3 was dissolved in 2 parts of benzene. Three parts of a platinum catalyst, and a tetramethylcyclotetraoxane as a cyclic polyoxyalkylene compound were added thereto, and reacted at K1 〇 5 〇 c for 2 hours. At 7〇. The solvent was distilled off under reduced pressure, and then washed with 1 part of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 7 ° Cc to obtain a compound (A 2 ) containing ruthenium. As a result of analysis of Gpc, the molecular weight of the compound (A_2) containing ruthenium was Mw = 42, ruthenium. [Example 4] 100 parts of the acyclic polyaluminoxane compound (bl-2) obtained in Synthesis Example 3 was dissolved in 200 parts of toluene, '3 parts of platinum catalyst was added, and 1 a 1,3,5,7-tetradecyl-1,3,5,7-tetraethylcyclotetrazepine as a cyclic polyoxyalkylene compound having an unsaturated bond, such that The reaction was carried out at 105 C for 2 hours. After removing the solvent at 70 ° C, the solvent was washed with 1 part of acetonitrile. Thereafter, the solvent was removed under reduced pressure at 70 ° C to obtain a compound (B-2) containing. As a result of analysis by GPC, the molecular weight of the compound containing the compound (b-2) was Mw = 42,000. [Synthesis Example 4] 100 parts of dichlorodioxane was added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution at 105 ° C. Reaction for 5 hours. The obtained reaction solution was washed with water in an amount of 500 parts of ion-exchanged water. Thereafter, the toluene solution was dehydrated. Two parts of pyridine was added, and further 0.5 parts of tetrachloromethane was added and allowed to stand at room temperature for 3 minutes and further at 70. (: Stir for 3 minutes, then divide the solution into two equal parts. In one of the solutions, add 2.5 parts of the dimethyl group as 130805.doc -29-200911887 monofunctional sinter compound with unsaturated bond Teether-based gas decane was mixed at room temperature for 30 minutes' and further at 7 Torr. (: stirring for 30 minutes, followed by washing with ion-exchanged water, thereby removing pyridine hydrochloride to obtain an unsaturated bond. Acyclic polyoxyalkylene compound (al_3). Add 2.5 parts of dimethylchloromethane as a compound introduced into the Si-H group in another solution, and stir at room temperature for 30 minutes, and then at 7 ( The mixture was stirred at rc for 30 minutes, and then washed with ion-exchanged water to thereby remove the pyridine hydrochloride' to obtain a non-cyclic polyoxyalkylene compound (b 1 -3). [Example 5] 100% of the synthetic Example 4 The obtained non-cyclic polyoxy siloxane compound (al-3) having an unsaturated bond is dissolved in 200 parts of toluene, 3 parts of platinum catalyst is added, and 10 parts are used as unsaturated bonds. a 1,3,5,7-tetradecylcyclotetraoxane of a cyclic polyoxyalkylene compound, which is made κ1〇Γ (: The next reaction was carried out for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C, and then washed with 1 part of acetonitrile, and then at 70. (The solvent was distilled off under reduced pressure to obtain a compound containing oxime (A- 3) The analysis result of GPC is that the molecular weight of the compound containing ruthenium (A_3) is Mw = 52,000. [Example 6] 100 parts of the acyclic polysiloxane compound obtained in Synthesis Example 4 (bi-3) Dissolved in 200 parts of toluene, adding 3 parts of a tweezers, and 10 parts of 1,3,5,7-tetramethyl group as a cyclic polyoxyalkylene compound having an unsaturated bond. 1,3,5,7-vinylcyclotetraoxane, allowed to react at 1 〇 5 ° C for 2 hours at 70 ° (:: distilling off the solvent under reduced pressure, and then washing with 1 part of acetonitrile Thereafter, the solvent was distilled off under reduced pressure at 70 ° C to obtain a compound (B-3) containing hydrazine 130805.doc -30- 200911887. The analysis result of GPC was that the molecular weight of the compound containing ruthenium (B_3) was Mw. = 52,000. [Example 7] In a mixture of 50 parts of the ruthenium-containing compound (n) obtained in Example 1 and 5 parts of the ruthenium-containing compound obtained in Example 2, mixed 〇_ 5 parts of platinum-carboxyethyl methyl complex as a hydrogenation reaction catalyst (c)' to obtain a curable composition N 〇. 1. [Example 8] In 50 parts of Example 3 The obtained ruthenium-containing compound (A_2) was mixed with 5 parts of the ruthenium-containing compound (B _ 2) obtained in Example 4, and 0.005 part of the mixture was mixed as a ruthenium hydrogenation catalyst (c). The platinum-carboxyvinylmethyl complex' obtained a curable composition N〇. [Example 9] Among 50 parts of the compound containing the scorpion (A_3) obtained in Example 5 and 5 parts of the compound containing ruthenium (B_3) obtained in Example 6, 0.005 parts of platinum-carboxyvinylmethyl complex as a hydrogenation reaction catalyst (c) was mixed to obtain a curable composition N〇. [Comparative Example 1] A non-cyclic polyfluorene obtained in the above Synthesis Example 2 obtained by dissolving 50 parts of the above-mentioned synthesis example oxime, a non-volatile polyoxyalkylene (al-1) having an unsaturated bond, and 50 parts. A mixture of oxane compounds (bl-i) was mixed with 5 parts of platinum-carboxyvinylmethyl complex as a curing catalyst to obtain a comparatively curable composition (ratio _ 丨) . [Comparative Example 2] J30805.doc 31 200911887 Polyoxyalkylene which was obtained by randomly condensing 50 parts of dimercaptodimethoxydecane and vinylmercaptodimethoxydecane as a monomer ( Mw : 3 〇,000, vinyl amount: 3.5 mmol/g), and 50 parts of decyldimethoxy decane and methyl dimethoxy decane as monomers to make them randomly condensed In the mixture of Shixi Oxygen (Mw=30, 〇〇〇, Si_H basis: 3·5 mm〇1/g), 0.005 parts of platinum-carboxyvinylmethyl group as a hardening catalyst is mixed. The composition was used to obtain a comparatively hardening composition (ratio-2). [Comparative Example 3] In a ratio of 50 parts of vinyltrimethoxy decane, decyltrimethoxydecane, and dimercaptodimethoxydecane as a monomer and a molar ratio of 丨: 4:5 Randomly condensed polyoxyalkylene resin (Mw: 3 〇, 〇〇〇, vinyl amount · '3.5 mmol / g), with 50 parts of trimethoxy decane, decyl tridecyl decane and - Polydecylane resin obtained by random condensation of mercapto dimethoxydecane as a monomer and molar ratio of "4.5": (8) 〇, S!-H basis amount: 3.5 mm 〇1 /g) In the mixture, 5 parts of a white ruthenyl vinyl fluorenyl complex as a curing catalyst was mixed, and a comparatively curable composition was obtained (ratio [Comparative Example 4] The compound containing ruthenium (8_1) obtained in the Example of 50 wounds was mixed with the polydimethyl siloxane (Mw: 2 〇, 〇〇〇) in which both of the wounds were vinyl groups. In the same manner, 5 parts of G GG was mixed as a hardening catalyst (tetra)-ethylglycine methyl complex, and a comparatively hardening composition was obtained (Comparative Example 5) obtained in Example 2 Compound containing Shi Xi B_ 1) and 130805.doc •32· 200911887 5 0 The two ends of the wound are mixed with _11-based polydioxanyl alkane (1^冒: 2〇, 〇〇〇), mixed 〇 〇〇 5 parts of platinum-carboxyvinyl methyl complex as a hardening catalyst' obtained a comparatively hardening composition (ratio-5). [Comparative Example 6] 90 parts of dichlorodifluorenyl group was mixed.矽 与 and 9 parts of dichlorodiphenyl decane, added dropwise to a mixture of 1 part of ion-exchanged water, 5 parts of toluene and 45 parts of 48% aqueous sodium hydroxide solution. Polymerization was carried out for 5 hours at C. The obtained reaction solution was washed with 500-injected ion-exchanged water, and then the formazan/gluten solution was dehydrated, and 2 parts of the mixture was added, and 20 parts of the mixture was further added thereto. The mercapto vinyl decane was stirred at 701 for 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off at 15 Torr under reduced pressure, followed by washing with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 7 ° C to obtain an acyclic polyoxane compound having an unsaturated bond (ratio than al-Ι). An acyclic polyoxane compound having an unsaturated bond (ratio than al-Ι) is dissolved in 2 parts of toluene, 3 parts of platinum catalyst is added, and ίο parts are used as a cyclic polymerization. i,3,5 7 tetramethylcyclotetraoxane of a oxoxane compound, which is allowed to react at 105 ° C for 2 hours. The solvent is distilled off under reduced pressure at 70 ° C, followed by 1 part of acetonitrile. After washing, the solvent was removed from the decompression chamber at 7crc to obtain a compound containing ruthenium (compared with A-1). As a result of GPC analysis, the molecular weight of the compound containing ruthenium (compared with A-1) was Mw = 22,000. On the other hand 'mix 90 parts of dichlorodimethyl decane with 1 part of dichlorodiphenyl decane' added to 1 part of ion-exchanged water, 5 parts of benzene and 450 parts of 48° /. In a mixture of aqueous sodium hydroxide solution, make it 1 〇5. Underarm polymerization 130805.doc -33- 200911887 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, and 2 parts of D was added, and 20 parts of decyl chlorodecane was further added thereto. (The mixture was stirred for 3 minutes at rc. Then, after washing with 100 parts of ion-exchanged water, the solvent was removed under reduced pressure at 15 °t&gt;c, followed by washing with 1 part of acetonitrile, followed by 7 (The solvent is distilled off under reduced pressure at rc to obtain a non-cyclic polyoxosiloxane compound (ratio. 1 part of the obtained acyclic polyoxy siloxane compound (than bl_1} is dissolved in 200 parts of toluene, 0.003 parts of platinum catalyst, and 1 part of US as a cyclic polysiloxane compound having an unsaturated bond, 'tetramethyl-1,3,5,7-tetravinylcyclotetraoxane The reaction was carried out for 1 hour. The reaction was carried out for 2 hours under reduced pressure. The solvent was evaporated under reduced pressure at 70 ° C, and then washed with 100 parts of acetonitrile. The compound (ratio &amp; 丨). The analysis result of GPC is that the molecular weight of the compound containing 石夕 (比丨) is Mw=22,000. a compound of ruthenium (compared to 丨 丨) and 5 parts of the above ruthenium-containing compound (compared to B-丨), mixed with 5 parts of platinum-carboxyvinyl group as a hardening catalyst The base complex was obtained as a hardening composition for comparison (ratio to 6). [Comparative Example 7] 75 parts of dioxane dimethyl decane and 24 parts of dichlorodiphenyl decane were mixed and added dropwise to 100 parts. A mixture of ion-exchanged water, 5 parts of hydrazine and 45 parts of a 48% aqueous sodium hydroxide solution was polymerized at 1 Torr for 5 hours. The reaction was obtained with 500 parts of ion-exchanged water. The solution was washed with water, and then the 5 Hz toluene solution was dehydrated, 2 parts of pyridine was added, and 130805.doc -34 - 200911887 20 parts of dimethylvinylchloromethane was further added thereto, and stirred at 7 (rc). Then, after washing with 1 part of ion-exchanged water, the solvent was distilled off under reduced pressure at 15 ° C, then washed with 100 parts of acetonitrile, and then distilled under reduced pressure at 7 (rc). a solvent to obtain an acyclic polyoxosiloxane compound having an unsaturated bond (ratio to al-2). An unsaturated cyclic acyclic polyoxane compound (ratio-2) is dissolved in 200 parts of toluene, 3 parts of platinum catalyst is added, and ίο parts are used as a cyclic polyoxyalkylene compound. Tetrakilyl was coated with tetraoxane and allowed to react under K105 〇c for 2 hours. After 7 Torr, the solvent was evaporated under reduced pressure and washed with 100 parts of acetonitrile. The compound containing ruthenium (specifically, A_2) was obtained. As a result of GPC analysis, the molecular weight of the compound containing ruthenium (compared with A-2) was Mw=22, 〇〇〇. On the other hand, 75 parts of dioxane was mixed. The decane was calcined with 24 parts of dioxane, and added dropwise to 100 parts of ion-exchanged water, 5 parts of toluene, and 45 〇 of 48/. In a mixture of aqueous sodium hydroxide solution, make it 1 . The obtained reaction solution was washed with water by submerging a 5-hour portion of ion-exchanged water, and then the toluene solution was dehydrated, and 2 parts of pyridine was added thereto, and 20 parts of dimethyl decane was further added thereto, at 7 Hey. Stir under the arm for 3 minutes. Then, after washing with 1 Torr of ion-exchanged water, the solvent was distilled off under reduced pressure. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure to obtain an acyclic polyoxo-oxygen compound (bi_2). 1 part of the obtained acyclic polydecane compound (than bl_2) was dissolved in 200 toluene toluene, 3 parts of platinum catalyst was added, and a portion as a ring having an unsaturated bond was added. The tetrahydrocarbazide compound is obtained by using tetramethyl-130805.doc-35-200911887 1,3,5,7-tetravinylcyclotetraoxane at a temperature of 1〇5. (: The reaction was carried out for 2 hours. After removing the solvent in a decompression chamber at 70 ° C, it was washed with 100 parts of acetonitrile. Thereafter, the solvent was removed at 70 ° C under reduced pressure to obtain a compound containing Shi Xi (b-2). The analysis result of GPC is that the molecular weight of the compound containing ruthenium (b-2) is Mw=22,000 °, and 50 parts of the above-mentioned compound containing ruthenium (compared with A_2) and 5 parts of the above-mentioned compound containing ruthenium (ratio B-2) In the mixture, 005 parts of a platinum-carboxyvinyl fluorenyl complex as a curing catalyst was mixed to obtain a curable composition for comparison (ratio-7). -12, Comparative Examples 8 to 12] The curable compositions obtained in the above-mentioned Examples 7 to 9 and the comparative curable compositions obtained in Comparative Examples 1 to 5 and Comparative Examples 1 to 5 were used. A film having a film thickness of about 1 mm was prepared in a ratio of _ 1) to (by -5), and was cured by heating at 150 ° C for 30 minutes to obtain cured materials No. 1 to 3 and a cured product ratio of 1 to 5. Further, the number of the curable composition to be used corresponds to the number of the cured product obtained, and the hardened state is evaluated in the following manner and the 180 degree bend is obtained in the following manner. The hardening state is judged to be a state of maneuverability based on the presence or absence of a feeling of adhesion of the cured film after a specific hardening time, and the fluidity is not evaluated but the degree of adhesion is evaluated as Δ~. The evaluation was ◎. In the 180-degree bending test, the cured film obtained by forming a film having a film thickness of about 1 mm on the name plate was observed to have a state of film bending at 18 。 degrees. The samples of cracking and peeling were evaluated as: 'When the f is folded at 180 °C, the crack is not broken and the sample is not peeled and the peeling is evaluated as △, 130805.doc -36· 200911887 will be bent at 90 degrees The crack-producing sample was evaluated as the results shown in Table 1. [Table 1] Hardened state of the cured product Example 10 Example 11 No. 1 No. 2 ΐδυ度臂曲曲为为例12 No. 3 _ ◎ δ ~~'~ + X --- Comparative Example 8 vs. 1 X Comparative Example 9 Comparative Example 10 1 tb2 Not evaluated X Comparative Example 11 Comparative Example 12 Ratio 4 to 5 ◎ 〇Δ ~ Δ~~' 〇•~~... As shown in Table 1, the hardened materials of Examples 10 to 12 and the cured products of Comparative Examples 9 to 12 were harder than the cured ones of 2 to 5; The degree of improvement was also improved, and the evaluation results of the 180-degree bending test were improved. Further, a sufficient solid cured product could not be obtained from the curable composition (ratio-1), thereby confirming that the composition of the present invention was employed The hardened state and the softness were improved. [Examples 13 to 15, Comparative Examples 13 and 14] The curable compositions obtained in the above Examples 7 to 9 were N.. and the above, Comparative Example 6, The hardening composition obtained in 7 (ratio _6) and (ratio _7) were respectively injected into a mold of 20 mm x 20 mm x 3 mm 'at 15 〇. The underarm was heated for 1 hr' to obtain a cured product No. 4 to 6 having a thickness of 3 mm and a ratio of 6 to 7. The photo-degradation test was carried out using a high-pressure mercury lamp for the hardened material, and the photo-deterioration test was carried out by irradiating the radiation of 9.96 W/cm at 365 nm for 2 hours. The transmittance at 400 nm before and after the photodegradation test is shown in Table 2. 130805.doc -37- 200911887 [Table 2] Hardenable composition cured product before irradiation transmittance After irradiation Example 13 No. 1 No. 4 92 92 Example 14 No. 2 No. 5 92 92 Example 15 No. 3 No. 6 92 92 Comparative Example 11 Ratio·6 Ratio 6 91 86 Comparative Example 12 Ratio-7 Ratio 7 90 80 As shown in Table 2, Example 1 3 to 15 cured products No. 4 to 6 and In Comparative Examples 11 and 12, the cured product was improved in comparison with the ratio of 6 to 6. From this, it was confirmed that Ra to Re is a cured product obtained by curing only a curable composition composed of an aliphatic group, and the light resistance is good. 130805.doc •38-

Claims (1)

200911887 十、申請專利範圍： 1. 一種含有矽之化合物，其係以下述通式所表 [化1]200911887 X. Patent application scope: 1. A compound containing ruthenium, which is represented by the following formula [Chemical Formula 1] (式中，Ra〜Rd為既可相同亦可不同之碳原子數為“(wherein, Ra to Rd are the same or different carbon atoms) 飽和脂肪㈣基；RL子數為丨〜以鮮脂肪族炉 基、或可以飽和脂肪族烴基取代之碳原子數為⑽之： 香族烴基，當存在複數個，該等Re既可相同亦可: 同；Y為碳原子數為2〜4之伸⑮基，z為氮原+或碳 數為2〜4之烯基或炔基，〖為2〜7之數，叫〜7之數，p Μ之數；Μ為使以通式⑴表示之含有石夕之化合物的質 量平均分子量為3000〜1〇〇萬之數）。 2. -種含切之化合物’其仙下㈣式⑺所表 [化2]Saturated fat (tetra) group; RL sub-number is 丨~ The number of carbon atoms substituted by fresh aliphatic furnace base or saturated aliphatic hydrocarbon group is (10): Fragrant hydrocarbon group, when there are plural, the Re can be the same : the same; Y is a 15 atomic group having a carbon number of 2 to 4, z is a nitrogen atom + or an alkenyl group or alkynyl group having a carbon number of 2 to 4, and is a number of 2 to 7, called a number of ~7, The number of p Μ is Μ, so that the mass average molecular weight of the compound containing the compound represented by the general formula (1) is 3,000 to 1,000,000. 2. - A compound containing cuts, which is represented by the formula (4) (7) ⑵ μ π% j不同之碳原子數為丨〜12之 ΓΓ族烴基；Re為碳原子數為1〜12之飽和脂卿 基、或可以飽和脂誠烴基取代之碳原子數為6〜12之^ 130805.doc 200911887 香族烴基，當存在複數個Re時，該等Re既可相同亦η 同；Υ為碳原子數為2〜4之伸烷基，ζ為氫原子或碳原不 數為2〜4之烯基或炔基，k為2〜7之數，ρ為之數/、子 使以通式（2)表示之含有矽之化合物的質量平均分子旦厂 3000〜1 〇〇萬之數）。 為 3. 如請求項1或2之含有矽之化合物，其中Re為碳原子數為 1〜12之飽和脂肪族烴基。 4. 如請求項1或2之含有矽之化合物，其中Ra〜Re全部為 5. 種硬化性組合物，其係含有（A 1)上述通式（1)中之z為 氫原子的如請求項i之含有矽之化合物、（B1)上述通式 (1) 中之Z為碳原子數為2〜4之烯基或块基的如請求項 含有矽之化合物、及（C)矽氫化反應觸媒而形成者。 6· 一種硬化性組合物’其係含有（A2)上述通式（2)中之z為 氫原子的如睛求項2之含有石夕之化合物、（b2)上述通式 (2) 中之Z為碳原子數為2〜4之烯基或炔基的如請求項2之 含有石夕之化合物、及（C)矽氫化反應觸媒者。 7.如請求項5之硬化性組合物，其中上述（A1)成分的含有矽 之化合物及上述（B1)成分的含有矽之化合物中任一者的 上述通式（1)中之Ra〜Re全部為曱基。 8 _如請求項6之硬化性組合物，其中上述（A2)成分的含有矽 之化合物及上述（B2)成分的含有石夕之化合物中任一者的 上述通式（2)中之Ra〜Re全部為甲基。 9. 一種硬化物，其係使如請求項5至8中任一項之硬化性組 合物硬化而形成者。 130805.doc 200911887 七、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：(2) a sulfonium group having a carbon number of 丨~12 different from μ π% j; a saturated aliphatic group having a carbon number of 1 to 12, or a carbon atom having a saturated aliphatic hydrocarbon group of 6 to 12; ^ 130805.doc 200911887 Aromatic hydrocarbon group, when there are multiple Re, the Re can be the same and η the same; Υ is an alkylene group having 2~4 carbon atoms, ζ is a hydrogen atom or the carbon is not 2 to 4 alkenyl or alkynyl group, k is a number of 2 to 7, and ρ is the number /, and the mass average molecular weight of the compound containing ruthenium represented by the general formula (2) is 3000 to 1 million. Number). 3. The compound containing hydrazine according to claim 1 or 2, wherein Re is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. 4. The compound containing hydrazine according to claim 1 or 2, wherein all of Ra to Re are 5. a sclerosing composition containing (A 1) wherein z in the above formula (1) is a hydrogen atom as claimed The compound containing ruthenium of item i, (B1) wherein Z in the above formula (1) is an alkenyl group or a block group having 2 to 4 carbon atoms, the compound containing ruthenium as claimed, and (C) hydrogenation reaction of ruthenium Formed by the catalyst. 6. A curable composition which contains (A2) a compound of the above formula (2) wherein z in the above formula (2) is a hydrogen atom, and (b2) in the above formula (2) Z is an alkenyl group or alkynyl group having 2 to 4 carbon atoms, and the compound containing the compound of claim 2, and (C) a hydrogenation reaction catalyst. 7. The sclerosing composition of claim 5, wherein the argon-containing compound of the component (A1) and the bismuth-containing compound of the component (B1) are Ra~Re in the above formula (1) All are sulfhydryl groups. The sclerosing composition of claim 6, wherein the arsenic-containing compound of the component (A2) and the arsenic-containing compound of the component (B2) are in the above formula (2) Re is all methyl. A cured product formed by hardening a curable composition according to any one of claims 5 to 8. 130805.doc 200911887 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 130805.doc130805.doc