TWI425028B - A compound containing silicon, a hardened composition and a hardened product - Google Patents

A compound containing silicon, a hardened composition and a hardened product Download PDF

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TWI425028B
TWI425028B TW097114897A TW97114897A TWI425028B TW I425028 B TWI425028 B TW I425028B TW 097114897 A TW097114897 A TW 097114897A TW 97114897 A TW97114897 A TW 97114897A TW I425028 B TWI425028 B TW I425028B
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hydrocarbon group
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TW200911886A (en
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Takashi Sueyoshi
Kenji Hara
Seiichi Saito
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Description

含有矽之化合物、硬化性組合物及硬化物a compound containing bismuth, a curable composition, and a cured product

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、及使該硬化性組合物硬化而成之硬化物。該含有矽之化合物係具有導入有環氧基之環矽氧烷結構的高分子化合物，藉由使用環氧硬化性化合物並使之硬化，可形成可用作密封材料、高電壓絕緣材料等之硬化物。The present invention relates to a novel cerium-containing compound having a specific structure, a curable composition containing the compound, and a cured product obtained by curing the curable composition. The ruthenium-containing compound is a polymer compound having a cyclopentane structure in which an epoxy group is introduced, and is cured by using an epoxy-curable compound to form a sealing material, a high-voltage insulating material, or the like. Hardened material.

對於將有機原材料及無機原材料組合而成之複合材料，業者一直在進行各種研究，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，故雖然可將一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。For composite materials that combine organic raw materials and inorganic raw materials, the industry has been conducting various researches. In the industry, the method of compounding inorganic fillers with organic polymers or modifying the surface of metal with organic polymers is also used. Coating method, etc. For these organic/inorganic composite materials, since the raw materials constituting the composite materials have a size of a micron or more, although some physical properties can be increased to a predetermined value or more, most other properties or physical properties are only expressed according to organic raw materials. And the value expected by the addition rule of the performance or physical properties of each of the inorganic raw materials.

另一方面，近年來，對以下有機/無機複合材料之研究較為盛行：有機原材料及無機原材料各原材料範疇(domain)之大小為奈米級，進而以分子等級(molecular level)組合而成之有機/無機複合材料。業者期望此類材料成為如下材料：不僅兼具各原材料之特性，而且兼具各原材料之優點，進而具有加成規則無法預料的與各原材料自身完全不同之新功能性。On the other hand, in recent years, research on the following organic/inorganic composite materials has become more prevalent: the size of each raw material domain of organic raw materials and inorganic raw materials is nanometer-scale, and then organically combined with molecular levels. /Inorganic composite materials. The industry expects such materials to be materials that not only combine the characteristics of each raw material, but also have the advantages of each raw material, and thus have new functions that are completely different from the raw materials themselves, which are unpredictable by the addition rules.

此種有機/無機複合材料中，存在一方之原材料及另一方之原材料以分子等級經由共價鍵而鍵結之化學鍵結型、以及以一方之原材料作為基質並使另一方之原材料細微地分散於此基質中並複合化的混合型。至於合成該等有機/無機複合材料中所使用之無機原材料的方法，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-凝膠法所獲得之無機原材料，有在短期間內膠化等保存穩定性差之問題。In such an organic/inorganic composite material, one of the raw materials and the other raw material are chemically bonded by a covalent bond at a molecular level, and one of the raw materials is used as a substrate, and the other raw material is finely dispersed. A hybrid type that is combined in this matrix. As a method of synthesizing the inorganic raw materials used in the organic/inorganic composite materials, a sol-gel method is used, which means that the hydrolysis by the precursor molecules and the subsequent polymerization are carried out. The condensation reaction, while obtaining a reaction of the crosslinked inorganic oxide at a low temperature. The inorganic raw material obtained by the sol-gel method has a problem of poor storage stability such as gelation in a short period of time.

非專利文獻1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烷基三烷氧基矽烷，對聚矽氧烷中之矽醇基進行封端；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。In Non-Patent Document 1, 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, and the polymerization in methyltrimethoxydecane. After condensation, a long-chain alkyltrialkoxydecane having a slow polycondensation rate is added to block the sterol group in the polyoxyalkylene; further, the polycondensation of methyltrimethoxydecane is carried out using an aluminum catalyst. In the reaction, acetamidine acetone is added at a specific molecular weight, and ligand exchange is carried out in the reaction system. However, these methods are not adequate for improving storage stability. Further, the inorganic raw material obtained by the sol-gel method has a problem of flexibility.

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(B)、及鉑系觸媒(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、在短時間內獲得具有充分之性能的硬化物。On the other hand, as 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, and having a crosslinked structure and having a fluorenyl group.矽 polymer (B), and platinum-based catalyst (D), and excellent in workability and hardenability, and the obtained cured product Excellent heat resistance. However, the curable composition containing bismuth has a problem that the hardening property is not necessarily sufficient, and a cured product having sufficient performance cannot be obtained at a low temperature in a short time.

又，專利文獻2中揭示有如下導入有環氧基之環氧聚矽氧樹脂組合物：其係藉由聚有機氫化矽氧烷與含有烯基之環氧化合物的加成反應而獲得，機械強度、耐濕性、耐熱性及作業性良好；但此處所揭示者並不提供具有充分之耐熱性及可撓性之硬化物。Further, Patent Document 2 discloses an epoxy polyoxyxene resin composition into which an epoxy group is introduced, which is obtained by an addition reaction of a polyorganohydrogen hydride and an epoxy group containing an alkenyl group, and a mechanical Strength, moisture resistance, heat resistance, and workability are good; however, those disclosed herein do not provide a cured product having sufficient heat resistance and flexibility.

[非專利文獻1]日本化學會雜誌，No.9，571(1998)[Non-Patent Document 1] Journal of the Chemical Society of Japan, No. 9, 571 (1998)

[專利文獻1]日本專利特開2005－325174號公報[專利文獻2]日本專利特開平5－287077號公報[Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-325174 (Patent Document 2) Japanese Patent Laid-Open No. Hei 5-287077

本發明之目的在於提供一種所獲得之硬化物的耐熱性及可撓性優異之硬化性組合物。An object of the present invention is to provide a curable composition which is excellent in heat resistance and flexibility of the obtained cured product.

本發明者等人為解決上述課題而進行研究，結果發現，於環矽氧烷結構中導入有環氧基的含有矽之化合物可解決上述課題，從而完成本發明。In order to solve the above problems, the inventors of the present invention have found that a compound containing ruthenium having an epoxy group introduced into a cyclopentane structure can solve the above problems, and the present invention has been completed.

亦即，本發明提供一種以下述通式(0)表示之含有矽之化合物： [化1] (式中，Ra ~Rg 既可相同亦可不同，其係碳原子數為1~12之飽和脂肪族烴基、或可以飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基；Y為碳原子數2~4之伸烷基，Z為以下述式(2)~(6)中任一者所表示之基，K為2~7之數，T為1~7之數，以T為重複數之聚合部分與以K-T為重複數之聚合部分既可為嵌段狀亦可為隨機狀；P為0~3之數；M及N為N：M=1：1~1：100、且所有M與所有N之合計值為15以上之數，且係使以通式(0)表示之含有矽之化合物的質量平均分子量為3000~100萬之數；又，以M為重複數之聚合部分與以N為重複數之聚合部分既可為嵌段狀亦可為隨機狀)。That is, the present invention provides a compound containing ruthenium represented by the following general formula (0): [Chemical Formula 1] (wherein R a to R g may be the same or different, and are a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group. Y is an alkylene group having 2 to 4 carbon atoms, Z is a group represented by any one of the following formulas (2) to (6), K is a number of 2 to 7, and T is a number of 1 to 7. The polymerization portion in which T is a repeating number and the polymerization portion in which KT is a repeating number may be either block-shaped or random; P is a number from 0 to 3; M and N are N: M = 1:1. 1:100, and the total value of all M and all N is 15 or more, and the mass average molecular weight of the compound containing oxime represented by the general formula (0) is 3,000 to 1,000,000; The polymerized portion which is a repeating number and the polymerized portion which has a repeating number of N may be either block-shaped or random.

(式中，Xa ~Xc 表示亞甲基可以氧原子及/或酯鍵取代的碳原子數為1~8之烷二基、-COO-或單鍵；Rh ~Rj 表示氫原子或甲基；r表示0或1)。 (wherein, X a to X c represents an alkanediyl group having 1 to 8 carbon atoms or a -COO- or a single bond in which a methylene group may be substituted with an oxygen atom and/or an ester bond; and R h to R j represents a hydrogen atom; Or methyl; r represents 0 or 1).

又，本發明提供一種硬化性組合物，其中，相對於100質量份之上述含有矽之化合物，含有0.01~20質量份之環氧硬化性化合物。Furthermore, the present invention provides a curable composition containing 0.01 to 20 parts by mass of an epoxy curable compound per 100 parts by mass of the above-mentioned compound containing ruthenium.

又，本發明提供一種硬化性組合物，其中，相對於100質量份之上述含有矽之化合物，含有0.01~30質量份之環氧硬化性化合物。Furthermore, the present invention provides a curable composition containing 0.01 to 30 parts by mass of an epoxy curable compound per 100 parts by mass of the above-mentioned compound containing ruthenium.

又，本發明提供一種硬化性組合物，其中，相對於100質量份之上述含有矽之化合物，含有0.01~30質量份之環 氧硬化性化合物及1~50質量份之環氧化合物。Furthermore, the present invention provides a curable composition containing 0.01 to 30 parts by mass of the above-mentioned compound containing ruthenium in an amount of 100 parts by mass. An oxygen curable compound and 1 to 50 parts by mass of an epoxy compound.

又，本發明提供一種使上述硬化性組合物硬化而形成之硬化物。Moreover, the present invention provides a cured product obtained by curing the curable composition.

根據本發明，可提供一種新穎的含有矽之化合物，該含有矽之化合物若與環氧硬化性化合物一併使用，則成為硬化性優異之硬化性組合物，可形成耐熱性及可撓性優異之硬化物。According to the present invention, it is possible to provide a novel cerium-containing compound which, when used together with an epoxy-curable compound, is a curable composition excellent in curability, and is excellent in heat resistance and flexibility. Hardened matter.

首先，對以上述通式(0)表示之本發明的含有矽之化合物加以說明。First, the compound containing ruthenium of the present invention represented by the above formula (0) will be described.

上述通式(0)中，作為以Ra ~Rg 表示之碳原子數為1~12之飽和脂肪族烴基，可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、己基、2－己基、3－己基、環己基、1－甲基環己基、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、癸基、十二烷基等。In the above formula (0), the saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R a to R g may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. Dibutyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2- Heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, decyl, dodecyl Wait.

又，以Ra ~Rg 表示之可由飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基，係亦包括取代基即飽和脂肪族烴基的整體之碳原子數為6~12者。作為取代基即飽和脂肪族 烴基，例如，可採用上述所例示之飽和脂肪族烴基中可滿足上述碳原子數者。因此，作為以Ra ~Rg 表示之可由飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基，可列舉：苯基、萘基、2－甲基苯基、3－甲基苯基、4－甲基苯基、3－異丙基苯基、4－異丙基苯基、4－丁基苯基、4－異丁基苯基、4－第三丁基苯基、4－己基苯基、4－環己基苯基、2,3－二甲基苯基、2,4－二甲基苯基、2,5－二甲基苯基、2,6－二甲基苯基、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。Further, the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group, which is represented by R a to R g , also includes a substituent, that is, a saturated aliphatic hydrocarbon group, and the total number of carbon atoms is 6 to 12 . As the substituent, that is, the saturated aliphatic hydrocarbon group, for example, those having a carbon atom number satisfying the above-described saturated aliphatic hydrocarbon group can be used. Therefore, examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group represented by R a to R g include a phenyl group, a naphthyl group, a 2-methylphenyl group, and a 3-methyl group. Phenyl, 4-methylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethyl Phenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, and the like.

又，作為以Y表示之碳原子數為2~4之伸烷基，可列舉－CH2 CH2 －、－CH2 CH2 CH2 －、－CH2 CH2 CH2 CH2 －、－CH(CH3 )CH2 －、－CH2 CH(CH3 )－等。Further, examples of the alkylene group having 2 to 4 carbon atoms represented by Y include -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH. (CH 3 )CH 2 -, -CH 2 CH(CH 3 )-, and the like.

上述通式(0)中之Z為以上述式(2)~(6)中任一者所表示之含有環氧基的基。上述式(2)、(4)、(5)中之Xa ~Xc 為亞甲基可由氧原子及/或酯鍵取代的碳原子數為1~8之烷二基、－COO－或單鍵。作為該烷二基，例如可列舉－CH2 －、－CH2 CH2 －、－CH2 CH2 CH2 －、－CH2 CH2 CH2 CH2 －、－CH(CH3 )CH2 －、－CH2 CH(CH3 )－，作為亞甲基由氧原子所取代者、亞甲基由酯鍵所取代者、亞甲基由氧及酯鍵所取代者，例如可列舉下述[化3]所示者。Z in the above formula (0) is an epoxy group-containing group represented by any one of the above formulas (2) to (6). X a to X c in the above formulas (2), (4), and (5) are alkanediyl groups having 1 to 8 carbon atoms which may be substituted by an oxygen atom and/or an ester bond, -COO- or single bond. Examples of the alkanediyl group include -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 - And -CH 2 CH(CH 3 )-, wherein the methylene group is substituted by an oxygen atom, the methylene group is substituted by an ester bond, and the methylene group is replaced by an oxygen or an ester bond, for example, the following [ 3].

以上述通式(0)表示之本發明的含有矽之化合物的較好形態為以下述通式(1)表示之含有矽之化合物。以下述通式(1)表示之含有矽之化合物，係以上述通式(0)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(1)表示之含有矽之化合物，或複數種以上述通式(0)表示之含有矽之化合物的混合物，其係將以下述通式(1)表示之含有矽之化合物作為主成分者。例如，即便使用多官能之以(Ra SiHO)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(0)之K-T為大於1之數的化合物之生成量亦極少。其原因在於，非環狀之聚矽氧烷經由Y而與環聚矽氧烷的2個以上之Si-H鍵結而成的化合物之生成在能量方面非常不利。A preferred embodiment of the ruthenium-containing compound of the present invention represented by the above formula (0) is a compound containing ruthenium represented by the following formula (1). The compound containing ruthenium represented by the following formula (1) is T=K in the compound containing ruthenium represented by the above formula (0). The compound obtained by the usual synthesis method is a compound containing ruthenium represented by the following formula (1), or a mixture of a plurality of compounds containing ruthenium represented by the above formula (0), which will have the following formula (1) A compound containing ruthenium as a main component. For example, even when a polyfunctional polycyclopentadiene represented by (R a SiHO) K is used as a compound introduced into a cyclic polyoxyalkylene ring, the KT of the above formula (0) is a compound having a number greater than 1 The amount is also very small. The reason for this is that the formation of a compound in which an acyclic polyoxyalkylene is bonded to two or more Si-H groups of a cyclopolyoxyalkylene via Y is extremely disadvantageous in terms of energy.

(式中，Ra ~Rg 既可相同亦可不同，係碳原子數為1~12之飽和脂肪族烴基、或可由飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基，Y為碳原子數為2~4之伸烷基，Z為與上述通式(0)相同之基，k為2~7之數，p為1~4之數。m及n為n：m=1：1~1：100且m+n≧15之數，且係使以通式(1)表示之含有矽之化合物的質量平均分子量為3000~100萬之 數。又，以m為重複數之聚合部分與以n為重複數之聚合部分既可為嵌段狀亦可為隨機狀)。 (wherein R a to R g may be the same or different, and are a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group, Y is an alkylene group having 2 to 4 carbon atoms, Z is the same group as the above formula (0), k is a number from 2 to 7, and p is a number from 1 to 4. m and n are n: m = 1:1 to 1:100 and m + n ≧ 15 , and the mass average molecular weight of the compound containing hydrazine represented by the general formula (1) is 3,000 to 1,000,000. Further, repeating with m The polymerized portion of the number and the polymerized portion having a repeating number of n may be either block-shaped or random.

作為上述通式(0)或通式(1)中之Z，最好的是下述結構，其原因在於，製造含有矽之化合物時之操作性、含有矽之化合物及後述硬化性組合物之保存穩定性、以及硬化物之熱性、電氣特性、硬化性及力學特性良好。The Z in the above formula (0) or (1) is preferably the following structure because of the workability in the production of a compound containing ruthenium, the compound containing ruthenium, and the sclerosing composition described later. The storage stability and the heat, electrical properties, hardenability and mechanical properties of the cured product are good.

本發明之含有矽之化合物中，Ra ~Rg 中，若增大飽和脂肪族烴基之比例，則所獲得之硬化物之可撓性提高，若增大芳香族烴基之比例，則所獲得之硬化物之耐熱性及硬度提高。飽和脂肪族烴基與芳香族烴基之比例可根據硬化物所需求之物性而任意設定。本發明之含有矽之化合物中，Re 及Rf 為可由飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基的含有矽之化合物，由於可容易地控制飽和脂肪族烴基與芳香族烴基之比例，故較好。In the ruthenium-containing compound of the present invention, when the ratio of the saturated aliphatic hydrocarbon group is increased in R a to R g , the flexibility of the obtained cured product is increased, and if the ratio of the aromatic hydrocarbon group is increased, the obtained is obtained. The heat resistance and hardness of the cured product are improved. The ratio of the saturated aliphatic hydrocarbon group to the aromatic hydrocarbon group can be arbitrarily set depending on the physical properties required for the cured product. In the ruthenium-containing compound of the present invention, R e and R f are a ruthenium-containing compound having an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group, since the saturated aliphatic hydrocarbon group and the aromatic group can be easily controlled. The proportion of the hydrocarbon group is preferred.

本發明之含有矽之化合物的以Ra ~Rg 表示之基中，碳原子數為1~12之飽和脂肪族烴基與可由飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基的較好比例(數)為，前者：後者為100：1~1：2，更好的是20：1~1：1。又，作為碳原子數為1~12之飽和脂肪族烴基，較好的是甲基，其原因在於耐熱性良好，作為可由飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基，較好的是苯基，其原因在於 耐熱性良好。In the group represented by R a to R g of the ruthenium-containing compound of the present invention, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group The better ratio (number) is, the former: the latter is 100:1~1:2, and the better is 20:1~1:1. Further, the saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferably a methyl group because of its excellent heat resistance, and is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group. A phenyl group is preferred because of its good heat resistance.

上述通式(1)中之k為2~7。若可大於7，則官能基數過多，無法獲得所得硬化物所需之可撓性。k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。In the above formula (1), k is 2 to 7. If it 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 k is 2 to 5, it is industrially easy to obtain a raw material, and the number of functional groups is appropriate. Therefore, it is preferable that k is 3.

本發明之含有矽之化合物的質量平均分子量為3000~100萬。若質量平均分子量小於3000，則所獲得之硬化物之耐熱性不充分，若質量平均分子量大於100萬則黏度會變大，而妨礙操作。質量平均分子量較好的是5000~50萬，更好的是1萬~10萬。The ruthenium-containing compound of the present invention has a mass average molecular weight of 3,000 to 1,000,000. If the mass average molecular weight is less than 3,000, the heat resistance of the obtained cured product is insufficient, and if the mass average molecular weight is more than 1,000,000, the viscosity becomes large and the operation is hindered. The average mass molecular weight is preferably 5,000 to 500,000, more preferably 10,000 to 100,000.

本發明之含有矽之化合物視其製造方法而不同，並無特別限制，可應用眾所周知之反應來製造。以下製造方法係將本發明的含有矽之化合物中以上述通式(1)表示者作為代表而進行說明。The ruthenium-containing compound of the present invention is not particularly limited as long as it is produced by a known method, and can be produced by a known reaction. In the following production method, the oxime-containing compound of the present invention is represented by the above formula (1).

含有矽之化合物例如可由如下方式而獲得：將具有不飽和鍵之環狀聚矽氧烷化合物(a1)作為前驅物，使其與環狀聚矽氧烷化合物(a2)反應而獲得聚矽氧烷中間體(a3)，使導入Z基之環氧化合物(a4)與該聚矽氧烷中間體(a3)反應而獲得；或者使導入Z基之環氧化合物(a4)與環狀聚矽氧烷化合物(a2)反應而獲得含有環氧基之環狀聚矽氧烷化合物(a5)，再使具有不飽和鍵之非環狀聚矽氧烷化合物(a1)與該含有環氧基之環狀聚矽氧烷化合物(a5)反應而獲得。考慮到製造上之作業性，較好的是前者之經由聚矽氧烷中間體(a3)的方法。The ruthenium-containing compound can be obtained, for example, by using a cyclic polyoxy siloxane compound (a1) having an unsaturated bond as a precursor to react with a cyclic polyaluminoxane compound (a2) to obtain a polyfluorene oxide. An alkane intermediate (a3) obtained by reacting an epoxy compound (a4) introduced into a Z group with the polyoxyalkylene intermediate (a3); or an epoxy compound (a4) introduced into a Z group and a cyclic polyfluorene The oxane compound (a2) is reacted to obtain an epoxy group-containing cyclic polyoxy siloxane compound (a5), and an acyclic polysiloxane compound (a1) having an unsaturated bond and the epoxy group-containing compound are obtained. The cyclic polyoxyalkylene compound (a5) is obtained by a reaction. In view of the workability in manufacturing, the former method of passing the polyoxyalkylene intermediate (a3) is preferred.

上述具有不飽和鍵之非環狀聚矽氧烷化合物(a1)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p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，可於縮合反應之後與具有不飽和基之單官能矽烷化合物反應而獲得。作為該等矽烷化合物之官能基，代表性者為烷氧基、鹵基或羥基。具有不飽和鍵之非環狀聚矽氧烷化合物(a1)與環狀聚矽氧烷化合物(a2)係藉由(a1)之不飽和鍵結碳與(a2)之Si－H基的反應而鍵結。The acyclic polyoxy siloxane compound (a1) 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 p 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 p is 4, and further reacted with a monofunctional decane compound having an unsaturated group. When p is 2, it can be obtained by reacting with a monofunctional decane compound having an unsaturated group after the condensation reaction. The functional group of the decane compound is typically an alkoxy group, a halogen group or a hydroxyl group. The acyclic polyoxy siloxane compound (a1) having an unsaturated bond and the cyclic polyoxy siloxane compound (a2) are reacted with the unsaturated bonded carbon of (a1) and the Si-H group of (a2) And the key knot.

作為上述具有不飽和鍵之非環狀聚矽氧烷化合物(a1)的製造中所使用之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、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、甲基苯基二甲氧基矽烷、甲基苯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1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之單矽烷化合物；由2個以上之該等單矽烷化合物縮合而成之二矽氧烷化合物及低聚矽氧烷化合物。Examples of the above-mentioned difunctional decane compound used in the production of the above-mentioned acyclic polysiloxane compound (a1) having an unsaturated bond include dimethyldimethoxydecane and dimethyldiethoxylate. a dialkoxy monodecane compound such as decane, diphenyldimethoxydecane, diphenyldiethoxydecane, methylphenyldimethoxydecane or methylphenyldiethoxydecane; One or two alkoxy groups of the above dialkoxymonodecane compounds are substituted with a halogen atom or a hydroxyl group of a monodecane compound selected from the group consisting of fluorine, chlorine, bromine and iodine; A dioxane compound and an oligomeric alkoxylate compound obtained by condensing a monodecane compound.

作為上述單官能單矽烷化合物，例如可列舉：三甲基乙氧基矽烷、三甲基甲氧基矽烷、三苯基乙氧基矽烷、三苯基甲氧基矽烷、甲基二苯基乙氧基矽烷、二甲基苯基乙氧基矽烷等單烷氧基矽烷化合物；將該等單烷氧基矽烷化合 物之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之單矽烷化合物。Examples of the monofunctional monodecane compound include trimethylethoxydecane, trimethylmethoxydecane, triphenylethoxydecane, triphenylmethoxydecane, and methyldiphenylethyl. a monoalkoxydecane compound such as oxydecane or dimethylphenylethoxysilane; the monoalkoxydecane compound The alkoxy group of the substance is a monodecane compound selected from a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

作為上述三官能單矽烷化合物，例如可列舉：三乙氧基甲基矽烷、三甲氧基甲基矽烷，三乙氧基苯基矽烷、三甲氧基苯基矽烷等三烷氧基矽烷化合物；將該等三烷氧基矽烷化合物之1~3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之單矽烷化合物。Examples of the trifunctional monodecane compound include a trialkoxy decane compound such as triethoxymethyl decane, trimethoxymethyl decane, triethoxyphenyl decane or trimethoxyphenyl decane; The 1-3 alkoxy group of the trialkoxy decane compound is substituted with a halogen atom or a hydroxy group monodecane compound selected from the group consisting of fluorine, chlorine, bromine and iodine.

作為上述四官能單矽烷化合物，例如可列舉：四乙氧基矽烷、四甲氧基矽烷等四烷氧基矽烷化合物；將該等四烷氧基矽烷化合物之1~4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之單矽烷化合物。Examples of the tetrafunctional monodecane compound include a tetraalkoxydecane compound such as tetraethoxysilane or tetramethoxydecane; and 1 to 4 alkoxy groups of the above tetraalkoxydecane compound are substituted with A halogen atom or a monodecane compound of a hydroxyl group in a group consisting of fluorine, chlorine, bromine and iodine is selected.

作為上述具有不飽和基之單官能矽烷化合物，可列舉：二甲基乙烯基氯矽烷、二甲基乙烯基甲氧基矽烷、二甲基乙烯基乙氧基矽烷、二苯基乙烯基氯矽烷、二苯基乙烯基乙氧基矽烷、二苯基乙烯基甲氧基矽烷、甲基苯基乙烯基氯矽烷、甲基苯基乙氧基矽烷、甲基苯基甲氧基矽烷等。Examples of the monofunctional decane compound having an unsaturated group include dimethyl vinyl chlorodecane, dimethyl vinyl methoxy decane, dimethyl vinyl ethoxy decane, and diphenyl vinyl chloro decane. , diphenylvinylethoxy decane, diphenylvinyl methoxy decane, methyl phenyl vinyl chloro decane, methyl phenyl ethoxy decane, methyl phenyl methoxy decane, and the like.

作為上述環狀聚矽氧烷化合物(a2)，可列舉：1,3,5－三甲基環三矽氧烷、1,3,5,7－四甲基環四矽氧烷、1,3,5,7,9－五甲基環五矽氧烷、1,3,5,7,9,11－六甲基環六矽氧烷、1,3,5,7,9,11,13－七甲基環七矽氧烷、1,3,5,7,9,11,13,15－八甲基環八矽氧烷、1,3,5－三乙基環三矽氧烷、1,3,5,7－四乙基環四矽氧烷、1,3,5,7,9－五乙基環五矽氧烷、1,3,5,7,9,11－六乙基環六矽氧烷、1,3,5－三苯基環三矽氧烷、1,3,5,7－四苯基環四矽氧烷、1,3,5,7,9－五苯基環五矽 氧烷、1,3,5,7,9,11－六苯基環六矽氧烷等。The cyclic polyaluminoxane compound (a2) may, for example, be 1,3,5-trimethylcyclotrioxane or 1,3,5,7-tetramethylcyclotetraoxane or 1, 3,5,7,9-pentamethylcyclopentaoxane, 1,3,5,7,9,11-hexamethylcyclohexaoxane, 1,3,5,7,9,11, 13-heptamethylcyclopentaoxane, 1,3,5,7,9,11,13,15-octamethylcyclooctadecane, 1,3,5-triethylcyclotrioxane 1,3,5,7-tetraethylcyclotetraoxane, 1,3,5,7,9-pentaethylcyclopentaoxane, 1,3,5,7,9,11-six Ethylcyclohexaoxane, 1,3,5-triphenylcyclotrioxane, 1,3,5,7-tetraphenylcyclotetraoxane, 1,3,5,7,9- Pentaphenyl ring Oxytomane, 1,3,5,7,9,11-hexaphenylcyclohexaoxane, and the like.

作為導入Z基之上述環氧化合物(a4)，例如可列舉：具有與上述聚矽氧烷中間體(a3)或上述環狀聚矽氧烷(a2)中之環狀聚矽氧烷結構中的Si－H基反應之不飽和鍵結基的環氧化合物，具體例可列舉以下所示之化合物。The epoxy compound (a4) which is introduced into the Z group may, for example, be in the form of a cyclic polysiloxane having the polyoxoxane intermediate (a3) or the above cyclic polyoxane (a2). Specific examples of the epoxy compound of the Si-H group-based unsaturated bond group include the compounds shown below.

用以獲得含有矽之化合物的前驅物即具有不飽和鍵之非環狀聚矽氧烷化合物(a1)的利用水解所進行之縮合反應，可藉由所謂之溶膠－凝膠反應來進行。二官能矽烷化合物之水解－縮合反應可藉由如下方式而進行：烷氧基或鹵基藉由水進行水解而生成矽醇基(Si－OH基)，該所生成之矽醇基彼此、矽醇基與烷氧基、或矽醇基與鹵基進行縮合。為使該水解反應迅速進行，較好的是加入適量之水，亦可加入觸媒。又，該縮合反應亦藉由空氧中之水分、或水以外之溶劑中所含的微量水而進行。該反應中亦可使用溶 劑，溶劑並無特別限定，具體而言，例如可列舉：水，或甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、丙酮、甲基乙基酮、二噁烷、四氫呋喃等親水性有機溶劑，該等溶劑可使用1種或混合使用2種以上。The condensation reaction by hydrolysis to obtain a precursor containing a ruthenium compound, that is, a non-cyclic polyoxy siloxane compound (a1) having an unsaturated bond, can be carried out by a so-called sol-gel reaction. The hydrolysis-condensation reaction of the difunctional decane compound can be carried out by hydrolyzing an alkoxy group or a halogen group to form a decyl group (Si-OH group), and the resulting sterol groups are each other, 矽The alcohol group is condensed with an alkoxy group or a decyl group and a halogen group. In order to allow the hydrolysis reaction to proceed rapidly, it is preferred to add an appropriate amount of water or to add a catalyst. Further, the condensation reaction is also carried out by moisture in the oxygen or a trace amount of water contained in a solvent other than water. Solvent can also be used in this reaction The solvent and the solvent are not particularly limited, and specific examples thereof include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, and dioxane. A hydrophilic organic solvent such as tetrahydrofuran may be used alone or in combination of two or more.

又，作為上述觸媒，可使用酸或鹼，具體而言，例如可列舉：鹽酸、磷酸、硫酸等無機酸類；乙酸、對甲苯磺酸、磷酸單異丙酯等有機酸類；氫氧化鈉、氫氧化鉀、氫氧化鋰、氨等無機鹼類；三甲胺、三乙胺、單乙醇胺、二乙醇胺等胺化合物(有機鹼)類；鈦酸四異丙酯、鈦酸四丁酯等鈦化合物類；月桂酸二丁基錫、辛基錫酸等錫化合物類；三氟化硼等硼化合物類；三乙醯丙酮鋁等鋁化合物類；鐵、鈷、錳、鋅等金屬之氯化物，以及該等金屬之環烷酸鹽及辛酸鹽等金屬羧酸鹽類等，該等觸媒可使用1種或併用2種以上。又，由2種以上之二官能矽烷化合物進行水解－縮合反應時，亦可分別單獨進行某種程度之水解後將兩者混合而進一步進行水解縮合反應，亦可將該等所有二官能矽烷化合物混合而一起進行水解－縮合反應。Further, as the catalyst, an acid or a base can be used, and specific examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid; organic acids such as acetic acid, p-toluenesulfonic acid, and monoisopropyl phosphate; and sodium hydroxide; An inorganic base such as potassium hydroxide, lithium hydroxide or ammonia; an amine compound (organic base) such as trimethylamine, triethylamine, monoethanolamine or diethanolamine; a titanium compound such as tetraisopropyl titanate or tetrabutyl titanate; a tin compound such as dibutyltin laurate or octylstannic acid; a boron compound such as boron trifluoride; an aluminum compound such as aluminum triacetate; a chloride of a metal such as iron, cobalt, manganese or zinc; For the metal carboxylate such as a metal naphthenate or an octanoate, the catalyst may be used alone or in combination of two or more. Further, when the hydrolysis-condensation reaction is carried out by using two or more kinds of difunctional decane compounds, the hydrolysis may be carried out by separately hydrolyzing to some extent, and then the two may be further hydrolyzed and condensed, or all of the difunctional decane compounds may be used. The hydrolysis-condensation reaction is carried out together by mixing.

如上所述，前驅物即具有不飽和鍵之非環狀聚矽氧烷化合物(a1)可藉由如下方式而獲得：進行上述水解－縮合反應之後，當p為1時進一步與單官能單矽烷化合物反應，當p為3時進一步與三官能單矽烷化合物反應，當p為4時進一步與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單官能矽烷化合物反應而獲得。As described above, the precursor, that is, the acyclic polyoxy siloxane compound (a1) having an unsaturated bond can be obtained by further performing a hydrolysis-condensation reaction after the above-mentioned hydrolysis-condensation reaction, and further reacting with a monofunctional monodecane when p is 1. The compound reaction is further reacted with a trifunctional monodecane compound when p is 3, further reacted with a tetrafunctional monodecane compound when p is 4, and then reacted with a monofunctional decane compound having an unsaturated group; when p is 2 It can be obtained by reacting with a monofunctional decane compound having an unsaturated group.

前驅物即具有不飽和鍵之非環狀聚矽氧烷化合物(a1)與環狀聚矽氧烷化合物(a2)的反應中，可使用利用矽氫化反應之方法。例如，聚矽氧烷中間體(a3)可藉由如下方式而獲得：混合非環狀聚矽氧烷化合物(a1)與環狀聚矽氧烷化合物(a2)，添加任意量之矽氫化反應觸媒後進行加熱。又，導入Z基之環氧化合物(a4)與環狀聚矽氧烷結構中之Si－H基的反應，亦同樣可使用矽氫化反應。In the reaction of the precursor, that is, the acyclic polyoxy siloxane compound (a1) having an unsaturated bond with the cyclic polyoxy siloxane compound (a2), a method using a hydrazine hydrogenation reaction can be used. For example, the polyoxyalkylene intermediate (a3) can be obtained by mixing a non-cyclic polyoxyalkylene compound (a1) with a cyclic polyoxyalkylene compound (a2), and adding any amount of hydrazine hydrogenation reaction. Heating after the catalyst. Further, a reaction of introducing a Z-based epoxy compound (a4) with a Si-H group in a cyclic polyoxyalkylene structure can also be carried out by a hydrogenation reaction.

作為上述矽氫化反應觸媒，例如可列舉：含有選自由鉑、鈀及銠所組成之群中的一種以上金屬之眾所周知之觸媒。例如，作為鉑系觸媒，可列舉鉑－羧基乙烯基甲基錯合物、鉑－二乙烯基四甲基二矽氧烷錯合物、鉑－環乙烯基甲基矽氧烷錯合物、鉑－辛基醛錯合物等鉑系觸媒。作為鈀系觸媒及銠系觸媒，例如可列舉：在該鉑系觸媒中代替鉑而含有同為鉑系金屬的鈀或銠之化合物。該等矽氫化反應觸媒既可使用一種，亦可併用兩種以上。尤其是就硬化性之觀點而言，較好的是含有鉑者，具體而言，較好的是鉑－羧基乙烯基甲基錯合物。又，三(三苯基膦)氯化銠(I)等含有上述鉑系金屬的所謂之Wilkinson觸媒，亦包含在上述矽氫化反應觸媒中。該等矽氫化反應觸媒之使用量較好的是反應物總量之5質量%以下，更好的是0.0001~1.0質量%。The above-mentioned hydrogenation-reactive catalyst may, for example, be a well-known catalyst containing one or more metals selected from the group consisting of platinum, palladium and rhodium. For example, examples of the platinum-based catalyst include platinum-carboxyvinylmethyl complex, platinum-divinyltetramethyldioxane complex, and platinum-cyclovinylmethyloxane complex. A platinum-based catalyst such as a platinum-octyl aldehyde complex. Examples of the palladium-based catalyst and the ruthenium-based catalyst include a compound of palladium or rhodium which is a platinum-based metal in place of platinum in the platinum-based catalyst. These hydrogenation catalysts may be used alone or in combination of two or more. In particular, from the viewpoint of hardenability, it is preferred to contain platinum, and specifically, a platinum-carboxyvinylmethyl complex is preferred. Further, a so-called Wilkinson catalyst containing the above platinum-based metal such as tris(triphenylphosphine)iridium chloride (I) is also contained in the above-mentioned hydrogenation-reactive catalyst. The amount of the rhodium hydrogenation catalyst to be used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass based on the total amount of the reactants.

本發明之含有矽之化合物除如下所述可用作硬化性組合物之主成分以外，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、塑膠改質劑等用途中。The ruthenium-containing compound of the present invention can be used as a main component of the curable composition as described below, and can be used in a resin, a plastic modifier or the like in combination with other polymer compounds or polymer compositions.

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(0)或(1)中之非環狀矽氧烷鏈中，可導入硼、鎂、鋁、磷、鈦、鋯、鉿、鐵、鋅、鈮、鉭、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而進行水解－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。Further, in addition to the range of the ruthenium-containing compound of the present invention, boron, magnesium, aluminum, phosphorus, and titanium may be introduced into the acyclic siloxane chain in the above formula (0) or (1). Other than zirconium, hafnium, iron, zinc, antimony, bismuth, tin, antimony and the like. As a method, for example, a hydrolysis-condensation reaction is carried out by supplying a derivative of these other elements, 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.

其次，對本發明之硬化性組合物加以說明。Next, the curable composition of the present invention will be described.

本發明之硬化性組合物係含有上述含有矽之化合物及環氧硬化性化合物而形成者。本發明之硬化性組合物中，當僅含有上述含有矽之化合物作為含有環氧基之成分時，環氧硬化性化合物之含量較好的是，相對於100質量份之含有矽之化合物為0.01~20質量份。又，當含有含有矽之化合物及後述環氧化合物作為含有環氧基之成分時，環氧硬化性化合物之含量較好的是，相對於兩者之總質量100質量份為0.01~20質量份。若環氧硬化性化合物之含量少於0.01質量份，則可能無法充分地硬化，若環氧硬化性化合物之使用量超過20質量份，則可能會影響所獲得之硬化物之耐熱性。The curable composition of the present invention comprises the above-mentioned compound containing ruthenium and an epoxy curable compound. In the curable composition of the present invention, when the compound containing ruthenium is contained as the component containing an epoxy group, the content of the epoxy-curable compound is preferably 0.01 with respect to 100 parts by mass of the compound containing ruthenium. ~20 parts by mass. In addition, when a compound containing ruthenium and an epoxy compound to be described later are contained as a component containing an epoxy group, the content of the epoxy-curable compound is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the total mass of the two. . When the content of the epoxy curable compound is less than 0.01 parts by mass, the curing may not be sufficiently cured. If the epoxy curable compound is used in an amount exceeding 20 parts by mass, the heat resistance of the obtained cured product may be affected.

上述環氧硬化性化合物可為眾所周知之通常的環氧硬化劑，可較好地使用藉由熱、能量線等之作用而使環氧樹脂硬化者。作為環氧硬化性化合物，可使用酚系硬化劑、胺系硬化劑、醯胺系硬化劑、醯亞胺系硬化劑、咪唑錯合物系硬化劑、酸酐系硬化劑、有機鎓鹽系硬化劑、茂金屬系 硬化劑、芳茂鐵系硬化劑等，亦可使用市售之環氧硬化劑或陽離子聚合起始劑。The epoxy curable compound may be a conventionally known epoxy curing agent, and those which cure the epoxy resin by the action of heat, energy rays or the like can be preferably used. As the epoxy-curable compound, a phenol-based curing agent, an amine-based curing agent, a guanamine-based curing agent, a quinone-based curing agent, an imidazole-based curing agent, an acid anhydride-based curing agent, or an organic cerium-based hardening can be used. Agent, metallocene system As the hardener, the ferrocene-based hardener, or the like, a commercially available epoxy hardener or a cationic polymerization initiator may be used.

該等之中，較好的是胺系硬化劑、有機鎓鹽系硬化劑，其原因在於，與上述含有矽之化合物之相容性良好。Among these, an amine-based curing agent and an organic onium salt-based curing agent are preferred because of good compatibility with the above-mentioned compound containing ruthenium.

作為上述胺系硬化劑，可列舉：二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、二乙基胺基丙基胺、N－胺基乙基哌嗪、間苯二胺、聚(氧丙烯)二胺、p,p'－二胺基二苯基甲烷、p,p'－二胺基二苯基碸、p,p'－二胺基二苯醚、苯胺－BF3 、對甲苯胺－BF3 、鄰甲苯胺－BF3 、二甲基苯胺－BF3 、N－甲基苯胺－BF3 、N－乙基苯胺－BF3 、N,N'－二甲基苯胺－BF3 、N,N'－二乙基苯胺－BF3 、乙胺－BF3 、正丁胺－BF3 、哌啶－BF3 、二苯基胺－BF3 、鄰二甲基胺基甲基苯酚、2,4,6－三(二甲基胺基甲基)苯酚、三乙醇胺－硼酸鹽等。Examples of the amine-based curing agent include di-ethyltriamine, tri-ethylidenetetraamine, tetraethylidenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, and Phenylenediamine, poly(oxypropylene)diamine, p,p'-diaminodiphenylmethane, p,p'-diaminodiphenylanthracene, p,p'-diaminodiphenyl ether, Aniline-BF 3 , p-toluidine-BF 3 , o-toluidine-BF 3 , dimethylaniline-BF 3 , N-methylaniline-BF 3 , N-ethylaniline-BF 3 , N,N'- Dimethylaniline-BF 3 , N,N'-diethylaniline-BF 3 , ethylamine-BF 3 , n-butylamine-BF 3 , piperidine-BF 3 , diphenylamine-BF 3 , ortho Methylaminomethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, triethanolamine-borate, and the like.

作為上述有機鎓鹽系硬化劑，可列舉重氮鎓鹽、錪鹽、鋶鹽等，該等既可為利用熱進行陽離子聚合而硬化者，亦可為利用光等能量線照射而硬化者。一般而言，前者係使用脂肪族鎓鹽，後者係使用芳香族鎓鹽。有機鎓鹽系硬化劑能以較少之使用量獲得良好之硬化，因此主要在利用能量線照射進行硬化時較有用，作為本發明中所使用者，較好的是芳香族錪鹽、芳香族鋶鹽，其原因在於與含有矽之化合物的相容性較好。Examples of the organic onium salt-based curing agent include a diazonium salt, a phosphonium salt, and a phosphonium salt. These may be cured by cationic polymerization by heat, or may be cured by irradiation with energy rays such as light. In general, the former uses an aliphatic sulfonium salt and the latter uses an aromatic sulfonium salt. The organic onium salt-based hardener can obtain good hardening in a small amount of use, and therefore is mainly useful in hardening by energy ray irradiation. As a user of the present invention, an aromatic sulfonium salt or an aromatic is preferred. The cerium salt is preferred because it has good compatibility with the compound containing cerium.

作為上述芳香族錪鹽，可列舉：4－異丙氧基－4'－甲基二苯基錪四(五氟苯基)硼酸鹽、4－異丙氧基－4'－甲基二苯基錪六氟磷酸鹽、4－異丙氧基－4'－甲基二苯基錪六氟銻酸鹽、 (甲苯基異丙苯基)錪六氟磷酸鹽、(甲苯基異丙苯基)錪六氟銻酸鹽、(甲苯基異丙苯基)錪四(五氟苯基)硼酸鹽、雙(第三丁基苯基)錪六氟磷酸鹽、雙(第三丁基苯基)錪六氟銻酸鹽、雙(第三丁基苯基)錪四(五氟苯基)硼酸鹽等。Examples of the above aromatic onium salt include 4-isopropoxy-4'-methyldiphenylphosphonium tetrakis(pentafluorophenyl)borate and 4-isopropoxy-4'-methyldiphenyl. Based on hexafluorophosphate, 4-isopropoxy-4'-methyldiphenylphosphonium hexafluoroantimonate, (toluylcumyl)phosphonium hexafluorophosphate, (tolylcumyl)phosphonium hexafluoroantimonate, (tolylpyridyl)phosphonium tetrakis(pentafluorophenyl)borate, double ( Tert-butylphenyl)phosphonium hexafluorophosphate, bis(t-butylphenyl)phosphonium hexafluoroantimonate, bis(t-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and the like.

作為上述芳香族鋶鹽，可列舉4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽、4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟磷酸鹽、4－(4－苯甲醯基－苯硫基)苯基－二－(4－氟苯基)鋶六氟磷酸鹽、4,4'－雙[雙((β－羥基乙氧基)苯基)鋶基]苯硫醚雙六氟磷酸鹽、4,4'－雙[雙((β－羥基乙氧基)苯基)鋶基]苯硫醚雙六氟銻酸鹽、4,4'－雙[雙(氟苯基)鋶基]苯硫醚雙六氟磷酸鹽、4,4'－雙[雙(氟苯基)鋶基]苯硫醚雙六氟銻酸鹽、4,4'－雙(二苯基鋶基)苯硫醚雙六氟磷酸鹽、4,4'－雙(二苯基鋶基)苯硫醚雙六氟銻酸鹽、4－(4－苯甲醯基苯硫基)苯基－二－(4－(β－羥基乙氧基)苯基)鋶六氟磷酸鹽、4－(4－苯甲醯基苯硫基)苯基－二－(4－(β－羥基乙氧基)苯基)鋶六氟銻酸鹽、4－(4－苯甲醯基苯硫基)苯基－二－(4－氟苯基)鋶六氟磷酸鹽、4－(4－苯甲醯基苯硫基)苯基－二－(4－氟苯基)鋶六氟銻酸鹽、4－(4－苯甲醯基苯硫基)苯基－二苯基鋶六氟磷酸鹽、4－(4－苯甲醯基苯硫基)苯基－二苯基鋶六氟銻酸鹽、4－(苯硫基)苯基－二－(4－(β－羥基乙氧基)苯基)鋶六氟磷酸鹽、4－(苯硫基)苯基－二－(4－(β－羥基乙氧基)苯基)鋶六氟銻酸鹽、4－(苯硫基)苯基－二－(4－氟苯基)鋶六氟磷酸鹽、4－(苯硫基)苯基－二－(4－氟苯基)鋶六氟銻酸鹽、4－(苯硫基)苯基－二苯基鋶六氟磷酸鹽、4－(苯硫基)苯基－二苯基鋶六氟銻酸 鹽、4－(2－氯－4－苯甲醯基苯硫基)苯基雙(4－氟苯基)鋶六氟磷酸鹽、4－(2－氯－4－苯甲醯基苯硫基)苯基雙(4－氟苯基)鋶六氟銻酸鹽、4－(2－氯－4－苯甲醯基苯硫基)苯基二苯基鋶六氟磷酸鹽、4－(2－氯－4－苯甲醯基苯硫基)苯基二苯基鋶六氟銻酸鹽、4－(2－氯－4－苯甲醯基苯硫基)苯基雙(4－羥基苯基)鋶六氟磷酸鹽、4－(2－氯－4－苯甲醯基苯硫基)苯基雙(4－羥基苯基)鋶六氟銻酸鹽、三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、4－乙醯氧基苯基二甲基鋶六氟磷酸鹽、4－乙醯氧基苯基二甲基鋶六氟銻酸鹽、4－甲氧基羧基氧基苯基二甲基鋶六氟磷酸鹽、4－甲氧基羧基氧基苯基二甲基鋶六氟銻酸鹽、4－乙氧基羧基氧基苯基二甲基鋶六氟磷酸鹽、4－乙氧基羧基氧基苯基二甲基鋶六氟銻酸鹽等。Examples of the above aromatic onium salt include 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl]thioether bishexafluoroantimonate, and 4,4'-bis[di(4). -heptyloxyphenyl)nonylphenyl]thioether bishexafluorophosphate, 4-(4-benzylidene-phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate Salt, 4,4'-bis[bis((β-hydroxyethoxy)phenyl)indolyl]phenyl sulfide dihexafluorophosphate, 4,4'-bis[bis((β-hydroxyethoxy) Phenyl) indenyl] phenyl sulfide dihexafluoroantimonate, 4,4'-bis[bis(fluorophenyl)indenyl]phenyl sulfide dihexafluorophosphate, 4,4'-double [double (fluorophenyl) fluorenyl] phenyl sulfide dihexafluoroantimonate, 4,4'-bis(diphenylfluorenyl) phenyl sulfide dihexafluorophosphate, 4,4'-bis(diphenyl Thiophene) phenyl sulfide dihexafluoroantimonate, 4-(4-benzylidenephenylthio)phenyl-di-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate 4-(4-Benzylmercaptophenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate, 4-(4-benzoguanidinobenzene Thio)phenyl-bis-(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl- -(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(4-benzylidenephenylthio)phenyl-diphenylphosphonium hexafluorophosphate, 4-(4-benzoguanidinobenzene Thio)phenyl-diphenylphosphonium hexafluoroantimonate, 4-(phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4- (phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate, 4-(phenylthio)phenyl-di-(4-fluorophenyl) Hexafluorophosphate, 4-(phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(phenylthio)phenyl-diphenylphosphonium hexafluorophosphate 4-(phenylthio)phenyl-diphenylphosphonium hexafluoroantimonate Salt, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylsulfonate Phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenyldiphenylphosphonium hexafluorophosphate, 4-( 2-chloro-4-benzylidene phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-hydroxyl Phenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-hydroxyphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate Salt, triphenylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylphosphonium hexafluorophosphate, 4-ethyloxyphenyl dimethyl hexafluoroantimonate, 4-methyl Oxycarboxyloxyphenyldimethylphosphonium hexafluorophosphate, 4-methoxycarboxyoxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethoxycarboxyoxyphenyldimethylhydrazine Hexafluorophosphate, 4-ethoxycarboxyoxyphenyldimethylhydrazine hexafluoroantimonate, and the like.

又，作為上述醯胺系硬化劑，可列舉：聚醯胺樹脂、二丙酮丙烯醯胺錯合物、二氰基二醯胺等。作為上述酸酐系硬化劑，可列舉：鄰苯二甲酸酐、偏苯三甲酸酐、二苯甲酮四甲酸酐、順丁烯二酸酐、六氫鄰苯二甲酸酐、甲基耐地酸酐、戊二酸酐、均苯四甲酸酐、伸苯基－雙(3－丁烷－1,2－二羧酸)酐、四溴鄰苯二甲酸酐等。Moreover, examples of the guanamine-based curing agent include a polyamine resin, a diacetone acrylamide complex, and dicyanodiamine. Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methylic acid anhydride, and pentane. Diacid anhydride, pyromellitic anhydride, phenyl-bis(3-butane-1,2-dicarboxylic acid) anhydride, tetrabromophthalic anhydride, and the like.

接著，對在本發明之硬化性組合物中作為任意成分而調配之環氧化合物加以說明。Next, an epoxy compound to be blended as an optional component in the curable composition of the present invention will be described.

本發明之硬化性組合物中，若使用環氧化合物，則可提高使硬化性組合物硬化所得的硬化物之機械強度。當用於上述目的時，該環氧化合物之含量相對於100質量份之含有矽之化合物較好的是1~50質量份。更好的使用量為5~25 質量份，進而更好的是10~20質量份。又，使用環氧化合物時，上述環氧硬化性化合物之含量相對於100質量份之上述含有矽之化合物較好的是0.01~30質量份。In the curable composition of the present invention, when an epoxy compound is used, the mechanical strength of the cured product obtained by curing the curable composition can be improved. When used for the above purpose, the content of the epoxy compound is preferably from 1 to 50 parts by mass based on 100 parts by mass of the compound containing ruthenium. Better usage is 5~25 The mass fraction, and more preferably 10-20 parts by mass. Further, when an epoxy compound is used, the content of the epoxy-curable compound is preferably 0.01 to 30 parts by mass based on 100 parts by mass of the above-mentioned compound containing ruthenium.

上述環氧化合物係分子中具有1個或2個以上之環氧基的化合物，且為單體性、二聚物性、低聚物性或聚合物性之化合物。又，該等環氧化合物之環氧基可作為末端基而存在，亦可作為側基而存在。作為上述環氧化合物，可列舉：2,2－雙(3,4－環氧環己基)丙烷、3,4－環氧環己基甲基(3,4－環氧)環己烷羧酸酯、2－(3,4－環氧)環己基－5,1－螺(3,4－環氧)環己基－間二噁烷、雙[(3,4－環氧環己基)甲基]己二酸酯、6－(3,4－環氧環己烷羧基氧基)己酸(3,4－環氧環己基)甲酯等脂環式環氧化合物；雙酚A之二縮水甘油醚、雙酚F之二縮水甘油醚、雙酚S之二縮水甘油醚此類雙酚型環氧樹脂；苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、羥基苯甲醛酚醛清漆環氧樹脂此類酚醛清漆型環氧樹脂；四羥基苯基甲烷之縮水甘油醚、四羥基二苯甲酮之縮水甘油醚、環氧化聚乙烯酚此類多官能型環氧樹脂等芳香族環氧樹脂；脂肪族多元醇之聚縮水甘油醚；脂肪族多元醇之環氧烷加成物之聚縮水甘油醚；脂肪族多元醇與脂肪族多元羧酸之聚酯多元醇之聚縮水甘油醚；脂肪族多元羧酸之聚縮水甘油酯；脂肪族多元醇與脂肪族多元羧酸之聚酯多羧酸之聚縮水甘油酯；由丙烯酸縮水甘油酯或甲基丙烯縮水甘油酸酯之乙烯基聚合所獲得之二聚物、低聚物、聚合物；由丙烯酸縮水甘油酯或甲基丙烯酸縮水甘油酯與其他 乙烯基單體之乙烯基聚合所獲得之低聚物、聚合物；環氧化植物油；環氧化植物油之酯交換體；環氧化聚丁二烯等。The epoxy compound is a compound having one or two or more epoxy groups in the molecule, and is a monomeric, dimeric, oligomeric or polymeric compound. Further, the epoxy group of the epoxy compound may be present as a terminal group or may be present as a side group. Examples of the epoxy compound include 2,2-bis(3,4-epoxycyclohexyl)propane and 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate. , 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane, bis[(3,4-epoxycyclohexyl)methyl] An alicyclic epoxy compound such as adipate, 6-(3,4-epoxycyclohexanecarboxyoxy)hexanoic acid (3,4-epoxycyclohexyl)methyl ester; bisphenol A diglycidyl Ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol epoxy resin; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde novolac epoxy Resin such a novolac type epoxy resin; glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, and other aromatic epoxy resins such as polyfunctional epoxy resin Polyglycidyl ether of an aliphatic polyol; polyglycidyl ether of an alkylene oxide adduct of an aliphatic polyol; polyglycidyl ether of a polyester polyol of an aliphatic polyhydric alcohol and an aliphatic polycarboxylic acid; fat Family Polyglycidyl ester of a metacarboxylic acid; polyglycidyl ester of a polyester polycarboxylic acid of an aliphatic polyhydric alcohol and an aliphatic polycarboxylic acid; obtained by vinyl polymerization of glycidyl acrylate or methyl propylene glycidyl ester Dimers, oligomers, polymers; glycidyl acrylate or glycidyl methacrylate and others An oligomer, a polymer obtained by vinyl polymerization of a vinyl monomer; an epoxidized vegetable oil; a transesterified product of an epoxidized vegetable oil; an epoxidized polybutadiene or the like.

作為上述環氧化合物，分子量為100~1000者顯著提高所獲得之硬化物之機械強度，故較好，又，環氧當量較好的是100~2000 g/mol。As the epoxy compound, a molecular weight of from 100 to 1,000 remarkably improves the mechanical strength of the obtained cured product, and therefore, the epoxy equivalent is preferably from 100 to 2,000 g/mol.

其次，對本發明之硬化性組合物中作為任意成分而調配之金屬氧化物微粉末加以說明。Next, the metal oxide fine powder which is prepared as an optional component in the curable composition of the present invention will be described.

該金屬氧化物微粉末，例如，可用於改善硬化後之各物性或作為填充劑而使用所需量。當用於該等目的時，該金屬氧化物微粉末之含量相對於100質量份之上述含有矽之化合物較好的是1~1000質量份。更好之使用量為5~500質量份，進而更好的是10~100質量份。The metal oxide fine powder can be used, for example, to improve the physical properties after hardening or to use a desired amount as a filler. When used for such purposes, the content of the metal oxide fine powder is preferably from 1 to 1,000 parts by mass based on 100 parts by mass of the above-mentioned compound containing ruthenium. A better use amount is 5 to 500 parts by mass, and more preferably 10 to 100 parts by mass.

作為上述金屬氧化物微粉末，例如可列舉礦物等無機材料。具體可列舉：膠體二氧化矽、二氧化矽填充料、二氧化矽凝膠等二氧化矽類；氧化鋁、氧化鋅、氧化鈦等金屬氧化物；雲母、蒙脫土、矽石、矽藻土類、絹雲母、高嶺石、燧石、長石粉、蛭石、厄帖浦石、滑石、鐵滑石、葉臘石等礦物類等，又，亦可為藉由有機改性處理等對該等加以改質者。該等之中較好的是二氧化矽類。Examples of the metal oxide fine powder include inorganic materials such as minerals. Specific examples include colloidal cerium oxide, cerium oxide filler, cerium oxide gel, and the like; metal oxides such as alumina, zinc oxide, and titanium oxide; mica, montmorillonite, vermiculite, and algae Minerals such as soil, sericite, kaolinite, vermiculite, feldspar powder, vermiculite, erbium, talc, iron talc, pyrophyllite, etc., or may be treated by organic modification Those who have been upgraded. Of these, preferred are cerium oxides.

就耐熱性之觀點而言，上述金屬氧化物微粒子之粒徑較好的是100 μm以下，更好的是50 μm以下。From the viewpoint of heat resistance, the particle diameter of the metal oxide fine particles is preferably 100 μm or less, more preferably 50 μm or less.

本發明之含有矽之硬化性組合物中，可進一步調配耐候性賦予劑作為任意成分。作為耐候性賦予劑，可使用光穩 定劑、紫外線吸收劑、酚系抗氧化劑、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，紫外線吸收劑可列舉2－羥基二苯甲酮類、2－(2－羥基苯基)苯并***類、2－(2－羥基苯基)－4,6－二芳基－1,3,5－三嗪類、苯甲酸酯類、氰基丙烯酸酯類，酚系抗氧化劑可列舉三乙二醇－雙[3－(3－第三丁基－5－甲基－4－羥基苯基)丙酸酯]、二丁基羥基甲苯(BHT)、2,6－二－第三丁基－對甲酚(DBPC)等，硫系抗氧化劑可列舉二烷硫基二丙酸酯類、β－烷基巰基丙酸酯類，磷系抗氧化劑可列舉有機亞磷酸酯類。In the curable composition containing bismuth of the present invention, a weather resistance imparting agent can be further formulated as an optional component. As a weather resistance imparting agent, light stabilization can be used. Conventional users such as fixatives, ultraviolet absorbers, phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants are well known. For example, examples of the light stabilizer include hindered amines, and examples of the ultraviolet absorber include 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)benzotriazoles, and 2-(2-hydroxyphenyl)- 4,6-diaryl-1,3,5-triazines, benzoates, cyanoacrylates, phenolic antioxidants can be cited as triethylene glycol-bis[3-(3-third 5--5-methyl-4-hydroxyphenyl)propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-p-cresol (DBPC), etc., sulfur-based antioxidants Examples thereof include dialkylthiodipropionates and β-alkylmercaptopropionates, and examples of the phosphorus-based antioxidants include organic phosphites.

使用上述耐候性賦予劑時，就耐熱性、電氣特性、硬化性、力學特性、保存穩定性、操作性之觀點而言，在本發明之硬化性組合物中其含量較好的是0.0001~50質量%，更好的是0.001~10質量%。When the weather resistance imparting agent is used, the content of the curable composition of the present invention is preferably 0.0001 to 50 in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability, and workability. The mass% is more preferably 0.001 to 10% by mass.

本發明之硬化性組合物中，可於不損及本發明之目標性能之範圍內調配其他眾所周知之各種樹脂、填充劑、添加劑等。作為可任意調配之各種樹脂之例，可列舉聚醯亞胺樹脂、聚乙二醇或聚丙二醇等聚醚樹脂、聚胺基甲酸酯樹脂、環氧樹脂、酚樹脂、聚酯樹脂、三聚氰胺樹脂、聚醯胺樹脂、聚苯硫醚樹脂等，作為可任意調配之添加劑之例，可列舉抗靜電劑、光敏劑、酸增殖劑等。為了不損及本發明之目標性能，該等任意成分(其中將上述環氧化合物及上述金屬氧化物微粉末除外)之調配量，相對於100質量份之含有矽之化合物，較好的是合計量為10質量份以 下。In the curable composition of the present invention, other well-known various resins, fillers, additives and the like can be formulated within a range not impairing the target properties of the present invention. Examples of the various resins which can be arbitrarily formulated include polyether resins such as polyimine resins, polyethylene glycol or polypropylene glycol, polyurethane resins, epoxy resins, phenol resins, polyester resins, and melamine. Examples of the resin which can be arbitrarily formulated, such as a resin, a polyamide resin, and a polyphenylene sulfide resin, include an antistatic agent, a photosensitizer, and an acid multiplying agent. In order not to impair the target performance of the present invention, the blending amount of the optional components (excluding the epoxy compound and the metal oxide fine powder described above) is preferably a total amount based on 100 parts by mass of the compound containing ruthenium. The amount is 10 parts by mass under.

本發明之硬化性組合物在室溫(25℃)下具有良好之流動性，因而操作性優異。關於流動性，在不含金屬氧化物微粉末之狀態下於室溫(25℃)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。The curable composition of the present invention has good fluidity at room temperature (25 ° C) and is therefore excellent in handleability. Regarding the fluidity, the viscosity measured by an E-type viscometer at room temperature (25 ° C) in the absence of the metal oxide fine powder is preferably 50 Pa. Below S, better is 10 Pa. S below.

藉由選擇上述環氧硬化性化合物，本發明之硬化性組合物的硬化種類可選擇熱硬化、光硬化、或利用光及熱兩者之硬化。進行熱硬化時之硬化溫度較好的是60~200℃，更好的是80~150℃。硬化時間較好的是0.1~10小時，更好的是1~6小時。進行光硬化時，可使用之活性能量線有紫外線、電子射線、X射線、放射線、高頻波等，紫外線在經濟方面最好。紫外線之光源有紫外線雷射、水銀燈、高壓水銀燈、氙氣燈、鈉燈、鹼金屬燈等。此處所使用之紫外線源較好的是高壓水銀燈。照射能量之最佳條件視所塗佈之膜厚而不同，通常在100~10000 mJ/cm2 之範圍內。又，在光硬化之後進行熱硬化時，通常可於60~150℃之範圍內加熱。By selecting the epoxy curable compound, the hardening type of the curable composition of the present invention can be selected from thermosetting, photocuring, or hardening using both light and heat. The hardening temperature at the time of heat hardening is preferably 60 to 200 ° C, more preferably 80 to 150 ° C. The hardening time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours. When performing photohardening, the active energy rays that can be used include ultraviolet rays, electron rays, X-rays, radiation, high-frequency waves, and the like, and ultraviolet rays are economically preferable. Ultraviolet light sources include ultraviolet lasers, mercury lamps, high pressure mercury lamps, xenon lamps, sodium lamps, and alkali metal lamps. The ultraviolet source used herein is preferably a high pressure mercury lamp. The optimum conditions for the irradiation energy vary depending on the film thickness to be applied, and are usually in the range of 100 to 10,000 mJ/cm 2 . Further, when thermal curing is performed after photocuring, it is usually heated in the range of 60 to 150 °C.

於如上所述之條件下使本發明之硬化性組合物硬化而成之硬化物，成為透明性、耐龜裂性、耐熱性、耐溶劑性、耐鹼性、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。The cured product obtained by curing the curable composition of the present invention under the above conditions has transparency, crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, stain resistance, and resistance. A material excellent in mechanical properties such as flammability, moisture resistance, gas barrier properties, flexibility, elongation or strength, electrical insulation properties, low dielectric constant, optical properties, electrical properties, and the like.

含有本發明之含有矽之化合物而形成的硬化性組合物，穩定性、硬化性等優異，進而其硬化物之耐龜裂性、耐熱 性、耐溶劑性、耐鹼性、耐候性、光學特性、電氣特性等各物性優異。本發明之硬化性組合物可應用於電氣/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/防濕為目的之灌注/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、O環、顯示裝置用密封劑/保護材料、光波導管、光纖保護材料、光學透鏡、光學設備用接著劑、高耐熱性接著劑、高散熱性材料、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、影印機用感光鼓、氣體分離膜等。又，亦可應用於土木/建材領域之混凝土保護材料、襯砌、土壤注入劑、密封劑、蓄冷蓄熱材料、玻璃鍍膜等，進而於醫療用材料領域中，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。The curable composition containing the ruthenium-containing compound of the present invention is excellent in stability, curability, and the like, and further has crack resistance and heat resistance of the cured product. It is excellent in physical properties such as properties, solvent resistance, alkali resistance, weather resistance, optical properties, and electrical properties. The curable composition of the present invention can be applied to a display material of an electric/electronic material field, a sealing material for a light material/recording material/semiconductor, a high voltage insulating material, a perfusion for the purpose of insulation/anti-vibration/waterproof/moisture resistance. / Sealing materials, prototypes of plastic parts, coating materials, interlayer insulating films, packaging for insulation, heat shrinkable rubber tubes, O-rings, sealants/protective materials for display devices, optical waveguides, optical fiber protective materials, optical lenses, Adhesive for optical equipment, high heat-resistant adhesive, high heat-dissipating material, high heat-resistant sealing material, solar cell/fuel cell member, solid electrolyte for battery, insulating coating material, photosensitive drum for photocopier, gas separation film, etc. . Moreover, it can also be applied to concrete protection materials, linings, soil injection agents, sealants, cold storage materials, glass coatings, etc. in the field of civil engineering/building materials, and can also be applied to test tubes, sealing materials, and coatings in the field of medical materials. Cloth material, sealing material for sterilization treatment device, contact lens, oxygen-rich film, and the like.

[實施例][Examples]

以下，藉由實施例等進一步說明本發明，但本發明並不因該等實施例而受到限定。又，只要無特別說明，則實施例中之「份」或「%」係以質量為基準者。Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by the examples. Further, unless otherwise stated, the "parts" or "%" in the examples are based on mass.

[合成例1][Synthesis Example 1]

將100份之二氯二甲基矽烷滴加於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℃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20 份之吡啶，於其中進一步加入10份之二甲基乙烯基氯矽烷，於70℃下攪拌30分鐘。然後，以100份之離子交換水進行水洗之後，於150℃下減壓餾去溶劑。繼而以100份之乙腈進行清洗，其後於70℃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(a1－0)。下述條件下之GPC分析之結果為非環狀聚矽氧烷化合物(a1－0)之分子量為Mw＝20,000。再者，以下GPC均係在該條件下進行。100 parts of dichlorodimethyl decane 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, and 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 and added to 20 The pyridine was further added with 10 parts of dimethylvinylchloromethane and stirred at 70 ° C for 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain an acyclic polysiloxane compound (a1-0) having an unsaturated bond. As a result of GPC analysis under the following conditions, the molecular weight of the acyclic polysiloxane compound (a1-0) was Mw = 20,000. Furthermore, the following GPCs were carried out under these conditions.

(GPC之測定條件) 管柱：TOSOH股份有限公司製造之TSK－GEL MULTIPORE HXL M，7.8 mm×300 mm展開溶劑：四氫呋喃(Measurement conditions for GPC) Pipe column: TSK-GEL MULTIPORE HXL M manufactured by TOSOH Co., Ltd., 7.8 mm × 300 mm developing solvent: tetrahydrofuran

[合成例2][Synthesis Example 2]

將100份之合成例1中所獲得之非環狀聚矽氧烷(a1－0)溶解於200份之甲苯中，加入0.003份之鉑觸媒、及10份之作為環狀聚矽氧烷化合物的1,3,5,7－四甲基環四矽氧烷，使之於105℃下反應2小時。於70℃下減壓餾去溶劑之後以100份之乙腈進行清洗。其後於70℃下減壓餾去溶劑，獲得聚矽氧烷中間體(a3－0)。GPC之分析結果為聚矽氧烷中間體(a3－0)之分子量為Mw＝22,000。100 parts of the acyclic polyaluminoxane (a1-0) obtained in Synthesis Example 1 was dissolved in 200 parts of toluene, 0.003 parts of a platinum catalyst, and 10 parts of a cyclic polyoxane were added. The compound of 1,3,5,7-tetramethylcyclotetraoxane was allowed to react at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C, and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C to obtain a polyoxane intermediate (a3-0). As a result of analysis by GPC, the molecular weight of the polyoxyalkylene intermediate (a3-0) was Mw = 22,000.

[實施例1]含有矽之化合物(A－0)之製造[Example 1] Production of a compound containing ruthenium (A-0)

將100份之合成例2中所獲得之聚矽氧烷中間體(a3－0)溶解於200份之甲苯中，加入19份之作為導入Z之環氧化合物的3－乙烯基－7－氧雜雙環[4,1,0]庚烷，於105℃下攪拌2小時。於70℃下減壓餾去溶劑之後以100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－0)。GPC之分析結果為含有矽之化合物(A－0)之分子量為Mw＝30,000，利用依據JIS規格K7236之電位差滴定法所求出之環氧當量(每單位數量之環氧基之分子量)為3000 g/mmol。再者，以下之環氧當量均係利用該方法測定。100 parts of the polyoxyalkylene intermediate (a3-0) obtained in Synthesis Example 2 was dissolved in 200 parts of toluene, and 19 parts of 3-vinyl-7-oxygen as an epoxy compound introduced into Z was added. Heterobicyclo[4,1,0]heptane was stirred at 105 ° C for 2 hours. After distilling off the solvent under reduced pressure at 70 ° C, it was purified with 100 parts of acetonitrile. After washing, the solvent was distilled off under reduced pressure at 70 ° C to obtain a compound (A-0) containing oxime. As a result of analysis by GPC, the molecular weight of the compound containing ruthenium (A-0) was Mw=30,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) determined by potentiometric titration according to JIS specification K7236 was 3000. g/mmol. Further, the following epoxy equivalents were measured by this method.

[合成例3][Synthesis Example 3]

混合90份之二氯二甲基矽烷與9份之二氯二苯基矽烷，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℃下聚合5小時。以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20份之吡啶，於其中進一步加入10份之二甲基乙烯基氯矽烷，於70℃下攪拌30分鐘。然後，以100份之離子交換水進行水洗之後，於150℃下減壓餾去溶劑。繼而以100份之乙腈進行清洗，其後於70℃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(a1－1)。非環狀聚矽氧烷(a1－1)之分子量為Mw＝20,000。Mixing 90 parts of dichlorodimethyl decane with 9 parts of dichlorodiphenyl decane, and adding dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, Polymerization was carried out 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, 20 parts of pyridine was added thereto, and 10 parts of dimethylvinylchloromethane was further added thereto, and the mixture was stirred at 70 ° C. minute. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain an acyclic polysiloxane compound (a1-1) having an unsaturated bond. The molecular weight of the acyclic polyaluminoxane (a1-1) is Mw = 20,000.

[合成例4][Synthesis Example 4]

將100份之合成例3中所獲得之非環狀聚矽氧烷(a1－1)溶解於200份之甲苯中，加入0.003份之鉑觸媒、及10份之作為環狀聚矽氧烷化合物的1,3,5,7－四甲基環四矽氧烷，使之於105℃下反應2小時。於70℃下減壓餾去溶劑之後以100份之乙腈進行清洗。然後，於70℃下減壓餾去溶劑，獲得聚矽氧烷中間體(a3－1)。GPC之分析結果為聚矽氧烷中間體(a3－1)之分子量為Mw＝22,000。100 parts of the acyclic polyaluminoxane (a1-1) obtained in Synthesis Example 3 was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts of the cyclic polysiloxane was added. The compound of 1,3,5,7-tetramethylcyclotetraoxane was allowed to react at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C, and then washed with 100 parts of acetonitrile. Then, the solvent was distilled off under reduced pressure at 70 ° C to obtain a polyoxane intermediate (a3-1). As a result of analysis by GPC, the molecular weight of the polyoxyalkylene intermediate (a3-1) was Mw = 22,000.

[實施例2]含有矽之化合物(A－1)之製造[Example 2] Production of a compound containing ruthenium (A-1)

將100份之合成例4中所獲得之聚矽氧烷中間體(a3－1)溶解於200份之甲苯中，加入19份之作為導入Z之環氧化合物的3－乙烯基－7－氧雜雙環[4,1,0]庚烷，於105℃下攪拌2小時。於70℃下減壓餾去溶劑之後以100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－1)。GPC之分析結果為含有矽之化合物(A－1)之分子量為Mw＝30,000，環氧當量(每單位數量之環氧基之分子量)為3000 g/mmol。100 parts of the polyoxyalkylene intermediate (a3-1) obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, and 19 parts of 3-vinyl-7-oxygen as an epoxy compound introduced into Z was added. Heterobicyclo[4,1,0]heptane was stirred at 105 ° C for 2 hours. After the solvent was distilled off under reduced pressure at 70 ° C, the solvent was washed with 100 parts of acetonitrile, and then the solvent was evaporated under reduced pressure at 70 ° C to afford compound (A-1). As a result of analysis by GPC, the molecular weight of the compound (A-1) containing ruthenium was Mw = 30,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) was 3000 g/mmol.

[實施例3]含有矽之化合物(A－2)之製造[Example 3] Production of a compound containing ruthenium (A-2)

將100份之合成例4中所獲得之聚矽氧烷中間體(a3－1)溶解於200份之甲苯中，加入19份之作為導入Z之環氧化合物的烯丙基縮水甘油醚，於105℃下攪拌2小時。於70℃下減壓餾去溶劑之後以100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－2)。GPC之分析結果為含有矽之化合物(A－2)之分子量為Mw＝30,000，環氧當量(每單位數量之環氧基之分子量)為3000 g/mmol。100 parts of the polyoxyalkylene intermediate (a3-1) obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, and 19 parts of allyl glycidyl ether as an epoxy compound introduced into Z was added thereto. Stir at 105 ° C for 2 hours. After the solvent was distilled off under reduced pressure at 70 ° C, the solvent was washed with 100 parts of acetonitrile, and then the solvent was evaporated under reduced pressure at 70 ° C to afford compound (A-2). As a result of analysis by GPC, the molecular weight of the compound (A-2) containing ruthenium was Mw = 30,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) was 3000 g/mmol.

[合成例5][Synthesis Example 5]

混合90份之二氯二甲基矽烷與9份之二氯二苯基矽烷，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℃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20份之吡啶及0.5份之苯基三氯矽烷，於室溫下攪拌30分鐘，接著於70℃下攪拌30分鐘。 於其中加入15份之二甲基乙烯基氯矽烷，於室溫下攪拌30分鐘，接著於70℃下攪拌30分鐘。然後，以100份之離子交換水進行水洗之後，於150℃下減壓餾去溶劑。繼而以100份之乙腈進行清洗，其後於70℃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(a1－2)。GPC之分析結果為非環狀聚矽氧烷(a1－2)之分子量為Mw＝33,000。Mixing 90 parts of dichlorodimethyl decane with 9 parts of dichlorodiphenyl decane, and adding dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, Polymerization was carried out 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, and 20 parts of pyridine and 0.5 part of phenyltrichloromethane were added thereto, and stirred at room temperature for 30 minutes, followed by 70 Stir at °C for 30 minutes. 15 parts of dimethylvinylchloromethane was added thereto, and the mixture was stirred at room temperature for 30 minutes, followed by stirring at 70 ° C for 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain an acyclic polysiloxane compound (a1-2) having an unsaturated bond. As a result of analysis by GPC, the molecular weight of the acyclic polysiloxane (a1-2) was Mw = 33,000.

[合成例6][Synthesis Example 6]

將100份之合成例5中所獲得之作為前驅物的非環狀聚矽氧烷化合物(a1－2)溶解於200份之甲苯中，加入0.003份之鉑觸媒及10份之1,3,5,7－四甲基環四矽氧烷，使之於105℃下反應2小時。於70℃下減壓餾去溶劑之後以100份之乙腈進行清洗後，於70℃下減壓餾去溶劑，獲得聚矽氧烷中間體(a3－2)。GPC之分析結果為聚矽氧烷中間體(a3－2)之分子量為Mw＝36,000。100 parts of the acyclic polyoxy siloxane compound (a1-2) obtained as a precursor in Synthesis Example 5 was dissolved in 200 parts of toluene, and 0.003 parts of platinum catalyst and 10 parts of 3, 3 were added. 5,7-Tetramethylcyclotetraoxane was allowed to react at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C, and then washed with 100 parts of acetonitrile, and the solvent was evaporated under reduced pressure at 70 ° C to obtain a polyoxane intermediate (a3-2). As a result of analysis by GPC, the molecular weight of the polyoxyalkylene intermediate (a3-2) was Mw = 36,000.

[實施例4]含有矽之化合物(A－3)之製造[Example 4] Production of ruthenium-containing compound (A-3)

將100份之合成例6中所獲得之聚矽氧烷中間體(a3－2)溶解於200份之甲苯中，加入19份之烯丙基縮水甘油醚，於105℃下攪拌2小時。於70℃下減壓餾去溶劑之後以100份之乙腈進行清洗，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＝36,000，環氧當量(每單位數量之環氧基之分子量)為2000 g/mmol。100 parts of the polyoxyalkylene intermediate (a3-2) obtained in Synthesis Example 6 was dissolved in 200 parts of toluene, 19 parts of allyl glycidyl ether was added, and the mixture was stirred at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C, and washed with 100 parts of acetonitrile, and the solvent was evaporated under reduced pressure at 70 ° C to afford compound (A-3). As a result of analysis by GPC, the molecular weight of the compound (A-3) containing ruthenium was Mw = 36,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) was 2000 g/mmol.

[合成例7][Synthesis Example 7]

混合90份之二氯二甲基矽烷與9份之二氯二苯基矽烷，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℃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20份之吡啶及0.5份之四氯矽烷，於室溫下攪拌30分鐘，繼而於70℃下攪拌30分鐘。於其中加入15份之二甲基乙烯基氯矽烷，於室溫下攪拌30分鐘，繼而於70℃下攪拌30分鐘。然後，以100份之離子交換水進行水洗之後，於150℃下減壓餾去溶劑。繼而以100份之乙腈進行清洗，其後於70℃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(a1－3)。GPC之分析結果為非環狀聚矽氧烷(a1－3)之分子量為Mw＝40,000。Mixing 90 parts of dichlorodimethyl decane with 9 parts of dichlorodiphenyl decane, and adding dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, Polymerization was carried out 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, and 20 parts of pyridine and 0.5 part of tetrachloromethane were added thereto, and stirred at room temperature for 30 minutes, followed by 70 ° C. Stir for 30 minutes. 15 parts of dimethylvinylchloromethane was added thereto, and the mixture was stirred at room temperature for 30 minutes, followed by stirring at 70 ° C for 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain an acyclic polysiloxane compound (a1-3) having an unsaturated bond. As a result of analysis by GPC, the molecular weight of the acyclic polysiloxane (a1-3) was Mw = 40,000.

[合成例8][Synthesis Example 8]

將100份之合成例7中所獲得之作為前驅物的非環狀聚矽氧烷化合物(a1－3)溶解於200份之甲苯中，加入0.003份之鉑觸媒及10份之1,3,5,7－四甲基環四矽氧烷，使之於105℃下反應2小時。於70℃下減壓餾去溶劑之後以100份之乙腈進行清洗後，於70℃下減壓餾去溶劑，獲得聚矽氧烷中間體(a3－3)。GPC之分析結果為聚矽氧烷中間體(a3－3)之分子量為Mw＝44,000。100 parts of the acyclic polyoxy siloxane compound (a1-3) obtained as a precursor in Synthesis Example 7 was dissolved in 200 parts of toluene, and 0.003 part of platinum catalyst and 10 parts of 3, 3 were added. 5,7-Tetramethylcyclotetraoxane was allowed to react at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C, and then washed with 100 parts of acetonitrile, and the solvent was evaporated under reduced pressure at 70 ° C to obtain a polyoxane intermediate (a3-3). As a result of analysis by GPC, the molecular weight of the polyoxyalkylene intermediate (a3-3) was Mw = 44,000.

[實施例5]含有矽之化合物(A－4)之製造[Example 5] Production of a compound containing ruthenium (A-4)

將100份之合成例8中所獲得之聚矽氧烷中間體(a3－3)溶解於200份之甲苯中，加入19份之烯丙基縮水甘油醚，於105℃下攪拌2小時。於70℃下減壓餾去溶劑之後以100份 之乙腈進行清洗，於70℃下減壓餾去溶劑，獲得含有矽之化合物(A－4)。GPC之分析結果為含有矽之化合物(A－4)之分子量為Mw＝44,000，環氧當量(每單位數量之環氧基之分子量)為1000 g/mmol。100 parts of the polyoxyalkylene intermediate (a3-3) obtained in Synthesis Example 8 was dissolved in 200 parts of toluene, 19 parts of allyl glycidyl ether was added, and the mixture was stirred at 105 ° C for 2 hours. After distilling off the solvent under reduced pressure at 70 ° C, 100 parts The acetonitrile was washed, and the solvent was evaporated under reduced pressure at 70 ° C to give Compound (A-4). As a result of analysis by GPC, the molecular weight of the compound (A-4) containing ruthenium was Mw = 44,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) was 1000 g/mmol.

[實施例6]硬化性組合物No.1之製造[Example 6] Production of curable composition No. 1

將99.9份之上述實施例1中所獲得的含有矽之化合物(A－0)、及0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物No.1。99.9 parts of the ruthenium-containing compound (A-0) obtained in the above Example 1 and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide The bishexafluoroantimonate was mixed to obtain a hardenable composition No. 1.

[實施例7]硬化性組合物No.2之製造[Example 7] Production of Curable Composition No. 2

將90份之上述實施例1中所獲得的含有矽之化合物(A－0)、及10份之JEFFAMIN D－2000(HUNTSMAN公司製造，二胺系硬化劑)加以混合，獲得硬化性組合物No.2。90 parts of the ruthenium-containing compound (A-0) obtained in the above Example 1 and 10 parts of JEFFAMIN D-2000 (manufactured by HUNTSMAN, a diamine-based curing agent) were mixed to obtain a curable composition No. .2.

[實施例8]硬化性組合物No.3之製造[Example 8] Production of Curable Composition No. 3

將99.9份之上述實施例2中所獲得的含有矽之化合物(A－1)、及0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物No.3。99.9 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide The bishexafluoroantimonate was mixed to obtain a curable composition No. 3.

[實施例9]硬化性組合物No.4之製造[Example 9] Production of curable composition No. 4

將99.9份之上述實施例2中所獲得的含有矽之化合物(A－1)、及0.1份之4－異丙氧基－4'－甲基二苯基錪四(五氟苯基)硼酸鹽加以混合，獲得硬化性組合物No.4。99.9 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, and 0.1 part of 4-isopropoxy-4'-methyldiphenylphosphonium tetrakis(pentafluorophenyl)borate The salt was mixed to obtain a curable composition No. 4.

[實施例10]硬化性組合物No.5之製造[Example 10] Production of Curable Composition No. 5

將99.9份之上述實施例4中所獲得的含有矽之化合物(A－3)、及0.1份之4,4－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物No.5。99.9 parts of the ruthenium-containing compound (A-3) obtained in the above Example 4, and 0.1 part of 4,4-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide double The hexafluoroantimonate was mixed to obtain a hardenable composition No. 5.

[實施例11]硬化性組合物No.6之製造[Example 11] Production of curable composition No. 6

將99.9份之上述實施例3中所獲得的含有矽之化合物(A－4)、及0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物No.6。99.9 parts of the ruthenium-containing compound (A-4) obtained in the above Example 3, and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide The bishexafluoroantimonate was mixed to obtain a hardenable composition No. 6.

[實施例12]硬化性組合物No.7之製造[Example 12] Production of curable composition No. 7

將99.9份之上述實施例2中所獲得的含有矽之化合物(A－1)、0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽、及5份之二氧化矽填充料(FB－7SDC；電氣化學工業製造)加以混合，獲得硬化性組合物No.5。99.9 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide double Hexafluoroantimonate and 5 parts of ruthenium dioxide filler (FB-7SDC; manufactured by Electric Chemical Industry Co., Ltd.) were mixed to obtain a curable composition No. 5.

[實施例13]硬化性組合物No.8之製造[Example 13] Production of curable composition No. 8

將84份之上述實施例2中所獲得的含有矽之化合物(A－1)、0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽、及15份之2,2－雙(3,4－環氧環己基)丙烷加以混合，獲得硬化性組合物No.8。84 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide double Hexafluoroantimonate and 15 parts of 2,2-bis(3,4-epoxycyclohexyl)propane were mixed to obtain a curable composition No. 8.

[實施例14]硬化性組合物No.9之製造[Example 14] Production of Curable Composition No. 9

將90份之上述實施例2中所獲得的含有矽之化合物(A－1)、及10份之JEFFAMIN D－2000(HUNTSMAN公司製造，二胺系硬化劑)加以混合，獲得硬化性組合物No.9。90 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, and 10 parts of JEFFAMIN D-2000 (manufactured by HUNTSMAN, a diamine-based curing agent) were mixed to obtain a curable composition No. .9.

[實施例15]硬化性組合物No.10之製造[Example 15] Production of Curable Composition No. 10

將85份之上述實施例2中所獲得的含有矽之化合物(A－1)、10份之JEFFAMIN D－2000(HUNTSMAN公司製造，二胺系硬化劑)、及5份之二氧化矽填充料(FB－7SDC；電氣化學工業製造)加以混合，獲得硬化性組合物No.10。85 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, 10 parts of JEFFAMIN D-2000 (manufactured by HUNTSMAN, a diamine-based hardener), and 5 parts of cerium oxide filler (FB-7SDC; manufactured by the electric chemical industry) was mixed to obtain a curable composition No. 10.

[實施例16]硬化性組合物No.11之製造[Example 16] Production of curable composition No. 11

將90份之上述實施例2中所獲得的含有矽之化合物(A－1)、及10份之ADEKA Hardener EH－220(ADEKA製造，混合系環氧硬化劑)加以混合，獲得硬化性組合物No.11。90 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, and 10 parts of ADEKA Hardener EH-220 (manufactured by Adeka, mixed epoxy curing agent) were mixed to obtain a curable composition. No.11.

[比較例1]硬化性組合物比較用1之製造[Comparative Example 1] Comparison of curable composition for comparison 1

將99.9份之KF－102(信越化學製造，以側位(pendant)型鍵結有3,4－環氧環己基之聚甲基矽氧烷；環氧當量為3600 g/mmol)、及0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物比較用1。99.9 parts of KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd., a 3,4-epoxycyclohexyl polymethyloxirane bonded to a pendant type; an epoxy equivalent of 3600 g/mmol), and 0.1 The 4,4'-bis[bis(4-heptyloxyphenyl) nonylphenyl] thioether hexafluoroantimonate was mixed to obtain a comparative composition for the curable composition.

[比較例2]硬化性組合物比較用2之製造[Comparative Example 2] Comparison of curable composition for comparison 2

將99.9份之X－22－169B(信越化學製造，末端為3,4－環氧環己烷之聚二甲基矽氧烷；環氧當量為1700 g/mmol)、及0.1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物比較用2。99.9 parts of X-22-169B (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethyl methoxyoxane having a terminal of 3,4-epoxycyclohexane; epoxy equivalent of 1700 g/mmol), and 4 parts by weight, 4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide dihexafluoroantimonate was mixed to obtain a comparative composition for the curable composition.

[比較例3]硬化性組合物比較用3之製造[Comparative Example 3] Comparison of curable composition for comparison with 3

將90份之KF－101(信越化學製造，以側位型鍵結有縮水甘油基之聚二甲基矽氧烷；環氧當量為350 g/mmol)、及10份之ADEKA Hardener EH－220(ADEKA製造，混合系環氧硬化劑)加以混合，獲得硬化性組合物比較用3。90 parts of KF-101 (manufactured by Shin-Etsu Chemical, polyglycidyl group with glycidyl group bonded to the lateral position; epoxy equivalent of 350 g/mmol), and 10 parts of ADEKA Hardener EH-220 (manufactured by ADEKA, mixed epoxy curing agent), and mixed, to obtain a comparative composition 3 for the curable composition.

[比較例4]硬化性組合物比較用4之製造[Comparative Example 4] Comparison of curable composition for comparison 4

將99.0份之1,3,5,7－四甲基－1,3,5,7－四(3,4－環氧環己基乙基)環四矽氧烷、及1份之4,4'－雙[二(4－庚氧基苯基)鋶基苯基]硫醚雙六氟銻酸鹽加以混合，獲得硬化性組合物比較用4。99.0 parts of 1,3,5,7-tetramethyl-1,3,5,7-tetrakis(3,4-epoxycyclohexylethyl)cyclotetraoxane, and 4 parts of 4,4 '-Bis[bis(4-heptyloxyphenyl) nonylphenyl] thioether hexafluoroantimonate was mixed to obtain a comparative composition for the curable composition.

[實施例17~27、比較例5~8][Examples 17 to 27, Comparative Examples 5 to 8]

於鋁板上將上述實施例6~16中所獲得之硬化性組合物No.1~11及比較例1~4中所獲得之硬化性組合物比較用1~4分別製成膜厚約為1 mm之膜，於表1、2之條件下進行硬化，獲得硬化物1~11、硬化物比較1~4。又，表1中之硬化條件表示，使用高壓水銀燈在上段之條件下進行光硬化之後，在下段之條件下進行加熱處理。The curable compositions obtained in the curable compositions Nos. 1 to 11 and the comparative examples 1 to 4 obtained in the above Examples 6 to 16 were compared on the aluminum plate to have a film thickness of about 1 to 1 each. The film of mm was hardened under the conditions of Tables 1 and 2 to obtain hardened materials 1 to 11 and hardened materials 1 to 4. Further, the hardening conditions in Table 1 indicate that the high-pressure mercury lamp was subjected to photohardening under the conditions of the upper stage, and then heat-treated under the conditions of the lower stage.

以如下方式對該等硬化物進行硬化狀態之評價、耐熱性試驗及180度彎曲試驗。The cured product was evaluated for the hardened state, the heat resistance test, and the 180 degree bending test in the following manner.

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，將具有流動性之狀態評價為×，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◎。The hardening state is judged based on whether or not the cured film has a feeling of adhesion after a specific hardening time, and the state of fluidity is evaluated as ×, and there is no fluidity, but the adhesiveness is evaluated as Δ~○ depending on the degree, and the evaluation is not sticky. It is ◎.

耐熱性試驗中，測定空氣環境下之TG/DTA之5質量%減少溫度。In the heat resistance test, the temperature was reduced by 5 mass% of TG/DTA in an air atmosphere.

於180度彎曲試驗中，對在鋁板上製作膜厚約為1 mm之膜而獲得之硬化膜觀察彎曲180度時的膜之狀態。將彎折180度時膜並無龜裂及剝離之樣品評價為○，將彎折180度時產生龜裂而彎折90度時未產生龜裂及剝離之樣品評價為△，將彎折90度時產生龜裂之樣品評價為×。In the 180-degree bending test, the state of the film when the film was bent at 180 degrees was observed on a cured film obtained by forming a film having a film thickness of about 1 mm on an aluminum plate. The sample which was not cracked and peeled off when the film was bent at 180 degrees was evaluated as ○, and the sample which was cracked when it was bent at 180 degrees and cracked and peeled at 90 degrees was evaluated as Δ, and the bending was 90. The sample in which the crack occurred at the time was evaluated as ×.

將結果示於表1、2中。又，表1中記載的是使用有機鎓鹽系硬化劑作為環氧硬化性化合物的硬化性組合物之硬化物，表2中記載的是使用胺系硬化劑或混合系硬化劑作為環氧硬化性化合物的硬化性組合物之硬化物。The results are shown in Tables 1 and 2. Further, in Table 1, the cured product of the curable composition using the organic onium salt-based curing agent as the epoxy-curable compound is described, and in Table 2, the amine-based curing agent or the mixed-type curing agent is used as the epoxy curing. A cured product of a curable composition of a compound.

由表1可確認，作為本發明之硬化性組合物的硬化性組合物No.1、No.3~8與硬化性組合物比較用1、2相比，顯示良好之硬化狀態。又可確認，使作為本發明之硬化性組合物的硬化性組合物No.1，No.3~8硬化而獲得之作為本發明之硬化物的硬化物1~7，與硬化物比較3相比耐熱性良好，與硬化物比較3相比可撓性亦良好。由此可知，藉由本發明之含有矽之化合物之特徵即於環矽氧烷環中導入環氧基，可提高硬化性組合物之硬化性、以及硬化物之耐熱性及可撓性。From Table 1, it was confirmed that the curable compositions No. 1 and Nos. 3 to 8 which are curable compositions of the present invention showed a good hardened state as compared with the curable compositions 1 and 2. In addition, it is confirmed that the cured products 1 to 7 which are obtained as the cured product of the present invention obtained by curing the curable composition No. 1 and No. 3 to 8 which are curable compositions of the present invention are compared with the cured product. It has better specific heat resistance and is also more flexible than the cured product. From this, it is understood that the epoxy group-introducing compound introduces an epoxy group into the cyclodecane ring, thereby improving the curability of the curable composition and the heat resistance and flexibility of the cured product.

又，由硬化物1與硬化物2之比較可確認，藉由對含有矽之化合物之Re 、Rf 導入芳香族基，所獲得之硬化物之耐熱性會進一步提高。又，由硬化物2與硬化物6之比較可確認，藉由使用金屬氧化物微粉末，亦可進一步賦予耐熱性。Further, from the comparison between the cured product 1 and the cured product 2, it was confirmed that the heat resistance of the cured product obtained was further improved by introducing an aromatic group into R e and R f of the compound containing ruthenium. Further, from the comparison between the cured product 2 and the cured product 6, it was confirmed that heat resistance can be further imparted by using the fine metal oxide powder.

由表2可確認，僅藉由熱硬化而使本發明之硬化性組合物硬化所獲得之硬化物8~11，與硬化物比較4相比，耐熱性及可撓性良好。由此可知，藉由本發明之含有矽之化合物之特徵即於環矽氧烷環中導入環氧基，硬化物之耐熱性及可撓性會提高。From Table 2, it was confirmed that the cured products 8 to 11 obtained by curing only the curable composition of the present invention by thermal curing have better heat resistance and flexibility than the cured product 4. From this, it is understood that the epoxy group is introduced into the cyclodecane ring by the feature of the ruthenium-containing compound of the present invention, and the heat resistance and flexibility of the cured product are improved.

又，由硬化物8與硬化物9之比較可確認，藉由對含有矽之化合物之Re 、Rf 導入芳香族基，所獲得之硬化物之耐熱性會進一步提高，又，由硬化物19與硬化物10之比較可確認，藉由使用金屬氧化物微粉末，亦可進一步賦予耐熱性。Further, from the comparison between the cured product 8 and the cured product 9, it was confirmed that the heat resistance of the cured product obtained was further improved by introducing an aromatic group into R e and R f of the compound containing ruthenium, and further, the cured product was obtained. In comparison with the cured product 10, it was confirmed that heat resistance can be further imparted by using the metal oxide fine powder.

Claims (7)

一種含有矽之化合物，其係以下述通式(0)所表示者： (式中，Ra ~Rd 及Rg 既可相同亦可不同，係碳原子數為1~12之飽和脂肪族烴基、或可以飽和脂肪族烴基取代之碳原子數為6~12之芳香族烴基；Re 及Rf 既可相同亦可不同，係可以飽和脂肪族烴基取代之碳原子數為6~12之芳香族烴基；Y為碳原子數為2~4之伸烷基，Z為以下述式(2)~(6)中之任一者所表示之基： (式中，Xa ~Xc 表示亞甲基可以氧原子及/或酯鍵取代的碳原子數為1~8之烷二基、-COO-或單鍵；Rh ~Rj 表示氫原子或甲基；r表示0或1)；K為2~7之數，T為1~7之數，以T為重複數之聚合部分與以K-T為重複數之聚合部分既可為嵌段狀亦可為隨機狀；P為0~3之數；M及N為N：M=1：1~1：100、且所有M與所有N之合計值為15以上之數，且係使以通式(0)表 示之含有矽之化合物的質量平均分子量為3000~100萬之數；又，以M為重複數之聚合部分與以N為重複數之聚合部分既可為嵌段狀亦可為隨機狀)。A compound containing ruthenium represented by the following formula (0): (wherein R a to R d and R g may be the same or different, and are a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or a 6 to 12 carbon atom which may be substituted by a saturated aliphatic hydrocarbon group. a hydrocarbon group; R e and R f may be the same or different, and may be an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group; Y is an alkylene group having 2 to 4 carbon atoms, Z It is a base represented by any one of the following formulas (2) to (6): (wherein, X a to X c represents an alkanediyl group having 1 to 8 carbon atoms or a -COO- or a single bond in which a methylene group may be substituted with an oxygen atom and/or an ester bond; and R h to R j represents a hydrogen atom; Or methyl; r represents 0 or 1); K is a number from 2 to 7, T is a number from 1 to 7, and the polymerized portion having a repeating number of T and the polymerized portion having a repeating number of KT may be in the form of a block It can also be random; P is 0~3; M and N are N:M=1:1~1:100, and the total value of all M and all N is 15 or more, and the system is The mass average molecular weight of the compound containing ruthenium represented by the formula (0) is 3,000 to 1,000,000; and the polymerized portion having a repeating number of M and the polymerized portion having a repeating number of N may be in the form of a block or a Random). 一種含有矽之化合物，其係以下述通式(1)所表示者： (式中，Ra ~Rd 及Rg 既可相同亦可不同，其係碳原子數為1~12之飽和脂肪族烴基、或可以飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基；Re 及Rf 既可相同亦可不同，係可以飽和脂肪族烴基取代之碳原子數為6~12之芳香族烴基；Y為碳原子數為2~4之伸烷基，Z為以下述式(2)~(6)中之任一者所表示之基，k為2~7之數，p為1~4之數；m及n為n：m=1：1~1：100、且m+n≧15之數，且係使以通式(1)表示之含有矽之化合物的質量平均分子量為3000~100萬之數；又，以m為重複數之聚合部分與以n為重複數之聚合部分既可為嵌段狀亦可為隨機狀)； (式中，Xa ~Xc 表示亞甲基可以氧原子及/或酯鍵取代的碳原子數為1~8之烷二基、-COO-或單鍵；Rh ~Rj 表示氫原 子或甲基；r表示0或1)。A compound containing ruthenium represented by the following formula (1): (wherein R a to R d and R g may be the same or different, and are a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or a carbon atom which may be substituted with a saturated aliphatic hydrocarbon group of 6 to 12; An aromatic hydrocarbon group; R e and R f may be the same or different, and may be an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group; and Y is an alkylene group having 2 to 4 carbon atoms. Z is a group represented by any one of the following formulas (2) to (6), k is a number from 2 to 7, and p is a number from 1 to 4; m and n are n: m = 1:1. 1:100, and m+n≧15, and the mass average molecular weight of the compound containing ruthenium represented by the general formula (1) is 3,000 to 1,000,000; and the polymerization portion of m is a repeating number The polymerized portion having a repeating number of n may be either block-shaped or random); (wherein, X a to X c represents an alkanediyl group having 1 to 8 carbon atoms or a -COO- or a single bond in which a methylene group may be substituted with an oxygen atom and/or an ester bond; and R h to R j represents a hydrogen atom; Or methyl; r represents 0 or 1). 如請求項1或2之含有矽之化合物，其中以Ra ~Rg 表示之基中，碳原子數為1~12之飽和脂肪族烴基與可以飽和脂肪族烴基取代的碳原子數為6~12之芳香族烴基之比例(前者：後者)為100：1~1：2。A compound containing ruthenium according to claim 1 or 2, wherein a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms and a carbon atom which may be substituted with a saturated aliphatic hydrocarbon group is 6 in a group represented by R a to R g The proportion of 12 aromatic hydrocarbon groups (the former: the latter) is 100:1 to 1:2. 一種硬化性組合物，其係相對於100質量份之如請求項1至3中任一項之含有矽之化合物、含有0.01~20質量份之環氧硬化性化合物者。 A curable composition which is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the compound containing cerium according to any one of claims 1 to 3, and an epoxy hardening compound. 一種硬化性組合物，其係相對於100質量份之如請求項1至3中任一項之含有矽之化合物、含有0.01~30質量份之環氧硬化性化合物及1~50質量份之環氧化合物者。 A curable composition containing 0.01 to 30 parts by mass of an epoxy hardening compound and 1 to 50 parts by mass with respect to 100 parts by mass of the compound containing cerium according to any one of claims 1 to 3, Oxygen compounds. 如請求項4或5之硬化性組合物，其進一步含有1~1000質量份之金屬氧化物微粉末。 The curable composition according to claim 4 or 5, which further contains 1 to 1000 parts by mass of the metal oxide fine powder. 一種硬化物，其係使如請求項4至6中任一項之硬化性組合物硬化而成者。 A cured product obtained by hardening a curable composition according to any one of claims 4 to 6.
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