TW565589B

TW565589B - Cycloolefin composition, process for producing the same, molding material, and molded object

Info

Publication number: TW565589B
Application number: TW089103284A
Authority: TW
Inventors: Hitoshi Yamazaki; Tomoaki Aoki; Hiromasa Kawai; Masami Yusa; Yoshiki Inoue
Original assignee: Hitachi Chemical Co Ltd
Priority date: 1999-02-26
Filing date: 2000-02-24
Publication date: 2003-12-11
Also published as: AU2693600A; MY135880A; WO2000050513A1; KR100436989B1; KR20010110448A

Abstract

A cycloolefin composition which comprises a cycloolefin monomer capable of undergoing metathesis polymerization, a coupling agent which is a metallic coupling agent or a reactive polysiloxane, and a metathesis polymerization catalyst; a process for producing the composition; a molding material comprising the composition; and a molded object which is a cured article obtained from the molding material.

Description

565589 A7 B7 五、發明說明（1 ) (請先閱讀背面之注意事項再填寫本頁) 本發明係有關含有環烯烴類之環烯烴組成物及其製造方法以及使用該組成物之成形材料以及使該成形材料硬化後取得之成形體者。先行技術中，環烯烴類係藉由複分解（易位）聚合觸媒後開環易位聚合者爲公知者。例如：J. Am. Chem. Soc.， 1 960, Vol· 82, Ρ· 23 37所載之原菠烷藉由易位觸媒系後，進行開環易位聚合者，如：Angew. Chem. Int. Edn.，1964，565589 A7 B7 V. Description of the invention (1) (Please read the notes on the back before filling out this page) The present invention relates to a cycloolefin composition containing cyclic olefins, a method for manufacturing the same, a molding material using the composition, and a A molded body obtained by curing the molding material. In the prior art, cycloolefins are known by metathesis (metathesis) polymerization catalysts after ring-opening metathesis polymerization. For example: The original spinane contained in J. Am. Chem. Soc., 1 960, Vol. 82, P. 23 37 undergoes a ring-opening metathesis polymerization after the metathesis catalyst system, such as: Angew. Chem Int. Edn., 1964,

Vol. 3, P. 7 23所載之環戊烯係藉由易位觸媒系 [Μ 〇 C 1 2 / A 1 ( C 2 Η 5 ) 3〕後，進行開環易位聚合者。又，環烯烴類經開環易位聚合後製造聚合物之方法亦爲公知者。例如：特開昭5 0 - 1 3 0 9 0 0號公報、特開昭5 2 - 3 3 0 0 0號公報公開以鎢、鉬等之鹵化物與有機鋁化合物所成之易位觸媒系製造開環易位聚合聚合物之方法。經濟部智慧財產局員工消費合作社印製另外，使二環戊二烯、三環戊二烯等之原菠烷型單體藉由反應射出成形（R I Μ )後進行塊狀聚合後，取得交聯聚合物成形物之方法亦爲公知者。此反應射出成形係將相互反應2種類溶液經碰撞混合之其混合液直接以液狀注入模具內之後，以塊狀進行開環易位聚合之成形方法者。例如：特開昭5 8 - 1 2 7 7 2 8號公報、特開昭 5 8 — 1 2 9 0 1 3號公報公開易位觸媒系之觸媒成份及單體混合物所成之溶液Α與易位觸媒系之活性化劑及單體混合物所成之溶液B經反應射出成形後取得交聯聚合物成 -4- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 A7 B7 五、發明說明（2 ) 形物之方法者。特開昭5 9 — 5 1 9 1 1號公報公開選自鎢及鉬之有機銨鹽之觸媒成份與選自烷氧基烷基鋁氯化物及芳基氧基鋁氯化物之活性化劑相互組合之易位觸媒系使用之後，使原菠烷型單體進行反應射出成形後，製造交聯聚合物成形體之方法者。另外，特開平3 — 2 0 5 4 0 9號公報公開選自六氯化鎢及氧基四氯化鎢之觸媒成份與選自氯化二乙基鋁與二氯化乙基鋁之活性化劑之組合易位觸媒系使用後，以反應射出成形法製造交聯之二環戊二烯聚合物之方法者。此等易位觸媒系中，觸媒成份係藉由活性化劑被活化，使原菠烷型單體進行開環易位聚合者。另外，其易位觸媒系中，觸媒成份係藉由其觸媒（活性化劑）成份被活化，使原菠烷型環烯烴類進行開環易位聚合者。此取得之硬化物（亦即環烯烴聚合物）具有良好之機械特性、電氣性特性及耐水性等爲公知者。例如：進行彎曲試驗後，出現降伏現象，更且，易彎率亦非常大，比起環氧樹脂、不飽和聚酯樹脂等之其他熱硬化性樹脂較具靭性者。惟，此環烯烴組成物係添加塡充材後明顯之黏度增力口、作業性變差。因此，先行技術使用塡充材時，爲降低粘度而期以添加偶合劑。例如：特開平0 2 — 1 8 5 5 5 8 號公報中之原菠烷系矽烷偶合劑、特開平〇2 — 2 7 6 8 5 2號公報中之烯丙基系矽烷偶合劑、乙本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注音？事項再填寫本頁) i — — — — — — — — — 經濟部智慧財產局員工消費合作社印製 -5- 565589 A7 B7 五、發明說明（3 ) 烯系矽烷偶合劑、特開平9 — 1 8 3 8 3 3號公報中一般之矽烷偶合劑被提出。 (請先閱讀背面之注意事項再填寫本頁) 惟，使用矽烷偶合劑後，藉由樹脂與塡充材間相互接合後，其聚合物之彈性率上昇，更且，彎曲試驗時之彎度亦變小。出現環烯烴組成物特徵之一之靭性消失之問題。本發明係以提供一種即使使用塡充材仍具良好作業性及機械特性之環烯烴組成物，該組成物之製造方法、成形材料及成形體爲目的者。爲達成此目的，本發明者針對各種偶合劑進行硏討結果發現藉由使用特定之偶合劑可確保環烯烴類之靭性及組成物之作業性，同時可大量添加塡充材，進而完成本發明。亦即，本發明中，提供含有可易位聚合之環烯烴類單體與偶合劑及易位聚合觸媒之環烯烴組成物者，含有含金屬偶合劑或反應性聚矽氧烷做爲偶合劑者。本發明之環烯烴組成物可含有塡充材者。更且，本發明中提供此本發明之組成物製造方法與含有該組成物之成形材料及其硬化物之成形體者。經濟部智慧財產局員工消費合作社印製含金屬偶合劑其環烯烴類及塡充材之反應快可維持機械特性，提昇作業性。使用本發明之含金屬偶合劑與先行技術之矽烷偶合劑不同，雖未具碳酸鈣等之氫氧基之塡充材亦有效果。且，爲使偶合劑與塡充材反應之加熱處理時間極短可完成爲其優點者。又，反應性聚矽氧烷可使樹脂與塡充材兩相歪斜下進行吸收，因此可維持聚合物之靭性，其他特性亦比先行技 -6- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）經濟部智慧財產局員工消費合作社印製 565589 A7 B7 五、發明說明（4 ) 術同等以上之效果。本發明所使用之反應性聚矽氧烷由於具有良好接合性，藉由塡充材與樹脂之界面剝離現象後，可迴避耐水性及電氣絕緣性之下降者。〔發明實施之最佳形態〕 A .環烯烴類單體本發明所使用之環烯烴類單體只要於易位聚合中爲有用者即可。其中又以原菠烷、二環戊二烯、二氫二環戊二烯等之取代或非取代原菠烷型環烯烴類爲較適使用者。做爲原菠烷型環烯烴類之例者如：原菠烷、甲基原菠烷、二甲基原菠烷、乙基原菠烷、亞乙烯基原菠烷、丁基原菠烷等二環原菠烷、二環戊二烯（環戊二烯之二量體）、二氫二環戊二烯、甲基二環戊二烯、二甲基二環戊二烯等之三環原菠烷、四環十二烯、甲基四環十二烯、二甲基四環十二烯等之四環原菠烷、以及三環戊二烯（環戊二烯之三量體）、四環戊二烯（環戊二烯之四量體）等之五環以上之原菠烷之例。又，環丁烯、環戊烯、環辛烯、環辛二烯、環辛三烯、環十二基三烯等均可使用之。更可使用二環戊二烯進行熱聚合、陽離子聚合後取得之二環戊二烯系石油樹脂等者。此等環烯烴類可以1種或2種以上組合者使用之。又，具有2個以上之原菠烷基之化合物之例可以原菠烷基二烯、四環十二基二烯、對稱型三環戊基二烯等做爲本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公~ (請先閱讀背面之注音？事項再填寫本頁) i 訂--------- 565589 A7 ___B7 五、發明說明（5 ) 多官能交聯劑使用者。 (請先閱讀背面之注意事項再填寫本頁) 上述環烯烴類之中由易於取得，經濟性面，以二環戊二烯、甲基四環十二烯、亞乙烯基原菠烷、三環戊二烯、四環戊二烯者宜，特別以二環戊二烯爲更理想。另外，一般市販之二環戊二烯係以乙烯基原菠烷、四氫茚、甲基乙烯基原菠烷、甲基四氫茚、甲基二環戊二嫌、二甲基二環戊二烯、三環戊二烯等做爲不純物含有者，各種純度之二環戊二烯被市販之。本發明所使用之二環戊二烯之例依其取得聚合物之使用目的不同而異，通常以 8 0 %以上之純度者宜，更佳者以9 0 %以上之純度者使用之。使用二環戊二烯時，預先藉由加熱處理後，將部份二環戊二烯做成三環戊二烯、四環戊二烯等之環戊二烯低聚物，可使不純物之乙烯基原菠烷、甲基乙烯基原菠烷呈四氫茚、甲基四氫茚進行異性化者。此預先加熱處理通常於 1 2 0〜2 5 0 °C下進行0 · 5〜1 0小時者。經濟部智慧財產局員工消費合作社印製本發明所使用之環烯烴類中，必要時可添加氧化防止劑。又，一般被市販之二環戊二烯中已含有2，6 —二（第3 — 丁基）一 4 一甲基苯酚、4 一第3 — 丁基與茶酚等氧化防止劑。使用時去除所含之氧化防止劑，或新增添力口亦可。做爲所使用之氧化防止劑者，只要有防止氧化能力即可，別無限定，較理想者如：受阻酚系之氧化防止劑之例。例如：2，6 —二（第3 —丁基）一 4 一甲基苯酌、2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） Tq： ------- 565589 發明說明（6 ) 弟3 -丁基）一 4 一乙基本酹、硬脂烯一羥基苯基}丙酸酯、 6 —二（ 3，5 —二（第 3 —丁基）一 4 四一〔亞甲基一 3 5 4 羥苯基}丙酸酯〕甲烷、2 一乙基—6 —第3 —丁基苯酚）、4 2，6 -二（第3 — 丁基）苯酚}、三{ 3，5 —二（，3 ，5 —三{ 3 一（弟 3 —丁基）_ 2 /〜亞甲基雙（4 ，4，一亞甲基雙{ 甲基 2 ，4 6 第3 — 丁基）_ 4 羥基苄基}苯 (第 ( 之種針經濟部智慧財產局員工消費合作社印製The cyclopentene system contained in Vol. 3, P. 7 23 is subjected to a ring-opening metathesis polymerization using a metathesis catalyst system [Moc 1 2 / A 1 (C 2 Η 5) 3]. Further, a method for producing a polymer by ring-opening metathesis polymerization of a cycloolefin is also known. For example: JP-A No. 5 0-1 3 0 9 0 0, JP-A No. 5 2-3 3 0 0 0 discloses a metathesis catalyst formed by a halide of tungsten, molybdenum, etc. and an organoaluminum compound. It is a method for producing ring-opening metathesis polymer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the original spinane monomers such as dicyclopentadiene and tricyclopentadiene were subjected to block polymerization by reaction injection molding (RI M), and then obtained. A method of forming a polymer is also known. This reaction injection molding method is a molding method in which two kinds of solutions that react with each other are directly mixed into the mold in a liquid state after collision and mixing, and the ring-opening metathesis polymerization is performed in a block shape. For example, JP 5-8-1 2 7 7 2 8 and JP 5 8-1 2 9 0 1 3 disclose the solution A of the catalyst component and monomer mixture of the metathesis catalyst system. Solution B formed with the activation agent and monomer mixture of the metathesis catalyst system is reacted and injection-molded to obtain a cross-linked polymer. -4- This paper size is applicable to China National Standard (CNS) A4 (210 X 297). (Centi) 565589 A7 B7 V. Description of the invention (2) The person who shaped the object. Japanese Patent Laid-Open No. 5 9 — 5 1 9 1 1 discloses a catalyst component selected from organic ammonium salts of tungsten and molybdenum and an activating agent selected from alkoxyalkyl aluminum chlorides and aryloxy aluminum chlorides. The combined metathesis catalyst is a method for producing a crosslinked polymer molded body by reacting and injection-forming an orthospinoid monomer after use. In addition, Japanese Unexamined Patent Publication No. 3-2 0 5 4 0 9 discloses a catalyst component selected from tungsten hexachloride and oxytungsten tetrachloride and an activity selected from diethylaluminum chloride and ethylaluminum dichloride. The combined metathesis catalyst of the chemical agent is a method for producing a crosslinked dicyclopentadiene polymer by a reaction injection molding method after use. In these metathesis catalyst systems, the catalyst component is activated by an activating agent to cause the ring-opening metathesis polymerization of the original spinane-type monomer. In addition, in the metathesis catalyst system, the catalyst component is activated by its catalyst (activator) component, and the original spinane-type cycloolefins are subjected to ring-opening metathesis polymerization. It is known that the obtained hardened material (that is, a cycloolefin polymer) has good mechanical properties, electrical properties, and water resistance. For example, after the bending test, there is a dropout phenomenon. Moreover, the bendability is very large, and it is more flexible than other thermosetting resins such as epoxy resins and unsaturated polyester resins. However, this cycloolefin composition has a significant viscosity increase after the addition of rhenium filling material, and the workability becomes worse. Therefore, in the prior art, when a radon filling material is used, a coupling agent is added in order to reduce the viscosity. For example: Proto-Spinane-based silane coupling agent in JP-A No. 0 2-1 8 5 5 5 8; Allyl-based silane coupling agent in JP-A No. 02-2 7 6 8 5 2; Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) i — — — — — — — — — Staff Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs Printed -5- 565589 A7 B7 V. Description of the invention (3) Ethylene-based silane coupling agent, JP-A 9-1 8 3 8 3 General silane coupling agent is proposed. (Please read the precautions on the back before filling this page.) However, after using a silane coupling agent, the resin and the filling material are bonded to each other, the elasticity of the polymer increases, and the bending degree during the bending test is also Get smaller. There is a problem that the toughness, which is one of the characteristics of the cycloolefin composition, disappears. The present invention aims to provide a cyclic olefin composition having good workability and mechanical properties even when a rhenium filling material is used, a method for producing the composition, a molding material, and a molded body. In order to achieve this purpose, the inventors have conducted discussions on various coupling agents and found that the use of specific coupling agents can ensure the toughness of cycloolefins and the workability of the composition, and at the same time, a large amount of rhenium filling materials can be added to complete the present invention. . That is, in the present invention, a cyclic olefin composition containing a metathesis-polymerizable cyclic olefin-based monomer, a coupling agent, and a metathesis polymerization catalyst is provided, which contains a metal-containing coupling agent or a reactive polysiloxane as a coupling agent. Mixer. The cyclic olefin composition of the present invention may contain a rhenium filler. Furthermore, the present invention provides a method for manufacturing the composition of the present invention, and a molding material containing the composition and a molded body thereof. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The fast reaction of cyclic olefins and plutonium filling materials containing metal coupling agents can maintain mechanical characteristics and improve workability. The use of the metal-containing coupling agent of the present invention is different from the prior art silane coupling agent, and it is effective even if it has no hydroxyl group such as calcium carbonate. In addition, the heat treatment time for reacting the coupling agent with the rhenium filling material is extremely short and can be completed as its advantage. In addition, the reactive polysiloxane can absorb the resin and rhenium filling materials in two-phase skew, so it can maintain the toughness of the polymer, and other characteristics are also better than the leading technology-6- This paper is applicable to Chinese National Standard (CNS) A4 Specifications (210 X 297 Public Love) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 565589 A7 B7 V. Description of the invention (4) The technical effect is equal to or more than the same. Since the reactive polysiloxane used in the present invention has good bonding properties, it is possible to avoid the decrease in water resistance and electrical insulation after the phenomenon of interfacial peeling between the filler and the resin. [Best Mode for Carrying Out the Invention] A. Cycloolefin-based monomer The cycloolefin-based monomer used in the present invention is only required to be useful in metathesis polymerization. Among them, substituted or non-substituted ortho-cyclopentadienes such as orane-cyclopentadiene, dihydrodicyclopentadiene and the like are more suitable for users. Examples of ortho-cyclopentane cycloolefins are: ortho-cyclopentane, methyl-ortho-cyclopentane, dimethyl-ortho-cyclopentane, ethyl-ortho-cyclopentane, vinylidene-ortho-cyclopentane, butyl-ortho-cyclopentane and the like Protospinane, dicyclopentadiene (dicyclopentadiene), trihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, etc. Tetracyclododecane, tetracyclododecene, methyl tetracyclododecene, dimethyl tetracyclododecene, etc., and tricyclopentadiene (the triad of cyclopentadiene), tetracycline Examples of cyclopentadiene (quaternary body of cyclopentadiene) and other pentacyclic orthorane. Cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecyltriene, and the like can be used. Dicyclopentadiene-based petroleum resins obtained by thermal polymerization and cationic polymerization can also be used. These cycloolefins may be used singly or in combination of two or more kinds. In addition, examples of compounds having two or more orthospinyl groups may include orthospinyl diene, tetracyclododecyl diene, symmetric tricyclopentyl diene, etc. as the paper standard. Chinese national standards ( CNS) A4 specification (210 X 297 male ~ (Please read the note on the back? Matters before filling out this page) i Order --------- 565589 A7 ___B7 V. Description of the invention (5) Multifunctional crosslinking agent Users (Please read the notes on the back before filling out this page) Among the above cycloolefins, it is easy to obtain and economical, with dicyclopentadiene, methyl tetracyclododecene, and vinylidene Alkane, tricyclopentadiene, and tetracyclopentadiene are preferred, and dicyclopentadiene is particularly preferred. In addition, general commercial dicyclopentadiene is vinylorane, tetrahydroindane, methyl Divinyl prospinane, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, etc. as impurities, dicyclopentadiene of various purity It is sold by the market. The examples of dicyclopentadiene used in the present invention vary depending on the purpose for which the polymer is obtained, and it is usually 80% or more. For purity, it is better to use it with a purity of more than 90%. When using dicyclopentadiene, some dicyclopentadiene is made into tricyclopentadiene and tetracyclopentadiene by heat treatment beforehand. Cyclopentadiene oligomers, such as cyclopentadiene, can make the impure vinyl ortho-pinane and methyl vinyl ortho-pinane into tetrahydroindene or methyltetrahydroindene. It is usually carried out at 120 to 250 ° C for 0.5 to 10 hours. The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the cycloolefins used in the present invention, and an oxidation inhibitor can be added if necessary. Also, dicyclopentadiene, which is generally sold by the market, already contains oxidation inhibitors such as 2,6-bis (3-butyl) -4methylphenol, 4-3-butyl, and theophylol. When used It is also possible to remove the oxidation inhibitor contained in it or add a new one. As the oxidation inhibitor used, there is no limitation as long as it has the ability to prevent oxidation. Ideal ones are: hindered phenol-based oxidation inhibitors Example: For example: 2,6-di (3-butyl) -4 methylbenzene, 2 papers Degree Applicable to Chinese National Standard (CNS) A4 Specification (210 X 297 mm) Tq: ------- 565589 Description of Invention (6) Brother 3-butyl) -4 4-ethylbenzidine, stearyl-hydroxyl Phenyl} propionate, 6-bis (3,5-bis (3-butyl) -1,4-tetrakis [methylene-3,5-4hydroxyphenyl} propionate] methane, 2-ethyl- 6-three-butylphenol), 4 2,6-bis (3-butyl) phenol}, tris {3,5-di (, 3,5, tris {3-(di 3-butyl) _ 2 / ~ methylenebis (4,4, monomethylenebis {methyl2,4 6 3rd-butyl) _ 4 hydroxybenzyl} benzene (the employee of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives

劑 0 B 丁基）一 1 Η、3 氧化防止使用，亦對環烯烴更可倂用又，爲環戊膦、之適當量 .001 4 —經基卡基} —S —二嗪一 2，4， Η、5 劑、熱可2種時一般紫外線調整聚三丁膦一般針〜1 0 Η )三酮等例。又劣化防止劑亦可使以上組合使用之。爲1 0〜1 0 ，〇吸收劑、光安定劑合反應，亦可添加、三異丙膦等之反對原料單體1 〇〇重量份者。 ’胺系、硫系、磷系用之。此等可單獨1 氧化防止劑之添加量〇0ppm者。另外等。三苯膦、三環己膦、應調整劑。反應調整重量份時爲 .塡充材本發明之組成物及成形材料可含有塡充材。做爲本發適當之塡充材者如：氧化物系、氫氧化物系、碳酸鹽系硫酸鹽系、矽酸鹽系之塡充材之例。塡充材可單獨使用亦可使用2種以上組合者，無特別限定者。 c請先閱讀背面之注音？事項再填寫本頁) .9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9 - 565589 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（7 ) 做爲氧化物系之塡充材者如：二氧化矽、矽藻土、鋁氧粉、氧化鋅、氧化鈦、氧化鈣、氧化鎂、氧化鐵、氧化錫、氧化銻、鐵酸鹽類等例。做爲氫氧化物系之塡充材者如：氫氧化鈣、氫氧化鎂、氫氧化鋁、鹽基性碳酸鎂等例。做爲碳酸鹽系之塡充材者如：碳酸鈣、碳酸鎂、碳酸鋅、碳酸鋇、碳酸鈉鋁石（dewsomte )水滑石等例。硫酸鹽系之塡充材例如：硫酸鈣、硫酸鋇、石膏纖維等例。矽酸鹽系之塡充材例如：矽酸鈣（矽灰石、硬矽鈣石、滑石、粘土、陶土、雲母、蒙脫石、膨潤土、活性白土、海泡石、（ImogoUte )、絹雲母、玻璃粉、玻璃纖維、玻璃珠、玻璃球、白砂球等例。做爲氮化物系之塡充材者如：氧化鋁、氮化硼、氮化矽等例。炭系之塡充材例如··炭黑、石墨、碳纖維、炭球、木炭粉、膨脹石墨等例。其他塡充材例如：各種金屬粉末、金屬纖維、鈦酸鉀等之晶鬚、熱塑性樹脂、熱硬化性樹脂之粉末，更有矽砂、碎石、砂礫等天然物等例。此等塡充材中特別以玻璃、二氧化矽、鋁氧粉、氫氧化鎂、氫氧化銘、砂砂爲較理想者。塡充材之添加量爲總組成物之1〜9 9重量％者宜’ 5〜9 5重量％爲較佳，3 0〜9 0重量％爲更佳者。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- II ——I------MW--------T ------- (請先閱讀背面之注意事項再填寫本頁) 565589 經濟部智慧財產局員工消費合作社印製 A7 ____B7_____ 五、發明說明（8 ) C ·偶合劑本發明組成物及成形材料係以至少任一含有含金屬偶合劑及反應性聚矽氧烷者做爲偶合劑。此等可單一使用亦可合倂使用之。本發明所使用之偶合劑使用量爲當1 0 0重量份塡充材時爲0 · 0 5〜2 0重量份者宜，更佳者爲0 · 1〜5 重量份。其理由係當小於此比例使用量時，則塡充材與樹脂之濕潤性將不足，則改善複合材料之機械性特性等之效果無法充份取得。又，多於此比例之使用量時，則機械特性、耐水性無法更爲提昇、經濟面不理想。偶合劑可使用預先處理之塡充材者，亦可於混合樹脂材料與塡充材之添加時使用者。預先處理塡充材時，可與先行技術之藉由進行偶合劑處理方法相同方法進行之。例如：若爲粉體狀之無機塡充材可將偶合劑直接或溶媒稀釋後進行添加之後，藉由hens hell mixer、super mixer等攪拌器後混合之後，加熱處理後 ’使偶合劑與無機塡充材相互反應即可。加熱處理以室溫〜1 4 0 °C下進行〇 · 5〜6小時者宜。又，纖維狀之塡充材時，於稀釋偶合劑之溶液中浸漬纖維後，相同加熱條件下進行處理即可。又，於樹脂材料與塡充材混合時添加偶合劑時，例如 :將偶合劑加入樹脂材料中或塡充材中分散之後，使樹脂材料與塡充材混合後，隨後，必要時將上述塡充材與預先處理時相同進行加熱處理即可。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11 - -------------------訂---------^一^ (請先閱讀背面之注音？事項再填寫本頁) 565589 A7 B7Agent 0 B butyl)-1 Η, 3 to prevent the use of oxidation, but also more suitable for cyclic olefins, and is the appropriate amount of cyclopentylphosphine. 001 4-via kikayl} -S-diazine-2, 4, fluorene, 5 agents, heat can be two kinds of general ultraviolet adjustment polytributylphosphine general needle ~ 10 Η) triketones and other examples. The deterioration preventing agent may be used in combination. It is a combination of 10 ~ 10, 0 absorber and light stabilizer, and it can also add 100 parts by weight of the raw material monomer, such as triisophosphine. It is used for amine system, sulfur system and phosphorus system. These can be added separately to the oxidation inhibitor OOppm. In addition, etc. Triphenylphosphine, tricyclohexylphosphine, should be adjusted. Reaction adjustment The weight part is. 塡 filler. The composition and molding material of the present invention may contain a 塡 filler. Examples of suitable radon filling materials for the present invention are: oxide-based, hydroxide-based, carbonate-based sulfate-based, and silicate-based radon filling materials.塡 The filler can be used alone or in combination of two or more, without particular limitation. c Please read the Zhuyin on the back first? Please fill in this page again for matters) .9 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -9-565589 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (7) As oxide filling materials such as: silica, diatomaceous earth, alumina powder, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrite, etc. example. As the hydroxide filling materials such as: calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and other examples. As carbonate filling materials such as: calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, sodium bicarbonate (dewsomte) hydrotalcite and other examples. Examples of sulfate-based concrete filling materials include calcium sulfate, barium sulfate, and gypsum fiber. Silicate-based filling materials such as: calcium silicate (wollastonite, wollastonite, talc, clay, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, (ImogoUte), sericite , Glass powder, glass fiber, glass beads, glass ball, white sand ball, etc. As examples of nitride-based samarium filling materials such as: alumina, boron nitride, silicon nitride, etc. Examples of carbon-based samarium filling materials ·· Examples of carbon black, graphite, carbon fiber, carbon ball, charcoal powder, expanded graphite, etc. Other concrete filling materials such as: whiskers of various metal powders, metal fibers, potassium titanate, thermoplastic resin, powder of thermosetting resin There are also examples of natural objects such as silica sand, crushed stone, gravel, etc. Among these concrete filling materials, glass, silicon dioxide, aluminum oxide powder, magnesium hydroxide, hydroxide hydroxide, and sand are the ideal ones. 塡The filler is added in an amount of 1 to 99% by weight of the total composition. It is better to use 5 to 95% by weight, and 30 to 90% by weight. The paper size is subject to the Chinese National Standard (CNS). ) A4 specification (210 X 297 mm) -10- II ——I ------ MW -------- T ------- (Please Read the notes on the back and fill in this page) 565589 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____B7_____ V. Description of the invention (8) C. Couplings The composition and forming materials of the present invention are made of at least one Mixtures and reactive polysiloxanes are used as coupling agents. These can be used singly or in combination. The amount of coupling agent used in the present invention is 0 · 0 when 100 parts by weight of 塡 filling material. 5 to 20 parts by weight, more preferably 0 · 1 to 5 parts by weight. The reason is that when the ratio is less than this amount, the wettability of the filler and resin will be insufficient, and the mechanical properties of the composite material will be improved. Effects such as sexual properties cannot be fully obtained. In addition, when the amount is more than this ratio, mechanical properties and water resistance cannot be improved, and the economic aspect is not ideal. Coupling agents can use pre-treated concrete filling materials, also It can be used by the user when adding the resin material and the concrete filling material. When the concrete filling material is processed in advance, it can be performed in the same way as the prior art by performing a coupling agent treatment method. For example, if it is a powdery inorganic concrete filling material The coupling agent can be added directly after dilution of the coupling agent or the solvent, and then mixed with a stirrer such as a hens hell mixer or a super mixer. After the heat treatment, the coupling agent and the inorganic concrete filling material can be reacted with each other. It is preferable to perform it for 0.5 to 6 hours at a temperature of ~ 140 ° C. When the fibrous tincture is filled, the fiber is immersed in the solution of the dilute coupling agent, and then the treatment may be performed under the same heating conditions. When adding a coupling agent when the resin material is mixed with the concrete filling material, for example, after adding the coupling agent to the resin material or dispersing it in the concrete filling material, after mixing the resin material and the concrete filling material, then, if necessary, the above concrete filling material is mixed. The heat treatment may be performed as in the case of the pretreatment. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -11-------------------- Order -------- -^ 一 ^ (Please read the phonetic on the back? Matters before filling out this page) 565589 A7 B7

經濟部智慧財產局員工消費合作社印製五、發明說明（9 ) (a )含金屬偶合劑本發明所使用之含金屬偶合劑係於分子內含有金屬原子之化合物者，無機材料與有機材料之複合系，或不同種之有機材料相互之複合系中，化學性兩者結合，或伴隨化學反應性改善親和性之材料者。做爲此含金屬偶合劑者通常使用於金屬結合水解性基者。做爲含於含金屬偶合劑中之金屬例如：鈦、鋁、鉻、鐵、鈣、鎂、鋅等例，特別以鈦、鋁、锆爲較佳者。另外，做爲水解性基之例者並無特限定，而一般以烷氧基爲較佳者。做爲本發明中適當之鈦系偶合劑者如：異丙三異硬脂醯鈦酸酯、異丙基三-正月桂基苯磺醯鈦酸酯、異丙基三 (二辛基焦磷酸酯）鈦酸酯、四異丙基雙（二辛基磷酸酯 )鈦酸酯、四辛基雙（二三癸基磷酸酯）鈦酸酯、四（2， 2 -二烯丙基氧甲基一 1 — 丁基）雙（二三癸基磷酸酯） )鈦酸酯、雙（二辛基焦磷酸酯）乙烯鈦酸酯、異丙基三辛氧基鈦酸酯、異丙基二甲基丙烯醯基異硬脂醯鈦酸酯、異丙基異硬脂醯二丙烯基鈦酸酯、異丙基三（二辛基磷酸酯）鈦酸酯、異丙基三枯基苯基鈦酸酯、異丙基三（正一胺基乙基-胺基乙基）鈦酸酯、四異丙基鈦酸酯、四正丁基鈦酸酯、丁基鈦酸酯二聚物、四（2 —乙基己基）鈦酸酯、四硬脂烯鈦酸酯、四甲基鈦酸酯、二乙氧基雙（乙醯基乙酮酸酯）鈦、二異丙基雙（乙醯乙酮酸酯）鈦、二異丙氧基雙（乙基乙醯之酸酯）鈦、異丙氧基（2 一乙基一 ------1-------------訂--------- -m (請先閱讀背面之注音？事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 12- 565589 A7 _ B7 五、發明說明（1〇 ) 1 ’ 3 —己二黃酮）鈦、二（2 —乙基己氧基）雙（2 — 乙基一 1 ，3 —己二黃酮）鈦、二（正一丁氧基）雙（三 (請先閱讀背面之注意事項再填寫本頁) 乙醇醯胺化）鈦、四乙醯基乙酮酸酯鈦、羥基雙（乳酸）鈦等例。又’本發明適當之鋁系合金屬偶合劑之例爲乙醯烷氧基鋁二異丙酸酯等、锆系之例如：锆乙醯乙酮酸酯雙乙基乙酮酸酯等例。此等可單獨1種使用之，亦可2種以上合倂使用者。此等之含金屬偶合劑中特別以四（2，2 —二烯丙基氧甲基一 1 一丁基）雙{二（三癸基）}磷酸酯鈦酸酯、雙（二辛基焦磷酸酯）氧基乙酸酯鈦酸酯、異丙基三硬脂醯基鈦酸酯、以及乙醯烷氧基鋁二異丙酸酯爲更佳者。此等不具有阻礙易位聚合之硬化之胺基等，由於偶合效果高所致。經濟部智慧財產局員工消費合作社印製又，除上述之含金屬偶合劑更可倂用矽烷偶合劑等其他之偶合劑者。特別是以鈦系化合物做爲含金屬偶合劑使用時，其鈦系化合物亦做爲矽烷偶合劑之矽烷醇縮合反應觸媒之作用，因此，倂用矽烷偶合劑適於本發明者。做爲可倂用之矽烷偶合劑者可使用如：乙烯基矽烷化合物（乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等）、環氧基矽烷化合物（/3 -（ 3，4 一環氧基環己基）乙基三甲氧基矽烷、r-環氧丙氧基丙基三甲氧基矽烷等）、胺基矽烷化合物（r -胺基丙基三乙氧基矽烷、正- /5 ( 胺基乙基）r一胺基丙基甲基二甲氧基矽烷等）、甲基丙 13· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 A7 B7 五、發明說明（11 ) 烯醯矽烷化合物（r -胺基丙基甲基二甲氧基矽烷等）、甲基丙烯醯矽烷化合物（r -甲基丙烯醯基丙基三甲氧基矽烷等）或烷基矽烷化合物（甲基三甲氧基矽烷、甲基三乙氧基矽烷等）之公知之矽烷偶合劑、二甲氧基二甲基矽烷、二乙氧基二甲基矽烷、四甲氧基矽烷、四乙氧基矽烷等之烷氧基矽烷等者。 (b)反應性聚矽氧烷本發明所使用之反應性聚矽氧烷只要備有結合於矽原子之水解性基之聚矽氧烷者，並無特別限定。做爲水解性基者如：氫原子、烷氧基、烯丙氧基、酮肟酸鹽、胺基、胺氧基、氫硫基、脂烯基氧基等，又以烷氧基爲較佳者。做爲適於本發明理想之反應性聚矽氧烷者如：下記一般式（1 )〜（3 )任一所示之化合物之例者。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) (a) Metal-containing coupling agent The metal-containing coupling agent used in the present invention is a compound containing a metal atom in the molecule, an inorganic material and an organic material. Composite systems, or composite systems of different kinds of organic materials, where the two are chemically combined, or materials that improve affinity with chemical reactivity. For this purpose, metal-containing coupling agents are usually used for metal-binding hydrolyzable groups. As the metal contained in the metal-containing coupling agent, for example: titanium, aluminum, chromium, iron, calcium, magnesium, zinc, etc., titanium, aluminum, and zirconium are particularly preferred. In addition, examples of the hydrolyzable group are not particularly limited, and an alkoxy group is generally preferred. Examples of suitable titanium-based coupling agents in the present invention include isopropyltriisostearate, titanate, isopropyltri-n-laurylbenzenesulfonium titanate, and isopropyltris (dioctyl pyrophosphate). Ester) titanate, tetraisopropylbis (dioctylphosphate) titanate, tetraoctylbis (ditridecylphosphate) titanate, tetra (2,2-diallyloxymethyl) 1-butyl) bis (ditridecyl phosphate)) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctyl titanate, isopropyl di Methacryl isostearate 醯 titanate, isopropyl isostearate 醯 dipropenyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl Titanate, isopropyltris (n-monoaminoethyl-aminoethyl) titanate, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, Tetrakis (2-ethylhexyl) titanate, tetrastearyl titanate, tetramethyltitanate, diethoxybis (ethenylacetone) titanium, diisopropylbis (ethyl醯 Ethyl ketone ester) titanium, diisopropoxy bis (ethyl acetic acid) Acid ester) titanium, isopropoxy (2 monoethyl -------- 1 ------------- order --------- -m (please first Read the phonetic on the back? Matters need to fill in this page again) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 12- 565589 A7 _ B7 V. Description of the invention (1〇) 1 '3 —Second Flavones) titanium, bis (2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediflavones) titanium, bis (n-butoxy) bis (tri (please read the precautions on the back first) Fill out this page again) Examples of ethanol amidation) titanium, titanium tetraethylfluorenone ketate, and hydroxybis (lactic acid) titanium. Examples of suitable aluminum-based metal coupling agents of the present invention include acetoxyalkoxyaluminum diisopropylate and the like, and zirconium-based examples such as zirconium acetoacetonate diethylacetone and the like. These can be used alone or in combination of two or more. Among these metal-containing coupling agents, tetra (2,2-diallyloxymethyl-1 1-butyl) bis {di (tridecyl)} phosphate titanate, bis (dioctyl coke) Phosphate ester) oxyacetate titanate, isopropyl tristearate fluorinated titanate, and acetoalkoxy aluminum diisopropylate are more preferred. These hardened amine groups which do not hinder metathesis polymerization are due to the high coupling effect. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition to the above-mentioned metal-containing coupling agents, other coupling agents such as silane coupling agents can be used. In particular, when a titanium-based compound is used as a metal-containing coupling agent, the titanium-based compound also functions as a silanol condensation reaction catalyst for the silane coupling agent. Therefore, a silane coupling agent for use is suitable for the present inventors. As a usable silane coupling agent, for example: vinyl silane compounds (vinyl trimethoxy silane, vinyl triethoxy silane, etc.), epoxy silane compounds (/ 3-(3, 4- Epoxycyclohexyl) ethyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, etc.), aminosilane compounds (r-aminopropyltriethoxysilane, n- / 5 (Aminoethyl) r-aminopropylmethyldimethoxysilane, etc.), Methylpropane 13 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 565589 A7 B7 5 Explanation of the invention (11) Allyl silane compounds (r-aminopropylmethyldimethoxysilane, etc.), methacrylic silane compounds (r-methacrylmethylpropyltrimethoxysilane, etc.), or Alkylsilane compounds (methyltrimethoxysilane, methyltriethoxysilane, etc.) are well-known silane coupling agents, dimethoxydimethylsilane, diethoxydimethylsilane, tetramethoxy Alkoxysilanes such as silane, tetraethoxysilane, etc. (b) Reactive polysiloxane The reactive polysiloxane used in the present invention is not particularly limited as long as it is provided with a polysiloxane that is hydrolyzed to a silicon atom. Examples of hydrolyzable groups include: hydrogen atom, alkoxy group, allyloxy group, ketoxime salt, amine group, amineoxy group, hydrogenthio group, and aliphatic alkenyloxy group. The best. Examples of the reactive polysiloxane suitable for the present invention include the compounds represented by any one of the following general formulae (1) to (3).

R R R R RR R R R R

1 1 . I I I I M -（SiO)a-(Si〇)「(Si〇)d—(SiOh-Si-M1 …（1)1 1. I I I I M-(SiO) a- (Si〇) "(Si〇) d— (SiOh-Si-M1… (1)

' I I I I'I I I I

Q (請先閱讀背面之注意事項再填寫本頁) R Y z 經濟部智慧財產局員工消費合作社印製Q (Please read the notes on the back before filling out this page) R Y z Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

R R I R I R R 1 M2 -（SiO)f I 1 -(SiO)g-1 1 1 -（SiO)h— Si — Μ2 …（2 ) R 1 Y 1 Z 1 R R | R I R R Μ3 - Si - 〇 1 一（SiO)厂 | (SiO)k- 1 Si — M3 • · · (3 R I R Z R -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（12) 其中各R分別爲獨立選自氫原子、一價烴基或鹵化烷基代表之。一分子中之R可均爲相同者、部份或全部相異者亦可。做爲一價烴基者如：甲基、乙基、丙基、丁基、辛基、月桂基、苯基、苯乙烯基等例。又，鹵化烷基之例如：三氟丙基、氯丙基之例。R特別以一價烴基或鹵化烷基爲較佳，更以甲基、及氟烷基爲更理想。 Y係如下記一般式（4 )所示之有機反應性官能基。 -R 1 - X ...... (4) 其中，R 1代表直接結合或碳原子數1〜2 0之二價烴基，X代表具有有機反應性之官能基者。又，做爲R 1之例者如：―CH2 —、- C Η 2 C Η 2 -, -CH2CH2CH2-. - C Η ( C Η 3 ) CH2 —、 (C Η 2 ) 4 — Λ — (CH2)6 -、—（CH2)8 —、 -CH2CH2C6H4 - (CH2) 12-. ( c Η 2 ) 16- 之例，較佳者爲兩烯基者。又，做爲X之例者如：環氧基、胺基、氫氧基、羧基、醯基、氫硫基、甲基丙烯基、異氰酸酯基、脲基、乙烯基、醯胺基、亞胺基、脒基、醒基、硝基、腈基、肟基、偶氮基、腙基等等之例。做爲γ基之具體例者如：（CH2)3〇H、 ( C Η 2 ) 3 S Η . —(CH2) 3ΝΗ2、一（CH2) 7C〇〇H 等例’惟’ 並非僅限於此等。 Z係代表如水解性基或下記一般式（5 )所示之縮合 (請先閱讀背面之注意事項再填寫本頁)RRIRIRR 1 M2-(SiO) f I 1-(SiO) g-1 1 1-(SiO) h— Si — M2… (2) R 1 Y 1 Z 1 RR | RIRR M3-Si-〇1 one (SiO ) Factory | (SiO) k- 1 Si — M3 • · · (3 RIRZR -14- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 565589 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation A7 B7 V. Description of the invention (12) wherein each R is independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group. R in a molecule may be all the same, partly or completely different. Yes. Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, octyl, lauryl, phenyl, and styryl. Examples of halogenated alkyl groups include trifluoropropyl, Examples of chloropropyl. R is particularly preferably a monovalent hydrocarbon group or a halogenated alkyl group, more preferably a methyl group and a fluoroalkyl group. Y is an organic reactive functional group represented by the following general formula (4) -R 1-X ...... (4) wherein R 1 represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity. Also, Examples of R 1 are: -CH2 —,-C Η 2 C Η 2-, -CH2CH2CH2-.-C Η (C Η 3) CH2 —, (C Η 2) 4 — Λ — (CH2) 6- , — (CH2) 8 —, -CH2CH2C6H4-(CH2) 12-. (C Η 2) 16-, preferably two alkenyl groups. As examples of X, epoxy groups, Amine, hydroxyl, carboxyl, fluorenyl, hydrogenthio, methacryl, isocyanate, urea, vinyl, fluorenyl, imino, fluorenyl, methyl, nitro, nitrile, Examples of oxime group, azo group, fluorenyl group, etc. Specific examples of γ group are: (CH2) 3OH, (C Η 2) 3 S Η. — (CH2) 3N 32, one (CH2) 7C〇〇H and other examples 'but' are not limited to these. Z represents the condensation such as the hydrolyzable group or the general formula (5) below (please read the precautions on the back before filling this page)

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- 經濟部智慧財產局員工消費合作社印製 565589 A7 B7 五、發明說明（13) 性甲矽烷基者。 - R2 — Si -（〇R4) r 丨 .·· （ 5 ) U3) 3 — Γ 其中，R2代表碳原子數2〜5之亞烷基、R3及R4 互爲獨立之選自氫原子或碳原子數1〜5之烷基、r爲2 或3者，惟由反應性之面觀之，以2爲較佳者。 R2爲碳原子數2〜5之亞院基，如： —CH2CH2 —、— CH2CH2CH2 —、 CH(CH3)CH2-、（CH2)4 —、 ( C Η 2 ) 5 - 等者，較佳者爲乙烯。R3及R4互爲獨立選自氫原子或碳原子數1〜5之烷基者。例如：甲基、乙基、丙基、丁基者。R3爲甲基、R4爲甲基或乙基者佳。做爲Z基之具體例者如：一 CH2CH2Si ( 0 C Η 3 ) a . -C Η 2 C Η 2 S i ( 0 C 2 Η 5 ) 3 , -C Η 2 C Η 2 S i ( C H 3 ) ( 0 C H 3 ) 2 > -C H 2 C H 2 S i 〔〇CH(CH3)2〕3、 -(C H 2 ) 3 S i ( C H 3 ) ( O C 2 H 5 ) 2 , -(C H 2 ) 5 S i ( C 2 H 5 )(〇C2H5)2 等例，惟，並非僅限於此。 Q代表下記一般式（6 )所示之聚氧亞烷基者。 -(CH2)p-0-(C2H4〇)m-(C3H6〇)n-R5......(6) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- ------τ-------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 565589 A7 B7 五、發明說明（14 ) 其中，R5代表氫原子、醯基或一價烴基、p代表0或正整數，m及η爲〇或1 5 0以下之正整數者，以2爲較理想者。惟，m + η爲1〜1 5 0之整數者。做爲適於R5 使用之醯基之例者如：乙醯基或丙醯基之例。又，一價烴基之例如：甲基、乙基、丙基、丁基、苯基或乙烯基之例者。 Μ1爲互爲獨立之選自該R、Υ、Ζ及Q之基者。Μ2 爲互爲獨立之選自該R、 Υ及Ζ之基者。Μ3爲互爲獨立選自該R及Υ之基者。一分子中2個Μ1〜Μ3可爲相同，亦可爲相異者。 a爲〇〜500之整數者，b爲0〜200之整數， d爲0〜2〇0之整數，e爲0〜200之整數，惟，b 爲0時，Μ1爲Y，且d及e均爲1以上之整數者。d爲0 時M1爲Z者，且b及e均爲1以上之整數者。e爲〇時， M1爲Q時，且，b及d均爲1以上之整數者。 f爲0〜500之整數，g爲0〜200之整數者， h爲0〜200之整數者。惟，g爲0時，M2爲Y，且， h爲1以上之整數者。h爲〇時，M2爲Z者，且，f爲1 以上之整數者。 j爲0〜500之整數，k爲0〜500之整數者。惟k爲0時Μ 3爲Z者。又，做爲一般式（1 )之化合物者如：Υ爲環氧基者，Ζ爲具結合於矽之烷氧基之縮合性甲矽烷基者，Q爲聚醚之化合物，而由日本Unika股份公司以MAC — 2 1 0 1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------tr---------. 經濟部智慧財產局員工消費合作社印製 -17- 565589 Α7 _ _ Β7 五、發明說明（15 ) 被販賣之。 (請先閱讀背面之注意事項再填寫本頁) D·易位聚合觸媒本發明所使用之易位聚合觸媒係只要做爲環烯烴系化合物之開環易位聚合用觸媒之公知觸媒系者均可適用，例如：2成份型觸媒、1成份型觸媒之例，並無特別限定。惟，由空氣中之安定性良好度之面觀之，以1成份型之金屬聚炔型觸媒爲較佳。易位觸媒之添加量通常當總計1 0 0重量份之環烯烴類單體時，爲0 · 0 0 1〜5重量份者，由經濟性面觀之，以0 · 0 1〜1重量份者爲較佳。 2成份型易位聚合觸媒係觸媒成份與活性化劑所組合之觸媒系者。本發明所使用之2成份型易位聚合觸媒例如含：鈦、釩、鉬、鎢、銶、銥、釕、及餓，等過渡金屬類者，絡合金屬鹵化物、金屬聚炔或齊格勒一納塔法型之配位觸媒等者。經濟部智慧財產局員工消費合作社印製具體例如：六氯化鎢、氧基四氯化鎢、氧化鎢、三癸基銨鎢等之鎢化合物、五氯化鉬、氧基三氯化鉬、氧化鉬、三癸基胺鉬等之鉬化合物、五氯化鉬等之鉬化合物、以及〔（環己基）3磷〕2二氯化釕、〔（苯基）3磷〕3二氯化釕、（環己基）3磷（對一傘花烴）二氯化釕、〔（苯基）3磷〕3 ( C〇）R U Η 2等之釕化合物等例。此等2成份系易位聚合觸媒中，必要時可倂用公知之共觸媒（活性化劑）。其具體例如：烷基鋁鹵化物、烷氧 -18- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）五、發明說明（16 ) 基烷基鋁鹵化物、等例。 1成份型易位由空氣中之水份，失去觸媒活性之環爲此1成份型易位聚炔結構做爲中心中心金屬配位之結位觸媒之例。做爲此等釕或 565589 Α7 一 Β7 芳基氧基烷基鋁鹵化物、有機錫化合物聚合觸媒與2成份型之觸媒系不同，藉固體表面之吸著水以易位反應可使不易烯烴系化合物進行開環易位聚合之。做聚合觸媒之具體例如：以釕或餓之金屬骨架之立體障礙大之配位子藉由取得往構後對於水份可安定化之金屬聚炔型配餓之金屬聚炔型配位觸媒之理想例者如 :下記一般式（7 )〜（9 )任一所代表化合物例者。此等中，由觸媒活性之高低、合成收率之高低、以及經濟面視之，特別以一般式（9 )所代表之化合物者。 Q 1 (請先閱讀背面之注咅？事項再填寫本頁) 1This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -15- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 565589 A7 B7 V. Description of the invention (13) Sexual silyl group. -R2 — Si-(〇R4) r 丨. · (5) U3) 3 — Γ, wherein R2 represents an alkylene group having 2 to 5 carbon atoms, R3 and R4 are each independently selected from a hydrogen atom or carbon An alkyl group having 1 to 5 atoms and r is 2 or 3, but from the viewpoint of reactivity, 2 is preferred. R2 is a sub-radical with 2 to 5 carbon atoms, such as: —CH2CH2 —, — CH2CH2CH2 —, CH (CH3) CH2-, (CH2) 4 —, (C Η 2) 5-etc., preferably, Ethylene. R3 and R4 are each independently selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. For example: methyl, ethyl, propyl, butyl. R3 is preferably methyl, and R4 is preferably methyl or ethyl. As specific examples of the Z group, such as: -CH2CH2Si (0 C Η 3) a. -C Η 2 C Η 2 S i (0 C 2 Η 5) 3, -C Η 2 C Η 2 S i (CH 3 ) (0 CH 3) 2 > -CH 2 CH 2 S i [〇CH (CH3) 2] 3,-(CH 2) 3 S i (CH 3) (OC 2 H 5) 2,-(CH 2 ) 5 S i (C 2 H 5) (〇C2H5) 2, etc., but it is not limited to this. Q represents a polyoxyalkylene group represented by the following general formula (6). -(CH2) p-0- (C2H4〇) m- (C3H6〇) n-R5 ...... (6) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- 16- ------ τ ------------- Order --------- (Please read the notes on the back before filling this page) 565589 A7 B7 V. Description of the invention (14) wherein R5 represents a hydrogen atom, a fluorenyl group or a monovalent hydrocarbon group, p represents 0 or a positive integer, and m and η are positive integers of 0 or less than 150, and 2 is more preferable. However, m + η is an integer of 1 to 1 50. Examples of fluorenyl groups suitable for use with R5 are, for example, ethenyl or propionyl. Examples of the monovalent hydrocarbon group include methyl, ethyl, propyl, butyl, phenyl, and vinyl. M1 is a group independently selected from the group consisting of R, Y, Z, and Q. M2 is an independent group selected from R, Υ, and Z. M3 is independently selected from the bases of R and Υ. Two M1 to M3 in one molecule can be the same or different. a is an integer from 0 to 500, b is an integer from 0 to 200, d is an integer from 0 to 200, and e is an integer from 0 to 200, but when b is 0, M1 is Y, and d and e Both are integers of 1 or more. When d is 0, M1 is Z, and b and e are both integers of 1 or more. When e is 0, M1 is Q, and b and d are both integers of 1 or more. f is an integer from 0 to 500, g is an integer from 0 to 200, and h is an integer from 0 to 200. However, when g is 0, M2 is Y, and h is an integer of 1 or more. When h is 0, M2 is Z, and f is an integer of 1 or more. j is an integer from 0 to 500, and k is an integer from 0 to 500. However, when k is 0, M 3 is Z. In addition, as a compound of general formula (1), for example: Υ is an epoxy group, Z is a condensable silyl group having an alkoxy group bonded to silicon, Q is a polyether compound, and Japan ’s Unika Joint stock company with MAC — 2 1 0 1 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- tr ---------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -17-565589 Α7 _ _B7 V. Description of Invention (15) It was trafficked. (Please read the precautions on the back before filling this page) D. Metathesis Polymerization Catalysts The metathesis polymerization catalysts used in the present invention need only be known catalysts for ring-opening metathesis polymerization of cycloolefin compounds. It can be applied by any media person. For example, the examples of the two-component type catalyst and the one-component type catalyst are not particularly limited. However, from the perspective of good stability in the air, a one-component metal polyacetylene type catalyst is preferred. The addition amount of the metathesis catalyst is usually 0 · 0 0 1 to 5 parts by weight when the total amount of cyclic olefin monomer is 100 parts by weight. From the perspective of economy, it is 0 · 0 1 to 1 part by weight. Participants are better. Two-component type metathesis polymerization catalyst is a catalyst system in which the catalyst component and the activating agent are combined. The two-component metathesis polymerization catalyst used in the present invention includes, for example, titanium, vanadium, molybdenum, tungsten, osmium, iridium, ruthenium, and other transition metals, such as complex metal halides, metal polyacetylenes, or oligomers. Geller-Natta type coordination catalyst and others. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example: tungsten compounds such as tungsten hexachloride, tungsten oxytetrachloride, tungsten oxide, tridecylammonium tungsten, molybdenum pentachloride, molybdenum oxytrichloride, Molybdenum compounds such as molybdenum oxide, tridecylamine molybdenum, molybdenum compounds such as molybdenum pentachloride, and [(cyclohexyl) 3 phosphorus] 2 ruthenium dichloride, [(phenyl) 3 phosphorus] 3 ruthenium dichloride Examples of ruthenium compounds such as (cyclohexyl) 3 phosphorus (p-cymene) ruthenium dichloride, [(phenyl) 3 phosphorus] 3 (C0) RU Η 2 and the like. Among these two-component metathesis polymerization catalysts, a known cocatalyst (activator) may be used if necessary. The specific examples are: Aluminium alkyl halides, alkoxy-18- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) V. Description of the invention (16) Aluminium alkyl halides, etc. . 1-component metathesis A ring that loses catalyst activity due to water in the air. This is a 1-component metathesis polyacetylene structure as an example of a central metal coordination junction catalyst. For this purpose, ruthenium or 565589 Α7-B7 aryloxyalkyl aluminum halide, organotin compound polymerization catalyst is different from the two-component type catalyst system, which can be made difficult by the metathesis reaction of absorbed water on the solid surface. The olefin-based compound undergoes ring-opening metathesis polymerization. Specific examples of polymerization catalysts are: ruthenium or a metal skeletal metal with a large steric hindrance, and a metal polyacetylene-type metal coordination system that can stabilize the water after obtaining the previous structure. Examples of ideal examples of the media are as follows: Examples of compounds represented by any of the following general formulae (7) to (9). Among these, the level of catalyst activity, the level of synthetic yield, and the economic aspect, particularly those represented by the general formula (9), are those. Q 1 (Please read the note on the back? Matters before filling out this page) 1

X 1 LX 1 L

X \ I Μ =/ I 2 L 2X \ I Μ = / I 2 L 2

C (7 ) Q2 經濟部智慧財產局員工消費合作社印製 X 1 L 1\ I Μ =/ I X 2 L 2 X 1 L 1\ I Μ =/ I X 2 L 2C (7) Q2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs X 1 L 1 \ I Μ = / I X 2 L 2 X 1 L 1 \ I Μ = / I X 2 L 2

Q C = C \ Q R 7 / C R 5 \ / C = C / \ H R 6 (8) 2 (9 ) -19- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 Α7 Β7 經濟部智慧財產局員工消費合作社印製五、發明說明（17 ) 其中，Μ代表釕或餓。 X 1及X 2分別獨立之選自陰離子性配位子者。陰離子性配位子係指超出中心金屬之配位時具陰性電荷之原子或原子團者。做爲此陰離子性配位子之例者如：氫、鹵素、 C F a , C〇2、 C H a C 0 2 . C F Η 2 C Ο 2 . (CH3) 3C〇、 (CF3) 2 (CH3) C〇、 (C F 3 ) (CH3)2C〇、碳數1〜5之烷基、碳數1 〜5之烷氧基、苯基、苯氧基、甲苯基、甲磺醯、三氟甲烷磺酸酯基等者。X1及X2當兩者共爲鹵素（特別是，氯 )爲特別理想者。 L 1及L 2分別爲獨立選取中性之配位子者。又，所謂中性之配位子係指超出中心金屬配位之範圍時，具有中性電荷之原子或原子團者。做爲此等基之例者如： P R 8 R 9 R 1 ° (其中R 8代表分別選自2級之烷基或環烷基者、R9及R1C)爲芳基、碳數1〜10之1級烷基及2 級烷基、以及環烷基之基者）之膦系電子供與體之例者。 L1及L2兩者共爲P (環己基）3、P (環戊基）3、或 P (異丙基）3者爲特別理想者。做爲配位基可爲例如：吡啶、對-氟吡啶、亞咪唑基等之例者。做爲亞咪唑基化合物者以下記一般式（1 0 ) 或（1 1 )所示之複環式化合物者宜。此等中特別以式（ 1 1 )所示之化合物做爲配位子者爲更理想者。QC = C \ QR 7 / CR 5 \ / C = C / \ HR 6 (8) 2 (9) -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 565589 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention (17), where M stands for ruthenium or hungry. X 1 and X 2 are each independently selected from anionic ligands. Anionic ligands refer to those atoms or groups of atoms that have a negative charge when they exceed the coordination of the central metal. Examples of this anionic ligand are: hydrogen, halogen, CF a, C02, CH a C 0 2. CF Η 2 C 〇 2. (CH3) 3C〇, (CF3) 2 (CH3) C0, (CF 3) (CH3) 2C0, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, phenyl group, phenoxy group, tolyl group, methanesulfonium, trifluoromethanesulfonate Ester based and others. X1 and X2 are particularly desirable when both are halogen (especially, chlorine). L 1 and L 2 are those who independently select neutral ligands. The term "neutral ligand" refers to an atom or a group of atoms having a neutral charge when it exceeds the range of central metal coordination. Examples of such groups are: PR 8 R 9 R 1 ° (where R 8 represents a group selected from a 2nd-order alkyl or cycloalkyl group, R9 and R1C respectively) is an aryl group, and a carbon number of 1 to 10 Examples of a primary alkyl group, a secondary alkyl group, and a cycloalkyl group) are phosphine-based electron donors. It is particularly desirable that both of L1 and L2 are P (cyclohexyl) 3, P (cyclopentyl) 3, or P (isopropyl) 3. Examples of the ligand include pyridine, p-fluoropyridine, and imidazolyl. Those who are imidazolyl compounds are preferably those having a complex ring compound represented by the general formula (1 0) or (1 1) below. Among these, a compound represented by the formula (1 1) is particularly preferred as a ligand.

R 11 r=\R 11 r = \

•N—R 12 (10) (請先閱讀背面之注音？事項再填寫本頁) * ϋ memam I ϋ· ϋ i^i · 本紙張尺度適用中國國家4¾準（CNS)A4規格（210 X 297公釐） -20 - 565589 Α7 Β7 (11) 五、發明說明（你） R11一R12 其中，R11及R12分別爲獨立之選自碳數1〜20之院基、碳數2〜2 0之脂烯基、碳數2〜2 0之炔基、環院基、芳基者。又，RH及R12被碳數1〜1 〇之烷基、碳數1〜i 〇之烷氧基、芳基取代亦可，更且，此等基被歯素’碳數1〜5之烷基，碳數1〜5之烷氧基、苯基取代亦可。由熱安定性之面觀之，R 1 1及R 1 2之至少單面以如下記一般式（1 2 )所示之基者佳。 (請先閱讀背面之注意事項再填寫本頁)• N—R 12 (10) (Please read the note on the back? Matters before filling out this page) * ϋ memam I ϋ · ϋ i ^ i · This paper size applies to China National Standard 4¾ (CNS) A4 (210 X 297) (Mm) -20-565589 Α7 Β7 (11) V. Description of the invention (you) R11-R12 Among them, R11 and R12 are each independently selected from the group consisting of a carbon number of 1 to 20 and a fat number of 2 to 20. Alkenyl, alkynyl with 2 to 20 carbon atoms, cyclohexyl and aryl. In addition, RH and R12 may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group, and these groups may be substituted with a halogen compound having 1 to 5 carbon atoms. It may be substituted by alkoxy or phenyl having 1 to 5 carbon atoms. From the perspective of thermal stability, it is preferable that at least one side of R 1 1 and R 1 2 is based on the following formula (1 2). (Please read the notes on the back before filling this page)

R 經濟部智慧財產局員工消費合作社印製此式（1 2 )中，R 1 3及R 1 4分別代表氫，碳數1 ^ 3之烷基或碳數1〜3之烷氧基者，R15爲氫，碳數1〜 1〇之ί兀基、方基、經基、硫醇基、硫目迷基、醒基、醒基、酯基、醚基、胺基、脒基、醯胺基、硝基、羧酸基、二硫化物基、碳酸酯基、異氰酸酯基、羧基二亞胺基、羧基烷氧基、胺基甲酸酯、鹵素等者。可做爲配位基使用之具體例可爲亞咪唑化合物之例者如：下記結構式（1 3 )或結構式（1 4 )所示之聚炔之例。其中又以一般式（1 4 )之亞咪唑基化合物由聚合活性之面爲特佳者。本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） -21 - 565589 A7 B7 五、發明說明（19R The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed this formula (1 2), where R 1 3 and R 1 4 represent hydrogen, an alkyl group having 1 ^ 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, R15 is hydrogen, carbon, 1 to 10 carbon atoms, square group, warp group, thiol group, thimemyl group, awake group, awake group, ester group, ether group, amine group, fluorenyl group, amidine Group, nitro group, carboxylic acid group, disulfide group, carbonate group, isocyanate group, carboxydiimide group, carboxyalkoxy group, carbamate, halogen, and the like. Specific examples that can be used as a ligand can be examples of imidazole compounds. Examples are polyacetylenes represented by the following structural formula (1 3) or (1 4). Among them, the imidazolyl compound of general formula (1 4) is particularly preferred from the viewpoint of polymerization activity. The size of this paper applies to China National Standard (CNS) A4 (210 χ 297 mm) -21-565589 A7 B7 V. Description of the invention (19

ch3 CH 3 H3c (13) h3c- -ΝγΝ—ch3 CH 3 H3c (13) h3c- -ΝγΝ—

-CH 丨3 ".(14) CH3 HgC做爲適於本發明使用之觸媒例如以下結構式（1 5 ) (1 7 )所示。-CH 丨 3 (14) CH3 HgC is a catalyst suitable for use in the present invention, for example, as shown in the following structural formula (1 5) (1 7).

(請先閱讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)

太Μ張尺疳滴用中國國宠標進ΓΓΝΑΑΛ楣枚πΐη X 9Q7八笤、 -99 - 565589 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（2〇 )Taimu Zhang Zhidi used the Chinese national pet to mark ΓΓΝΑΑΛ 楣 πΐη X 9Q7 笤, -99-565589 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (20)

Q 1及Q 2分別爲獨立之選自氫基、烷基、脂烯基或芳香族基者，烷基、脂烯基或芳杏族基亦可具有取代基者。 R 5及R 6分別爲獨立之選自碳數1〜1 8之烷基，碳數2〜18之脂烯基，碳數2〜18之炔基、芳基，碳數 1〜1 8之羧酸酯，碳數1〜1 8之烷氧基，碳數2〜 1 8之脂烯氧基，碳數2〜1 8之炔氧基，碳數2〜1 8 之烯丙氧基，碳數2〜1 8之烷氧基碳基，碳數1〜1 8 之烷基硫基，碳數1〜1 8之烷基磺醯基或碳數1〜1 8 之烷基亞磺醯基者，R7代表氫、芳基或碳數1〜1 8之院基者。此金屬聚快化合物可藉由公知之合成法取得。例如：有機金屬第16卷，18號，3867頁（1997年）所示之兩烯基氯化物所使用方法之例者。以下代表觸纟某2 合成例（參考文獻：有機金屬第1 6卷1 8號3 8 6 了胃 (1997年））。又，cy代表環己基者。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 23 -----------MW--------訂 (請先閱讀背面之注咅^事項再填寫本頁)Q 1 and Q 2 are each independently selected from a hydrogen group, an alkyl group, an aliphatic alkenyl group, or an aromatic group, and an alkyl group, an aliphatic alkenyl group, or an aromatic alkenyl group may have a substituent. R 5 and R 6 are each independently selected from alkyl groups having 1 to 18 carbons, aliphatic alkenyl groups having 2 to 18 carbons, alkynyl and aryl groups having 2 to 18 carbons, and 1 to 18 carbons Carboxylic acid esters, alkoxy groups having 1 to 18 carbons, aliphatic alkenyl groups having 2 to 18 carbons, alkynyl groups having 2 to 18 carbons, allyloxy groups having 2 to 18 carbons, Alkoxy carbon group with 2 to 18 carbons, alkylthio group with 1 to 18 carbons, alkylsulfonyl group with 1 to 18 carbons or alkylsulfinyl group with 1 to 18 carbons For radicals, R7 represents hydrogen, aryl, or radicals with 1 to 18 carbon atoms. This metal polyfast compound can be obtained by a known synthesis method. For example: An example of the method used for dienyl chlorides shown in Organic Metals Vol. 16, No. 18, p. 3867 (1997). The following represents a synthesis example of a catapult 2 (Reference: Organic Metals Vol. 16 No. 18 No. 3 8 6 Stomach (1997)). In addition, cy stands for cyclohexyl. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 23 ----------- MW -------- Order (please read the note on the back first ^ (Fill in this page again)

565589 A7 _ B7 五、發明說明（21 ) 合成例 (請先閱讀背面之注意事項再填寫本頁) 於5 0 0 之Fisher-Porter bottle中置入環辛二烯釕二氯化物（2 lmmo 1 )、三環己磷（42mmo 1 )、氫氧化鈉（7 · 2g)、以及脫氧之次一丁醇2504之後，於2 0 0 k P a之氫氣下以9 0 °C進行加熱。重覆數次加壓至氫吸收結束後，持續攪拌一個晚上。加氫壓力下冷却至室溫後取得淡黃色沈澱物。加入3 0 水過濾沈澱物，於氫氣流中乾燥之後，取得565589 A7 _ B7 V. Description of the invention (21) Synthesis example (please read the precautions on the back before filling this page) Put cyclooctadiene ruthenium dichloride (2 lmmo 1 in a Fisher-Porter bottle of 5 0 0 ), Tricyclohexylphosphine (42mmo 1), sodium hydroxide (7.2 g), and deoxygenated monobutanol 2504, and then heated at 90 ° C under a hydrogen atmosphere of 2000 kPa. After repeated pressurization until the end of hydrogen absorption, stirring was continued for one night. After cooling to room temperature under hydrogenation pressure, a pale yellow precipitate was obtained. Add 30 water to filter the precipitate and dry it in a hydrogen stream.

Ru (H)2(H2)2(P (cy)3)2(收率約 80% )。再將此 Ru (Η) 2 (H2) 2 (P (cy3) 2 (1 · 5mmo 1)溶於30m£之二氯乙烷，冷却至 —3〇C。加入3 —氣一 3 —甲基一 1 一丁快（1 · 5 mmol)。溶液立即變紅紫色，直接反應1 5分鐘後，離開冷却浴，加入脫氣體之甲醇（2 0 )後，出現紫色結晶沈澱。以甲醇洗淨後，乾燥之後取得R u聚炔觸媒 (C 1 ) 2 ( P (cy) 3) 2Ru = CH— CH =C ( C Η 3 ) 2 )(收率 95%)。經濟部智慧財產局員工消費合作社印製 E .熱塑性樹脂本發明環烯烴組成物及成形材料中，爲提昇接合性，降低收縮化等，必要時可加入熱塑性樹脂。適於使用之熱塑性樹脂並無特別限定，一般如，；C希烴系樹脂及其變性體（變性烯烴系樹脂）、苯乙烯系樹脂及其變性體（變性苯乙烯系樹脂）、離子鍵聚合物樹脂、聚 -24- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 A7 ___ B7__ 五、發明說明（22 ) (請先閱讀背面之注意事項再填寫本頁) 甲基丙烯酸甲酯、聚丁二烯、聚異戊二烯、聚胺酯、聚氯化乙烯、聚氯化亞乙烯、聚醋酸乙烯酯、氟樹脂、聚醯胺、飽和聚酯、石油樹脂等例。 F .添加劑本發明之環烯烴組成物及成形材料中，爲改善物性，外觀、成形作業性之目的下可含有搖變劑、著色劑、消泡劑、分散劑、氧化防止劑、可塑劑等各種添加劑。做爲搖變劑之例如：二氧化矽、石棉粉、脂肪酸處理碳酸鈣等之無機搖變劑、有機膨潤土、變性聚酯聚酚形之有機搖變劑、膠體二氧化矽、脂肪酸醯胺蠟、硬脂酸醢胺等例。做爲著色劑之例者亦可添加氧化鈦、鈷藍、鎘黃、鉬紅、氧化絡、錦氧粉白等之無機顏料、炭黑、丙胺黑、月太菁、喹吖酮等有機系顏料等。做爲消泡劑之例者如聚砂氧系之油、界面、活性齊彳等宜他市販品（如：By kchemi、楠本化成等所市販者）可使用之。經濟部智慧財產局員工消費合作社印製 G.製造方法及成形方法本發明之環烯烴組成物及成形材料可藉由上述各成份於胃?盘$加熱τ均句？昆合後取得^又’必要時亦可藉由減壓進行脫泡。本發明之環烯烴組成物或成形材料注彳莫射出成形本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）- 565589 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（23 ) 、中空成形、擠壓成形、壓縮成形、旋轉成形等公知之成形法經適用後可成形任意形狀。成形時’必要時亦可加熱之。本發明之成形體可適用於配線板、絕緣材等之電氣、電子零件之外，如：淨化槽、浴缸、廚房天花板、畜水池、壁砍、下水槽、配水管、波板之建築材料、玩具、遊覽船、等之娱樂品、浴室用品、廚房用品寺曰用品之各種塑料製品者。實施例以下藉由實施例進行本發明說明。又，以下實施例及比較例中，「份」係指重量份者。又，二環戊二烯簡稱爲 D C P D。以下各實施例及各比較例中使用下記化學式（ 5 )所示之易位聚合觸媒者。 /CH3Ru (H) 2 (H2) 2 (P (cy) 3) 2 (the yield is about 80%). This Ru (Η) 2 (H2) 2 (P (cy3) 2 (1.5 mmo 1) was dissolved in 30 m 2 of dichloroethane and cooled to -30 ° C. 3 -gas-3 -methyl One to one fast (1.5 mmol). The solution turned red-purple immediately. After 15 minutes of direct reaction, left the cooling bath and added degassed methanol (20). A purple crystal precipitated. After washing with methanol After drying, a Ru polyacetylene catalyst (C 1) 2 (P (cy) 3) 2Ru = CH— CH = C (C Η 3) 2) was obtained (yield 95%). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. E. Thermoplastic resin In the cycloolefin composition and molding material of the present invention, a thermoplastic resin may be added if necessary to improve bonding and reduce shrinkage. Suitable thermoplastic resins are not particularly limited, and are generally, for example, C-Hydrocarbon resins and their denaturants (modified olefin resins), styrene resins and their denatures (modified styrene resins), and ionomer polymerization Resin, Poly-24- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 565589 A7 ___ B7__ V. Description of the invention (22) (Please read the precautions on the back before filling this page) Examples of methyl methacrylate, polybutadiene, polyisoprene, polyurethane, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, fluororesin, polyamide, saturated polyester, petroleum resin, etc. . F. Additives The cycloolefin composition and the molding material of the present invention may contain a shaker, a colorant, a defoamer, a dispersant, an oxidation inhibitor, a plasticizer, etc. for the purpose of improving physical properties, appearance, and molding workability. Various additives. Examples of shakers: inorganic shakers such as silica, asbestos powder, fatty acid-treated calcium carbonate, organic bentonite, organic shakers in the form of denatured polyester polyphenols, colloidal silica, fatty acid ammonium wax , Ammonium stearate and other examples. As an example of the colorant, inorganic pigments such as titanium oxide, cobalt blue, cadmium yellow, molybdenum red, oxidized complex, and white powder, carbon black, propylamine black, moon cyanine, and quinacridone can be added. Pigments, etc. Examples of defoamers such as poly-sand oxygen-based oils, interfaces, and active ingredients can be used in other cities (such as By kchemi, Nanben Chemicals, etc.). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs G. Manufacturing method and forming method The cyclic olefin composition and the forming material of the present invention can be heated in the stomach with the above-mentioned ingredients. Obtained after kneading can be defoamed by depressurizing if necessary. The cyclic olefin composition or molding material of the present invention is not injection-molded. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm)-565589 A7 B7. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Description of the invention (23), known molding methods such as hollow molding, extrusion molding, compression molding, and rotational molding can be formed into any shape after being applied. When molding ', it may be heated if necessary. The formed body of the present invention can be used in addition to electrical and electronic parts such as wiring boards, insulation materials, such as: cleaning tanks, bathtubs, kitchen ceilings, animal pools, sidings, sinks, distribution pipes, wave board construction materials, Toys, excursion boats, and other entertainment products, bathroom supplies, kitchen supplies and various plastic products. Examples The present invention will be described below with reference to examples. In the following examples and comparative examples, "parts" refers to parts by weight. In addition, dicyclopentadiene is abbreviated as D C P D. The following examples and comparative examples each use a metathesis polymerization catalyst represented by the following chemical formula (5). / CH3

CLCL

Cl -(0)3 :Ru 二Cl-(0) 3: Ru II

:CH 、CH3 (15 A ·實施例1〜3、比較例1〜6 此等各實施例中，此反應性聚矽氧烷做爲偶合劑使用後調製環烯烴組成物之D C P D樹脂液後，於此加入塡充材後，使螺旋翼之後，以4 0 〇 r p m進行攪拌5分鐘後，調製成混合體（亦即複合材料）。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -26- !!,-----.f--------訂一------$ (請先閱讀背面之注意事項再填寫本頁) 565589 A7 ---------B7_— —__ 五、發明說明（24 ) (請先閱讀背面之注意事項再填寫本頁) 所取得之混合體於6 0 °C下進行加熱4小時後，隨後冷却至約3 5 °C後使用之。首先，於此混合體中加入〇 · 1份之易位聚合觸媒，進行混合後，使混合體進行減壓脫泡後，取得環烯烴組成物之成形材料。使用此成形材料後使試驗片成形後，藉由以下方法進行各種特性之評定〇 I .彎曲特性 (a )試驗片製作方法將上述成形材料於厚度3 m m平板之模具中進行沸鑄，隨後，將此模具於烤箱中4 0 °C下進行5小時加熱， 1 3 0 °C下進行2小時加熱後，取得平板狀之硬化物。 (b )彎曲試驗由平板切取寬2 5 m m，長8 0 m m之彎曲試驗片，以J I S K 7 2 0 3爲基準後，進行彎曲試驗（試驗速經濟部智慧財產局員工消費合作社印製率彎易曲彎取求式下由 2 ) 藉 Lm} ，/mm} 時 V cmm 此 d 量 {m 。 6 之度彳 } II 彎厚離 η } 易之距 i%時片間 m{壞驗點 \ 率損試支 m 彎 ...... ΓΪΊ易 dvL 2 度 -27- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 A7 _______B7 五、發明說明（25 ) I I .耐水性由加壓蒸煮試驗（p c T )試驗前後之絕緣損壞強度求取保持率。 (a )試驗片製作方法於厚度2 m m之平板模具中將上述成形材料進行沸鑄，隨後將此模具於4 0 t：下進行5小時加熱，1 3 0。(：下進行2小時加熱後取得平板狀之硬化物。 (b )絕緣損壞之強度以J I S K 6 9 1 1爲基準進行測定。又，P C T 之條件爲溫度：1 2 1 °C，壓力：2 2 2 k P a ，時間： 5〇小時。評定結果如表1所示。由此表證明使用反應性聚矽氧烷之各實施例混合體所取得之成形體與各比較例相比後其易彎率大具靭性者。又，各實施例其P C T後之絕緣損壞強度均無降低，具良好耐水性。 -----1-----MW--------V··------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -28- 565589 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（26 ) 表1 _ 彎曲特性絕緣破壞之強度彎曲強彎曲彈撓曲率初期 Pd 保持率度（MPa) 性（GPa) (%) (KV/mm) (KV/mm) (%) 實施例1 52.8 6.40 4.6 20.9 21.3 102 實施例2 55.5 6.52 3.0 21.0 20.4 97.1 實施例3 57.8 6,61 4.2 19.9 19.7 99.0 比較例1 39.5 6.20 1.0 19.8 11.2 56.6 比較例2 116 7.10 2.0 19.8 19.0 96.0 比較例3 52.5 6.75 1.8 20.2 17.9 88.6 比較例4 49.5 6.70 1.3 21.0 16.0 76.2 比較例5 56.1 6.66 2.6 21.4 18.0 84.0 比較例6 58.8 6.60 1.4 20.5 18.5 90.2 <實施例1 > 於1 0 0份之純度約9 8 %之D C P D中加入2份之 Sunnlaza BHT (住友化學工業股份公司製商品名，氧化防止劑）’ 0 · 0 5份之三苯基膦（和光純藥工業股份公司製，試藥特級），2 · 0份之FZ3778 (日本Unika股份公司製商品名，乙氧基甲基氫二烯聚矽氧烷）後，調製被分散之D C P D樹脂液。隨後，加入1 5 0份之熔融二氧化矽（平均粒徑5 μ m )混合後，取得混合體。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -29- ------------Avw--------訂--------- (請先閱讀背面之注咅？事項再填寫本頁) 565589 A7 ----B7 五、發明說明（27 ) 〈實施例2 > (請先閱讀背面之注意事項再填寫本頁) 以MAC — 2101 (日本Unika股份公司製商品名，環氧基及縮合性甲矽烷基之聚矽氧烷）2 · 0份取代 F z 3 7 7 8之外，與實施例相同取得混合體。 <實施例3 > 以聚合物型矽烷偶合劑F Z 3 7 0 4 (日本Umka股份公司製商品名，聚乙氧基甲基矽氧烷）2 · 0份取代 F Z 3 7 7 8之外，與實施例1相同取得混合體。 <比較例1 > 於純度約9 8 %之D C P D 1 〇〇份中加入2 . 0份之Sumilaiza BHT，0 · 0 6份之三苯基磷（特級）後，調製分散之D C P C樹脂液。隨後，添加1 5 0份之熔融二氧化矽（股份公司龍森製，平均粒徑約7 // m )，混合後取得混合體。 <比較例2 > 經濟部智慧財產局員工消費合作社印製於純度約9 8 %之D C P D 1 〇〇份中加入2 · 0份之Sumilaiza BHT，0 · 0 6份之三苯基磷（特級）， 2 · 0份之矽烷偶合劑A - 1 7 1 (日本Unika股份公司製商品名，乙烯三甲氧基矽烷）後，調製分散之D C P D樹脂液。隨後，加入1 5 0份之熔融二氧化矽（平均粒徑約 5 // m )進行混合後取得混合體。 -30- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）經濟部智慧財產局員工消費合作社印製 565589 A7 一 B7 五、發明說明（28) <比較例3 > 做爲矽烷偶合劑者除以2 · 〇份之A - 1 8 7 (曰本 Unika股份公司製商品名，r -環氧丙氧基丙基甲氧基矽烷 )取代矽烷偶合劑之外，與比較例2同法取得混合物。 <比較例4 > 以2 · 0份之A—16 3 (日本Unika股份公司製商品名，甲基三甲氧基矽烷）取代A — 1 7 1做爲矽烷偶合劑之外，與比較例2同法取得混合體。 <比較例5 > 以2 · 0份之A— 137 (日本Unika股份公司製商品名，正一辛基三乙氧基矽烷）取代A - 1 7 1做爲矽烷偶合劑之外’與比較例2同法取得混合體。 <比較例6 > 以2 · 0份之A —153 (日本Unika股份公司製，苯基三乙氧基矽烷）取代A - 1 7 1做爲矽烷偶合劑之外，與比較例2同法取得混合體。 B ·實施例4、比較例7〜8 此等實施例與比較例中，於環烯烴類單體中以 D C P D與環辛二烯調製d C P D樹脂液後，於此加入塡充材後，與實施例1同法攪拌後調製混合體。本紙張尺度適用中國國家標準（CNS)A4規袼（21〇 X 297公爱） -31 - (請先閱讀背面之注音？事項再填寫本頁) f tr'i·------- 565589 Α7 --------Β7____ 五、發明說明（29 ) 所取混合體於6 0 °C下加熱4小時後，約以3 5 °C進行冷却後使用之。首先，於此混合體中加入〇 · 1 5份之易位聚合觸媒，進行混合後，使混合體進行減壓脫泡後，取得成形材料。以取得之成形材料使試驗片成形後，藉由以下方法評定各種特性。又’試驗片之製作方法及各種特性之評定方法與上述實施例1〜3同法進行者。其評定結果如表2所不° 表2 彎曲特性絕緣破壞之強度彎曲強彎曲彈撓曲率初期 Pd 保持率度（MPa) 性（GPa) (%) (KV/mm) (KV/mm) (%) 實施例4 1.51 15.7 20< 20.0 20.3 102 比較例7 1.02 13.2 20< 19.5 8.9 45.6 比較例8 1.48 16.9 20< 20.7 19.5 94.2 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) <實施例4 > 以5 0份之純度約9 8 %之D C P D及5 0份之環辛二烯（東京化成工業股份公司製試藥）取代1 〇〇份之 D C P D之外，與實施例1同法取得混合物。 <比較例7 > 於1 0 0份D C P D中更加入5 0份之環辛二烯（東本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565589 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（30 ) 京化成工業股份公司製試藥）做爲環烯烴類單體之外，與比較例1同法取得混合體。 <比較例8 > 於1 0 0份D C PD中更加入5 0份之環辛二烯做爲環烯烴類單體之外與比較例2同法取得混合體。 C ·貫施例5〜1 〇、比較例9〜1 2 此等各實施例中，以含金屬偶合劑作爲偶合劑調製 D C P D樹脂液後，於此加入塡充材之後，與實施例1同法攪拌後調製成混合體。於此混合體加入〇 · 1 2份之易位聚合觸媒，進行混合後’將混合體進行減壓脫泡，取得成形材料。以此取得成材材料形成試驗片後，藉由以下方法進行各種評定。又，試驗片之製作方法與彎曲特性之各評定方法與上述實施例1〜3同法進行之。又’偶合劑與塡充材之反應度於混合體粘度降低下進行評定。粘度之評定係針對製作後1小時混合體之粘度與 3 5 °C下放置2 0小時之混合體粘度依J I S K 6 9 0 1爲基準進行評定。測定條件以溫度：3 5 °C，粘度計：B L型旋轉粘度計，旋轉數：6 0 r p m者。評定結果如表3所示。如表3可證明含金屬偶合劑添加品之彎曲特性比未添加之彎添加品較爲優異，與矽矽烷偶合劑具同等特性者。又，含金屬偶合劑添加品比矽烷系 I --------tr--------- -- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -33- 565589 A7 ___B7____ 五、發明說明（31 ) 偶合劑添加品較爲快速降低粘度，因此，偶合劑與塡充材之反應較快速。表3 彎曲特性粘度（N · s / m 2 ) 彎曲強度 (MPa) 撓曲率（％) 1時間後 20時間後實施例5 80.2 3.0 0.10 0.10 實施例6 60.1 2.9 0.15 0.10 實施例7 58.0 2.6 0.30 0.10 實施例8 95.2 4.0 0.10 0.10 實施例9 36.0 1.0 0.30 0.30 實施例10 60.1 2.9 0.10 0.09 比較例9 36.5 2.2 2 ^ 2 ^ 比較例1 0 96.9 2.4 0.40 0.10 比較例11 59.6 3.0 0.52 0.11 比較例1 2 30.0 0.9 2 ^ 2 ^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 <實施例5 > 以1 . 5份之Prenact KR55 (味之素股份公司製商品名，具烯丙基之鈦系偶合劑、四（2，2 —二烯丙基氧基甲基一 1 一丁基）雙{二（三癸基）}磷酸酯鈦酸酯及雙 (二辛基焦磷酸酯）氧基乙酸酯鈦酸酯）取代 F Z 3 7 7 8做爲偶合劑後，做成1 〇〇份之熔融二氧化本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公爱） 34 - 565589 A7 _ _ B7 五、發明說明（32) 石夕添加量之外，與實施例1同法取得混合體。 (請先閱讀背面之注意事項再填寫本頁) <實施例6 > 以1 · 5份之Prenact AL-M (味之素股份公司製商品名’乙醯丨兀氧基銘一異丙酸酯）取代Prenact KR55之外，與實施例5同法取得混合體。 <實施例7 > 以1 · 0份之Orgatix ZC-5 70 (鉻乙醯乙酮酸酯雙乙基乙酮酸酯，松本製藥工業股份公司製商品名）取代Prenact KR55之外，與實施例5同法取得混合體。 <實施例8 > 以 Prenact KR55 (0.5 份）與 A— 163(1.5 份）取代F Z 3 7 7 8做爲偶合劑之外，與實施例1同法取得混合體。 <實施例9 > 經濟部智慧財產局員工消費合作社印製將Prenact KP5 5之添加量做成1·〇份，A—163 之添加量3 · 0份，熔融二氧化矽之添加量爲2 0 〇份之外，與實施例8同法取得混合體。 <實施例1 0 > 以1 · 0份之Prenact KRTTS (味之素又份公司製商 -35 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）經濟部智慧財產局員工消費合作社印製 565589 A7 B7 五、發明說明（33 ) 品名，異丙基三異硬脂醯基鈦酸酯）取代F Z 3 7 7 8做爲偶合劑，熔融二氧化矽之添加量做成1 〇〇份之外，與實施例1同法取得混合體。 <比較例9 > 三苯基膦之添加量爲0 · 0 5份，熔融二氧化矽添加量爲1 0 0份之外，與比較例1同法取得混合體。 <比較例1 0 > 三苯基膦之添加量爲0 · 0 5份，矽烷偶合劑A — 1 7 1之添加量爲1 · 5份，熔融二氧化矽添加量爲 1〇0重量份之外，與比較例2同法取得混合體。 <比較例1 1 > 三苯基膦添加量爲0 · 0 5份，熔融二氧化砂添加量爲1 0 0份之外，與比較例5同法取得混合體。 <比較例1 2 > 以A - 1 6 3取3 · 0份取代A - 1 7 1，做爲矽烷偶合劑，熔融二氧化矽添加量爲2 0 0份之外，與比較例 2同法取得混合物。 D ·實施例1 1〜1 2，比較例1 3〜1 4 此等實施例與比較例中，以碳酸鈣做爲塡充材使用後 -----1-----ΜΨ--------訂---------^9 (請先閱讀背面之注音？事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -36- 565589 A7 ---- B7_ 五、發明說明（34 ) ’調製混合體。又，調製混合體時之攪拌係使用渦輪翼，以2 6 0 〇 r pm進行6 Q分鐘。 (請先閱讀背面之注意事項再填寫本頁} 於此混合體中加入〇 . 1 2份之易位聚合觸媒，進行混合後，使混合體進行減壓脫泡後，取得成形材料。以戶斤取得成形材料使試驗片成形後，藉由以下方法，進行評定各種特性。又，試驗片之製作方法及彎曲特性之評定方法與上述實施例1〜3同法進行之。評定結果如表4所示。由表4證明含金屬偶合劑添加品比無添加品較具良好彎曲強度，更比矽垸偶合劑添加品更優異者。表4 彎曲特性粘度（N · _ _ 晒—---- s / m 2 ) 彎曲強度撓曲率（％) 1時間後 2 0時間後 (MPa) 實施例 11 7.50 2.9 0.20 ---—, 0.15 實施例 12 68.0 6 ^ 0.10 0.07 比較例 13 36.5 2.9 2 ^ 2 ^ 比較例 14 5 5.6 6 ^ 1.69 1.18 經濟部智慧財產局員工消費合作社印製 <實施例1 1 >: CH, CH3 (15 A · Examples 1 to 3, Comparative Examples 1 to 6 In each of these examples, after the reactive polysiloxane is used as a coupling agent, a DCPD resin liquid of a cycloolefin composition is prepared, After adding the filling material, the spiral wing was stirred at 400 rpm for 5 minutes, and then mixed into a mixture (that is, a composite material). This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) -26- !!, -----. F -------- Order one ------ $ (Please read the notes on the back before filling this page) 565589 A7- -------- B7_— —__ V. Description of the invention (24) (Please read the notes on the back before filling this page) The obtained mixture is heated at 60 ° C for 4 hours, and then Use it after cooling to about 3 5 ° C. First, add 0.1 parts of metathesis polymerization catalyst to this mixture, mix it, degas the mixture under reduced pressure, and obtain the cycloolefin composition. Molding material. After forming a test piece using this molding material, various characteristics are evaluated by the following methods. I. Bending characteristics (a) Test piece production method The shaped material is subjected to boiling casting in a mold with a thickness of 3 mm. Subsequently, the mold is heated in an oven at 40 ° C for 5 hours, and heated at 130 ° C for 2 hours to obtain a plate-shaped hardened material. (B) Bending test A bending test piece with a width of 25 mm and a length of 80 mm was cut from a flat plate, and the bending test was performed after taking JISK 7203 as the benchmark. The formula for bending and bending is given by 2) V cmm when borrowing Lm}, / mm} This amount of d {m. 6 degrees 彳} II bending thickness away from η} when the distance i% between the pieces {{bad test Point \ Rate loss test support m bend ... ΓΪΊ 易 dvL 2 ° -27- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 565589 A7 _______B7 V. Description of the invention (25 II. Water resistance The retention rate was determined from the insulation damage strength before and after the pressure cooking test (pc T) test. (A) Method for making test pieces The above-mentioned forming materials were subjected to boiling casting in a flat mold with a thickness of 2 mm, and then The mold is heated at 40 t for 5 hours, and it is heated at 130. (After 2 hours for 2 hours Obtain a flat plate-like hardened material. (B) The strength of the insulation damage is measured based on JISK 6 9 1 1. The conditions for PCT are temperature: 1 2 1 ° C, pressure: 2 2 2 k P a, time: 50 hours. The evaluation results are shown in Table 1. From this table, it was proved that the formed bodies obtained by using the mixtures of the respective examples of the reactive polysiloxane had greater flexibility and toughness than the comparative examples. In addition, the insulation damage strength after PCT was not reduced in each of the examples, and it had good water resistance. ----- 1 ----- MW -------- V ·· ------- (Please read the precautions on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economy Consumption The paper size printed by the cooperative is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -28- 565589 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (26) Table 1 _ Bending characteristics Insulation failure strength Bending strong bending elasticity Initial Pd retention rate (MPa) Property (GPa) (%) (KV / mm) (KV / mm) (%) Example 1 52.8 6.40 4.6 20.9 21.3 102 Example 2 55.5 6.52 3.0 21.0 20.4 97.1 Example 3 57.8 6,61 4.2 19.9 19.7 99.0 Comparative Example 1 39.5 6.20 1.0 19.8 11.2 56.6 Comparative Example 2 116 7.10 2.0 19.8 19.0 96.0 Comparative Example 3 52.5 6.75 1.8 20.2 17.9 88.6 Comparative Example 4 49.5 6.70 1.3 21.0 16.0 76.2 Comparative Example 5 56.1 6.66 2.6 21.4 18.0 84.0 Comparative Example 6 58.8 6.60 1.4 20.5 18.5 90.2 < Example 1 > To 100 parts of DCPD with a purity of about 98%, 2 parts of Sunnlaza BHT (Sumitomo Chemical Industry Co., Ltd. trade name, oxidation inhibitor) '0 · 0 5 parts of triphenyl (Made by Wako Pure Chemical Industries, Ltd., a special test reagent), 2.0 parts of FZ3778 (trade name of Unika Corporation of Japan, ethoxymethylhydrodiene polysiloxane), and then disperse the DCPD resin liquid. Subsequently, 150 parts of fused silica (average particle diameter: 5 μm) was added and mixed to obtain a mixture. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -29- ------------ Avw -------- Order ------ --- (Please read the note on the back? Matters before filling out this page) 565589 A7 ---- B7 V. Description of the invention (27) <Example 2 > (Please read the precautions on the back before filling out this page ) MAC 2101 (trade name of Unika Co., Ltd., a polysiloxane of epoxy group and condensable silyl group) was replaced by 2 · 0 parts in the same manner as in the example to obtain a mixture. . < Example 3 > A polymer-type silane coupling agent FZ 3 7 0 4 (trade name made by Umka Corporation of Japan, polyethoxymethylsiloxane) was replaced with 2 · 0 parts of FZ 3 7 7 8 In the same manner as in Example 1, a mixture was obtained. < Comparative Example 1 > After adding 2.0 parts of Sumilaiza BHT and 0.6 parts of triphenylphosphonium (special grade) to DCPD 100 parts having a purity of about 98%, a dispersed DCPC resin solution was prepared. . Subsequently, 150 parts of fused silica (manufactured by Longsen Co., Ltd., with an average particle diameter of about 7 // m) was added, and the mixture was obtained after mixing. < Comparative Example 2 > Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on 100 parts of DCPD with a purity of 98%, 2.0 parts of Sumilaiza BHT and 0.6 parts of triphenylphosphine ( Special grade), 2.0 parts of Silane Coupling Agent A-171 (trade name of Unika Corporation, ethylene trimethoxysilane), and then disperse the DCPD resin solution. Subsequently, 150 parts of fused silica (average particle diameter of about 5 // m) was added and mixed to obtain a mixture. -30- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 565589 A7 B7 V. Description of Invention (28) < Comparative Example 3 > As a silane coupling agent, except that the silane coupling agent is replaced by 2-0 parts of A-1 8 7 (the trade name of Unika Co., Ltd., r-glycidoxypropylmethoxysilane), and Comparative Example 2 A mixture was obtained in the same manner. < Comparative Example 4 > Instead of A — 1 7 1 as a silane coupling agent, 2.0-16 parts of A-16 3 (trade name of Unika Corporation of Japan, methyltrimethoxysilane) was used as a silane coupling agent. 2 Obtain the mixture in the same way. < Comparative Example 5 > A-137 (a trade name of Unika Corporation of Japan, n-octyltriethoxysilane) was replaced by 2.0 parts of A-137 as a silane coupling agent. Comparative Example 2 A mixture was obtained in the same manner. < Comparative Example 6 > Same as Comparative Example 2 except that 2.0-0 parts of A-153 (manufactured by Unika Corporation of Japan, phenyltriethoxysilane) was used instead of A-1 7 1 as a silane coupling agent. Method to obtain a hybrid. B. Example 4 and Comparative Examples 7 to 8 In these examples and comparative examples, after the d CPD resin solution was prepared by using DCPD and cyclooctadiene in a cycloolefin monomer, after adding rhenium filling material, and Example 1 was prepared by stirring in the same manner. This paper size applies the Chinese National Standard (CNS) A4 regulations (21〇X 297 public love) -31-(Please read the note on the back? Matters before filling out this page) f tr'i · ------- 565589 Α7 -------- Β7 ____ 5. Description of the invention (29) After the mixture is heated at 60 ° C for 4 hours, it is used after cooling at about 3 5 ° C. First, 0.15 parts of a metathesis polymerization catalyst was added to the mixture, and after mixing, the mixture was degassed under reduced pressure to obtain a molding material. After forming the test piece from the obtained molding material, various characteristics were evaluated by the following methods. The method of producing test pieces and the methods of evaluating various characteristics were performed in the same manner as in Examples 1 to 3 described above. The evaluation results are as shown in Table 2. Table 2 Bending characteristics Strength of insulation failure Bending strong bending elasticity Pd retention rate (MPa) Property (GPa) (%) (KV / mm) (KV / mm) (% ) Example 4 1.51 15.7 20 < 20.0 20.3 102 Comparative Example 7 1.02 13.2 20 < 19.5 8.9 45.6 Comparative Example 8 1.48 16.9 20 < 20.7 19.5 94.2 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (Fill in this page) < Example 4 > Replace 50 parts of DCPD with 50 parts of DCPD with a purity of about 98% and 50 parts of cyclooctadiene (produced by Tokyo Chemical Industry Co., Ltd.). A mixture was obtained in the same manner as in Example 1. < Comparative Example 7 > Add 50 parts of cyclooctadiene to 100 parts of DCPD (East paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 565589 Intellectual property of Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of the Invention (30) Except for the cyclic olefin monomers produced by Jinghuacheng Industrial Co., Ltd., a mixture was obtained in the same manner as in Comparative Example 1. < Comparative Example 8 > A mixture was obtained in the same manner as in Comparative Example 2 except that 50 parts of cyclooctadiene was added to 100 parts of D C PD as a cycloolefin type monomer. C. Examples 5 to 10 and Comparative Examples 9 to 1 2 In each of these examples, a metal-containing coupling agent was used as a coupling agent to prepare a DCPD resin solution, and then a cymbal filling material was added thereto, which is the same as Example 1. After mixing, prepare a mixture. 0.12 parts of a metathesis polymerization catalyst was added to the mixture, and after mixing, the mixture was degassed under reduced pressure to obtain a molding material. After obtaining the material to form a test piece, various evaluations were performed by the following methods. In addition, the test piece production method and each evaluation method of the bending characteristics were performed in the same manner as in the above-mentioned Examples 1 to 3. The degree of reactivity between the 'coupling agent' and the rhenium filling material was evaluated with the decrease in the viscosity of the mixture. The evaluation of the viscosity is based on J I S K 6 901 for the viscosity of the mixture 1 hour after production and the viscosity of the mixture left at 35 ° C for 20 hours. The measurement conditions were temperature: 3 5 ° C, viscometer: B L-type rotational viscometer, rotation number: 60 r p m. The evaluation results are shown in Table 3. As shown in Table 3, it can be proved that the bending characteristics of the additive containing the metal coupling agent are better than those of the non-added bending additive, and those having the same characteristics as the silane coupling agent. In addition, the additive containing metal coupling agent is more than silane series I -------- tr ----------(Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -33- 565589 A7 ___B7____ V. Description of the Invention (31) Additives for coupling agents reduce viscosity quickly, so the reaction between the coupling agent and concrete filling material is faster. Table 3 Bending intrinsic viscosity (N · s / m 2) Bending strength (MPa) Deflection (%) Example 5 after 20 time Example 5 80.2 3.0 0.10 0.10 Example 6 60.1 2.9 0.15 0.10 Example 7 58.0 2.6 0.30 0.10 Example 8 95.2 4.0 0.10 0.10 Example 9 36.0 1.0 0.30 0.30 Example 10 60.1 2.9 0.10 0.09 Comparative Example 9 36.5 2.2 2 ^ 2 ^ Comparative Example 1 0 96.9 2.4 0.40 0.10 Comparative Example 11 59.6 3.0 0.52 0.11 Comparative Example 1 2 30.0 0.9 2 ^ 2 ^ (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy < Example 5 > 1.5 copies of Prenact KR55 (made by Ajinomoto Corporation) Trade name, titanium-based coupling agent with allyl, tetra (2,2-diallyloxymethyl-1 1-butyl) bis {di (tridecyl)} phosphate titanate and bis ( Dioctyl pyrophosphate) oxyacetate titanate) was substituted for FZ 3 7 7 8 as a coupling agent, and then made into 100 parts of fused dioxide. This paper is sized for China National Standard (CNS) A4 Specifications (210 X 297 public love) 34-565589 A7 _ _ B7 V. Description of the invention (32) Stone For the addition amount, to obtain a mixture of the same method as in Example 1. (Please read the precautions on the reverse side before filling out this page) < Example 6 > With 1 · 5 parts of Prenact AL-M Except for the acid ester) instead of Prenact KR55, a mixture was obtained in the same manner as in Example 5. < Example 7 > Instead of Prenact KR55, 1.0 part of Orgatix ZC-5 70 (chromium acetoacetone diethyl ethyl ketone ester, trade name of Matsumoto Pharmaceutical Industry Co., Ltd.) was replaced with Example 5 A mixture was obtained in the same manner. < Example 8 > A mixture was obtained in the same manner as in Example 1 except that FZ 3 7 7 8 was replaced by Prenact KR55 (0.5 parts) and A-163 (1.5 parts) as a coupling agent. < Example 9 > Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the additive amount of Prenact KP5 5 was made 1.0 parts, the additive amount of A-163 was 3.0 parts, and the added amount of fused silica was A mixture was obtained in the same manner as in Example 8 except for 200 parts. < Example 1 0 > With 1.0 · 10 parts of Prenact KRTTS (Ajinomoto Co., Ltd.-35-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm)) Printed by the Consumer Cooperative of the Property Bureau 565589 A7 B7 V. Description of the invention (33) Product name, isopropyl triisostearyl titanate) instead of FZ 3 7 7 8 as a coupling agent, the amount of fused silica added Except for 100 parts, a mixture was obtained in the same manner as in Example 1. < Comparative Example 9 > A mixed body was obtained in the same manner as in Comparative Example 1 except that the amount of triphenylphosphine added was 0.5 parts and the amount of fused silica was 100 parts. < Comparative Example 1 0 > The amount of triphenylphosphine added was 0.55 parts, the amount of silane coupling agent A — 1 71 was 1.5 parts, and the amount of fused silica was 100 weight. A mixture was obtained in the same manner as in Comparative Example 2 except that it was equal to or less. < Comparative Example 1 1 > A mixture was obtained in the same manner as in Comparative Example 5 except that the amount of triphenylphosphine added was 0.55 parts and the amount of molten sand dioxide was 100 parts. < Comparative Example 1 2 > Take A · 1 6 3 and take 3 · 0 parts instead of A · 1 7 1 as a silane coupling agent. The amount of fused silica added is not more than 200 parts. Obtain the mixture in the same way. D · Example 1 1 ~ 12, Comparative Example 1 3 ~ 1 4 In these examples and comparative examples, after calcium carbonate was used as the radon filling material ----- 1 ----- ΜΨ-- ------ Order --------- ^ 9 (Please read the note on the back? Matters before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) -36- 565589 A7 ---- B7_ 5. Description of the invention (34) 'Modulation mixture. In addition, the agitation when preparing the mixture was performed using a turbine wing for 6 Q minutes at 2600 r pm. (Please read the precautions on the back before filling this page} Add 0.12 parts of metathesis polymerization catalyst to this mixture, mix them, decompress and defoam the mixture, and obtain the molding material. After the customer obtained the forming material and formed the test piece, various characteristics were evaluated by the following methods. The test piece production method and the evaluation method of the bending characteristics were performed in the same manner as in Examples 1 to 3 above. The evaluation results are shown in the table. Shown in Table 4. It is proved from Table 4 that the metal-containing coupling agent added product has better bending strength than the non-additive product, and is more excellent than the silicon hafnium coupling agent addition product. Table 4 Bending intrinsic viscosity (N · _ _ sun --- -s / m 2) Bending strength Deflection (%) After 1 time and after 20 time (MPa) Example 11 7.50 2.9 0.20 -----, 0.15 Example 12 68.0 6 ^ 0.10 0.07 Comparative Example 13 36.5 2.9 2 ^ 2 ^ Comparative Example 14 5 5.6 6 ^ 1.69 1.18 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs < Example 1 1 >

Preact KR55之添加量爲1 · 6份，熔融二氧化矽以 1 0 0份N S 4 0 0 (碳酸鈣，日東粉化工業股份公司製商品名）取代之外，與實施例5同法取得混合體。 -37- 本紙張尺度適用中國國彖標準（CNS)A4規格（210 X 297公釐） 565589 A7 B7 五、發明說明（35) <實施例1 2 > (請先閱讀背面之注音華項再填寫本頁) 以〇· 8 份之 Prenact KRTTS 取代 Prenact KR55 之外，與實施例1 1同法取得混合體。 <比較例1 3 > 以100份之NS400 (碳酸鈣，日東粉化工業股份公司製商品名）取代熔融二氧化矽之外，與比較例9同法取得混合體。 <比較例1 4 > 以100份之NS400 (碳酸鈣，日東粉化工業股份公司製商品名）取代熔融二氧化矽之外，與比較例1 〇同法取得混合體。〔產業上可利用性〕經濟部智慧財產局員工消費合作社印製本發明環烯烴組成物及成形材料不會降低其耐水性、電氣絕緣性、機械特性，同時可抑制降低靭性（特別是彎曲試驗時之易彎率）。由本發明環烯烴組成物及成形材料取得之成形體具有環烯烴聚合物之優異耐水性、耐沸性、機械特性、及電氣特性，可利用於如：淨化槽、浴缸、厨房天花板、蓄水池、組合衛浴、壁坎、遊覽船、下水槽、配水管、波板、配線板、絕緣材等成形品、電氣零件、電子零件等用途上。 38 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）弟89103284號專利申請案中文說明書修正頁 m 申請曰期 89年 2月24日案號 89103284 類別 K (以上各搁由本局填拄）公 A4 C4 565589 明新型專利説明書發明新型名稱發明創作> 中文英文姓名國籍住、居所姓名 (名稱）環烯烴組成物及其製造方法、成形材料以及成形髖Preact KR55 was added in an amount of 1.6 parts. Molten silica was replaced with 100 parts NS 4 0 0 (calcium carbonate, trade name of Nitto Powder Chemical Industry Co., Ltd.), and mixed with the same method as in Example 5. body. -37- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 565589 A7 B7 V. Description of the invention (35) < Example 1 2 > (Please read the phonetic item on the back first (Fill in this page again) Except replacing Prenact KR55 with 0.8 parts of Prenact KRTTS, obtain the mixture in the same way as in Example 11. < Comparative Example 1 3 > A mixture was obtained in the same manner as in Comparative Example 9 except that 100 parts of NS400 (calcium carbonate, trade name of Nitto Powder Chemical Industry Co., Ltd.) was used instead of fused silica. < Comparative Example 1 4 > A mixture was obtained in the same manner as Comparative Example 10 except that 100 parts of NS400 (calcium carbonate, a trade name of Nitto Powder Chemical Industry Co., Ltd.) was used instead of fused silica. [Industrial Applicability] The printing of the cycloolefin composition and molding material of the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs will not reduce its water resistance, electrical insulation, and mechanical properties, and it can also reduce the reduction of toughness (especially the bending test When the bend rate). The formed body obtained from the cyclic olefin composition and the molding material of the present invention has excellent water resistance, boiling resistance, mechanical properties, and electrical properties of the cyclic olefin polymer, and can be used in, for example, purification tanks, bathtubs, kitchen ceilings, and reservoirs. , Combined bathroom, wall sill, excursion boat, sink, water distribution pipe, wave board, wiring board, insulating materials and other shaped products, electrical parts, electronic parts and other uses. 38 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love), the Chinese Patent Application No. 89103284, amendment page of the Chinese specification m Application date February 24, 89 Case No. 89103284 Category K (Filled in this Bureau) Public A4 C4 565589 Ming patent patent invention invention new name invention creation> Chinese English name Nationality residence, residence name (name) Cycloolefin composition and its manufacturing method, forming material and forming hip

Cycloolefin composition, process for producing the samey molding materialf and molded object 明政仁知宏崎木合山青河 (1)(2)(3) (1)日本 (2)日本 ⑶ 日本 (1)日本國茨城縣筑波市和钤四八日立化成工業股份有限公司總合研究所内 (2)日本國茨城縣筑波市和钤四八日立化成工業股份有限公司總合研究所内 (3)日本國茨城縣筑波市和台四八日立化成工業股份有限公司總合研究所内 (ΐ) ΒΒιΐϋΐηιι^ 裝訂線經濟部智慈財是钩s工消費合作社印製國籍 (1)日本 (1)日本國東京都新宿區西新宿二丁目一番一號三、申請人住、居所 (事務所）代表人姓名 ⑴内崎功本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Cycloolefin composition, process for producing the samey molding materialf and molded object Meisei Renzhi Hongqi Qi Heshan Qinghe (1) (2) (3) (1) Japan (2) Japan ⑶ Japan (1) Tsukuba, Ibaraki Prefecture, and Inside the General Research Institute of Hitachi Chemical Industry Co., Ltd. (2) Inside the General Research Institute of Hitachi Chemical Industry Co., Ltd., Japan and (3) Hitachi Hitachi, Ibaraki Prefecture, Japan Chemical Industry Co., Ltd. General Research Institute (ΐ) ΒΒιΐϋΐηιι ^ Gutter is the Ministry of Economic Affairs's Chi Tzu Choi, a printed consumer nationality (1) Japan (1) Nishi-Shinjuku 2-chome, Shinjuku, Tokyo, Japan No. 3. Applicant's residence and residence (office) Name of representative ⑴ 内崎崎本 Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm)

Claims

565589

A8 B8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs VI. Patent Application 1 Annex 2 ·· 89103284 Patent Application Chinese Application Patent Scope Amendment The Republic of China_Corner B Replacement: Amendment • 1 · One Cyclic olefin composition, which contains Kevlar; cyclic olefin monomers, coupling agents, metathesis polymerization catalysts, and plutonium filling materials, in which the amount of metathesis polymerization catalyst added, in order to For cyclic olefin monomers, 100 parts by weight is from 0.1 to 1 part by weight. The amount of fluorene filler is 30 to 90% by weight based on the total amount of the composition. 〇〇parts are 0.1 to 5 parts by weight, and the coupling agent described above contains at least any one of a metal-containing coupling agent and a reactive polysiloxane. 2. The cyclic olefin composition according to item 1 of the application, wherein the coupling agent contains at least one metal coupling agent selected from titanium, aluminum, chromium, iron, calcium, magnesium, and zinc. 3. The cyclophosphine composition according to item 1 of the patent application scope, wherein the coupling agent contains at least one kind selected from tetra (2,2-diallyloxymethyl-1 monobutyl) bis {di (Tridecyl) 丨 Phosphate Titanate, Isopropyl Triisostearyl Titanate, Acetyl Alkoxy Aluminium Diisopropylate, and Ethyl Ethyl Acetate Diethyl Acetate By. 4. As the cyclic fuel composition of the scope of the patent application, the metathesis catalyst is a compound represented by the following general formula (9): X1 'L 1 R7 XI > M di C Ί L 2 Η C = C (please read the precautions on the back of the page before filling in this page) t Order the RR paper size 逋 Chinese National Standard (CNS) Α4 size (210 × 297 mm) (9) 565589 A8 B8 C8 D8 VI. Application Scope of patent (please read the note on the back of -Λ before filling out this page) (However, M is ruthenium or hungry, X 1 and X 2 represent halogen, L 1 and L 2 respectively represent P (cyclohexyl). 3. P (cyclopentyl) 3 or P (isopropyl) 3 'R5 and R6 are each independently an alkyl group having 1 to 18 carbon atoms, and R7 is a hydrogen atom). 5. The cyclic olefin composition according to item 1 of the patent application scope, wherein the concrete filling material contains at least one selected from the group consisting of glass, silicon dioxide, aluminum oxide powder, magnesium hydroxide, aluminum hydroxide, calcium carbonate, and silica sand. . 6. The cyclic olefin composition according to item 1 of the application, wherein the cyclic olefin monomer is a dicyclopentadiene-containing monomer. 7 · —A method for producing a cycloolefin composition, which comprises the steps of mixing a cycloolefin monomer that can be metathesized, a coupling agent, a metathesis catalyst, and a hydrazone filling material, wherein the steps described above include The step of heating the coupling agent and the optional filler at room temperature to 60 ° C for 0. 5 to 4 hours to carry out the reaction. The amount of the metathesis polymerization catalyst is added to 1,000 parts by weight of the cyclic olefin unit. 0.1 to 1 part by weight, the total amount of rhenium filling material is 30 to 90% by weight based on the total amount of the composition. Parts are 0.1 to 5 parts by weight, and the coupling agent described above contains at least any one of a metal-containing coupling agent and a reactive polysiloxane. 8 · A forming material whose characteristics are contained in the cycloolefin composition as described in the first item of the patent application. 9 · A shaped body, which is a hardened product obtained by hardening the shaped material as described in item 8 of the patent application. This paper size applies to China National Standard (CNS) A4 (210X297 mm)