1379870 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關附有黏著性之附加硬化型聚矽氧橡膠組 成物，更詳細者係有關附與硬化後之橡膠薄片即使曝露於 高溫其黏著力仍極少下降之橡膠薄片附加硬化型聚矽氧橡 膠組成物，及硬化此組成物所成之黏著橡膠薄片。 【先前技術】 先行技術中，橡膠薄片係做爲各種部品、道具類之固 定薄片者，如：用於醫院等之醫療器具的固定、餐廳、聚 會會場等食器類之固定等。又，利用其黏著力，適用於各 種微小部品、薄片部品之組裝步驟中搬運薄片。特別是， 具良好耐熱性之黏著橡膠薄片可用於黏著劑硬化、洗淨、 焊接再流動等務必加熱之步驟，亦可用於一般不適用於黏 著劑之用途者，各種電子零件如：電容器、啓動器、感應 器等製造步驟中做爲固定此等部品、搬運用途之使用。或 以可撓性印刷電路板爲始之薄板印刷電路板表面具有實裝 電子零件等之步驟、及於電子機器搭載該印刷電路板之步 驟之製造電子機器步驟中被使用之β如：特開2002-170788號公報（專利文獻1)所揭示之上述步驟使用之聚矽 氧黏著材料，惟，關於其聚矽氧之具體組成卻完全未記載 之。 黏著劑亦稱爲感壓黏著劑，具有以指尖輕壓之小壓力 下可輕易黏著於對象物表面之性質。此黏著劑用於如：透 (2) (2)1379870 明膠帶、電氣絕緣用乙烯膠帶、標識膠帶、黏著薄片等黏 著製品。做爲用於此等黏著膠帶、薄片之黏著劑者係以天 然橡膠、合成橡膠等爲主成份使用者，惟’此等黏著劑組 成物有遇熱、光等容易劣化、低溫下降低黏著性之問題點 存在。對於此，聚矽氧黏著劑具有聚矽氧特有之良好耐熱 性、耐寒性、電氣特性、且具有不損及此等特性之黏著性 。因此，廣泛利用於高度信賴性所需之各種黏著製品。 做爲此等聚矽氧黏著劑者公知者如具（CHdsSiOe.s單 位及Si02單位之聚矽氧烷與二甲基聚矽氧生橡膠之縮合物 所成之聚矽氧黏著劑，含烯基之有機聚矽氧烷與有機氫化 聚矽氧烷之氫矽烷化反應之加成之加成型聚矽氧烷黏著劑 (專利文獻2’ 3:特公昭54-37907號公報、特開昭63-22886號公報）。惟，此等黏著劑主要藉由塗層後形成薄膜 ’利用表面之黏著性者’因此’完全未觸及橡膠硬度、強 度。實際上’以此等組成物做爲橡膠薄片其黏著力亦充份 。惟’不具橡膠強度下，因此不適用於機架之固定薄片、 重覆使用之電子零件之製造步驟用者。特別是，各種電子 零件之製造線所使用之黏著材料在加熱步驟，因此，適於 使用耐熱性良好之聚矽氧橡膠。而，此等製造線中，如： 焊接再流動步驟寺闻至250。〇以上者亦有，更需要亘良好 耐熱性。 特開20〇4-189945號公報（專利文獻q中揭示有高強度 之聚矽氧橡膠黏著材料，惟，有關耐熱性並無報告亦無 添加耐熱賦予劑之具體的實施例。又，特開2〇〇4_i9〇〇i3 -5- (3) 13798701379870 (1) Nine, the invention belongs to the technical field of the invention. The present invention relates to an additional hardening type polyoxymethylene rubber composition with adhesiveness, and more specifically relates to a rubber sheet attached to a hardened state even if exposed to a high temperature. The rubber sheet which has little adhesion to the rubber sheet is added with a hardening type polyoxymethylene rubber composition, and an adhesive rubber sheet formed by hardening the composition. [Prior Art] In the prior art, the rubber sheet is used as a fixed sheet for various parts and props, such as fixing of medical instruments for hospitals, fixing of restaurants, gathering places, and the like. Further, the adhesive force is applied to convey the sheet in the assembly step of various minute parts and sheet parts. In particular, adhesive rubber sheets with good heat resistance can be used for the steps of heating, curing, soldering, reflow, etc., and for those generally not suitable for adhesives, various electronic parts such as capacitors and starters. In the manufacturing steps such as the device and the sensor, it is used to fix these parts and carry them. Or a step of manufacturing a printed circuit board with a flexible printed circuit board as a step of mounting an electronic component or the like, and a step of manufacturing an electronic device in the step of mounting the printed circuit board on an electronic device, such as: The polyoxynoxy adhesive material used in the above-described steps disclosed in Japanese Laid-Open Patent Publication No. 2002-170788 (Patent Document 1), but the specific composition of the polyfluorene oxide is not described at all. Adhesives, also known as pressure-sensitive adhesives, have the property of easily adhering to the surface of an object with a small pressure that is lightly pressed by the fingertips. The adhesive is used for, for example, (2) (2) 1379870 gel tape, vinyl tape for electrical insulation, marking tape, adhesive sheet, and the like. As the adhesive for these adhesive tapes and sheets, users such as natural rubber and synthetic rubber are the main components, but these adhesive compositions are prone to deterioration due to heat, light, etc., and low adhesion at low temperatures. The problem exists. In this regard, the polyoxyxylene adhesive has excellent heat resistance, cold resistance, electrical properties unique to polyoxymethylene, and has adhesive properties that do not impair such characteristics. Therefore, it is widely used in various adhesive products required for high reliability. It is known as a polyoxygenated adhesive for such a polyoxyl adhesive, such as a polyoxyl adhesive formed of a condensate of a polyoxane and a dimethylpolyoxyn rubber of CHdsSiOe.s unit and a SiO 2 unit, containing an ene group. Addition-molding polyoxane adhesive based on the addition of an organohydrogenated alkane to an organohydrogenated polyoxyalkylene (Patent Document 2' 3: Japanese Patent Publication No. 54-37907, JP-A-63-63 -22886. However, these adhesives mainly form a film by coating, and the adhesiveness of the surface is utilized, so that the rubber hardness and strength are not touched at all. In fact, the composition is used as a rubber sheet. The adhesiveness is also sufficient. However, it is not suitable for the manufacturing steps of the fixed sheet of the frame and the electronic parts used repeatedly. In particular, the adhesive materials used in the manufacturing lines of various electronic parts. In the heating step, therefore, it is suitable to use a polyoxymethylene rubber having good heat resistance. However, in such a manufacturing line, for example, the welding reflowing step is smothered to 250. There are also those which are more suitable for heat resistance. Special opening 20〇4-189945 (Patent Document q discloses a high-strength polyoxyxene rubber adhesive material, but specific examples of heat resistance are not reported and no heat-resistant imparting agent is added. Further, special opening 2〇〇4_i9〇〇i3 -5 - (3) 1379870
號公報（專利文獻5)中揭示有添加受阻胺做爲耐熱賦予劑 者，而，胺化合物爲聚矽氧橡膠之交聯反應之氫矽烷化觸 媒毒，因此爲不理想者，特別是不適用於短時間之成形。 [專利文獻1] 特開20 02-170788號公報 [專利文獻2] 特公昭54-37907號公報 [專利文獻3] 特開昭63-22886號公報 [專利文獻4] 特開2004-189 94 5號公報 [專利文獻5] 特開2004-190013號公報 【發明內容】 本發明鑑於上述問題，以提供一種具有良好成形性， 表面黏著性，適度的橡膠硬度及橡膠強度，因此，適用於 重覆使用之電子零件的製造線中該電子零件之黏著固定用 薄片，更因具有耐熱性，因此更具有可承受焊接再流動等 加熱步驟之硬化物附加硬化型聚矽氧橡膠組成物，及硬化 此組成物所成之黏著橡膠薄片爲其目的者。 本發明者爲達成上述目的，進行精密硏討後結果發現 ，做成含有下述（A)〜（D)成份所成之附加硬化型聚矽氧橡 膠組成物後，具良好成形性之此組成物硬化物具有表面黏 著性，且具有適度之橡膠硬度及橡膠強度，因此，適用於 重覆使用之電子零件製造線之黏著固定用薄片，更因具有 耐熱性，而可取得可承受焊接再流動等加熱步驟之黏著橡 膠薄片，進而完成本發明。 因此，本發明係提供一種以含有 -6- (4) 1379870 (A) 1分子中含有至少鍵結2個矽原子之烯基之有機聚 矽氧烷：30〜95質量份、 (B) 以RsSiOm單位（式中’ R爲非取代或取代之一價 烴基）與Si〇2單位爲主成份’ R3Si〇1/2單位與§丨〇2單位之莫 耳比[R3Si01/2/Si〇2]爲〇·5〜1 .5，R爲不含烯基、或即使含 有其總量亦僅爲0.0001 m〇 Ι/g以下之樹脂質共聚物：5~7〇 質量份 ^ (其中，（A)、（B)成份之合計爲1〇〇質量份）、 (C) 1分子中含有至少鍵結2個矽原子之氫原子之有機 氫化聚矽氧烷：0.2-30質量份 (D) 微粉末二氧化矽：1〜200質量份 (E) 耐熱賦予劑：0.05~50質量份 (F) 加成反應觸媒：觸媒量 所成’其硬化物具有表面黏著性者爲其特徵之附加硬化型 聚矽氧橡膠組成物’及硬化此組成物所成之黏著橡膠薄片 本發明附加硬化型聚矽氧橡膠組成物係具有良好的成 形性’其硬化物具高度橡膠強度及表面黏著性，高溫下曝 露仍極少降低黏著性之耐熱性良好的聚矽氧橡膠薄片。 【實施方式】 [發明實施之最佳形態] 本發明附加硬化型聚矽氧橡膠組成物之（A)成份係1分 子中含有至少鍵結2個矽原子之烯基之有機聚矽氧烷，做 (5) (5)1379870 爲此（A)成份之有機聚矽氧烷者可使用下述平均組成式（1) 所示者。 R1aSiO(4.a)/2 (1) 上述式（1)中’ R1爲互爲相同或相異之碳數1〜1〇，較 佳者爲碳數1〜8之非取代或取代—價烴基，而，r1中至少2 個爲烯基。a爲1.5〜2.8’較佳者爲18〜2.5，更佳者爲 1 .95〜2.05之正數 其中’做爲鍵結於上述R1所示矽原子之非取代或取代 一價烴基例者如：使甲基 '乙基、丙基、異丙基' 丁基、 異丁基、第三-丁基、戊基、新戊基 '己基、環己基、辛 基、壬基、癸基等烷基、苯基、甲苯基、二甲苯基、萘基 ，等之芳基、苄基、苯乙基 '苯丙基等芳烷基、乙烯基、 烯丙基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯基 、辛烯基等烯基，此等基之一部份或全部氫原子被氟、溴 、氯等鹵原子、氰基等所取代者，如：氯甲基、氯丙基、 溴乙基、三氟丙基 '氰乙基等例，而，其總R1之90莫耳％ 以上爲甲基者宜。 此時，R1中至少2個務必爲烯基（碳數2〜8者宜，更佳 者爲碳數2〜6’特別以乙烯基爲最佳。）。總！^1之0001〜10 莫耳％，特別以〇.〇1〜5莫耳％爲烯基者更佳。此烯基可鍵 結於分子鍵末端之矽原子，亦可鍵結於分子鏈途中之矽原 子，或鍵結於兩者均可。 -8 - (6) 1379870 此有機聚矽氧烷之構造基本上其主鏈由重覆二有機矽 氧烷單位所成者，分子鏈兩端具有以三有機矽氧烷基所封 • 鏈之直鏈狀構造者宜，而部份爲枝鏈狀、環狀構造等亦可 。有關分子量並未特別限定，無論黏度低之液狀或黏度高 之生橡膠狀均可使用，一般平均聚合度（如：重量平均聚 合度）或1分子中之矽原子數以100〜50,000者宜，較佳者爲 200〜20,000，更佳者爲 250〜10,000。 φ 本發明之（B)成份樹脂質共聚物係以R3Si01/2單位及Japanese Laid-Open Patent Publication No. 5 discloses that a hindered amine is added as a heat-resistant imparting agent, and an amine compound is a hydroquinone-catalyzed poison of a cross-linking reaction of a polyoxyxene rubber. Therefore, it is not preferable, and particularly not Suitable for short-term forming. [Patent Document 1] JP-A-54-37907 [Patent Document 3] Japanese Laid-Open Patent Publication No. JP-A No. Hei. [Patent Document 5] JP-A-2004-190013 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a rubber mold having a good formability, surface adhesion, and moderate rubber hardness and rubber strength. In the manufacturing line of the electronic component used, the adhesive sheet for the electronic component has heat resistance, and therefore has a hardened addition-type polysulfide rubber composition capable of withstanding a heating step such as solder reflow, and hardens the hardened material. Adhesive rubber sheets formed by the composition are intended for the purpose. In order to achieve the above object, the inventors of the present invention have found that the composition having good formability is obtained by adding an additional hardening type polyoxo rubber composition containing the following components (A) to (D). The cured material has surface adhesion and moderate rubber hardness and rubber strength. Therefore, it is suitable for the adhesive fixing sheet of the electronic component manufacturing line which is repeatedly used, and has heat resistance, and can withstand welding reflow. The present invention is completed by adhering a rubber sheet to the heating step. Accordingly, the present invention provides an organopolyoxane having an alkenyl group containing at least two ruthenium atoms in a molecule containing -6-(4) 1379870(A): 30 to 95 parts by mass, (B) RsSiOm unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and Si〇2 unit is the main component 'R3Si〇1/2 unit and §丨〇2 unit molar ratio [R3Si01/2/Si〇2 ] 〇·5~1 .5, R is a resin copolymer containing no alkenyl group or even a total amount of only 0.0001 m〇Ι/g or less: 5 to 7 Å by mass ^ (where, ( A), (B) is a total of 1 part by mass), (C) an organohydrogenated polyoxyalkylene containing at least two hydrogen atoms bonded to two halogen atoms: 0.2-30 parts by mass (D) Fine powder of cerium oxide: 1 to 200 parts by mass (E) Heat-resistant imparting agent: 0.05 to 50 parts by mass (F) Addition reaction catalyst: The amount of the catalyst is 'the characteristic of the hardened material having surface adhesion. Additional hardening type polyoxymethylene rubber composition' and adhesive rubber sheet formed by hardening the composition. The additional hardening type polyoxymethylene rubber composition of the present invention has good formability. Rubber strength and surface tack, high temperature exposure is still exposed reducing very little good heat resistance and adhesion of the polyethylene oxide silicone rubber sheet. [Embodiment] [Best Mode for Carrying Out the Invention] The (A) component of the addition-hardening polyxanthene rubber composition of the present invention is an organopolyoxane having at least one alkenyl group bonded to two deuterium atoms in one molecule. (5) (5) 1379870 For the organic polyoxane of the component (A), the following average composition formula (1) can be used. R1aSiO(4.a)/2 (1) In the above formula (1), 'R1 is a carbon number of 1 to 1 Å which is the same or different from each other, and preferably an unsubstituted or substituted valence of 1 to 8 carbon atoms. a hydrocarbon group, and at least two of r1 are alkenyl groups. a is 1.5 to 2.8' is preferably 18 to 2.5, and more preferably a positive number of 1.95 to 2.05, wherein 'as an unsubstituted or substituted monovalent hydrocarbon group bonded to the above-mentioned R1 atom as shown in the above R1, such as: Alkyl such as methyl 'ethyl, propyl, isopropyl 'butyl, isobutyl, tert-butyl, pentyl, neopentyl 'hexyl, cyclohexyl, octyl, decyl, decyl , phenyl, tolyl, xylyl, naphthyl, etc. aryl, benzyl, phenylethyl 'phenylpropyl and the like aralkyl, vinyl, allyl, propenyl, isopropenyl, butene An alkenyl group such as a hexyl group, a cyclohexenyl group or an octenyl group; or a part or all of the hydrogen atoms of these groups are replaced by a halogen atom such as fluorine, bromine or chlorine, a cyano group or the like, such as: Examples of the group, chloropropyl group, bromoethyl group, trifluoropropyl 'cyanoethyl group, and the like, and 90% by mole or more of the total R1 is preferably a methyl group. In this case, at least two of R1 must be an alkenyl group (a carbon number of 2 to 8 is preferable, and a carbon number of 2 to 6 is more preferable, and a vinyl group is particularly preferable). total! ^1 of 0001~10 Moer%, especially with 〇.〇1~5mol% as alkenyl is better. The alkenyl group may be bonded to a ruthenium atom at the end of the molecular bond, or may be bonded to the ruthenium atom in the middle of the molecular chain, or may be bonded to both. -8 - (6) 1379870 The structure of the organopolyoxane is basically composed of a repeating diorganotoxioxane unit, and the ends of the molecular chain are blocked by a triorganophosphonyl group. The linear structure is preferred, and the part may be a chain or a ring structure. The molecular weight is not particularly limited, and may be used in the form of a raw rubber having a low viscosity or a high viscosity. Generally, the average degree of polymerization (e.g., weight average degree of polymerization) or the number of germanium atoms in one molecule is preferably 100 to 50,000. The best is 200~20,000, and the better is 250~10,000. φ The (B) component resinous copolymer of the present invention is in units of R3Si01/2 and
Si02單位爲主成份。其中，R爲非取代或取代之一價烴基 ，碳數1~1〇者宜，特別以1~8爲更佳，做爲R所示之一價 烴基者如：甲基 '乙基、丙基 '異丙基、丁基、異丁基、 第三-丁基、戊基、新戊基、己基、環己基、辛基、壬基 、癸基、苄基、苯乙基、苯丙基等芳烷基' 乙烯基、烯丙 基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯、辛烯 基等烯基’此等基之部份或全部氫原子被氟、溴、氯等鹵 ® 原子、氰基等取代者，如：氯甲基、氯丙基、溴乙基'三 氟丙基、氰乙基等例。 (B)成份之樹脂質共聚物亦可由上述R3Si〇1/2單位及 Si〇2單位所成者，且於必要時，以R2Si〇單位，RSi〇3/2單 位（R爲以下所述）做爲此等合計量，對於總共聚物質量亦 可含50%以下，較佳者爲40%以下，而，R3Si〇1/2單位與 si〇2單位之莫耳比[R3Si0I/2/Si02]爲0.5〜1.5，更佳者爲 〇·5〜1_3。當此莫耳比小於05，或大於15均將降低黏著劑The Si02 unit is the main component. Wherein R is an unsubstituted or substituted one-valent hydrocarbon group, and the carbon number is 1 to 1 〇, particularly preferably 1 to 8, as one of the valent hydrocarbon groups represented by R, such as methyl 'ethyl, ethyl 'Isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, decyl, decyl, benzyl, phenethyl, phenylpropyl Alkenylalkyl, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexene, octenyl, etc. alkenyl groups, some or all of the hydrogen atoms of these groups are fluorine A halogen atom such as bromine or chlorine, or a cyano group such as a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group or a cyanoethyl group. The resinous copolymer of the component (B) may be composed of the above R3Si〇1/2 unit and Si〇2 unit, and if necessary, in units of R2Si〇, RSi〇3/2 units (R is as described below) For this total amount, the total copolymer mass may also be 50% or less, preferably 40% or less, and the molar ratio of R3Si〇1/2 unit to si〇2 unit [R3Si0I/2/SiO2 ] is 0.5~1.5, and the better is 〇·5~1_3. When the molar ratio is less than 05, or greater than 15, the adhesive will be lowered.
-9- (7) 1379870 • (B)成份之樹脂質共聚物更以其烯基含量爲〇·001 mol/g以下（亦即，0 mol/g以上、0.000 1 mol/g以下）者宜， 較佳者爲0.00005mol/g以下（亦即，〇〜〇.〇〇〇〇5mol/g)、更 佳者爲未含烯基。當烯基含量多於0.0001m〇l/g則黏著力 將不足。 又’上述樹脂質共聚物於常溫下（25 °C)可爲流動性之 液狀 '或非流動性之因體均可，而由硬化物之黏著性面視 • 之’又以常溫下爲固體者爲較佳。此樹脂質共聚物通常可 以該技術之公知方法將適當之氟矽烷、烷氧基矽烷藉由水 解製造之。 此等（B)成份之樹脂質共聚物配合量對於（A)成份與 (B)成份之合計量爲5〜70質量％之量者宜，較佳者爲10~60 質量％之量。當未達5質量％時，則無法取得足夠之黏著性 ，反之，超出70質量％則黏著性亦降低，橡膠物性亦明顯 下降。 • 本發明（C)成份係1分子中至少具有鍵結2個，較佳爲3 個矽原子之氫原子（Si-H基）之有機氫化聚矽氧烷、分子中 之Si-H基藉由鍵結於該（A)成份，（B)成份中之矽原子之烯 基與氫矽烷加成反應後交聯之，因使組成物硬化，做成硬 化劑作用者。此（C)成份之有機氫化聚矽氧烷係1分子中至 少具有2個（一般爲2 ~2 00個）、較佳爲3個以上（一般爲 3〜100個）、更佳者爲3〜50個之鍵結矽原子之氫原子者，適 用下述平均組成式（2)所示者。另外，此鍵結矽原子之氫 原子（Si-H基）。可存在於分子鏈末端（亦即，單官能性矽氧 -10- (8) (8)1379870 烷單位上），亦可存在於分子鏈途中（2官能性或3官能性矽 氧烷單位上），或存在於此兩者均可。 R2bHcSiO(4-b-c)/2 (2) (式中，R2爲碳數1〜10之取代或非取代之一價烴基， 又，b爲〇.7~2.1 ' c爲0.001〜1.0，且，滿足b + c爲0.8〜3.0之 正數者）。 其中，做爲R2之一價烴基者與R1所示例者相同之例， 惟又以不具脂肪族不飽和基者宜。又，b爲0.8〜2.0、c爲 0.01〜1.0' b + c爲1.0〜2.5者宜，有機氫化聚矽氧烷之分子 構造可任意爲直鏈狀、環狀、支鏈狀、三維網孔狀之構造 〇 此時，1分子中砂原子數（或聚合度）以2~300個、特別 以4〜150個之室溫（25 °C )下液狀爲適用者。另外，鍵結於 矽原子之氫原子可任意存在於分子鏈末端、分子鏈途中、 或存在於兩者中均可。 做爲上述（C)成份之有機氫化聚矽氧烷者如：1，1，3 ’ 3 -四甲基二矽氧烷、1，3，5，7 -四甲基環四矽氧烷' 甲基氫化矽氧烷環狀聚合物、甲基氫化矽氧烷、二甲基矽 氧烷環狀共聚物、三（二甲基氫化矽氧烷）甲基矽烷、三（ 二甲基氫化矽氧烷）苯基矽烷、兩末端三甲基矽氧烷基封 鏈甲基氫化聚矽氧烷、兩末端三甲基矽氧烷基封鏈二甲基 矽氧烷、甲基氫化矽氧烷共聚物、兩末端二甲基氫化矽氧 -11 - s§) (9) 1379870 • 烷基封鏈二甲基聚矽氧烷、兩末端二甲基氫化矽氧烷基封 鏈二甲基矽氧烷、甲基氫化矽氧烷共聚物、兩末端三甲基 砂氧院基封鏈甲基氫化砂氧垸、二苯基砂氧垸共聚物、兩 末端三甲基矽氧烷基封鏈甲基氫化矽氧烷、二苯基矽氧烷 、二甲基矽氧烷共聚物' (CH3)2HSiOW2單位與Si04/2單位 所成之共聚物、（CH3)2HSi01/2單位與Si04/2單位與 (C6H5)Si03/2單位所成之共聚物等例。 φ 此有機氫化聚矽氧烷之配合量對於（A)、（B)成份之合 計100質量份以0·2~30質量份者宜，更佳者爲0_5〜15質量 份。配合量若未達0.2質量.份，或超出30質量份則均將無 法取得充份的橡膠強度。 本發明（D)成份之微粉末二氧化矽係爲提昇橡膠強度 而添加者，只要以Si 02爲主成份者均可，較佳者可單獨1 種或組合2種以上選自矽鎂石、沈澱二氧化矽、矽藻土、. 粉碎石英、熔融石英使用之。 # 微粉末二氧化矽之平均粒徑以20μιη以下者宜，較佳 者爲ΙΟμιη以下，更佳者爲7μιη以下，當超出20μηι時，則 不僅無法提昇橡膠強度，反而降低其強度。另外，有關矽 錶石、沈澱二氧化矽以外之二氧化矽之平均粒徑以0.5 μιη 以上者宜，特別以1 μηι以上爲更佳。有關矽鎂石，及沈澱 二氧化矽之1次粒徑爲遠低於5μιυ( —般爲0.001〜1μπ〇，又 以比表面積之規格爲宜。此時，藉由BET法之比表面積以 50〜400m2/g者宜，更佳者爲80〜350m2/g。另外本發明之平 均粒徑可以如雷射光衍射法之粒度分佈測定中做成累積重 -12- 1379870 do) 量平均値d5〇(或中値粒徑）等進行測定之。 此等微粉末二氧化矽可直接使用，亦可預先以表面疏 水化處理劑先行處理後再使用之，或與（A)、（B)、（C)成份 之種或2種以上之聚矽氧油混煉時（亦即，組成物配合過程 中）添加表面處理劑進行處理後，再使用之。此等表面處理 劑只要是烷基烷氧基矽烷、烷基氯矽烷、烷基矽氨烷、矽 烷偶合劑、鈦酸酯系處理劑、脂肪酸酯等公知者均可使用 之，可單獨使用1種，亦可以不同時間點使用2種以上，或 同時使用2種以上均可。 又，此等微粉末二氧化矽之配合量對於（A)、（B)成份 合計100質量份爲1〜200質量份者宜、3〜100質量份爲更佳 。當配合量未達1質量份則無法取得充份之橡膠強度，反 之，超出200質量份則不易配合。 (E)成份之耐熱賦予劑係於聚矽氧橡膠以提昇耐熱性 爲目的者，可任意使用水合物、碳酸鹽、有機酸鹽、BHT 等各種有機抗氧化劑、金屬氧化物等。其中由不影響黏著 性、硬化性面觀之，特別以金屬氧化物爲較佳。做爲此金 屬氧化物例者如：氧化鐵、氧化欽、氧化鈽、氧化鎂、氧 化鋁、氧化鋅等例。特別以氧化鐵、氧化鈽爲較佳。此等 可單獨使用1種，亦可混合2種以上使用之。 此等耐熱賦予劑之配合量對於（A)、（B)成份之合計 100質量份爲0.05〜50質量份者宜，佳者爲〇.2〜20質量份 。配合量未達0.05質量份時，則幾乎無法提昇耐熱性，反 之，超出5〇質量份則將降低橡膠物性。 -13- (11) (11)1379870 做爲（F)成份之加成反應觸媒例者如：鉑黑、氯化鉑 、氯化鉑酸、氯化鉑酸與一價醇之反應物、氯化鉑酸與烯 烴類之錯化物、鉑雙乙醯乙酸酯等鉑系觸媒、鈀系觸媒、 铑系觸媒等例。另外，此加成反應觸媒之配合量可做爲觸 媒量，一般做爲鉑族金屬者對於（A)、（B)、（C)成份之合 計質量爲0.5〜l，000ppm者宜，特別以1〜500ppm爲最佳。 必要時，在不損及本發明目的之範圍下亦可配合其他 成份如：碳黑、導電性鋅白、金屬粉等導電劑、著色顏料 等塡充劑、更可適度配合含氮化合物、乙炔化合物、磷化 合物、腈化合物、羧酸酯、錫化合物、水銀化合物、硫黃 化合物等氫矽烷化反應抑制劑、二甲基聚矽氧油等內部脫 模劑、黏著賦予性劑、觸變賦予性劑等。 又，除此外，爲降低黏度之目的下，亦可添加溶劑。 做爲溶劑例者爲可溶解聚矽氧者，只要沸點爲200t以下 者均可。如：二甲苯、甲苯、苯 '庚烷、己烷、環己烷、 三氯乙烯、過氯乙烯、氯化甲撐、乙酸乙酯、甲基異丁酮 、丁酮、丁醇、石油醚、環己酮、二乙醚、石油醚、工業 用石油、橡膠揮發油、聚矽氧系溶劑等有機溶劑例，此等 可單獨使用1種，亦可組合2種以上做成混合溶劑使用之。 本發明黏著橡膠薄片係使含有上述成份之附加硬化型 聚矽氧橡膠組成物經由硬化後取得。此時，使用本發明聚 矽氧橡膠組成物取得黏著橡膠薄片之方法者，其具體例如 :使上述聚矽氧橡膠組成物藉由壓縮成形、注入成形、射 出成形等直接取得薄片之方法，藉由插入成形後，使薄片 -14- (12) 1379870 . 成形於金屬基板、樹脂基板、樹脂薄膜之方法、或藉由浸 、 漬、塗層、網版印刷等與基材做成一體化取得橡膠薄片之 方法等。 ， 做爲附加硬化型聚矽氧橡膠組成物之硬化條件者以溫 度8 0~2 5 0 °C，10秒〜1小時之範圍者宜β更爲去除低分子矽 氧烷爲目的下’亦可於120〜250°C之溫度下，進行1〜1〇〇小 時之後處理。另外’橡膠薄片本身之厚度以0.05〜50mm者 φ 宜，更佳者爲0.1〜20mm。若未達〇.〇5mm則將無法充份活 化薄片之彈性，反之超出5 0mm則不利成本面。 如此取得之橡膠薄片於表面具有黏著性者，藉由纖維 - 分析器（Texture Tech-nologies Corp.製）所測定之表面黏著 力以20〜300g者宜’特別以30〜200g爲更佳，本發明更於 2 5 0 °C下，放置於烤箱內1 2小時後，其冷卻之橡膠薄片之 黏著力以初期黏著力之70%以上爲宜，特別維持於80%以 上爲更佳者。 • 又，本發明橡膠薄片之硬度以硬度計A爲5~50者宜， 更佳者爲5〜4G。未達5時’則做爲橡膠之強度將不足，反 之’超出5 0則將降低黏著性。另外，做爲橡膠強度者’藉 由JIS K6249所測定中，以〇.5MPa以上者宜，更佳者爲 〇.8MPa以上。當未達〇_5MPa時，則將輕易破損電子零件 製造線之使用，恐不耐重覆使用。 本發明黏著橡膠薄片於電容器、啓動器、感應器等基 板型電子零件，可撓性印刷基板之實裝等，各種電子零件 之製造時，可做爲黏著固定用薄片之使用， -15- (13) 1379870 [實施例] 以下顯示實施例及比較例，進行本發明具體的說明， 惟，本發明並未受限於下述實施例。另外，各例中之份代 表質量份，平均粒徑係代表雷射光衍射法之粒度分佈測定 中以累積重量平均値（D5〇)所測定之値，比表面積係經由 BET法所測定之値。 [實施例1 ] , 兩末端被二甲基乙烯矽氧烷基所封鏈之平均聚合度爲 3 00之二甲基聚矽氧烷（1)60份，室溫下固體之 (CH3)3Si01/2單位及Si02單位所成之樹脂質共聚物 (2)[(CH3)3Si01/2 單位 /Si02 單位（莫耳比）= 0·75]40 份，微粉 末二氧化矽之比表面積爲1 10m2/g之疏水化處理之矽鎂石 ，（日本Aerozil(股份）製，R-972)8份，平均粒徑Ο.ΙΟμηι之 φ 氧化鐵（Fe203)l份置入行星混合器，混合30分鐘後，1次 通過3根滴輥。於此聚矽氧橡膠基劑100份中添加0.99份之 做爲交聯劑之分子側鏈中（亦即，分子鏈途中之聚矽氧烷 單位上）具有Si-H基之甲基氫化聚矽氧烷（3)(聚合度20， Si-H基量0.0060mol/g)，0.05份之做爲反應抑制劑之乙炔 環己醇，持續攪拌1 5分鐘後，取得聚矽氧橡膠組成物。此 聚矽氧橡膠組成物中混合鈾觸媒（Pt濃度1%)0.1份，120°C 下加壓處理10分鐘後，取得表面具黏著性之厚度2mm之橡 膠薄片。針對此硬化物由2mm之薄片依JIS K6249爲基準 -16- (14) (14)1379870 進行測定橡膠硬度（硬度計A)，拉伸強度，切斷時延伸之 測定結果示於表1。更由2 mm薄片，以纖維分析器（Texture Techonologies Corp·製）測定表面黏著力，將此橡膠薄片於 25 0°C之烤箱中放置12小時後，冷卻後，測定再度黏著力 。結果示於表1。 [實施例2] 1 5 0 °C下進行2小時混煉實施例1之二甲基聚矽氧烷 (1)70份，比表面積爲200m2/g之矽鎂石（日本Aerozil(股份） 製，Aerozil 2 00) 1 5份，六甲基二矽氨烷3份、水1份。其 中加入實施例1之樹脂質共聚物（2)30份，更於150 °C下持 續混煉2小時》於此聚矽氧橡膠基劑1 00份中添加平均粒徑 爲Ιμηι之氧化鈽0.5份及平均粒徑爲0.2μπι之氧化鈦2份， 做爲交聯劑之實施例1之分子側鏈中具有Si-H基之甲基氫 化聚矽氧烷（3) 1.26份’，做爲反應抑制劑之乙炔環己醇〇.〇5 份後，持續攪拌1 5分鐘後取得聚矽氧橡膠組成物。此聚矽 氧橡膠組成物中混合鉑觸媒（Pt濃度1%)0.1份，於120°C下 ’藉由加壓處理10分鐘取得表面具黏著性之厚度2mm之橡 膠薄片，針對此硬化物與實施例1同法進行測定橡膠硬度（ 硬度計A)、拉伸強度、切斷時之延伸、耐熱試驗前後之表 面黏著力。其結果示於表1。 [實施例3] 室溫下混合兩末端被三甲基矽氧烷基所封鏈，分子側-9- (7) 1379870 • The resin copolymer of (B) component should have an alkenyl content of 〇·001 mol/g or less (that is, 0 mol/g or more and 0.000 1 mol/g or less). Preferably, it is 0.00005 mol/g or less (that is, 〇~〇.〇〇〇〇5 mol/g), and more preferably it is not. When the alkenyl content is more than 0.0001 m〇l/g, the adhesion will be insufficient. Further, the above-mentioned resinous copolymer may be a liquid-like liquid or a non-flowing body at a normal temperature (25 ° C), and the adhesive surface of the cured product may be at a normal temperature. Solid is preferred. The resinous copolymer can be usually produced by hydrolysis of a suitable fluorononane or alkoxysilane in a manner known in the art. The amount of the resin copolymer of the component (B) is preferably from 5 to 70% by mass based on the total amount of the component (A) and the component (B), preferably from 10 to 60% by mass. When it is less than 5% by mass, sufficient adhesiveness cannot be obtained. On the contrary, when it exceeds 70% by mass, the adhesiveness is also lowered, and the rubber physical properties are also remarkably lowered. • The component (C) of the present invention is an organohydrogenated polyoxyalkylene having at least two hydrogen atoms (Si-H groups) bonded to one molecule, preferably three helium atoms, and a Si-H group in the molecule. The alkenyl group bonded to the (A) component and the argon atom in the component (B) is reacted with the hydroquinone to be crosslinked, and the composition is cured to form a hardener. The organic hydrogenated polyoxyalkylene group of the component (C) has at least two (generally 2 to 200), preferably 3 or more (generally 3 to 100), and more preferably 3 For those of the 50 atomic hydrogen atoms of the atom, the following average composition formula (2) is applied. In addition, this bond is a hydrogen atom (Si-H group) of a ruthenium atom. It may be present at the end of the molecular chain (ie, monofunctional oxime-10-(8) (8) 1379870 alkane units) or may be present on the molecular chain (on a bifunctional or trifunctional oxane unit) ), or both. R2bHcSiO(4-bc)/2 (2) (wherein R2 is a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and b is 〇.7 to 2.1' c is 0.001 to 1.0, and Satisfy b + c is a positive number of 0.8 to 3.0). Among them, the one which is a one-valent hydrocarbon group of R2 is the same as the one shown by R1, but it is suitable for those having no aliphatic unsaturated group. Further, b is 0.8 to 2.0, c is 0.01 to 1.0' b + c is 1.0 to 2.5, and the molecular structure of the organohydrogenated polyoxyalkylene may be any linear, cyclic, branched or three-dimensional mesh. In the case of the structure, the number of sand atoms (or the degree of polymerization) in one molecule is preferably from 2 to 300, particularly from 4 to 150 at room temperature (25 ° C). Further, a hydrogen atom bonded to a halogen atom may be present at the end of the molecular chain, in the middle of the molecular chain, or in both. As the organic hydrogenated polyoxane of the above (C) component, such as: 1,1,3 '3-tetramethyldioxane, 1,3,5,7-tetramethylcyclotetraoxane Methyl hydrogen hydride oxane cyclic polymer, methyl hydride hydride, dimethyl methoxy olefin cyclic copolymer, tris(dimethylhydroxane) methyl decane, tris(dimethylhydroquinone) Oxyalkylene phenyl decane, two-terminal trimethyl sulfoxyalkyl-encapsulated methyl hydrogenated polyoxy siloxane, two-terminal trimethyl sulfoxyalkyl-encapsulated dimethyl methoxy oxane, methyl hydride hydride Copolymer, two-terminal dimethylhydrogen oxyhydroxide-11 - s§) (9) 1379870 • Alkyl-encapsulated dimethyl polyoxane, two-terminal dimethylhydrogen oxyalkylene chain dimethyl hydrazine Oxyalkane, methylhydroperoxane copolymer, two-terminal trimethyl sulphate-based chain methyl hydrogenated cerium oxide, diphenyl samarium oxide copolymer, two-terminal trimethyl decyl oxyalkylene chain Copolymer of methyl hydride hydride, diphenyl siloxane, dimethyl methoxide copolymer '(CH3)2HSiOW2 unit and Si04/2 unit, (CH3)2HSi01/2 unit and Si04/2 Unit with (C6H5)Si03/2 unit Examples of the copolymers formed. φ The amount of the organic hydrogenated polyoxyalkylene is preferably from 0 to 2 parts by mass, more preferably from 0 to 5 parts by mass, per 100 parts by mass of the components (A) and (B). If the blending amount is less than 0.2 part by mass or exceeds 30 parts by mass, sufficient rubber strength will not be obtained. The fine powder of cerium oxide of the component (D) of the present invention is added to increase the strength of the rubber, and any one of Si 02 as a main component may be used. Preferably, one type or two or more types may be selected from the group consisting of strontium silicate. Precipitated cerium oxide, diatomaceous earth, pulverized quartz, fused silica. # The average particle size of the fine powder of cerium oxide is preferably 20 μm or less, preferably ΙΟμηη or less, more preferably 7 μηη or less, and when it exceeds 20 μηι, the rubber strength is not improved, but the strength is lowered. Further, the average particle diameter of the cerium oxide other than the ceramsite and the precipitated cerium oxide is preferably 0.5 μm or more, and more preferably 1 μη or more. The primary particle size of the tourmaline and the precipitated cerium oxide is much lower than 5 μm (generally 0.001 to 1 μπ〇, and the specific surface area is preferred. At this time, the specific surface area by the BET method is 50. Preferably, it is preferably from 400 to 350 m 2 /g, and more preferably from 80 to 350 m 2 /g. Further, the average particle diameter of the present invention can be made into a cumulative weight of -12 - 1379870 as measured by the particle size distribution of the laser light diffraction method. (or the median particle size), etc. are measured. These fine powdered cerium oxides may be used as they are, or may be treated with a surface hydrophobizing agent in advance, or may be used in combination with (A), (B), (C) or two or more kinds. When the oxygen oil is kneaded (that is, during the compounding process), a surface treatment agent is added for treatment, and then used. These surface treatment agents can be used alone as long as they are known as alkyl alkoxy decane, alkyl chlorodecane, alkyl decane, decane coupling agent, titanate-based treatment agent, or fatty acid ester. One type may be used in two or more different time points or two or more types may be used at the same time. In addition, the amount of the fine powder of cerium oxide is preferably from 1 to 200 parts by mass, and preferably from 3 to 100 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the amount is less than 1 part by mass, sufficient rubber strength cannot be obtained, and if it exceeds 200 parts by mass, it is difficult to match. The heat-resistant agent of the component (E) is used for the purpose of improving heat resistance, and various organic antioxidants such as hydrates, carbonates, organic acid salts, and BHT, metal oxides, and the like can be used arbitrarily. Among them, the metal oxide is preferable because it does not affect the adhesion and the hardenability. Examples of such metal oxides are: iron oxide, oxidized bismuth, cerium oxide, magnesium oxide, aluminum oxide, zinc oxide, and the like. Iron oxide and ruthenium oxide are particularly preferred. These may be used alone or in combination of two or more. The amount of the heat-resistant imparting agent is preferably 0.05 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (B), and preferably 2 to 20 parts by mass. When the amount is less than 0.05 parts by mass, the heat resistance is hardly improved, and if it exceeds 5 parts by mass, the rubber physical properties are lowered. -13- (11) (11) 1379870 As an additive reaction agent of (F) component, such as platinum black, platinum chloride, chloroplatinic acid, a reaction of chloroplatinic acid with a monovalent alcohol, Examples of a platinum-based catalyst such as a platinum chloride acid and an olefin, a platinum-based catalyst such as platinum acetoacetate, a palladium-based catalyst, or a ruthenium-based catalyst. In addition, the amount of the addition reaction catalyst can be used as the amount of the catalyst. Generally, the platinum group metal is suitable for the total mass of the components (A), (B), and (C) of 0.5 to 1,000 ppm. In particular, it is preferably 1 to 500 ppm. If necessary, other components such as carbon black, conductive zinc white, metal powder and other conductive agents, coloring pigments and the like may be blended, and nitrogen compounds, acetylene may be appropriately blended, if necessary, without damaging the object of the present invention. a hydroquinone reaction inhibitor such as a compound, a phosphorus compound, a nitrile compound, a carboxylic acid ester, a tin compound, a mercury compound or a sulfur compound, an internal mold release agent such as dimethylpolyphthalic acid oil, an adhesion-imparting agent, or a thixotropic imparting agent Sex agents, etc. Further, in addition to the purpose of reducing the viscosity, a solvent may be added. As a solvent, those who can dissolve polyoxo can be used as long as the boiling point is 200 t or less. Such as: xylene, toluene, benzene 'heptane, hexane, cyclohexane, trichloroethylene, perchloroethylene, methyl chloride, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, butanol, petroleum ether Examples of the organic solvent such as cyclohexanone, diethyl ether, petroleum ether, industrial petroleum, rubber volatile oil, and polyoxo-based solvent may be used singly or in combination of two or more. The adhesive rubber sheet of the present invention is obtained by hardening an additional hardening type polyoxymethylene rubber composition containing the above components. In this case, a method of obtaining a pressure-sensitive adhesive sheet using the polyoxyethylene rubber composition of the present invention is specifically a method of directly obtaining a sheet by compression molding, injection molding, injection molding, or the like. After insert molding, the sheet 14-(12) 1379870 is formed on a metal substrate, a resin substrate, a resin film, or integrated with a substrate by dipping, staining, coating, screen printing, or the like. The method of rubber sheet, and the like. As the hardening condition of the composition of the additional hardening type polyoxymethylene rubber, the temperature is 80 to 250 ° C, and the range of 10 seconds to 1 hour is better for the purpose of removing the low molecular weight oxirane. It can be processed at a temperature of 120 to 250 ° C for 1 to 1 hour. Further, the thickness of the rubber sheet itself is preferably 0.05 to 50 mm, more preferably 0.1 to 20 mm. If it is less than 〇.〇5mm, it will not fully revitalize the elasticity of the sheet, and if it exceeds 50mm, it will be unfavorable. The rubber sheet thus obtained is adhesive on the surface, and the surface adhesion measured by a fiber-analyzer (manufactured by Texture Tech-nologies Corp.) is preferably 20 to 300 g, particularly preferably 30 to 200 g. In the invention, after being placed in the oven for 12 hours at 250 ° C, the adhesion of the cooled rubber sheet is preferably 70% or more of the initial adhesion, and particularly preferably 80% or more. Further, the hardness of the rubber sheet of the present invention is preferably 5 to 50 in terms of hardness A, and more preferably 5 to 4 G in hardness. If it is less than 5 o', the strength of the rubber will be insufficient, and if it exceeds 50, the adhesion will be lowered. In addition, as a rubber strength, it is preferably 55 MPa or more, and more preferably 〇8 MPa or more, as measured by JIS K6249. When it is less than 55MPa, it will easily damage the use of the electronic parts manufacturing line, and it will not be able to be used repeatedly. The adhesive rubber sheet of the present invention can be used as a substrate for electronic components such as a capacitor, a starter, and an inductor, and a flexible printed circuit board. When manufacturing various electronic components, it can be used as an adhesive fixing sheet, -15- ( 13) 1379870 [Examples] The following examples and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following examples. Further, the parts in the respective examples represent the parts by mass, and the average particle diameter represents the enthalpy measured by the cumulative weight average enthalpy (D5 〇) in the particle size distribution measurement by the laser light diffraction method, and the specific surface area is measured by the BET method. [Example 1], 60 parts of dimethylpolyoxyalkylene (1) having an average degree of polymerization of 300% blocked by dimethyl oxirane, and (CH3)3Si01 at room temperature Resin copolymer made of /2 units and SiO 2 units (2) [(CH3)3Si01/2 unit / SiO 2 unit (mol ratio) = 0·75] 40 parts, the specific surface area of the fine powder of cerium oxide is 1 10m2/g hydrophobized tourmaline, 8 parts (R-972, manufactured by Aerozil Co., Ltd., Japan), average particle size Ο.ΙΟηηι φ Iron oxide (Fe203) 1 part placed in the planetary mixer, mixing 30 After one minute, three pass rolls were passed once. To 100 parts of the polyoxyethylene rubber base, 0.99 parts of a methylidene group having a Si-H group in a molecular side chain as a crosslinking agent (that is, a polyoxyalkylene unit in the molecular chain) is added. a decane (3) (degree of polymerization 20, a Si-H basis amount of 0.0060 mol/g), 0.05 part of acetylene cyclohexanol as a reaction inhibitor, and stirring for 15 minutes, obtaining a polyoxymethylene rubber composition . 0.1 parts of a uranium catalyst (Pt concentration: 1%) was mixed in the polyoxyethylene rubber composition, and after pressurization treatment at 120 ° C for 10 minutes, a rubber sheet having a thickness of 2 mm on the surface was obtained. The hardness of the cured product was measured on a sheet of 2 mm in accordance with JIS K6249 -16- (14) (14) 1379870. The rubber hardness (hardness meter A), tensile strength, and elongation at the time of cutting were shown in Table 1. Further, the surface adhesion was measured by a fiber analyzer (manufactured by Texture Techonologies Corp.) from a sheet of 2 mm, and the rubber sheet was allowed to stand in an oven at 25 ° C for 12 hours, and after cooling, the re-adhesion was measured. The results are shown in Table 1. [Example 2] 70 parts of the dimethyl polyoxyalkylene (1) of Example 1 was kneaded at 150 ° C for 2 hours, and the magnesite having a specific surface area of 200 m 2 /g (manufactured by Japan Aerozil Co., Ltd.) , Aerozil 2 00) 1 5 parts, 3 parts of hexamethyldioxane, 1 part of water. 30 parts of the resinous copolymer (2) of Example 1 was added thereto, and further kneading was further carried out at 150 ° C for 2 hours. In this 100 parts of the polyoxyethylene rubber base, cerium oxide having an average particle diameter of Ιμηι was added. 2 parts of titanium oxide having an average particle diameter of 0.2 μm, and a methyl hydrogenated polyoxyalkylene (3) having a Si-H group in the molecular side chain of Example 1 as a crosslinking agent 1.26 parts After 5 parts of acetylene cyclohexanol oxime of the reaction inhibitor, stirring was continued for 15 minutes to obtain a polyoxymethylene rubber composition. 0.1 parts of a platinum catalyst (Pt concentration: 1%) was mixed in the polyoxyethylene rubber composition, and a rubber sheet having a thickness of 2 mm on the surface was obtained by a pressure treatment for 10 minutes at 120 ° C, and the cured product was obtained. The rubber hardness (hardness meter A), tensile strength, elongation at the time of cutting, and surface adhesion before and after the heat resistance test were measured in the same manner as in Example 1. The results are shown in Table 1. [Example 3] The two ends of the mixture were blocked by a trimethylphosphonium group at room temperature, and the molecular side
-17- (15) (15)1379870 鏈中具有鍵結Si原子之乙烯基之平均聚合度爲500之二甲 基聚矽氧烷（4)(乙烯基含量0.0002 mol/g)60份’以甲苯溶 解之室溫下固體之（CH+SiChu單位，Si〇2單位及 (CH3)2SiO單位所成之樹脂質共聚物（5)[(CH3)3Si〇w2^位 /Si02單位（莫耳比）= 0.80，（CH3)2SiO之含有率15莫耳％]4〇 份（樹脂份），於減壓下，120°C進行3小時去除溶劑後，更 持續攪拌1小時。於此聚矽氧橡膠基劑1〇〇份中添加平均粒 徑爲7μιη之矽藻土 10份，平均粒徑2μηι之石英粉30份，平 均粒徑0.3μπι之氧化鐵（Fe203)l份，做爲交聯劑之實施例1 之分子側鏈中具Si-H基之甲基氫化聚矽氧烷（3)2.25份，做 爲反應抑制劑之乙炔環己醇0.05份，持續攪拌15分鐘後， 取得聚矽氧橡膠組成物。此聚矽氧橡膠組成物中混合鈾觸 媒（Pt濃度1%)0」份，120°C下10分鐘加壓處理後，取得表 面具有黏著性之厚度2 mm之橡膠薄片。針對此硬化物與實 施例1同法測定橡膠硬度（硬度計A)，拉伸強度，切斷時延 伸，耐熱試驗前後之表面黏著力。結果示於表1» [比較例1 ] 將實施例1之二甲基聚矽氧烷（1)60份，實施例1之樹 脂質共聚物（2)4〇份，微粉末二氧化矽之比表面積爲 ll〇m2/g之疏水化處理之矽_石（日本Aeorozil (股份）製， R-972)8份置入行星混合器，進行混合30分鐘，1次通過3 根滾輥。此聚矽氧橡膠基劑1 00份中加入做爲交聯劑之實 施例1分子側鏈中具有Si-H基之甲基氫化聚矽氧烷（3)0.99 -18- (16) (16)1379870 份，做爲反應抑制劑之乙炔環己醇0.05份’持續攪拌15分 鐘後，取得聚矽氧橡膠組成物。此聚矽氧橡膠組成物中混 合鉑觸媒（Pt濃度1%)〇.1份，於120°C下，加壓處理1〇分鐘 後，取得表面具黏著性之厚度2mm橡膠薄片。針對此硬 化物與實施例1同法進行測定橡膠硬度（硬度計A)，拉伸強 度，切斷時延伸，耐熱試驗前後之表面黏著力。結果示於 表1。 [比較例2] 於150°C下2小時混煉實施例1之二甲基聚矽氧烷（1)55 份，比表面積爲200m2/g之矽鎂石（日本Aerozil (股份）製， 八61"〇2丨1 200)15份，六甲基二矽氨烷3份、水1份。其中加 入實施例1之樹脂質共聚物（2)30份，更於150 °C下持續混 煉2小時。此聚砂氧橡膠基劑1 0 0份中添加做爲交聯劑之實 施例1分子側鍵中具有Si-H基之甲基氫化聚矽氧烷（3)1.26 份，做爲反應抑制劑之乙炔環己醇0.0 5，持續攪拌1 5分鐘 後取得聚矽氧橡膠組成物。此聚矽氧橡膠組成物中混合鉑 觸媒（Pt濃度1%)0.1份’ 120°C下進行加壓處理1〇分鐘，取 得表面具有黏著性之厚度2mm橡膠薄片。針對此硬化物， 與實施例1同法測定橡膠硬度（硬度計A)、拉伸強度、切斷 時延伸、耐熱試驗前後之表面黏著力。結果示於表1。 [比較例3] 室溫下混合實施例3之一甲基聚砂氧院（4)60份，甲苯 -19- (17) 1379870 所溶解之實施例3之樹脂質共聚物（5 )40份，減壓下，120 °C，進行3小時去除溶劑’更持續攪拌1小時。於此聚砂氧 橡膠基劑100份中，添加平均粒徑0·3μπι之氧化鐵（Fe2〇3)l 份，做爲交聯劑之實施例1分子側鏈中具Si-H基之甲基氫 化聚矽氧烷（3)2.5份，做爲反應抑制劑之乙炔環己醇005 份後，持續攪拌1 5分鐘之後，取得聚矽氧橡膠組成物。此 聚矽氧橡膠組成物中混合鈾觸媒（Pt濃度份，120°C 下，進行加壓處理10分鐘後，取得表面具有黏著性之厚度 2mm之橡膠薄片。針對此硬化物，與實施例1同法測定橡 膠硬度（硬度計A)、拉伸強度、切斷時延伸，及耐熱試驗 前後之表面黏著力。結果示於表1。-17- (15) (15) 1379870 The average degree of polymerization of a vinyl group having a bonded Si atom in the chain is 500 dimethyl polysiloxane (4) (vinyl content 0.0002 mol/g) 60 parts ' Resin copolymer (5) [(CH3)3Si〇w2^bit/SiO 2 unit (Mo Erbi) made of solid (CH+SiChu unit, Si〇2 unit and (CH3)2SiO unit) dissolved in toluene at room temperature ) = 0.80, (CH3) 2 SiO content: 15 mol%] 4 parts by weight (resin portion), and the solvent was removed under reduced pressure at 120 ° C for 3 hours, and stirring was further continued for 1 hour. 10 parts of diatomaceous earth having an average particle diameter of 7 μm, 30 parts of quartz powder having an average particle diameter of 2 μm, and 1 part of iron oxide (Fe203) having an average particle diameter of 0.3 μm were used as a crosslinking agent in one part of the rubber base. In the molecular side chain of Example 1, 2.25 parts of a methyl hydrogenated polyoxyalkylene (3) having a Si-H group, 0.05 part of acetylene cyclohexanol as a reaction inhibitor, and stirring was continued for 15 minutes to obtain a polyfluorene. Oxygen rubber composition. The polyaniline rubber composition is mixed with uranium catalyst (Pt concentration: 1%), 0 parts, and subjected to pressure treatment at 120 ° C for 10 minutes to obtain a thickness of 2 mm on the surface. Rubber sheet. The hardness of the rubber (hardness meter A), tensile strength, elongation at the time of cutting, and surface adhesion before and after the heat resistance test were measured in the same manner as in Example 1. The results are shown in Table 1» [Comparative Example 1] 60 parts of the dimethyl polyoxyalkylene (1) of Example 1, the resinous copolymer (2) of Example 1 (4), and the hydrophobic surface of the fine powder of ceria having a specific surface area of ll 〇 m 2 /g After the treatment, _ stone (made by Aeorozil Co., Ltd., R-972, Japan) was placed in a planetary mixer, mixed for 30 minutes, and passed through three rolls at a time. This polyoxyethylene rubber base was added to 100 parts. As a crosslinking agent, methyl hydrogenated polyoxane (3) 0.99 -18-(16) (16) 1379870 parts having a Si-H group in a molecular side chain as a crosslinking agent, as an acetylene ring as a reaction inhibitor After 0.05 parts of hexanol was continuously stirred for 15 minutes, a polyoxyxene rubber composition was obtained. The platinum catalyst (Pt concentration: 1%) 〇.1 part was mixed in the polyoxyethylene rubber composition, and pressurized at 120 ° C. After 1 minute of treatment, a 2 mm thick rubber sheet having a surface adhesiveness was obtained. The hardness of the cured product was measured in the same manner as in Example 1 (hardness meter A). Tensile strength, elongation at the time of cutting, and surface adhesion before and after the heat resistance test. The results are shown in Table 1. [Comparative Example 2] The dimethylpolyoxane of Example 1 was kneaded at 150 ° C for 2 hours (1) 55 parts, 15 parts of perovskite (manufactured by Japan Aerozil Co., Ltd., 861 "〇2丨1 200), 3 parts of hexamethyldioxane and 1 part of water. 30 parts of the resinous copolymer (2) of Example 1 was added thereto, and further kneading was further carried out at 150 °C for 2 hours. To the 100 parts of the polyoxyethylene rubber base, 1.26 parts of methylhydropolysiloxane (3) having Si-H group in the molecular side bond of Example 1 was added as a crosslinking agent, as a reaction inhibitor Acetylene cyclohexanol 0.0 5 was continuously stirred for 15 minutes to obtain a polyoxymethylene rubber composition. This polyoxyethylene rubber composition was mixed with a platinum catalyst (Pt concentration: 1%) at 0.1 part by weight treatment at 120 ° C for 1 minute to obtain a 2 mm thick rubber sheet having an adhesive surface. With respect to this cured product, the rubber hardness (hardness meter A), tensile strength, elongation at the time of cutting, and surface adhesion before and after the heat resistance test were measured in the same manner as in Example 1. The results are shown in Table 1. [Comparative Example 3] 60 parts of the resin copolymer (5) of Example 3 in which one of the methyl polyxides (4) of Example 3 was mixed at room temperature, and toluene-19-(17) 1379870 was mixed. The solvent was removed under reduced pressure at 120 ° C for 3 hours. Stirring was continued for 1 hour. In 100 parts of the polyoxyethylene rubber base, one part of iron oxide (Fe 2 〇 3) having an average particle diameter of 0·3 μm was added, and as a crosslinking agent, the side chain of the molecule having Si-H group in Example 1 was used. After 2.5 parts of hydrogenated polyoxyalkylene (3) and 005 parts of acetylene cyclohexanol as a reaction inhibitor, stirring was continued for 15 minutes, and then a polyoxymethylene rubber composition was obtained. The polyoxo rubber composition was mixed with a uranium catalyst (Pt concentration portion, and subjected to pressure treatment at 120 ° C for 10 minutes, and then a rubber sheet having a thickness of 2 mm having a surface adhesiveness was obtained. For the cured product, and the examples 1 The same method was used to measure the rubber hardness (hardness meter A), tensile strength, elongation at the time of cutting, and surface adhesion before and after the heat resistance test. The results are shown in Table 1.
[表1] 測定結果 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 橡膠硬度(硬度計A) 22 34 32 21 31 20 拉伸強度(MPa) 1.8 3.5 2.5 1.8 3.3 0.3 切斷時延伸(％) 380 330 290 390 350 180 表面黏著力(g)初期 65 50 56 66 52 63 表面黏著力(g)耐熱試驗後 60 42 51 25 20 56[Table 1] Measurement Results Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Rubber hardness (hardness meter A) 22 34 32 21 31 20 Tensile strength (MPa) 1.8 3.5 2.5 1.8 3.3 0.3 Cut Extension at break (%) 380 330 290 390 350 180 Surface adhesion (g) Initial 65 50 56 66 52 63 Surface adhesion (g) After heat resistance test 60 42 51 25 20 56