(4) 1356838 安定性優，對輥輪之黏附少作業性優。 即，本發明爲含有： (A)平均組成式（1)所示之有機聚砂氧院 100質量份、 (1) R1 n Si Ο (4-η) / (式中’ R1爲相同或相異之非取代或取代之一價烴基，， 爲1 .95〜2.04之正數） (B) —般式（2)所示之有機聚矽氧烷或有機矽烷、 或此等之混合物 0 . 1〜5 0質量份' R 〇 (Si R1 2 〇) m R2 (2) (式中’ R1爲相同或相異之非取代或取代之一價烴基’ m 爲1〜50之正數；R2爲烷基或氫原子） (C)比表面積爲50 m2 / g以上4質量％水性懸浮液 之 pH爲 7 11 ，含有 A 1 2 〇 3 及 Na2〇，a12〇3 / Na2° 質 量 比爲1 .2 以 下之 :沈降. 二氧化矽 5〜100質貴份及 (〇) 硬 化 劑 有效纛、 爲 特徵之 聚 矽 氧橡膠組 成物。 【發明的功效】 -9- (6) 1356838 又，η爲1.95 ~ 2.04，理想爲1.98 ~ 2.02之正霍 不爲此範圍時’所得之硬化物可能不顯示充分之橡膠 。因此該有機聚矽氧烷爲直鏈狀，在不損及橡膠彈性 可爲分岐狀。 又’該有機聚矽氧烷之分子鏈末端爲三甲基甲矽 、二甲基乙烯甲矽烷基、二甲基羥基甲矽烷基、甲基 烯甲矽烷基、三乙烯甲矽烷基等以三有機甲矽烷基封 爲理想’以至少具有1個乙烯基之三有機甲矽烷封鏈 理想。 又’於本發明該有機聚矽氧烷分子中至少以具有 鏈烯基爲理想，又，依組成物之硬化性或其硬化物之 彈性等’ R1中以〇.〇1〜5莫耳％，特別以〇.〇2〜0. 耳％爲鏈烯基爲理想。鏈烯基以乙烯基爲理想。 又，聚合度之下限，理想爲100，更理想爲3000 理想爲 4000，聚合度之上限理想爲 100,000，更理 20,000，最理想爲10,000。此等依目的可倂用2種以 同聚合度或分子構造。 依上述平均組成式（1)所示之有機聚矽氧烷之 例可例舉如下。 彈性 範圍 院基 二乙 鏈者 者爲 2個 橡膠 5莫 ，最 想爲 上不 具體 -11 - (7) 1356838 ch2=ch(4) 1356838 Excellent stability and excellent adhesion to the roller. That is, the present invention contains: (A) 100 parts by mass of the organic polyoxo hospital represented by the average composition formula (1), (1) R1 n Si Ο (4-η) / (wherein R1 is the same or phase a non-substituted or substituted one-valent hydrocarbon group, a positive number of 1.95 to 2.04) (B) an organopolyoxane or an organic decane of the general formula (2), or a mixture of the same. ～500 parts by mass of 'R 〇(Si R1 2 〇) m R2 (2) (wherein R1 is the same or different unsubstituted or substituted one-valent hydrocarbon group 'm is a positive number from 1 to 50; R2 is an alkane (C) specific surface area of 50 m2 / g or more 4 mass% aqueous suspension pH 7 11 , containing A 1 2 〇 3 and Na 2 〇, a12 〇 3 / Na 2 ° mass ratio of 1.2 The following: sedimentation. cerium oxide 5~100 precious parts and (〇) hardener is an effective 纛, characterized by a polyoxyethylene rubber composition. [Effects of the Invention] -9- (6) 1356838 Further, η is 1.95 to 2.04, and ideally 1.98 to 2.02 is not suitable for this range. The resulting cured product may not exhibit sufficient rubber. Therefore, the organopolyoxane is linear and can be branched without damaging the rubber elasticity. Further, the end of the molecular chain of the organopolyoxyalkylene is trimethylformamidine, dimethylvinylformamidine, dimethylhydroxycarbamylalkyl, methylmethenylalkyl, trivinylcarbenyl, etc. The organomethane alkyl seal is ideally ideal for blocking with at least one vinyl triorganomethane. Further, in the organic polyoxosiloxane molecule of the present invention, at least the alkenyl group is preferred, and the hardening property of the composition or the elasticity of the cured product thereof is '.〇1 to 5 mol%. In particular, 〇.〇2~0. Ear% is ideal for alkenyl. Alkenyl is ideal for vinyl. Further, the lower limit of the degree of polymerization is preferably 100, more preferably 3,000 is ideally 4,000, and the upper limit of the degree of polymerization is desirably 100,000, more preferably 20,000, and most preferably 10,000. These may be used in two different degrees of polymerization or molecular structure depending on the purpose. Examples of the organopolyoxane represented by the above average composition formula (1) can be exemplified as follows. Elastic range The base of the two-chain chain is 2 rubber 5 mo, most not as specific -11 - (7) 1356838 ch2=ch
Tz \ SiO—K (3) ?H3 \ |H3Tz \ SiO-K (3) ?H3 \ |H3
Si〇-----Ί~T~CH=CH2 CH=CH2 b CH3 ch3Si〇-----Ί~T~CH=CH2 CH=CH2 b CH3 ch3
ί 7 ch3 /a ch3 I SiO- I ch=ch2ί 7 ch3 /a ch3 I SiO- I ch=ch2
CH3 Si—CH3 ch3 (4) (上述式中，a爲loo以上之整數，b爲0以上之整數，c 爲2以上之整數） 其中，亦以上述一般式 （3)所示者爲理想。 [(B)成分] (B)成分爲下述一般式 （2)所示： R2 0 (Si R1 2 〇) m R2 (2) (式中，R1爲相同或相異之非取代或取代之一價烴基，m 爲1〜50之正數；R2爲烷基或氫原子） 有機聚矽氧烷或有機矽烷，或此等之混合物，分子鏈 末端具有烷氧基或羥基。（B)成分係作爲處理（〇成分 強化性二氧化矽之處理劑，或分散劑使用。 —般式中所示，R1爲相同或相異之非取代或取代之 理想碳數爲1 ~ 12、更理想爲碳數1〜8之一價烴基。R1 所示一價羥基之例可列舉如甲基、乙基 '丙基、丁基等之 烷基，環己基等之環烷基’乙烯基、烯丙基、丁燦基 '己 -12- (10) (10)1356838 質量份（A)成分超過100質量份時所得之聚矽氧橡膠組 成物之加工性降低。又，（C)成分之配合量，相對於100 質量份（A)成分低於5質量份時，其聚矽氧橡膠組成物 硬化所得之硬化物不具有充分之拉力強度、撕裂強度等之 機械強度。 [(D)成分] (D)成分爲硬化含有上述 （A) ~ (C)成分所成之組 成物（基本組成物）之硬化劑。硬化劑，可列舉如有機過 氧化物、加成交聯劑）有機氫二烯聚矽氧烷）與氫甲矽烷 化觸媒之組合等。 硬化劑所使用之有機過氧化物可列舉如苯醯過氧化物 '對甲基苯醯過氧化物、鄰甲基苯醯過氧化物、過氧化 2,5-二甲基-2，5-二-t-丁基己烷、過氧化t-丁基苯甲酸酯、 過氧化二枯烯、過氧化枯烯-t-丁基等。其中，常壓熱氣加 硫用以使用苯醯過氧化物、對甲基苯醯過氧化物、鄰甲基 苯醯過氧化物等之醯基系有機過氧化物爲合適。此等之過 氧化物可單獨使用1種，或倂用2種以上亦可。 此等有機過氧化物之添加量，相對於1〇〇質量份 （A) 成分之有機聚矽氧烷爲0.1 ~ 10質量份，理想爲0.3〜5 質量份。於此範圍交聯可充分進行，又，’依添加量可提高 硬化速度。於基本組成物添加此等之有機過氧化物以加熱 硬化，可容易得到聚矽氧橡膠。 硬化劑使用加成交聯劑（有機氫二烯聚矽氧烷）與氫 -15- (11) (11)1356838 甲矽烷化觸媒之組合時，（A)成分之有機聚矽氧烷選擇具 有2個鏈烯基者。 有機氫二烯聚矽氧烷可舉例如分子中過氧化矽原子結 合之氫原子爲具有2個以上者。 氫甲矽烷化觸媒可列舉如鉑系化合物、鍺系化合物等 〇 有機氫二烯聚矽氧烷之添加量，與該有機氫二烯聚矽 氧烷中之與矽原子結合之氫原子數與 （A)成分中之鏈烯 基數之比例 （S i H / S i -鏈烯基）爲〇 . 5〜5，理想量爲〇 . 7 〜2。又，氫甲矽烷化觸媒之添加量，相對於 （A)成分之 有機聚砂氧院爲0.1〜2000 ppm，理想爲1 ~ 1000 ppm， 更理想爲5 ~ 5 0 0 p p m。 [其他成分] 本發明之組成物，上述成分以外因應必要亦可添加粉 碎石英、結晶二氧化矽等之非強化性二氧化矽，乙炔碳黑 、爐碳黑、煙道碳黑等之碳黑，碳酸鈣等之塡充劑，著色 劑、撕裂強度提升劑、耐熱性提升劑、難燃性提升劑、受 酸劑、導熱率提升劑等之各種添加劑，脫模劑，碳功能矽 烷等。 [組成物之調製.硬化] 於由上述 （A)〜（C)成分所調製之組成物混合上述 (D)成分硬化，可得到橡膠狀彈性物。 -16- (14) 1356838 含有量0.26質量。/〇，Na20含有量〇.3l 面積193 m2/g之沈降二氧化矽（日 )4 0質量份以外，與實施例1同樣方法 [實施例3] 除（C)成使用 pH 8.0、Al2〇3 / 含有量0.06質量％，Na2O含有量0.Π 面積188 m2 / g之沈降二氧化矽（日 )40質量份以外，與實施例1同樣方法 [比較例1 ] 除（C)成使用 pH 6_1、Al2〇3 / 含有量0.26質量％，Na2O含有量0.18 面積201m2 / g之沈降二氧化矽（日： )40質量份以外，與實施例1同樣方法 [比較例2 ] 更另外添加硬脂酸鋅〇 . 〇 9份以外 方法製造橡膠組成物。 [質量％，BET比表 本二氧化矽（股）製 製造橡膠組成物。 Na2〇 = 〇- 32，A12 〇 3 >質量％，B E T比表 本二氧化矽（股）製 製造橡膠組成物。 Na2〇= 1 ·44 1 Al2〇3 質量％，Β Ε Τ比表 本二氧化矽（股）製 製造橡膠組成物。 ，與實施例1同樣 -19 -CH3 Si—CH3 ch3 (4) (In the above formula, a is an integer of loo or more, b is an integer of 0 or more, and c is an integer of 2 or more.) It is also preferably represented by the above general formula (3). [(B) component] The component (B) is represented by the following general formula (2): R2 0 (Si R1 2 〇) m R2 (2) (wherein R1 is the same or different unsubstituted or substituted A monovalent hydrocarbon group, m is a positive number of from 1 to 50; R2 is an alkyl group or a hydrogen atom; an organic polyoxane or an organic decane, or a mixture thereof, having an alkoxy group or a hydroxyl group at the terminal of the molecular chain. The component (B) is treated as a treatment agent for cerium-enhanced cerium oxide or a dispersing agent. As shown in the general formula, R1 is the same or different, and the undesired or substituted carbon number is 1 to 12 More preferably, it is a monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydroxyl group represented by R1 include an alkyl group such as a methyl group, an ethyl 'propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group. When the amount of the component (A) exceeds 100 parts by mass, the processability of the obtained polyoxyethylene rubber composition is lowered, and the component (C) is further reduced in the amount of the component (A). When the amount is less than 5 parts by mass based on 100 parts by mass of the component (A), the cured product obtained by curing the polyoxyethylene rubber composition does not have sufficient mechanical strength such as tensile strength and tear strength. [(D) (Component) The component (D) is a curing agent for curing a composition (basic composition) containing the above components (A) to (C). Examples of the curing agent include organic peroxides and addition crosslinking agents. A combination of a diene polyoxyalkylene oxide and a hydroformylation catalyst. Examples of the organic peroxide used in the hardener include phenylhydrazine peroxide 'p-methylphenylhydrazine peroxide, o-methylphenylhydrazine peroxide, and 2,5-dimethyl-2,5-peroxide. Di-t-butyl hexane, t-butyl benzoate peroxide, dicumyl peroxide, cumene peroxide-t-butyl, and the like. Among them, the atmospheric pressure hot gas is preferably used as a thiol-based organic peroxide such as phenylhydrazine peroxide, p-methylphenylhydrazine peroxide or o-methylphenylhydrazine peroxide. These oxides may be used singly or in combination of two or more. The amount of the organic peroxide to be added is 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per part by mass of the organopolysiloxane of the component (A). Crosslinking in this range can be sufficiently carried out, and the rate of hardening can be increased by the amount added. By adding these organic peroxides to the basic composition to heat-harden, the polyoxyxene rubber can be easily obtained. When the hardener is a combination of an addition crosslinking agent (organohydrogen diene polyoxyalkylene) and hydrogen-15-(11) (11) 1356838 formazanation catalyst, the organopolyoxane of component (A) is selected to have 2 alkenyl people. The organohydrogen diene polyoxane may, for example, have two or more hydrogen atoms bonded to a perylene peroxide atom in the molecule. Examples of the hydroformylation catalyst include the addition amount of a ruthenium organohydrogen diene polyoxane such as a platinum compound or a ruthenium compound, and the number of hydrogen atoms bonded to the ruthenium atom in the organohydrogen diene polysiloxane. The ratio of the number of alkenyl groups in the component (A) (S i H / S i -alkenyl) is 〇. 5 to 5, and the ideal amount is 〇. 7 〜2. Further, the amount of the hydroformylation catalyst to be added is 0.1 to 2000 ppm, preferably 1 to 1000 ppm, more preferably 5 to 500 p p m, based on the organic polyoxo of the component (A). [Other components] The composition of the present invention may be added with non-reinforcing cerium oxide such as pulverized quartz or crystalline cerium oxide, carbon black such as acetylene black, furnace carbon black or flue carbon black, if necessary. , additives such as calcium carbonate and the like, coloring agent, tear strength enhancer, heat resistance enhancer, flame retardant enhancer, acid acceptor, thermal conductivity enhancer, etc., release agent, carbon functional decane, etc. . [Preparation and hardening of the composition] The composition prepared by the above components (A) to (C) is mixed and the component (D) is cured to obtain a rubbery elastic material. -16- (14) 1356838 The content is 0.26 mass. /〇, Na20 content: 33l area 193 m2 / g of precipitated cerium oxide (day) 40 parts by mass, the same method as in Example 1 [Example 3] In addition to (C) using pH 8.0, Al2 〇 3 / The content of 0.06 mass%, Na2O content: 0. The area of 188 m2 / g of precipitated cerium oxide (day) 40 parts by mass, the same method as in Example 1 [Comparative Example 1] 6_1, Al2〇3 / content 0.26 mass%, Na2O content 0.18 area 201 m2 / g of precipitated cerium oxide (day: ) 40 parts by mass, the same method as in Example 1 [Comparative Example 2] Further addition of stearin Zinc acid strontium. A rubber composition was produced by a method other than 9 parts. [% by mass, BET ratio is prepared by the production of a rubber composition. Na2〇 = 〇-32, A12 〇 3 > mass%, B E T ratio The preparation of the rubber composition. Na2〇= 1 ·44 1 Al2〇3 mass%, Β Τ Τ 表 表 本 本 二 二 二 二 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造Same as in the first embodiment -19 -