200813137 九、發明說明 【發明所屬之技術領域】 本發明係有關始於建築玻璃墊圏，各種海棉薄片、吸 水用海棉、斷熱薄片、工業用滾輥、影印機、傳真機、印 表機、等畫像形成裝置之事務機用海棉滾輥，特別是熔融 定著滾輥，給紙滾輥，調色搬運滾輥及洗淨滾輥等所使用 之高連泡率聚矽氧橡膠海棉。 【先前技術】 聚矽氧橡膠海棉係具有聚矽氧橡膠特有之物理特性， 具良好的耐熱性、耐寒性、電氣絕緣性、難燃性、耐壓縮 永久變形性等。聚矽氧橡膠海棉基本上係可組合熱硬化性 聚矽氧橡膠組成物與硬化劑及發泡劑，藉由加熱後進行發 泡，硬化後形成之。此時，具良好發泡性，取得均勻、微 細之單元構造，且取得不損及聚矽氧橡膠特有之物理特性 # 的海棉爲極重要者。 又，做爲加工成形方法者，多半於可連續成形之常壓 熱氣中進行硬化、發泡。爲於常壓熱氣中之成形作成具有 均勻且微細之單元構造之海棉時，使發泡劑進行分解時所 產生之氣體於橡膠內部務必呈微細泡沬狀態進行擠壓。因 此，通常，於發泡劑分解以前，其橡膠組成物必須克服發 泡壓力將氣泡擠入其內部進行增黏、硬化之。 因此，於海棉成形時於橡膠內產生的反應順序通常如 下之順序。 -4- 200813137 1) 藉由硬化劑之基礎聚合物之有機聚矽氧烷之增黏（ 硬化），橡膠之表面硬化。 2) 藉由發泡劑分解產生氣體，形成海棉單元。 3) 基礎聚合物之有機聚矽氧烷之完全硬化。 實際上依上述順序產生反應調整加成交聯反應觸媒之 量後，控制反應，使有機過氧化物之分解溫度選擇相同於 發泡劑之分解溫度或較低，設定如上述之反應順序。 如此，通常海棉係使發泡壓力於交聯以擠壓方式作成 ，因此，海棉單元通常爲獨立泡、連泡率爲1 0%以下，空 氣鎖入於其中之狀態。海棉單元爲獨立泡之海棉成形物經 加熱後，鎖入之空氣藉由波義耳查理法則而產生熱膨脹。 其結果，佔滿如墊圈材料之密閉空間的海棉其空氣彈簧成 份變強，海棉硬度隨之變高。固定海棉滾輥等之滾輥材料 時，藉由熱膨脹其海棉經變大，因此固定壓力改變。反之 ，海棉滾輥呈冷卻狀態時，熱滾輥與承環滾輥之設定間隔 變寬，滾輥摩擦導致怪聲的產生源。特別是最近之具備固 定海棉滾輥之事務機等，由其省電力之觀點視之，於待機 狀態下其固定海棉滾輥相較於一般固定溫度爲較冷卻狀態 之機種增加，因此做爲固定海棉滾輥用途者，無須視其加 熱溫度即可期待其海棉單元輕易呈一定之高連泡率海棉。 專利文獻1中，做爲倂用非醯基系之有機過氧化物交 聯與有機偶氮化合物之發泡系者被揭示有使用1，6-雙（第 三-丁基過氧基羧基）己烷（過氧基酯系、分解溫度：163°C ) 及發泡劑之AIBN(偶氮異丁腈）之海棉。碳係藉由有機過 200813137 氧化物而阻礙交聨，因此含碳之導電性聚矽氧橡膠組成物 通常無法藉由醯系之有機過氧化物進行常壓熱氣硫化。專 利文獻1中掲示有可使含碳之導電性聚矽氧橡膠組成物進 行常壓熱氣硫化，且表面硬化性亦適於使用有機過氧化物 ，取得優質海棉之技術，惟所得海棉之單元爲獨立泡，又 ，並非特別提高海棉連泡率之技術，並未記載有關連泡率 〇 專利文獻2中被記載於具有無機鹽類之結晶水所發泡 之聚矽氧橡膠海棉組成物，惟未記載有關連泡型海棉。 [專利文獻1]特開平5-43 802號公報 [專利文獻2]特開平5 - 1 5606 1號公報 【發明內容】 本發明爲克服上述問題，而以提供一種無須考量橡膠 之交聯速度之控制、發泡氣體產生速度之微妙的均衡度， 可藉由常壓熱氣加硫（HAV)製作之，且良好的生產性，均 勻微細單位構造之高連泡率聚矽氧橡膠海棉爲其目的。 本發明做爲達成上述目的之手段者係提供一種使含有 (A)以下述平均組成式（I): R1 aSiO(4-a)/2 ⑴ (式中，R1爲相同或不同之非取代或取代之1價烴基，a 爲1.95〜2.04之正數） 所示之一分子中至少具有2個鍵結於矽原子之烯基之有機 聚矽氧烷與補強性二氧化矽經混合後，藉由熱處理取得之 -6 - 200813137 基材：100質量份、 (B) 有機發泡劑：0·5〜50質量份、 (C) 硬化劑：有效量及 (D) 濕式二氧化矽：0.1〜20質量份 之聚矽氧橡膠組成物藉由發泡，硬化後取得連泡率20%以 上之高速泡率聚矽氧橡膠海棉。 本發明係於熱處理後之聚矽氧橡膠基劑（（A)成份）中 Β 配合濕式二氧化矽後，利用硬化劑，有機發泡劑進行常壓 熱氣硫化後，可取得連泡率高的聚矽氧橡膠海棉。 【實施方式】 [發明實施之最佳形態] 以下，進行本發明之詳細說明。 -(A)成份- • (Α)成份係代表上述平均組成式（I)所示之一分子中至 少具有2個鍵結於矽原子之烯基之有機聚矽氧烷與補強性 二氧化矽經混合後，藉由熱處理取得之基材（以下亦稱「 (Α)成份之聚矽氧橡膠基材」）。（Α)成份可單獨使用一種 ’亦可倂用2種以上。 [有機聚矽氧烷] 平均組成式⑴中，做爲R1者如：相同或相異之非取 代或取代之碳原子數1〜12者宜，較佳者爲碳原子數1〜8 200813137 之1價烴基之例。做爲R1之具體例者如：甲基、乙基、 丙基、丁基、己基、月桂基等烷基；環己基等之環烷基； 乙嫌基、細丙基、丁儲基、己嫌基等之燃基；苯基、甲苯 基等之芳基；苯基丙基等之芳烷基；或此等烴基之部 份或全部鍵結於碳原子之氫原子被鹵原子、氰基等所取代 之氯甲基、三氟丙基、氰乙基等例。其中又以甲基、乙烯 基 '苯基、三氟丙基爲較佳，特別是對於總R1而言，甲 基之比例以80〜99.999莫耳％者宜，更佳者爲95〜99.99莫 耳％。 平均組成式⑴中，a爲1.95〜2.04之正數。此有機聚 矽氧烷實質上爲直鏈狀、具體而言，其主鏈主要由二有機 矽氧烷單位所成之直鏈狀之二有機聚矽氧烷，而，在不損 及硬化後聚矽氧橡膠海棉之橡膠彈性範圍下，亦可爲支鏈 狀。 此有機聚矽氧烷其分子鏈末端可以三甲基矽烷基、二 甲基乙烯矽烷基、二甲基羥基矽烷基、三乙烯矽烷基等進 行封鏈。 此有機聚矽氧烷係一分子中至少具有2個鍵結於矽原 子之烯基，具體而言R1中以0.001〜5莫耳％爲烯基，特別 爲乙烯基者宜，較佳者爲〇·〇1〜0.5莫耳％。 此有機聚矽氧烷通常因應含於其構造中之矽氧烷單位 比例可使相當於1種或2種以上有機鹵化矽烷藉由水解縮 合，或使環狀有機聚矽氧烷（有機矽氧烷之3量體或4量 體等）使用鹼性或酸性觸媒經由開環聚合後取得。 -8 - 200813137 此有機聚矽氧烷之平均聚合度爲質量平均聚合度之 200〜20,000者宜，較佳者爲 2,000〜1 0,000，更佳者爲 3,000〜8,000。該平均聚合度若於此範圍者則易使（A)成份 之聚矽氧橡膠基材配合於本發明組成物中，配合後易使該 組成物之黏度保持適當之高度，於該組成物之硬化物中易 取得足夠之橡膠感。另外，平均聚合度係以聚苯乙烯做爲 分子量指示器藉由GPC(凝膠滲透色譜法）測定數平均分子 量，可藉由式： 數平均聚合度=數平均分子量/(A)成份之重覆單位之分子 量計算求取之。（A)成份中含有複數類重覆單位時，上述 式中之「（A)成份重覆單位之分子量」爲此等複數類重覆 單位之數平均分子量。 此有機聚矽氧烷可單獨使用1種，亦可混合分子構造 、平均聚合度等不同2種或更多進行使用之。 [補強性二氧化矽] 補強性二氧化砂係爲取得機械性強度良好之聚砂氧橡 膠海棉而使用之。爲此目的’補強性二氧化矽之比表面積 以50m2/g以上者宜，更佳者爲100〜400m2/g。做爲補強 性二氧化砂者如：煙霧質二氧化砂（乾式二氧化砂）、沈殿 二氧化矽（濕式二氧化矽）例者’其中又以煙霧質二氧化矽 (乾式二氧化矽）爲較佳。又’此等表面亦可以有機聚矽氧 烷、有機聚砍氨院、氯政院、院氧基砂院_進行疏水化處 理。補強性二氧化砂可單獨使用1種’亦可倂用2種以上 200813137 。另外，補強性二氧化矽之添加量於上述有機聚矽氧烷 100質量份時以5〜100質量份者宜，更佳者爲10〜9 0質量 份，特別理想者爲30〜80質量份。當該添加量於此範圍時 ，則經由補強性二氧化矽易取得充分的補強效果，易使所 取得組成物之加工性及所得聚矽氧橡膠海棉之物理特性爲 良好者。 爲使補強性二氧化矽分散於上述有機聚矽氧烷，因此 ，於如：三甲基矽醇、二苯基矽烷二醇、六甲基矽氨烷、 分子鏈末端進行添加具有羥基之聚二甲基矽氧烷等分散劑 者宜。分散劑之配合量於上述補強性二氧化砂1 0 0質量份 時以0·5〜3 0質量份者宜，更佳者爲1〜20質量份。 上述有機聚矽氧院，上述補強性二氧化砂，較佳者上 述分散劑藉由使用先行技術公知之滾輥硏磨機、捏合機等 之方法進行混合後，將取得混合物藉由使用先行技術公知 之捏合器、乾燥機之方法進行熱處理後，取得（Α)成份之 聚矽氧橡膠基材。熱處理係爲去除揮發成份之目的、爲促 進補強性二氧化矽與分散劑之反應之目的下而進行之。熱 處理如於100〜25 0°c，較佳者爲150〜220°c之溫度範圍下 使上述混合物經由加熱1〜6小時後進行者。 -(B)成份- (B)成份之有機發泡劑例如：N，N’-二甲基-N，N’·二亞 硝基對苯二甲酸醯胺、N，N5-二亞硝基甲撐四胺等之亞硝 基化合物·；二甲基1，1 偶氮雙（1 -環己烷羧酸酯）、偶氮二 -10- 200813137 羰醯胺、偶氮雙異丁腈、偶氮環己腈、偶氮二胺基苯、 2,2’-偶氮雙-2-甲基丁腈、2,2’_偶氮雙-2,4-二甲基戊腈、 1，1’_偶氮雙（1-乙醯氧基-1-苯基乙烷）、偶氮二羰醯胺、鋇 偶氮二羧酸酯、1，1’ -偶氮雙（環己烷-1-甲基羧酸酯）、 1，1’·偶氮雙（環己烷-1-羰腈）、2,2’-偶氮雙[N-(2-丙醯基）-2-甲基丙醯胺]等之有機偶氮化合物·，苯磺醯醯肼、甲苯 磺醯醯胼、p，p’-氧基雙（苯磺醯醯胼）、二苯磺-3,3’-二磺 醯醯肼、4,4’-氧基雙（苯磺醯醯肼）、p-甲苯磺醯醯胼等之 磺醯醯胼化合物；鈣迭氮、4，4-二苯基二磺醯迭氮、p-甲 苯磺醯、等之迭氮化合物等例。其中又以分子內未具有阻 礙聚矽氧橡膠之硬化的硫黃化合物，磷酸鹽類、強胺類等 有機偶氮化合物，如：二甲基1，1’-偶氮雙（1-環己烷羧酸 酯）、偶氮雙異丁腈、2,2’-偶氮雙-2-甲基丁腈、2,2’-偶氮 雙-2,4-二甲基戊腈、1，1’-偶氮雙（1-乙醯氧基-1-苯基乙烷 )、1，1’-偶氮雙（環己烷-1-甲基羧酸酯）、1，1’_偶氮雙（環己 烷-1-羰腈）、2,2’-偶氮雙[N-(2-丙醯基）-2-甲基丙醯胺]等 爲較佳。（B)成份可單獨使用1種，亦可組合2種以上使 用之。 做爲（B)成份發泡劑之添加量者，對於100質量份（A) 成份之聚矽氧橡膠基材而言，一般以0.5〜50質量份者宜 ，較佳者爲1.0〜20質量份。當該添加量未達0.5質量份 時，則容易使產生氣體量不足，導致取得硬化物不易呈海 棉狀態，而不易提高連泡率。該添加量超出5 0質量份時 ，則使（B)成份與其他成份之混合有其物理性之困難點， -11 - 200813137 又，於海棉成形時所產生氣體變多，導致單元不均，所得 海棉由內部產生劣化。 -(C)成份- 做爲（C)成份之硬化劑者，只要可使本發明橡膠組成 物硬化即可，未特別限定，其理想例如：做爲橡膠用硬化 劑公知之（i)有機氫化聚矽氧烷與氫矽烷基化觸媒之組合， (ii)有機過氧化物，及（i)與（ii)之倂用系例。 (i)有機氫化聚矽氧烷與氫矽烷基化觸媒之組合 •氫矽烷基化觸媒 .上述（i)之硬化劑係利用經由加成反應之交聯之硬化劑 。用於此加成反應之氫矽烷基化觸媒係使（A)成份中之脂 肪族不飽和基（烯基、二炔基等）與（i)之硬化劑中有機氫化 聚矽氧烷之矽原子鍵結氫原子（即，SiH基）經加成反應之 觸媒。氫矽烷基化觸媒可單獨使用一種，亦可倂用二種以 做爲氫矽烷基化觸媒者如：鉑族之金屬單體，其化合 物等之鉑族金屬系觸媒例。做爲鉑族金屬系觸媒例者可使 用加成反應硬化型聚矽氧橡膠組成物之做爲觸媒的先行技 術公知者。其具體例如：二氧化矽、氧化鋁或矽膠類之載 體上所吸附之微粒子狀鈾金屬、氯化鉑、氯鉑酸、氯鉛酸 6鉬之醇溶液、鈀觸媒、铑觸媒等例’又以含鉛之鉑族金 屬者爲較佳者。 -12- 200813137 氫矽烷基化觸媒之添加量只要可促進上述加成反應之 有效量即可’通常換算成鉛族金屬量後對於（A)成份而言 ，爲Ippm(賛量基準，以下相同）〜1質量％之範圍，較佳 者爲10〜500ppm之範圍。當該添加量於此範圍時，則容 易充分促進加成反應，且，易於充分硬化、發泡、更因應 該添加量之增加後容易提昇加成反應之速度，因此亦利用 於經濟面。 φ 又，除上述觸媒之外，爲調整硬化速度之目的下，亦 可使用加成交聯控制劑。其具體例如··乙炔基環己醇、四 環甲基乙烯基聚矽氧烷等例。 •有機氫化聚矽氧烷 有機氫化聚矽氧烷係1分子中含有2個以上，較佳者 爲3個以上之S iH基範圍下，可爲直鏈狀及環狀之任意者 ’亦可爲支鏈狀。有機氫化聚矽氧烷可單獨使用1種，亦 ^ 可組合2種以上使用之。做爲此有機氫化聚矽氧烷者可使 用加成反應硬化型聚矽氧橡膠組成物之做爲交聯劑之公知 的有機氫化聚矽氧烷，如：下述平均組成式（V): R6pHqSiO(4-p.q)/2 (V) (式中，R6爲相同或相異之非取代或取代之一價烴基、p 及q爲滿足〇Sp<3、0<q^3、及0<p + qS3、較佳者爲1 ‘PS2.2、0.0 02Sq$l、及 l.〇〇2gp + q$3 之正數） -13-200813137 IX. Description of the invention [Technical field to which the invention pertains] The present invention relates to construction glass mats, various sponge sheets, absorbent sponges, heat-dissipating sheets, industrial rolls, photocopiers, facsimile machines, printers High-foaming rate polyoxyethylene rubber used for machine and other image forming apparatus, such as a sponge roll for a machine, particularly a melt-fixing roll, a paper feed roll, a color transfer roll, and a wash roll. Sponge. [Prior Art] Polyoxymethylene rubber sponge has the unique physical properties of polyoxyxene rubber, and has good heat resistance, cold resistance, electrical insulation, flame retardancy, and compression set resistance. The polyoxymethylene rubber sponge is basically a combination of a thermosetting polyoxymethylene rubber composition, a hardener and a foaming agent, which is formed by heating, foaming, and hardening. In this case, it is extremely important to obtain a uniform and fine cell structure with good foaming properties, and to obtain a sponge which does not impair the physical properties peculiar to the polyoxyxene rubber. Further, as a method of forming and molding, it is mostly hardened and foamed in a normal-pressure hot gas which can be continuously formed. In order to form a sponge having a uniform and fine cell structure in the formation of a normal-pressure hot gas, the gas generated when the foaming agent is decomposed must be extruded in a state of fine foam in the rubber. Therefore, usually, before the foaming agent is decomposed, the rubber composition must overcome the foaming pressure to squeeze the bubbles into the inside to be thickened and hardened. Therefore, the order of reaction generated in the rubber during the formation of the sponge is generally as follows. -4- 200813137 1) The surface of the rubber is hardened by the adhesion (hardening) of the organic polyoxyalkylene of the base polymer of the hardener. 2) A gas is generated by decomposition of a blowing agent to form a sponge unit. 3) Complete hardening of the organopolyoxane of the base polymer. Actually, after the reaction adjustment plus the amount of the crosslinking reaction catalyst is generated in the above order, the reaction is controlled so that the decomposition temperature of the organic peroxide is selected to be the same as the decomposition temperature of the blowing agent or lower, and the reaction sequence as described above is set. In this case, the sponge is usually formed by extrusion in a cross-linking manner. Therefore, the sponge unit is usually a single bubble, and the foaming rate is 10% or less, and the air is locked therein. The sponge unit is a separate foamed sponge formed by heating, and the locked air is thermally expanded by the Bower's law. As a result, the sponge which fills the sealed space such as the gasket material has a strong air spring component, and the sponge hardness becomes high. When the roll material such as a sponge roll is fixed, the sponge becomes large by thermal expansion, and thus the fixed pressure changes. On the other hand, when the sponge roller is cooled, the set interval between the hot roller and the ring roller is widened, and the roller friction causes a strange sound source. In particular, the recent business machines with fixed sponge rolls, etc., from the viewpoint of power saving, the fixed sponge rolls in the standby state are increased compared with the general fixed temperature, and therefore In order to fix the use of sponge rolls, it is not necessary to consider the heating temperature to expect that the sponge unit can easily exhibit a certain high foaming rate of sponge. In Patent Document 1, the use of a non-fluorene-based organic peroxide cross-linking and an organic azo compound foaming system has revealed the use of 1,6-bis(tri-butylperoxycarboxyl). A sponge of hexane (peroxy ester system, decomposition temperature: 163 ° C) and a blowing agent AIBN (azoisobutyronitrile). The carbon system is hindered by the organic oxides of 200813137. Therefore, the carbon-containing conductive polyoxymethylene rubber composition cannot usually be vulcanized by atmospheric pressure hot gas by the organic peroxide of the lanthanide series. Patent Document 1 discloses a technique in which a carbon-containing conductive polyoxyethylene rubber composition is vulcanized at atmospheric pressure, and surface hardenability is also suitable for using an organic peroxide to obtain a high-quality sponge, but the obtained sponge is used. The unit is a separate foam, and is not a technique for improving the foaming rate of the sponge. The foaming rate is not described in the polyether rubber sponge which is described in Patent Document 2 and is described in the crystal water having inorganic salts. Composition, but not related to the bubble type sponge. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 5- No. Hei. No. Hei. No. Hei. The subtle balance of control and foaming gas generation rate can be produced by atmospheric pressure hot gas vulcanization (HAV), and good productivity, high uniform foam ratio of uniform micro-unit structure, and polyoxyethylene rubber sponge purpose. The present invention provides a means for achieving the above object to provide (A) an average composition of the following formula (I): R1 aSiO(4-a)/2 (1) (wherein R1 is the same or different unsubstituted or a substituted monovalent hydrocarbon group, a is a positive number of 1.95 to 2.04), wherein one of the molecules shown in the molecule having at least two organic polyoxyalkylene bonded to the alkenyl group of the ruthenium atom is mixed with the reinforcing cerium oxide by Heat treatment -6 - 200813137 Substrate: 100 parts by mass, (B) Organic foaming agent: 0·5 to 50 parts by mass, (C) Hardener: Effective amount and (D) Wet cerium oxide: 0.1~ 20 parts by mass of the polyoxyethylene rubber composition is foamed and hardened to obtain a high-velocity polyoxyethylene rubber sponge having a continuous foaming rate of 20% or more. The present invention is based on the heat-treated polyoxyxene rubber base (component (A)). After the wet cerium oxide is blended with a hardener, the organic foaming agent is subjected to atmospheric pressure hot gas vulcanization, and the continuous foaming rate is high. Polyoxymethylene rubber sponge. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, a detailed description of the present invention will be made. - (A) component - • (Α) component represents an organopolysiloxane having at least two alkenyl groups bonded to a halogen atom in the molecule represented by the above average composition formula (I) and a reinforcing cerium oxide After mixing, the substrate obtained by heat treatment (hereinafter also referred to as "polyoxyethylene rubber substrate of "(Α) component)"). (Α) The ingredients may be used alone or in combination of two or more. [Organic Polyoxane] In the average composition formula (1), as R1, the same or different unsubstituted or substituted carbon atoms are preferably 1 to 12, preferably 1 to 8 carbon atoms. An example of a monovalent hydrocarbon group. Specific examples of R1 are: an alkyl group such as methyl, ethyl, propyl, butyl, hexyl or lauryl; a cycloalkyl group such as cyclohexyl; an alkyl group, a fine propyl group, a butyl group, and a stilbene group. An aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a phenylpropyl group; or a hydrogen atom to which a part or all of the hydrocarbon group is bonded to a carbon atom is a halogen atom or a cyano group. Examples of substituted chloromethyl, trifluoropropyl, cyanoethyl and the like. Among them, methyl, vinyl 'phenyl, trifluoropropyl is preferred, especially for total R1, the ratio of methyl is preferably 80 to 99.999 mol%, and more preferably 95 to 99.99. ear%. In the average composition formula (1), a is a positive number of 1.95 to 2.04. The organopolyoxane is substantially linear, specifically, a linear diorganopolyoxane whose main chain is mainly composed of a diorganosiloxane unit, and does not damage the hardened layer. The rubberized elastic range of the polyoxyethylene rubber sponge may also be branched. The organic polyoxyalkylene may have a molecular chain end which may be blocked by a trimethyldecyl group, a dimethylvinyl fluorenyl group, a dimethyl hydroxy decyl group, a trivinyl decyl group or the like. The organopolyoxyalkylene has at least two alkenyl groups bonded to a halogen atom in one molecule, and specifically, 0.001 to 5 mol% of R1 in the R1 group is an alkenyl group, particularly a vinyl group, preferably a 〇·〇1~0.5mol%. The organopolyoxyalkylene can be obtained by hydrolytic condensation of one or more organic halogenated decanes or by cyclic organopolyoxyalkylene (organic oxirane) in proportion to the proportion of oxoxane contained in the structure. An alkane or a tetradentate or the like is obtained by ring-opening polymerization using an alkaline or acidic catalyst. -8 - 200813137 The average degree of polymerization of the organopolyoxane is preferably 200 to 20,000 by mass average degree of polymerization, preferably 2,000 to 1,000,000, more preferably 3,000 to 8,000. If the average degree of polymerization is in this range, the polyoxyethylene rubber substrate of the component (A) is easily incorporated into the composition of the present invention, and the viscosity of the composition is easily maintained at an appropriate height after the compounding. A sufficient rubbery feeling is easily obtained in the hardened material. In addition, the average degree of polymerization is determined by GPC (gel permeation chromatography) using polystyrene as a molecular weight indicator, and can be determined by the formula: number average polymerization degree = number average molecular weight / (A) component weight Calculate the molecular weight of the overlay unit. (A) When the component contains a plurality of types of repeating units, the "molecular weight of the (A) component repeating unit in the above formula" is the number average molecular weight of the plurality of repeating units. The organic polyoxane may be used singly or in combination of two or more different molecular structures and average degrees of polymerization. [Reinforcing cerium oxide] The reinforcing sulphur dioxide is used to obtain a sand-oxygen rubber sponge with good mechanical strength. For this purpose, the specific surface area of the reinforcing cerium oxide is preferably 50 m 2 /g or more, and more preferably 100 to 400 m 2 /g. As reinforcing sulphur dioxide, such as: aerosol-type silica sand (dry silica sand), sedative cerium oxide (wet cerium oxide), which is also a fumed cerium oxide (dry cerium oxide) It is better. In addition, these surfaces can also be hydrophobized by organic polyoxane, organic poly-alkaline aquarium, chlorine administration, and hospital oxygen sands. Reinforcing silica sand can be used alone or in combination of two or more types 200813137. Further, the amount of the reinforcing cerium oxide added is preferably from 5 to 100 parts by mass, more preferably from 10 to 90 parts by mass, particularly preferably from 30 to 80 parts by mass, per 100 parts by mass of the above organopolysiloxane. . When the amount of the addition is in this range, a sufficient reinforcing effect is easily obtained by the reinforcing cerium oxide, and the processability of the obtained composition and the physical properties of the obtained polyoxymethylene rubber sponge are likely to be good. In order to disperse the reinforcing cerium oxide in the above organopolyoxane, for example, trimethyl decyl alcohol, diphenyl decane diol, hexamethyl decane, and a chain of a hydroxyl group are added at the end of the molecular chain. Dispersing agents such as dimethyloxane are preferred. The amount of the dispersing agent is preferably from 0.5 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the above-mentioned reinforcing silica sand. In the above-mentioned organopolyxide house, the above-mentioned reinforcing silica sand is preferred, and the dispersant is preferably mixed by using a roll honing machine, a kneader or the like known in the prior art, and the mixture is obtained by using the prior art. After the heat treatment by a known kneader or dryer, a poly(xylene oxide) base material having a (Α) composition is obtained. The heat treatment is carried out for the purpose of removing volatile components for the purpose of promoting the reaction of the reinforcing cerium oxide and the dispersing agent. The heat treatment is carried out by heating the mixture for 1 to 6 hours at a temperature of from 100 to 25 ° C, preferably from 150 to 220 ° C. - (B) Ingredients - (B) Ingredients for organic foaming agents such as: N,N'-dimethyl-N,N'. Dinitrosophthalic acid decylamine, N,N5-dinitroso a nitroso compound such as a tetramethyleneamine; dimethyl 1,1 azobis(1-cyclohexanecarboxylate), azobis-10-200813137 carbonyl decylamine, azobisisobutyronitrile, Azocyclohexyl nitrile, azodiaminobenzene, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1, 1'-Azobis(1-ethenyloxy-1-phenylethane), azodicarbonylamine, hydrazine azodicarboxylate, 1,1'-azobis(cyclohexane- 1-methylcarboxylate), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methyl Organic azo compounds such as propylamine], benzenesulfonate, toluenesulfonate, p,p'-oxybis(phenylsulfonate), diphenylsulfon-3,3'- Sulfonium compounds such as disulfonium, 4,4'-oxybis(phenylsulfonate), p-toluenesulfonate, etc.; calcium azide, 4,4-diphenyldisulfonate Examples of azide, p-toluenesulfonate, and the like. Among them, there are organic sulfur compounds such as sulfur compounds such as phosphates and strong amines, such as dimethyl 1,1'-azobis (1-cyclohexene), which do not have a hardening effect on the hardening of the polyoxyethylene rubber. Alkyl carboxylate), azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1, 1'-Azobis(1-ethenyloxy-1-phenylethane), 1,1'-azobis(cyclohexane-1-methylcarboxylate), 1,1'-even Nitrogen bis(cyclohexane-1-carbonylcarbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide] and the like are preferred. (B) The components may be used singly or in combination of two or more. As the additive amount of the component (B) foaming agent, it is generally 0.5 to 50 parts by mass, preferably 1.0 to 20 mass, for 100 parts by mass of the (A) component polyoxyethylene rubber substrate. Share. When the amount of addition is less than 0.5 part by mass, the amount of generated gas is liable to be insufficient, so that the cured product is less likely to be in a sponge state, and the continuous foaming rate is not easily increased. When the amount added exceeds 50 parts by mass, the mixing of the component (B) with other components has physical difficulties, and -11 - 200813137, in addition, the gas generated during the formation of the sponge is increased, resulting in unevenness of the unit. The resulting sponge is internally deteriorated. - (C) component - The hardening agent of the component (C) is not particularly limited as long as it can harden the rubber composition of the present invention, and is preferably known as a hardener for rubber (i) organic hydrogenation. A combination of a polyoxyalkylene oxide and a hydroquinone alkylation catalyst, (ii) an organic peroxide, and a combination of (i) and (ii). (i) Combination of an organic hydrogenated polyoxyalkylene oxide and a hydroquinone alkylation catalyst • Hydroquinone alkylation catalyst The hardener of the above (i) is a hardener which is crosslinked by an addition reaction. The hydroquinone alkylation catalyst used in the addition reaction is an organic hydrogenated polyoxyalkylene in the hardening agent (alkenyl group, diacetylene group, etc.) in the component (A) and the hardener in (i). The ruthenium atom bonds a hydrogen atom (ie, a SiH group) through a catalyst for addition reaction. The hydroquinone alkylation catalyst may be used singly or in the form of a platinum group metal catalyst which is used as a hydroquinone alkylation catalyst such as a platinum group metal monomer or a compound thereof. As a platinum group metal catalyst, those skilled in the art of using an addition reaction hardening type polyoxymethylene rubber composition as a catalyst can be used. Specifically, for example, a particulate uranium metal adsorbed on a carrier of cerium oxide, aluminum oxide or cerium gel, platinum chloride, chloroplatinic acid, an alcohol solution of chloroplatinic acid 6 molybdenum, a palladium catalyst, a ruthenium catalyst, and the like 'It is better to use lead-containing platinum group metals. -12- 200813137 The amount of the hydroquinone alkylation catalyst added can be adjusted to the amount of the lead group metal after the effective amount of the addition reaction can be promoted, and is 1 ppm for the component (A). The same) ranges from 1% by mass, preferably from 10 to 500 ppm. When the amount is in this range, the addition reaction can be sufficiently promoted, and it is easy to sufficiently harden and foam, and it is easy to increase the rate of the addition reaction in response to the increase in the amount of addition, and therefore it is also used in an economical aspect. φ Further, in addition to the above-mentioned catalyst, an addition-linking control agent may be used for the purpose of adjusting the hardening speed. Specific examples thereof include ethynylcyclohexanol and tetracyclomethylvinylpolyoxane. • The organic hydrogenated polyoxyalkylene organic hydrogenated polyoxyalkylene system contains two or more molecules, preferably three or more in the range of S iH groups, and may be any of a linear chain and a ring shape. It is branched. The organic hydrogenated polyoxyalkylene can be used singly or in combination of two or more. As the organic hydrogenated polyoxyalkylene, a known organic hydrogenated polyoxyalkylene as a crosslinking agent can be used as the crosslinking agent, such as the following average composition formula (V): R6pHqSiO(4-pq)/2 (V) (wherein R6 is the same or different unsubstituted or substituted one-valent hydrocarbon group, p and q are satisfying 〇Sp<3, 0<q^3, and 0<0>; p + qS3, preferably 1 'PS2.2, 0.0 02Sq$l, and l.〇〇2gp + q$3 positive number) -13-
200813137 所示之有機氫化聚矽氧烷。 上述平均組成式（V)中，R6爲相同或相 取代之碳原子數1〜1 2，較佳者爲碳原子數 基，以不含脂肪族不飽和鍵者宜。做爲R6 :甲基、乙基、丙基等烷基；環己基等之環 、烯丙基、丁烯基、己烯基等烯基；苯基、 ;苄基、2-苯基乙基、2-苯基丙基等之芳烷 原子等之鹵原子等取代部份或全部此等烴基 ，如·· 3,3,3-三氟丙基等例。 此有機氫化聚矽氧院爲直鏈狀時，SiH 末端及非分子鏈末端部份之任意者存在之， 者。又，此有機氫化聚矽氧烷之 25 0.5〜1 0,000mm2/s者宜，較佳者爲1〜3〇〇mm2 做爲此有機氫化聚矽氧烷之具體例者如 之化合物例。 異之非取代或 1〜8之一價烴 之具體例者如 爆基；乙嫌基 甲苯基等芳基 基；以及以氟 之氫原子之基 基可以分子鏈 亦可存在其兩 °C之黏度爲 /s 〇 :下述構造式Organic hydrogenated polyoxyalkylene shown in 200813137. In the above average composition formula (V), R6 is the same or a substituted carbon atom number of 1 to 12, preferably a carbon atom group, and preferably contains no aliphatic unsaturated bond. As R6: alkyl group such as methyl group, ethyl group, propyl group; cycloalkyl group such as cyclohexyl group, allyl group such as allyl group, butenyl group, hexenyl group; phenyl group; benzyl group; 2-phenylethyl group; A halogen atom such as an aralkyl atom such as a 2-phenylpropyl group or the like is substituted for some or all of such a hydrocarbon group, such as a 3,3,3-trifluoropropyl group. When the organic hydrogenated polyoxanium is linear, any of the SiH terminal and the non-molecular chain terminal portion may be present. Further, the organic hydrogenated polyoxyalkylene is preferably 25 0.5 to 10,000 mm 2 /s, more preferably 1 to 3 〇〇 mm 2 as a specific example of the organic hydrogenated polyoxyalkylene. Specific examples of the unsubstituted or 1 to 8 one-valent hydrocarbons such as a fluorenyl group; an aryl group such as an ethyl phenyl group; and a group of a hydrogen atom of fluorine may have a molecular chain of two degrees C. Viscosity is /s 〇: The following structural formula
Si(CH3)3 14- 200813137Si(CH3)3 14- 200813137
(式中，k爲2〜10之整數，s及t爲0〜10之整數） 上述有機氫化聚矽氧烷之配合量對於1個（A)成份中 之脂肪族不飽和鍵（烯基及二烯基等）而言，該有機氫化聚 矽氧烷中之SiH基之個數以 0.5〜10個者宜，更佳者爲 0.7〜5個之量。當該配合量爲此範圍內則易充分交聯，硬 化後其機械性強度容易充足，其他容易維持物理特性，特 別是耐熱性與耐壓縮永久變形性。此之配合量如：對於 100質量份之（A)成份而言，可藉由添加該有機氫化聚矽 氧烷較佳者爲0.1〜40質量份，更佳者爲0.2〜10質量份而 實現。 (ii)有機過氧化物 有機過氧化物係爲使（A)成份進行硬化所使用之硫化 劑。有機過氧化物可單獨使用1種，亦可組合2種以上使 用。做爲有機過氧化物例者如：苯甲醯過氧化物、2,4-二 氯苯甲醯過氧化物、P-甲基苯甲醯過氧化物、〇-甲基苯甲 醯過氧化物、2,4-二異丙苯基過氧化物、2,5-二甲基-雙 (2,5-第三-丁基過氧基）己烷、二-第三-丁基過氧化物、第 三-丁基過苯甲酸酯、1，6-己烷二醇-雙-第三-丁基過氧基 碳酸酯等例。 有機過氧化物之添加量以做爲硫化劑之有效量即可， -15 - 200813137 具體而言，對於100質量份之（A)成份時，以0.1〜15質量 份爲佳，特別以0.2〜10質量份者爲最佳。該添加量於此 範圍內則因應該添加量之增加後，易於提昇硬化速度’因 此，易有利於經濟面，且於短時間內容易由取得硬化物去 除未反應物、分解殘渣。 -(D)成份- (D)成份之濕式二氧化矽係爲取得高連泡率之聚矽氧 橡膠海棉而使用。爲此目的中，（D)成份之濕式二氧化矽 之比表面積爲50m2/g以上者宜，更佳者爲1〇〇〜40〇m2/g 。做爲（D)成份者如：NIPSIL(註冊商標）-LP(商品名、東 曹二氧化矽股份公司製），tocseal(註冊商標）USA(商品名 、股份公司得山製）Zeosil(註冊商標）132(商品名、 Rodiajapan製）等例。又，將此等表面以有機聚矽氧烷、 有機聚矽氨烷、氯矽烷、烷氧基矽烷等進行疏水化處理亦 可，而以未進行疏水化處理之未處理狀態之濕式二氧化矽 者宜。（D)成份可單獨使用1種，亦可倂用2種以上。 (D)成份之添加量對於100質量份（A)成份而言，以 0.1〜20質量份者宜，較佳者爲1〜10質量份，特別以1〜5 質量份爲最佳。該添加量若未達〇· 1質量份則不易取得充 足的連泡率之聚矽氧橡膠海棉。反之，該添加量多於20 質量份則取得組成物之加工性容易惡化，且取得聚矽氧橡 膠之物理性降低。 -16- 200813137 -其他成份- 本發明聚矽氧橡膠海棉亦可藉由添加導電性物質做成 導電性海棉。導電性物質之種類、配合量並未受限。一般 做爲導電性物質者可適用導電性碳黑、導電性金屬氧化物 微粒子，如：導電性氧化鋅、導電性氧化欽等。導電性物 質可單獨使用1種，亦可倂用2種以上。碳係經由有機過 氧化物做成交聯之阻礙物質，因此於含有有機過氧化物之 聚矽氧橡膠組成物中添加導電性碳黑時，增加有機過氧化 物之量，或前述之高溫型加成硬化劑，亦即將有機氫化聚 矽氧烷與氫矽烷基化觸媒之組合與有機過氧化物倂用者宜 〇 做爲導電性碳黑者一般可使用常用於導電性橡膠組成 物者，如：乙炔碳黑、導電爐黑（CF)、超導電爐黑（SCF) 、超高導電爐黑（XCF)、導電槽法碳黑（CC)、及 1 5 00〜3 0 0 0 °C之高溫下進行熱處理之爐黑或槽法碳黑等例 。做爲乙炔碳黑之具體例者如：DencablaCk(商品名，電 氣化學工業股份公司製）、Shernigen乙炔碳黑（商品名， Shernigan Chemical公司製）等例。做爲導電爐黑之具體例 如：Continex CF(商品名，Continentalcarbon 公司製）、 barean C(商品名，cabot公司製）等例。做爲超導電爐黑之 具體例者如：continex SCF(商品名’ continentalcarbon 公 司製）、parkan SC(商品名，cabot公司製）等例。做爲超高 導電爐黑之具體例者如：旭HS-500(商品名，旭碳股份公 司製）、baircan XC-72(商品名，cabot公司製）等例。做爲 -17- 200813137 導電槽法碳黑之具體例者如：corlax L(商品名，degoosa 公司製）等例。又，可亦可使用爐黑的一種之 kechenblack(註冊商標）EC 及 kechenblack EC-600 JD(同商 品名，kec hen black international股份公司製）。爐黑其不 純物量、特別是硫黃、硫黃化合物量換算成硫黃元素後， 以質量基準計爲6000ppm以下者宜，較佳者爲3 000ppm 以下。另外，此等中，乙炔碳黑其不純物含率低，且具有 成長之2次構造，故具有良好的導電性，特別適用於本發 明。又，具有卓越之大的比表面積，因此，即使低塡充量 仍顯現良好的導電性之kechenblack EC、kechenblack EC-600JD等均可使用之。 上述導電性碳黑之添加量對於1 〇〇質量份之上述（A) 成份聚矽氧橡膠基材而言，爲1〜1〇〇質量份者宜，特別以 5〜5 0質量份爲更佳。當該添加量於此範圍時，則易取得 所期待之導電性、易於對於取得組成物進行物理性混合， 易取得具有充足的機械性強度及做爲目的之橡膠彈性之硬 化物。 做爲導電性金屬氧化物微粒子例者如：導電性氧化鋅 、氧化鈦（如：白色導電性氧化鈦）、錫銻系氧化物微粒子 等例。做爲導電性氧化鋅之具體例者如：Haxitec(股份）製 之氧化鋅23-K(商品名）、本庄Chemical股份公司製之導 電性氧化鋅FX(商品名）之例。做爲白色導電性氧化鈦之 例者如：ET-500W(商品名，石原產業（股份）製）之例。導 電性金屬氧化物微粒子可單獨使用1種，亦可倂用2種以 -18- 200813137 上。另外’亦可使導電性金屬氧化物微粒子與導電性碳黑 倂用之。導電性金屬氧化物微粒子之添加量對於1 〇 0質量 份之上述（A)成份之聚矽氧橡膠基材而言，以1〜3〇〇質量 份者宜，更佳者爲1〜100質量份。當該添加量於此範圍時 ，則易取得所期待之導電性。 本發明聚矽氧橡膠組成物於必要時，可進一步添加做 爲導熱性賦予劑之粉碎石英、氧化鋅、氧化鋁、以氧化鋁 做成非補強性二氧化矽之矽藻土，其他亦可添加碳酸鈣等 之塡充劑、著色劑、耐熱提昇劑、難燃提昇劑、受酸劑、 導熱提昇劑等之添加劑、脫模劑、烷氧基矽烷、二苯基矽 烷二醇、碳官能基矽烷、兩末端矽醇封鏈低分子矽氧烷等 之分散劑等。 -製造方法- 本發明橡膠組成物之製造方法並未特別限定，一般可 使上述成份所定量以2根滾輥硏磨機、捏合器、密閃式混 煉機等經由混煉後取得。又，必要時亦可進行熱處理（加 熱下進行混煉）。具體而言，將（A)成份及其他成份進行混 煉·熱處理後，取得基劑橡膠混合物（（A)成份之聚矽氧橡 膠基材），接著，於冷卻後於該基劑橡膠混合物中添加（B) 、（C)及（D)成份之方法等例。上述熱處理之溫度、時間並 未特別限定，一般如：於1〇〇〜250°C，較佳者爲150〜200 °C下進行3 0分鐘至5小時之熱處理。 200813137 -發泡硬化方法- 爲提昇海棉單元之連泡率，本發明橡膠組成物之硬化 發泡方法以常壓熱氣硫化者宜，利用擠壓成形經由加熱爐 連續硫化，經由間歇式乾燥器之熱氣交聯等爲適用者。於 塑模內部確保充足的空間時，亦可適用塑模硫化。一般於 8 0〜4 00°C，特別於100〜300 °C之溫度下，進行5秒至1小 時之常壓熱氣硫化，經由發泡硬化後，可取得高連泡率海 棉。又，亦可於100〜230°C，較佳者爲150〜230°C下進行 1 〇分鐘至1 0小時之後處理。 [實施例] 以下如實施例及比較例所示，具體說明本發明，惟， 本發明未受限於下述之實施例。另外，下述例中份代表質 量份，黏度係藉由旋轉黏度計所測定之値。 [實施例1] 於捏合器中投入由二甲基矽氧烷單位99.825莫耳％， 甲基乙烯基矽氧烷單位0.15莫耳％、二甲基乙烯基矽氧烷 單位0.025莫耳％所成，平均聚合度約爲8,000之有機聚 矽氧烷100份、 BET表面積200m2/g之乾式二氧化矽Arosil 200(商品 名，日本Aerozil(股份）製）40份、 兩末端具有矽醇基，黏度爲29 m2/g(23°C)之二甲基 聚矽氧烷5份、 -20- 200813137 ，180°C下進行熱處理混煉2小時，製成基劑橡膠混合物 〇 對於1 0 0份之取得基劑橡膠混合物而言，進行添加、 有機發泡劑二甲基1，1’ -偶氮雙（1-環己烷羧酸酯）（和 光純藥（股份）製，商品名：VE-073)1.5份、 硬化劑2,5-二甲基-2,5-二第三-丁基過氧基己烷（日本 油脂（股份）製）〇·8份、 濕式二氧化矽NIPSIL(註冊商標）-LP(商品名、東曹二 氧化矽股份公司製）3份、 ，以2根滾輥硏磨器進行混合後，取得聚矽氧橡膠組成物 。將取得組成物進行成形後，製成厚度9mm之薄片。 將此厚度9mm之薄片於常壓下，230 °C之熱風乾燥器 下，進行常壓熱氣硫化3 0分鐘後，取得聚矽氧橡膠海棉 。之後，於200 °C下進行4小時之2次硫化。由取得海棉 去除表層後，進行下述檢測海棉特性之海棉硬度、發泡倍 率、平均單元徑、連泡率。其結果示於表1。 •海棉硬度：依JIS S6050爲基準，以ASCa C型橡膠硬度 計所測定。 •發泡倍率：發泡後之體積/發泡前之體積xl 00(%)。 •平均單元徑（μιη):海棉剪切面之單元徑之平均値。 •連泡率：如下所測定。 1 )測定海棉原料之聚矽氧橡膠組成物，亦即未發泡之 橡膠材料之比重。 2)測定海棉之比重與重量。 -21 - 200813137 3) 將海棉沈滲於置於真空容器之容器中之水中，於該 狀態下使真空容器內減壓爲lOmmHg以下。 4) 使真空容器內恢復爲常壓後，放置5分鐘後，海棉 進行吸水。 5) 吸水狀態下計測海棉之重量。再依以下之計算求出 連泡率。 [(減壓下吸水後之海棉重量-最初海棉重量）/水的比重 (1.00)]/[(1-(海棉比重/未發泡之橡膠材料比重））x(海棉重 量/海棉比重）]xl〇〇(°/。） [實施例2] 將濕式二氧化矽變更爲Zeosil(註冊商標）132(商品名 、Lodiajapan(股份）製）之外，與實施例1同法進行聚矽氧 橡膠海棉之成形，進行檢測上述海棉特性。其結果示於表 [實施例3] 將濕式二氧化矽變更爲tocseal(註冊商標）USA(商品 名、股份公司得山製）之外，與實施例1同法進行聚矽氧 橡膠海棉之成形，進行檢測上述海棉特性。其結果如表1 所示。 [實施例4] -22· 200813137 以二異丙苯基過氧化物1.0份取代硬化劑（有機過氧 化物）之2,5·二甲基-2,5-二-第三-丁基過氧基己烷0.8份使 用之外，與實施例1同法成形聚矽氧橡膠海棉後，進行檢 測上述海棉之特性。其結果示於表1。 [比較例1] 以乾式二氧化矽Arosil 200(商品名，日本Aerozil(股 份）製）3份取代濕式二氧化矽NIPSIL-LP(商品名、東曹二 氧化矽股份公司製）3份使用之外，與實施例1同法進行 聚矽氧橡膠海棉之成形，檢測上述海棉之特性。其結果示 於表1。 [比較例2] 未添加濕式二氧化矽NIPSIL-LP(商品名、東曹二氧 化矽股份公司製）之外’與實施例1同法進行聚矽氧橡膠 海棉之成形，檢測上述海棉之特性。其結果示於表1。 表1] 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 海棉特性 硬度(Asca-C) 25 26 25 26 40 29 發泡倍率(％) 220 230 230 240 220 200 單元徑(μιη) 150 150 150 200 100 200 連泡率(％) 95 90 95 75 4 8 -23-(wherein k is an integer of 2 to 10, and s and t are integers of 0 to 10) The amount of the above organohydrogenated polyoxyalkylene to be an aliphatic unsaturated bond (alkenyl group) in one (A) component The dialkyl group or the like has a number of SiH groups in the organohydrogenated polyoxyalkylene of 0.5 to 10, more preferably 0.7 to 5. When the compounding amount is within this range, it is easily crosslinked, and the mechanical strength is easily sufficient after hardening, and other physical properties are easily maintained, particularly heat resistance and compression set resistance. The amount of the compound is as follows: for 100 parts by mass of the component (A), it is preferably 0.1 to 40 parts by mass, more preferably 0.2 to 10 parts by mass, by adding the organohydrogenated polyoxyalkylene. . (ii) Organic peroxide The organic peroxide is a vulcanizing agent used for curing the component (A). The organic peroxide may be used singly or in combination of two or more. As organic peroxides such as: benzamidine peroxide, 2,4-dichlorobenzamide peroxide, P-methylbenzamide peroxide, 〇-methylbenzimidoxime peroxide , 2,4-diisopropylphenyl peroxide, 2,5-dimethyl-bis(2,5-tri-butylperoxy)hexane, di-tertiary-butyl peroxidation Examples of the compound, the third-butyl perbenzoate, the 1,6-hexanediol-bis-tert-butylperoxycarbonate, and the like. The amount of the organic peroxide added may be an effective amount as a vulcanizing agent, -15 - 200813137 Specifically, for 100 parts by mass of the component (A), it is preferably 0.1 to 15 parts by mass, particularly 0.2 to 0.2%. 10 mass parts are the best. When the amount of the addition is within this range, the amount of the addition is increased, and the curing rate is easily increased. Therefore, it is easy to be economical, and it is easy to remove the unreacted material and decompose the residue by obtaining the cured product in a short time. - (D) component - The wet cerium oxide of the component (D) is used for obtaining a high foaming rate of polyoxyethylene rubber sponge. For this purpose, the wet cerium oxide of the component (D) has a specific surface area of 50 m 2 /g or more, more preferably 1 〇〇 40 〇 m 2 /g. As a component of (D), such as: NIPSIL (registered trademark)-LP (trade name, manufactured by Tosoh Sesame Co., Ltd.), tocseal (registered trademark) USA (trade name, company acquired by the company) Zeosil (registered trademark) ) 132 (trade name, manufactured by Rodiajapan) and other examples. Further, these surfaces may be hydrophobized with an organic polyoxane, an organic polyaminated paraffin, a chlorodecane, an alkoxysilane or the like, and may be subjected to an untreated state of wet-type dioxide without hydrophobization. The best is suitable. (D) The components may be used singly or in combination of two or more. The amount of the component (D) to be added is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass per 100 parts by mass of the component (A). If the amount is not more than 1 part by mass, it is difficult to obtain a polyoxyethylene rubber sponge having a sufficient foaming rate. On the other hand, when the amount is more than 20 parts by mass, the processability of the composition is likely to be deteriorated, and the physical properties of the polyoxyxene rubber are lowered. -16- 200813137 - Other Ingredients - The polyoxyethylene rubber sponge of the present invention can also be made of conductive sponge by adding a conductive material. The type and amount of the conductive material are not limited. Generally, as the conductive material, conductive carbon black or conductive metal oxide fine particles such as conductive zinc oxide or conductive oxide can be used. The conductive material may be used singly or in combination of two or more. Carbon is a barrier substance for cross-linking through organic peroxides. Therefore, when conductive carbon black is added to a polyoxo rubber composition containing an organic peroxide, the amount of organic peroxide is increased, or the aforementioned high-temperature type is added. As a hardener, it is also a combination of an organic hydrogenated polyoxyalkylene oxide and a hydroquinone alkylation catalyst and an organic peroxide. It is generally used as a conductive carbon black. Generally, it is generally used for a conductive rubber composition. Such as: acetylene black, conductive furnace black (CF), superconducting furnace black (SCF), ultra-high conductive furnace black (XCF), conductive channel method carbon black (CC), and 1 5 00~3 0 0 °C Examples of furnace black or channel black which are heat-treated at a high temperature. Specific examples of the acetylene black are, for example, Dencabla Ck (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.), and Shernigen acetylene black (trade name, manufactured by Shernigan Chemical Co., Ltd.). Specific examples of the conductive furnace black are, for example, Continex CF (trade name, manufactured by Continentalcarbon Co., Ltd.), barean C (trade name, manufactured by Cabot Co., Ltd.), and the like. Specific examples of the superconducting furnace black include continex SCF (trade name 'Eurocarbon Co., Ltd.) and parkan SC (trade name, manufactured by Cabot Co., Ltd.). As a specific example of the ultra-high conductive furnace black, examples include: Asahi HS-500 (trade name, manufactured by Asahi Co., Ltd.), and baircan XC-72 (trade name, manufactured by Cabot Corporation). As a specific example of the conductive groove method carbon black as -17-200813137, for example, corlax L (trade name, manufactured by Degoosa Co., Ltd.) and the like. Further, kechenblack (registered trademark) EC and kechenblack EC-600 JD (combined product name, manufactured by Kec hen black International Co., Ltd.), which is a type of furnace black, may be used. The amount of impurities in the furnace black, particularly the amount of sulfur and sulfur compounds, is converted to a sulfur element, and is preferably 6000 ppm or less on a mass basis, preferably 3 000 ppm or less. Further, among these, acetylene black has a low impurity content and a secondary structure which grows, so it has good conductivity and is particularly suitable for use in the present invention. Further, it has a large specific surface area, and therefore, kechenblack EC, kechenblack EC-600JD, etc., which exhibit good conductivity even at low charge, can be used. The amount of the conductive carbon black to be added is preferably 1 to 1 part by mass, more preferably 5 to 50 parts by mass, per 1 part by mass of the (A) component polyoxyxene rubber substrate. good. When the amount of the addition is in this range, the desired conductivity is easily obtained, the composition is easily physically mixed, and a rubber elastic having sufficient mechanical strength and purpose is easily obtained. Examples of the conductive metal oxide fine particles include conductive zinc oxide, titanium oxide (e.g., white conductive titanium oxide), and tin antimony oxide fine particles. Specific examples of the conductive zinc oxide include zinc oxide 23-K (trade name) manufactured by Haxitec Co., Ltd., and conductive zinc oxide FX (trade name) manufactured by Honda Chemical Co., Ltd. As an example of the white conductive titanium oxide, an example of ET-500W (trade name, Ishihara Industry Co., Ltd.) is used. The conductive metal oxide fine particles may be used singly or in two types from -18 to 200813137. Further, conductive metal oxide fine particles and conductive carbon black may be used. The amount of the conductive metal oxide fine particles added is preferably 1 to 3 parts by mass, more preferably 1 to 100 parts by mass per 1 part by mass of the poly (A) rubber base material of the above (A) component. Share. When the amount of addition is in this range, the desired conductivity is easily obtained. The polyoxyxene rubber composition of the present invention may further contain pulverized quartz, zinc oxide, aluminum oxide, or diatomaceous earth made of non-reinforcing cerium oxide as alumina, if necessary, as a heat conductivity imparting agent. Adding a filler such as calcium carbonate or the like, a coloring agent, a heat-resistant enhancer, a flame retardant enhancer, an acid acceptor, an additive for a heat transfer enhancer, a mold release agent, an alkoxydecane, a diphenyldecanediol, and a carbon function A dispersing agent such as a decane, a two-terminal sterol-encapsulated low molecular siloxane or the like. -Manufacturing method - The method for producing the rubber composition of the present invention is not particularly limited, and generally, the above components can be obtained by kneading by two rolls, a kneader, a twinkling mixer or the like. Further, heat treatment (mixing under heating) may be carried out if necessary. Specifically, after the component (A) and other components are kneaded and heat-treated, a base rubber mixture (polyoxyethylene rubber substrate of the component (A)) is obtained, and then, after cooling, in the base rubber mixture. Examples of methods for adding (B), (C), and (D) components. The temperature and time of the above heat treatment are not particularly limited, and are generally performed at a temperature of from 1 Torr to 250 ° C, preferably from 150 ° C to 200 ° C, for 30 minutes to 5 hours. 200813137 - Foaming hardening method - In order to improve the foaming rate of the sponge unit, the hardening foaming method of the rubber composition of the present invention is preferably vulcanized by atmospheric pressure hot gas, continuously vulcanized by means of extrusion through a heating furnace, via a batch dryer The hot gas cross-linking, etc. are applicable. Mold vulcanization is also available when sufficient space is ensured inside the mold. Generally, at 80 to 400 ° C, particularly at a temperature of 100 to 300 ° C, atmospheric pressure hot gas vulcanization is carried out for 5 seconds to 1 hour, and after foaming and hardening, a high foaming rate sponge can be obtained. Further, it may be treated at 100 to 230 ° C, preferably 150 to 230 ° C, for 1 to 10 hours. [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples described below. In addition, the middle part of the following examples represents the mass fraction, and the viscosity is determined by a rotary viscometer. [Example 1] In the kneader, 99.825 mol%, methyl vinyl fluorene oxide unit 0.15 mol%, and dimethyl vinyl fluorene oxide unit 0.025 mol% were placed in a kneader. 100 parts of dry cerium oxide Arosil 200 (trade name, manufactured by Aerozil Co., Ltd.) having an average polymerization degree of about 8,000, 100 parts of organic polyoxane having a PEG surface area of about 200, and a sterol group at both ends. 5 parts of dimethyl polyoxane having a viscosity of 29 m2/g (23 ° C), -20-200813137, heat-kneaded at 180 ° C for 2 hours to prepare a base rubber mixture for 100 parts For the addition of the base rubber mixture, the organic foaming agent dimethyl 1,1'-azobis(1-cyclohexanecarboxylate) (Wako Pure Chemicals Co., Ltd., trade name: VE) -073) 1.5 parts, hardener 2,5-dimethyl-2,5-di-t-butylperoxy hexane (manufactured by Nippon Oil & Fats Co., Ltd.) 〇·8 parts, wet cerium oxide NIPSIL (registered trademark) - 3 parts of LP (trade name, manufactured by Tosoh Sebacillus Co., Ltd.), and mixed with two roll honing machines to obtain a polyoxymethylene rubber composition. After the obtained composition was molded, a sheet having a thickness of 9 mm was formed. The sheet having a thickness of 9 mm was subjected to atmospheric pressure hot air vulcanization under a normal pressure at 230 ° C for 30 minutes, and then a polyoxygenated rubber sponge was obtained. Thereafter, the vulcanization was performed twice at 200 ° C for 4 hours. After the surface layer was removed from the sponge, the sponge hardness, expansion ratio, average unit diameter, and continuous foaming rate of the sponge characteristics were measured as follows. The results are shown in Table 1. • Sponge hardness: measured according to JIS S6050, measured by ASCA C rubber hardness tester. • Foaming ratio: volume after foaming/volume before foaming xl 00 (%). • Average unit diameter (μιη): The average 値 of the unit diameter of the sponge shear plane. • Foaming rate: determined as follows. 1) The specific gravity of the polyfluorene rubber composition of the sponge material, that is, the unfoamed rubber material. 2) Determine the specific gravity and weight of the sponge. -21 - 200813137 3) The sponge is infiltrated into water in a container placed in a vacuum vessel, and in this state, the pressure inside the vacuum vessel is reduced to 10 mmHg or less. 4) After returning the inside of the vacuum vessel to normal pressure, the sponge is allowed to absorb water for 5 minutes. 5) Measure the weight of the sponge under water absorption. Then calculate the continuous foaming rate according to the following calculation. [(weight of sponge after water absorption under reduced pressure - weight of initial sponge) / specific gravity of water (1.00)] / [(1 - (specific gravity of sponge / weight of unfoamed rubber material)) x (weight of sponge / The following is the same as the first embodiment except that the wet ceria is changed to Zeosil (registered trademark) 132 (trade name, manufactured by Lodiajapan Co., Ltd.). The method of forming a polyoxyethylene rubber sponge is carried out to detect the characteristics of the above sponge. The results are shown in the table. [Example 3] A polyoxygenated rubber sponge was produced in the same manner as in Example 1 except that the wet cerium oxide was changed to a tocseal (registered trademark) USA (trade name, manufactured by Toyama Co., Ltd.). Forming and detecting the above characteristics of the sponge. The results are shown in Table 1. [Example 4] -22· 200813137 2,5·dimethyl-2,5-di-tertiary-butyl group substituted with hardening agent (organic peroxide) of 1.0 part of dicumyl peroxide The polysiloxane rubber sponge was formed in the same manner as in Example 1 except that 0.8 part of oxyhexane was used, and the characteristics of the above sponge were examined. The results are shown in Table 1. [Comparative Example 1] 3 parts of dry cerium oxide NIPSIL-LP (trade name, manufactured by Tosoh Sesame Co., Ltd.) was replaced with 3 parts of dry cerium oxide Arosil 200 (trade name, manufactured by Aerozil Co., Ltd.). In the same manner as in Example 1, the formation of the polyoxyethylene rubber sponge was carried out, and the characteristics of the above sponge were examined. The results are shown in Table 1. [Comparative Example 2] The formation of the polyoxyxene rubber sponge was carried out in the same manner as in Example 1 except that the wet cerium oxide NIPSIL-LP (trade name, manufactured by Tosoh Sesame Co., Ltd.) was not added. The characteristics of cotton. The results are shown in Table 1. Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Sponge characteristic hardness (Asca-C) 25 26 25 26 40 29 Expansion ratio (%) 220 230 230 240 220 200 Element diameter (μιη) 150 150 150 200 100 200 Continuous foaming rate (%) 95 90 95 75 4 8 -23-