200940630 九、發明說明 【發明所屬之技術領域】 本發明係關於可獲得押出加工性及機械特性優異之硫 化物之聚氯丁二烯彈性體組成物。 【先前技術】 聚氯丁二烯彈性體之機械特性、耐熱性、耐臭氧性、 φ 耐寒性、難燃性等優異，已被廣泛使用作爲工業用橡膠零 件用等之材料。對該等工業用橡膠零件之要求性能正顯著 提高，例如要求有可維持其特性同時又要求耐熱性、耐寒 性優異之製品。尤其，雨刷、汽車蛇管（ho se )、建築用 密封墊片、電纜等藉由押出成形獲得之製品由於在屋外使 用故會有冬天結晶化而使其機械強度降低之問題，因此期 望耐結晶性優異之氯丁二烯橡膠。另外，爲了降低於該等 用途之押出時之製造成本，因此期望押出性優異之氯丁二 〇 烯橡膠。 再者，氯丁二烯橡膠爲容易因機械剪斷力切斷分子鏈 使橡膠特性下降者，因而期望押出加工性優異之氯丁二烯 橡膠。 至於改善氯丁二烯橡膠耐結晶性之方法，已提出在氯 丁二烯橡膠中共聚合2,3·二氯-1,3-丁二烯之方法（例如， 參照專利文獻1)。又，改善押出加工性之方法已提出於 氯丁二烯橡膠中混合凝膠聚合物之方法（例如，參照專利 文獻2)。又，已提出藉由控制凝膠聚合物之甲苯膨潤度 -5- 200940630 範圍’以改善拉伸強度及押出加工性之均衡性之方法（例 如，參照專利文獻3)。 [專利文獻1 ]特開昭5 9 - 7 1 3 1 9 [專利文獻2]特開昭49-22444 [專利文獻3]特開2005-220190 容 內 明 發 [發明欲解決之課題] 本發明之目的係提供一種押出加工性及機械特性優異 之聚氯丁二烯彈性體組成物，另外亦提供該組成物之硫化 物。 [用以解決課題之方法] 本發明人等對於欲解決之上述課題積極檢討之結果， 發現混合聚氯丁二烯溶膠（A)與聚氯丁二烯凝膠（B)而 成之聚氯丁二烯彈性體組成物中，藉由使用以特定方法獲 得之聚氯丁二烯凝膠（B)可解決上述課題，因而完成本 發明。 亦即，本發明之主旨爲使聚氯丁二烯溶膠（A)與聚 氯丁二烯凝膠（B)以（A)與（B)之質量混合比率（（ A) / (B))爲3 0/7 0〜8 0/2 0之範圍混合而得之聚氯丁二 烯彈性體組成物。 聚氯丁二烯溶膠（A):係在〇.〇2〜3質量份分子量調 整劑存在下使1〇〇質量份2-氯-1，3-丁二烯與1〜1〇質量份 -6- 200940630 2,3 -二氯-1，3 -丁二烯混合而成之100質量份單體乳化聚合 時，將該等化合物全部一次投入聚合裝置內，經乳化聚合 而獲得之聚氯丁二烯溶膠。 聚氯丁二烯凝膠（B):使100質量份之2-氯-1,3-丁 二烯與1~4 5質量份之2,3-二氯-1,3-丁二烯混合而成之 1〇〇質量份單體與0.5〜2 5質量份之分子內具有2個或3個 以上之乙烯基之多官能性單體乳化聚合時，將2-氯-1，3-丁 φ 二烯及2,3-二氯·1，3-丁二烯之全部添加量中之5〜80質量 %投入聚合裝置內開始聚合，於聚合開始後使冷卻至比聚 合溫度低之溫度之剩餘2 -氯-1,3 -丁二烯及2,3 -二氯-1,3-丁二烯添加於聚合裝置內，經乳化聚合而獲得之聚氯丁二 烯凝膠。 此處，聚氯丁二烯凝膠（Β)較好爲自全部單體之轉 化率到達10〜70%之前之聚合時點到聚合結束之轉化率之 期間，將剩餘之2-氯-1,3-丁二烯及2,3-二氯-1，3-丁二烯 φ 添加於聚合裝置內而進行乳化聚合者。 又’聚氯丁二烯凝膠（Β)較好爲在乳化聚合時，進 而添加〇〜3質量份之分子量調整劑所得者。分子量調整劑 之添加較好係將全部添加量之5~80質量％投入聚合裝置內 開始聚合，且在聚合開始後將冷卻至低於聚合溫度之溫度 之剩餘之分子量調整劑添加於聚合裝置中。 上述多官能性單體較好係選自三涇甲基丙烷三甲基丙 烯酸酯及乙二醇二甲基丙烯酸酯之至少一種。 所得聚氯丁二烯彈性體組成物之慕尼（m〇oney)黏度 200940630 以40~1 10較佳。 所得聚氯丁二烯彈性體組成物可經硫化而成爲硫化物 〇 聚氯丁二烯彈性體組成物及該組成物之硫化物經押出 成形，可利用作爲雨刷材或蛇管材、建築用密封墊片材、 電纜材。 [發明效果] 藉由本發明可獲得押出加工性及機械特性優異之聚氯 丁二烯彈性體組成物，該聚氯丁二烯彈性體組成物經硫化 、押出成形，可利用作爲雨刷材、蛇管材、建築密封墊片 材、電纜材等。 【實施方式】 本發明之聚氯丁二烯溶膠（A)爲在分子量調整劑存 在下，使用聚合起始劑使2-氯-1，3-丁二烯與2,3-二氯-1，3-丁二烯乳化聚合獲得者。 2.3- 二氯-1,3-丁二烯爲用於提高所得聚氯丁二烯彈性 體組成物之耐結晶性者。 2.3- 二氯-1，3-丁二烯之添加量相對於100質量份之2- 氯-1,3-丁二烯爲1〜10質量份，較好爲3〜7質量份之範圍 〇 若2,3-二氯-1,3-丁二烯之添加量未達1質量份，則無 法提高所得聚氯丁二烯彈性體組成物之耐結晶性，而成爲 -8- 200940630 冬天機械強度降低之原因。 若調配量超過1 〇質量份，則成爲所得聚氯丁二烯彈 性體組成物之拉伸強度等之機械特性降低之原因。 分子量調整劑爲用於調整單體彼此之聚合速度者，雖 無特別限制，但可使用例如脂肪族硫醇或二烷基黃原酸二 硫醚化合物。 至於脂肪族硫醇舉例有正十二烷基硫醇、第三-十二 Φ 烷基硫醇、正辛基硫醇等，而二烷基黃原酸二硫醚化合物 舉例有二乙基黃原酸二硫醚或二異丙基黃原酸二硫醚、二 丁基黃原酸二硫醚等。 分子量調整劑之添加量相對於1 〇〇質量份之經聚合全 部單體爲0.02〜3質量份，且就進一步提高押出加工性及 機械物性之觀點而言較好爲〇.〇2~2質量份。 若分子量調整劑之添加量未達0.02質量份，則無法 調整單體之聚合速度，使所得聚氯丁二烯溶膠（A)之最 φ 終轉化率變大。 若添加量超過3質量份，則成爲阻礙單體聚合之原因 ，使所得聚氯丁二烯溶膠（A )之最終轉化率變小。 爲了對所得聚氯丁二烯彈性體組成物賦予額外各種特 性，聚氯丁二烯溶膠（A)可與可共聚合之其他單體共聚 合。 其他可共聚合之單體雖無特別限制，但可爲例如1 _ 氯-1，3-丁二烯、硫、苯乙烯、丙烯腈、甲基丙烯腈、異戊 間二烯、丁二烯及丙烯酸、甲基丙基酸及該等之酯類等。 -9 - 200940630 該等單體之添加量較好在20質量份以下，更好爲15 質量份以下。藉由在該範圍內，可不阻礙所得聚氯丁二烯 彈性體之特性而可賦予各種特性。 本發明之聚氯丁二烯凝膠（B)爲在特定之條件下使 用聚合起始劑，使2-氯-1,3-丁二烯、2,3-二氯-1，3-丁二烯 及分子內具有兩個或三個以上乙烯基之多官能性單體乳化 聚合獲得者。 2.3- 二氯-1，3-丁二烯爲用於提高所得聚氯丁二烯彈性 體組成物之耐結晶性者。 2.3- 二氯-1,3-丁二烯之添加量相對於100質量份之2- 氯-1,3-丁二烯爲1〜4 5質量份，較好在2〜15質量份之範圍 〇 若2，3-二氯-1,3-丁二烯之添加量未達1質量份，則無 法提高所得聚氯丁二烯彈性體組成物之耐結晶性，而成爲 冬天時機械強度降低之原因。 若添加量超過45質量份，則成爲所得聚氯丁二烯彈 性體組成物之拉伸強度等之機械特性降低之原因。 分子內具有兩個或三個以上乙烯基之多官能性單體係 用於調整聚氯丁二烯凝膠（B)之凝膠化度者。 分子內具有兩個乙烯基之多官能性單體並無特別限制 ，但可舉例爲乙二醇二甲基丙烯酸酯（以下稱爲EDM A ) 、三亞甲基二醇二甲基丙烯酸酯、四亞甲基二醇二甲基丙 烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯 酸酯、四乙二醇二甲基丙烯酸酯等。 -10- 200940630 分子內含有兩個乙烯基之多官能性單體之添加量相對 於使1〇〇質量份之2-氯-1,3-丁二烯及1〜45質量份之2,3-二氯·1，3-丁二烯混合而成之單體100質量份，爲〇.5〜25 質量份，且就進一步提高押出加工性及機械物性之觀點而 言，更好爲3~8質量份。 若多官能性單體之添加量未達0.5質量份，則由於所 得聚氯丁二烯凝膠無法充分凝膠化，因此無法提高所得聚 0 氯丁二烯彈性體組成物之押出加工性。 又，若添加超過25質量份之多官能性單體，則聚氯 丁二烯凝膠最後會凝膠化至超過所需，使所得聚氯丁二烯 彈性體組成物之機械強度降低。 含有三個乙烯基之多官能性單體並無特別限制，但可 舉例爲三羥甲基丙烷三甲基丙烯酸酯（以下稱爲ΤΜΡ)、 三羥甲基甲烷三甲基丙烯酸酯、三羥甲基乙烷三甲基丙烯 酸酯、三羥甲基羥基乙烷三甲基丙烯酸酯等三甲基丙烯酸 〇 酯衍生物，三甲基羥基乙烷三甲基丙烯酸酯、三甲基丙烯 基磷酸酯、三烯丙基異氰酸酯、1，3,5-三甲基丙烯酸酯基 苯等。 含有三個乙烯基之多官能性單體之添加量相對於使 1〇〇質量份之2-氯-1，3-丁二烯及1〜45質量份之2,3-二氯-1,3-丁二烯混合而成之單體100質量份，爲〇.5〜25質量份 ，且就進一步提高押出加工性及機械物性之觀點而言，更 好爲1〜5質量份。 若多官能性單體之添加量未達〇 · 5質量份，則由於所 -11 - 200940630 得聚氯丁二烯凝膠無法充分凝膠化，因此無法提高所得聚 氯丁二烯彈性體組成物之押出加工性。 另外，若添加超過25質量份之多官能性單體，則聚 氯丁二烯凝膠最後會凝膠化至超過所需，使所得聚氯丁二 烯彈性體組成物之機械強度降低。 該等多官能性單體可與該乙烯基數無關地倂用。當倂 用時，其合計之添加量相對於使100質量份之2-氯-1，3-丁 二烯及1~45質量份之2,3-二氯-1,3-丁二烯混合而成之單 體1〇〇質量份，以0.5〜25質量份較適當。 又，聚氯乙烯凝膠（B)較好爲在乳化聚合時進而添 加分子量調整劑所獲得者。 分子量調整劑爲輔助性使用於調整單體彼此之聚合速 度者，雖無特別限制，但可使用例如脂肪族硫醇或二烷基 黃原酸二硫醚化合物。 至於脂肪族硫醇舉例爲正十二烷基硫醇、第三-十二 烷基硫醇、正辛基硫醇等。至於二烷基黃原酸二硫醚化合 物舉例爲二乙基黃原酸二硫醚、二異丙基黃原酸二硫醚、 二丁基黃原酸二硫醚等。 分子量調整劑之添加量相對於1 〇〇質量份之經聚合全 部單體以0~3質量份較佳，且就提高押出加工性及機械物 性之觀點而言較好爲〇·02〜2質量份。 爲了對所得聚氯丁二烯彈性體組成物賦予額外各種特 性，聚氯丁二烯凝膠（B)可與其它可共聚合之單體共聚 合。 -12- 200940630 其他可共聚合之單體雖無特別限制，但可爲例如1 -氯-1，3-丁二烯、硫、苯乙烯、丙烯腈、甲基丙烯腈、異戊 間二烯、丁二烯及丙烯酸、甲基丙基酸及該等之酯類等。 該等單體之添加量較好在20質量份以下，更好爲15 質量份以下。藉由在該範圍內，可在不阻礙所得聚氯丁二 烯彈性體之特性下賦予各種特性。 聚氯丁二烯凝膠（B)之獲得，較好係將2-氯-1，3-丁 二烯及2,3-二氯-1,3-丁二烯之全部添加量之5~80質量％ 與多官能性單體及分子量調整劑之全部添加量投入聚合裝 置內開始聚合，且於開始聚合後於聚合裝置內後添加經冷 卻至比聚合溫度低之溫度之剩餘2 -氯-1,3 -丁二烯與2,3 -二 氯-1，3-丁二烯並進行聚合。 又，混合2-氯-1，3· 丁二烯與2,3-二氯-1,3-丁二烯而 得之單體之後添加，並非將剩餘混合單體一次添加，而是 分數次添加，且較好以少量連續添加。 藉由經過該後添加步驟，可提高分子內具有兩個或三 個以上乙烯基之多官能性單體相對於2-氯-1，3-丁二烯與 2,3-二氯-1，3-丁二烯之共聚合率。 據此，可獲得押出加工性獲得提高之聚氯丁二烯彈性 體組成物。 聚氯丁二烯凝膠（Β)亦可自全部單體之轉化率到達 10~70%之時點到聚合結束之轉化率之前之期間，將剩餘之 2-氯-1,3-丁二烯及2,3-二氯-1,3-丁二烯添加於聚合裝置內 進行聚合。 -13- 200940630 據此，可提高分子內具有兩個或三個以上乙烯基之多 官能性單體相對於2-氯-1，3-丁二烯與2,3-二氯-1,3-丁二 烯之共聚合率。 分子量調整劑之添加可在初期添加其總添加量之 5~80質量％開始聚合，且在聚合開始後將剩餘之分子量調 整劑後添加於聚合裝置內。 據此，可提高分子內具有兩個或三個以上乙烯基之多 官能性單體相對於2-氯-1，3-丁二烯與2,3-二氯-1，3-丁二 烯之共聚合率。 聚氯丁二烯凝膠（B)之凝膠分率以5〇~1 00%較佳， 且更好爲70~95%。藉由限制在該範圍內，得以獲得可獲 得押出加工性及機械特性優異之硫化物之聚氯丁二烯彈性 體。 2-氯-1,3-丁二烯與2,3-二氯-1，3-丁二烯通常係冷卻保 存以防止儲存中之聚合。該等單體之溫度較好在-120〜0°C 下添加於聚合裝置內。就經濟之觀點而言更好爲-20〜0°C。 聚氯丁二烯溶膠（A)及聚氯丁二烯凝膠（B)之聚合 溫度較好在20°C以上55°C以下之範圍，且更好爲30°C以上 5(TC以下。 聚氯丁二烯溶膠（A)及聚氯丁二烯凝膠（B)之聚合 起始劑係使用氯丁二烯之乳化聚合中常用之習知過硫酸鉀 、過硫酸銨、過硫酸鈉、過氧化氫、第三丁基過氧化氫等 有機過氧化物類。 聚合起始劑之使用量相對於1 00質量份之經聚合全部 -14- 200940630 單體爲0.01〜1質量份，較好爲0.05〜0.5質量份。 聚氯丁二烯溶膠（A)之聚合最終轉化率較好爲 4 0〜95%，更好爲50〜80%，聚氯丁二烯凝膠（B)之聚合 最終轉化率較好爲80%以上，更好爲85%以上。用以調整 最終轉化率，較好在成爲所需轉化率時，添加使聚合反應 停止之聚合抑制劑使聚合停止。 聚合抑制劑可使用慣用之抑制劑，雖無特別限制，但 0 有例如硫二苯基胺、4-第三丁基兒茶酚、2,2-亞甲基雙-4· 甲基-6-第三丁基酚等。 聚合反應中未反應單體係藉由例如蒸氣氣提法去除， 隨後添加過去習知之pH調整劑將乳膠之pH調整成 5.5〜7.5。 混合聚氯丁二烯溶膠（A)及聚氯丁二烯凝膠（B)可 對每100質量份之全部聚合物固成分，以（A)與（B)之 聚合物固成分中之質量混合比率（（A) / (B))爲 〇 30/70-80/20，較好爲40/60~70/30之比例，使二者以乳膠 狀態混合，且藉由常用之冷凍凝固、水洗、熱風乾燥等使 聚合物單離，獲得慕尼黏度40〜110，較好45〜80之聚氯 丁二烯彈性體組成物。若聚氯丁二烯溶膠（A)之比例超 過8 0質量％，則押出加工性劣化，且若未達3 0質量％， 則機械特性不足。因此，使所得之聚氯丁二烯彈性體組成 物難以押出成形加工成雨刷、汽車蛇管、建築用密封墊片 、電纜等製品。 又’聚氯丁二烯彈性體組成物之慕尼黏度未達40其 -15- 200940630 機械強度差，no以上則押出加工性差。 聚氯丁二烯彈性體組成物中亦可依據需要含有天然橡 膠、丁基橡膠、BR、NBR、EPDM等。 聚氯丁二烯彈性體組成物可添加以往氯丁二烯橡膠中 使用之硫化劑或硫化促進劑，於硫化溫度以下之溫度混練 後，成形成爲所需之各種形狀後，經硫化成爲硫化物。 又，亦可在成形前硫化，隨後成形成各種形狀。 硫化溫度可依據聚氯丁二烯彈性體組成物之添加比例 及硫化劑之種類適當設定，且通常較好在140〜190 °C，更 好在150〜180°C之範圍。 至於硫化劑可使用鈹、鎂、鋅、鈣、鋇、鍺、鈦、錫 、鉻、銻、釩、鉍、鉬、鎢、碲、硒、鐵、鎳、鈷、餓等 金屬單體，該等金屬之氧化物或該等金屬之氫氧化物。該 等金屬化合物中，氧化鈣、氧化鋅、二氧化銻、三氧化銻 、氧化鎂因硫化效果高故較佳。該等亦可兩種以上倂用。 將本發明之聚氯丁二烯彈性體組成物混練、成形、硫 化之裝置，以及將聚氯化丁二烯彈性體組成物之硫化物混 練、成形之裝置可使用一般橡膠工業中使用者。 本發明之聚氯丁二烯彈性體組成物可在供給於實用時 依據其目的添加軟化劑、塡充劑、補強劑、可塑劑、加工 助劑、潤滑劑、抗老化劑、安定劑、矽烷偶合劑等進行成 形、硫化。 塡充劑及補強劑可添加一般橡膠用途中使用之塡充劑 '補強劑等，有例如碳黑、氧化矽、灰石、滑石、碳酸鈣 -16- 200940630 等塡充劑，及補強劑。 該等塡充劑及補強劑之添加量其合計係相對於1 00質 量份之聚氯丁二烯彈性體組成物，較好爲30~100質量份 ，更好爲40〜70質量份。 至於可塑劑可添加一般橡膠用途所用之可塑劑，例如 苯二甲酸二辛酯、己二酸二辛酯等。 可塑劑之添加量相對於1 〇〇質量份之橡膠組成物以50 φ 質量份以下左右之範圍較佳，更好爲30質量份以下。 抗老化劑可添加一般橡膠用途中使用之抗老化劑，舉 例爲胺系抗老化劑、咪唑系抗老化劑、胺基甲酸金屬鹽、 酚系抗老化劑、蠟等，該等不限於單獨使用，亦可倂用。 至於耐熱性之改良效果大之抗老化劑種類舉例爲胺系抗老 化劑之4’-雙（α，α-二甲基苄基）二苯基胺、辛基化二苯基 胺等。 至於軟化劑可添加一般橡膠用途中使用之軟化劑，舉 φ 例爲潤滑油、處理油（Process Oil )、鏈烷、液體鏈烷、 凡士林、石油瀝青等石油系軟化劑、石油腦油、亞麻仁油 、蓖麻油、椰子油等植物系軟化劑。 [實施例] 以下，藉由本發明之實施例詳細說明，但本發明並不 解釋爲限定於該等。 <聚氯丁二烯溶膠（A)之調製> -17- 200940630 於內容積5升之4 口燒瓶中饋入130質量份純水、4 質量份之松脂酸鉀鹽、〇·5質量份之β·萘磺酸福馬林、94 質量份之2-氯-1，3-丁二烯、4質量份之2,3-二氯-1，3-丁二 烯、0.3質量份之正十二烷基硫醇及其他化學品後’以〇·1 質量份之過硫酸鉀作爲起使劑，在35 °C下及氮氣流中進行 聚合1 0小時。單體之轉化率達到6 3 %時，添加硫二苯基 胺停止聚合。接著，以蒸氣氣提法去除未反應之單體’獲 得聚氯丁二烯溶膠（A)之乳膠。 <聚氯丁二烯凝膠（B)之調製> 於內容積5升之四口燒瓶中饋入130質量份純水、5 質量份之松脂鉀鹽以及0.5質量份之β-萘磺酸福馬林，接 著依據表1中所述之聚合配方、聚合條件饋入單體及其他 化學品，以〇 . 1質量份之過硫酸鉀作爲起使劑，在3 5 t下 及氮氣流中進行聚合1 〇小時。單體之轉化率達到95 %時 ，添加硫二苯基胺停止聚合。接著，以蒸氣氣提法去除未 反應之單體，獲得聚氯丁二烯凝膠（B)之乳膠。 <聚氯丁二烯彈性體組成物之製作> 以表1及表2中所示之比例混合所得之聚氯丁二烯溶 膠（A)之乳膠及聚氯丁二烯凝膠（B)之乳膠，隨後，以 冷凍凝固乾燥法獲得聚氯丁二烯彈性體組成物。 依據JIS-K6300，測定所得聚氯丁二烯彈性體組成物 在10 0 °C下之慕尼黏度，結果列於表1及表2。 200940630 又，表1、表2中，2_氯-1，3-丁二烯等之添加量爲質 量份，而初期添加單體之比例（初期添加量/全部添加量 )等，以及組成物中之聚氯丁二烯溶膠（A)之量等均以 質量％表示。 <混練> 使用3升捏合機（32rpm，冷卻水溫度30°C )，相對 φ 於1〇〇質量份之所得聚氯丁二烯彈性體組成物，混練0.5 質量份之硬脂酸、1質量份之抗老化劑（大內新興化學工 業公司製造之NOCRAC PA) 、30質量份之SRF碳黑（旭 碳公司製造，#50) 、？？質量份之FEF碳黑（旭碳公司製 造，#60) 、12質量份之石油系處理油（出光興產業公司 製造之DAI ANA處理油）、1.5質量份之石蠟（日本精蠟 公司製造，石蠟130°F) 、1.5質量份之凡士林、以及4 質量份之氧化鎂。隨後，反轉再混練1分鐘並排出。使用 φ 8吋輥將5質量份之氧化鋅及0.5質量份之乙烯硫代尿素 添加於該化合物中，製作厚度2.3 mm之薄片》 <物性試驗> 使用各實施例及各比較例中所得之上述薄片製作測定 慕尼黏度之樣品。慕尼黏度之測定係使用慕尼黏度計，依 據JIS K6300進行。 又，以在160°C下放置30分鐘之條件對該薄片進行壓 製硫化’製作厚2mm之硫化物薄片。硫化物薄片之下列 -19- 200940630 物性試驗係使用3號鐘形片進行。 拉伸物性試驗係依據JIS K625 1，硬度測定係依據JIS K6253進行。 又，永久伸長試驗及永久壓縮試驗係依據JIS K6262 進行。 押出加工性係使用60Φ之押出機，在押出溫度50°C下 ，依據 ASTM D2230-77之 A法，使用格維氏模嘴（ Garvey die)測定押出速度、模嘴膨脹、押出時之吐出壓 力。 針對實施例及比較例之各物性試驗之測定結果一起列 於表1及表2中。另外’表1及表2中，例1~12、18及 19爲實施例’例13〜17及20爲比較例。 -20- 200940630[Technical Field] The present invention relates to a polychloroprene elastomer composition which can obtain a sulfide which is excellent in extrusion workability and mechanical properties. [Prior Art] The polychloroprene elastomer is excellent in mechanical properties, heat resistance, ozone resistance, φ cold resistance, flame retardancy, etc., and is widely used as a material for industrial rubber parts and the like. The required performance of these industrial rubber parts is remarkably improved, and for example, a product which can maintain its characteristics while requiring excellent heat resistance and cold resistance is required. In particular, a product obtained by extrusion molding of a wiper, a car hoist, a building gasket, a cable, etc., which is obtained by extrusion molding, has a problem of lowering mechanical strength due to crystallization in winter, and thus is expected to have crystallinity resistance. Excellent neoprene rubber. Further, in order to reduce the manufacturing cost at the time of extrusion for such applications, a chloroprene rubber excellent in extrudability is desired. Further, the chloroprene rubber is a chloroprene rubber which is excellent in workability because it is easy to cut the molecular chain by mechanical shearing force and to lower the rubber properties. As a method of improving the crystallinity of the chloroprene rubber, a method of copolymerizing 2,3·dichloro-1,3-butadiene in a chloroprene rubber has been proposed (for example, refer to Patent Document 1). Further, a method of improving the workability of extrusion has been proposed as a method of mixing a gel polymer in a chloroprene rubber (for example, refer to Patent Document 2). Further, a method of improving the balance between tensile strength and extrusion workability by controlling the range of toluene swelling of the gel polymer -5 - 200940630 has been proposed (for example, refer to Patent Document 3). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei- No. Sho 59-23444 [Patent Document 2] JP-A-2005-220190 The object of the present invention is to provide a polychloroprene elastomer composition which is excellent in workability and mechanical properties, and a sulfide of the composition. [Means for Solving the Problems] As a result of a positive review of the above-mentioned problems to be solved, the present inventors have found that polychlorinated polychloroprene sol (A) and polychloroprene gel (B) are mixed. The above problem can be solved by using a polychloroprene gel (B) obtained by a specific method in a butadiene elastomer composition, and thus the present invention has been completed. That is, the gist of the present invention is to make the polychloroprene sol (A) and the polychloroprene gel (B) have a mass mixing ratio of (A) and (B) ((A) / (B)) A polychloroprene elastomer composition obtained by mixing in the range of 3 0/7 0 to 8 0/2 0. Polychloroprene sol (A): 1 part by mass of 2-chloro-1,3-butadiene and 1 to 1 part by mass in the presence of 2 to 3 parts by mass of a molecular weight modifier. 6- 200940630 When 100 parts by mass of 2,3-dichloro-1,3-butadiene is mixed and emulsion-polymerized, the compounds are all put into the polymerization apparatus once and the polychloroprene obtained by emulsion polymerization is obtained. Diene sol. Polychloroprene gel (B): 100 parts by mass of 2-chloro-1,3-butadiene is mixed with 1 to 45 parts by mass of 2,3-dichloro-1,3-butadiene 2-chloro-1,3-pyrene is formed by emulsion polymerization of 1 to 5 parts by mass of a monomer and 0.5 to 2 parts by mass of a polyfunctional monomer having 2 or more vinyl groups in a molecule. 5 to 80% by mass of the total addition amount of φ diene and 2,3-dichloro-1,3-butadiene is introduced into the polymerization apparatus to start polymerization, and after cooling starts, it is cooled to a temperature lower than the polymerization temperature. The remaining 2-chloro-1,3-butadiene and 2,3-dichloro-1,3-butadiene were added to a polymerization apparatus to obtain a polychloroprene gel obtained by emulsion polymerization. Here, the polychloroprene gel (Β) is preferably a period from the polymerization point to the end of the polymerization before the conversion of all the monomers reaches 10 to 70%, and the remaining 2-chloro-1, 3-butadiene and 2,3-dichloro-1,3-butadiene φ are added to a polymerization apparatus to carry out emulsion polymerization. Further, the polychloroprene gel (Β) is preferably obtained by adding 〇3 parts by mass of a molecular weight modifier to the emulsion polymerization. The addition of the molecular weight modifier is preferably carried out by adding 5 to 80% by mass of the total amount of the addition to the polymerization apparatus to start polymerization, and adding the remaining molecular weight regulator cooled to a temperature lower than the polymerization temperature after the start of the polymerization to the polymerization apparatus. . The above polyfunctional monomer is preferably at least one selected from the group consisting of trimethylolpropane trimethyl acrylate and ethylene glycol dimethacrylate. The m〇oney viscosity of the obtained polychloroprene elastomer composition is preferably 40 to 110. The obtained polychloroprene elastomer composition can be vulcanized to form a sulfide lanthanum polychloroprene elastomer composition and a sulfide of the composition is formed by extrusion, and can be used as a wiper or snake tube, and a construction seal. Gasket and cable. [Effect of the Invention] According to the present invention, a polychloroprene elastomer composition excellent in extrusion workability and mechanical properties can be obtained, and the polychloroprene elastomer composition is vulcanized and extruded, and can be used as a wiper material, a snake. Pipe, building gaskets, cable materials, etc. [Embodiment] The polychloroprene sol (A) of the present invention is a 2-methyl-1,3-butadiene and 2,3-dichloro-1 using a polymerization initiator in the presence of a molecular weight modifier. , 3-butadiene emulsion polymerization winner. 2.3-Dichloro-1,3-butadiene is used to increase the crystallinity of the resulting polychloroprene elastomer composition. 2.3-Dichloro-1,3-butadiene is added in an amount of from 1 to 10 parts by mass, preferably from 3 to 7 parts by mass, per 100 parts by mass of 2-chloro-1,3-butadiene. When the amount of 2,3-dichloro-1,3-butadiene added is less than 1 part by mass, the crystallinity of the obtained polychloroprene elastomer composition cannot be improved, and it becomes -8-200940630 winter machine. The reason for the decrease in strength. When the amount is more than 1 part by mass, the mechanical properties such as tensile strength of the obtained polychloroprene elastomer composition are lowered. The molecular weight modifier is used for adjusting the polymerization rate of the monomers, and is not particularly limited, and for example, an aliphatic thiol or a dialkyl xanthogen disulfide compound can be used. As the aliphatic mercaptan, n-dodecyl mercaptan, third-twelf Φ alkyl mercaptan, n-octyl mercaptan, and the like are exemplified, and dialkyl xanthogen disulfide compound is exemplified by diethyl yellow. Raw acid disulfide or diisopropyl xanthogen disulfide, dibutyl xanthogen disulfide, and the like. The amount of the molecular weight modifier added is 0.02 to 3 parts by mass based on 1 part by mass of the total of the monomers to be polymerized, and is preferably 〇. 2 to 2 in terms of further improving the workability and mechanical properties of the extrusion. Share. When the amount of the molecular weight modifier added is less than 0.02 parts by mass, the polymerization rate of the monomer cannot be adjusted, and the final φ final conversion ratio of the obtained polychloroprene sol (A) is increased. When the amount is more than 3 parts by mass, the polymerization of the monomer is inhibited, and the final conversion ratio of the obtained polychloroprene sol (A) is made small. In order to impart additional various characteristics to the obtained polychloroprene elastomer composition, the polychloroprene sol (A) may be copolymerized with other monomers copolymerizable. The other copolymerizable monomer is not particularly limited, but may be, for example, 1 - chloro-1,3-butadiene, sulfur, styrene, acrylonitrile, methacrylonitrile, isoprene, butadiene. And acrylic acid, methyl propyl acid and the like. -9 - 200940630 The amount of the monomers added is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. Within this range, various properties can be imparted without hindering the properties of the obtained polychloroprene elastomer. The polychloroprene gel (B) of the present invention is a polymerization initiator which is used under specific conditions to give 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butyl An epoxy polymer obtained from a diene and a polyfunctional monomer having two or more vinyl groups in the molecule. 2.3-Dichloro-1,3-butadiene is used to increase the crystallinity of the resulting polychloroprene elastomer composition. 2.3-Dichloro-1,3-butadiene is added in an amount of from 1 to 4 parts by mass, preferably from 2 to 15 parts by mass, per 100 parts by mass of 2-chloro-1,3-butadiene. When the amount of 2,3-dichloro-1,3-butadiene added is less than 1 part by mass, the crystallinity of the obtained polychloroprene elastomer composition cannot be improved, and the mechanical strength is lowered in winter. The reason. When the amount is more than 45 parts by mass, the mechanical properties such as tensile strength of the obtained polychloroprene elastomer composition are lowered. A polyfunctional single system having two or more vinyl groups in the molecule is used to adjust the degree of gelation of the polychloroprene gel (B). The polyfunctional monomer having two vinyl groups in the molecule is not particularly limited, but may, for example, be ethylene glycol dimethacrylate (hereinafter referred to as EDM A ), trimethylene glycol dimethacrylate, or four. Methylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and the like. -10- 200940630 The amount of the polyfunctional monomer containing two vinyl groups in the molecule is 2,3 parts by mass relative to 2 parts by mass of 2-chloro-1,3-butadiene and 1 to 45 parts by mass. 100 parts by mass of a monomer obtained by mixing dichloro-1,3-butadiene, which is 〇5 to 25 parts by mass, and more preferably 3 to the viewpoint of further improving the workability and mechanical properties of the extrusion. 8 parts by mass. When the amount of the polyfunctional monomer added is less than 0.5 part by mass, the obtained polychloroprene gel cannot be sufficiently gelled, so that the extrusion processability of the obtained polychloroprene elastomer composition cannot be improved. Further, when more than 25 parts by mass of the polyfunctional monomer is added, the polychloroprene gel finally gels to more than necessary, and the mechanical strength of the obtained polychloroprene elastomer composition is lowered. The polyfunctional monomer having three vinyl groups is not particularly limited, but may, for example, be trimethylolpropane trimethacrylate (hereinafter referred to as hydrazine), trimethylol methane trimethacrylate, or trishydroxyl Ethyl trimethacrylate derivative such as methyl ethane trimethacrylate or trimethylol hydroxyethane trimethacrylate, trimethyl hydroxyethane trimethacrylate, trimethyl propylene phosphate Ester, triallyl isocyanate, 1,3,5-trimethacrylate benzene, and the like. The polyfunctional monomer containing three vinyl groups is added in an amount of 1 part by mass of 2-chloro-1,3-butadiene and 1 to 45 parts by mass of 2,3-dichloro-1. 100 parts by mass of the monomer in which 3-butadiene is mixed is 5% to 25 parts by mass, and more preferably 1 to 5 parts by mass from the viewpoint of further improving the workability and mechanical properties. If the amount of the polyfunctional monomer added is less than 5 parts by mass, the polychloroprene gel obtained by -11 - 200940630 cannot be sufficiently gelled, so that the obtained polychloroprene elastomer composition cannot be improved. The property is forced to process. Further, when more than 25 parts by mass of the polyfunctional monomer is added, the polychloroprene gel finally gels to more than necessary, and the mechanical strength of the obtained polychloroprene elastomer composition is lowered. These polyfunctional monomers can be used independently of the number of vinyl groups. When used, the total amount is added in an amount of 100 parts by mass of 2-chloro-1,3-butadiene and 1 to 45 parts by mass of 2,3-dichloro-1,3-butadiene. One part by mass of the monomer is suitably 0.5 to 25 parts by mass. Further, the polyvinyl chloride gel (B) is preferably obtained by further adding a molecular weight modifier during emulsion polymerization. The molecular weight modifier is used in an auxiliary manner for adjusting the polymerization rate of the monomers, and is not particularly limited, and for example, an aliphatic thiol or a dialkyl xanthogen disulfide compound can be used. As the aliphatic thiol, n-dodecyl mercaptan, tri-dodecyl mercaptan, n-octyl mercaptan and the like are exemplified. The dialkyl xanthogen disulfide compound is exemplified by diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, dibutyl xanthogen disulfide, and the like. The amount of the molecular weight modifier added is preferably from 0 to 3 parts by mass based on 1 part by mass of the total of the monomers to be polymerized, and is preferably from ○·02 to 2 in terms of improving the workability of the extrusion and the mechanical properties. Share. In order to impart additional various characteristics to the resulting polychloroprene elastomer composition, the polychloroprene gel (B) can be copolymerized with other copolymerizable monomers. -12- 200940630 Other copolymerizable monomers are not particularly limited, but may be, for example, 1-chloro-1,3-butadiene, sulfur, styrene, acrylonitrile, methacrylonitrile, isoprene. Butadiene and acrylic acid, methyl propyl acid and the like. The amount of the monomers added is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. Within this range, various characteristics can be imparted without impeding the properties of the obtained polychloroprene elastomer. The polychloroprene gel (B) is preferably obtained by adding all of 2-chloro-1,3-butadiene and 2,3-dichloro-1,3-butadiene to 5~ 80% by mass and all the addition amount of the polyfunctional monomer and the molecular weight modifier are introduced into the polymerization device to start polymerization, and after the polymerization is started, the remaining 2-chloro group cooled to a temperature lower than the polymerization temperature is added to the polymerization device. 1,3 -butadiene is polymerized with 2,3-dichloro-1,3-butadiene. Further, after adding a monomer obtained by mixing 2-chloro-1,3·butadiene and 2,3-dichloro-1,3-butadiene, the remaining mixed monomers are not added at once, but are fractionated times. Add, and preferably add in small amounts. By the post-addition step, a polyfunctional monomer having two or more vinyl groups in the molecule can be increased relative to 2-chloro-1,3-butadiene and 2,3-dichloro-1, The copolymerization ratio of 3-butadiene. According to this, a polychloroprene elastomer composition having improved extrusion workability can be obtained. The polychloroprene gel (Β) may also be the remaining 2-chloro-1,3-butadiene from the time when the conversion rate of all the monomers reaches 10 to 70% until the conversion rate at the end of the polymerization. And 2,3-dichloro-1,3-butadiene is added to the polymerization apparatus for polymerization. -13- 200940630 Accordingly, a polyfunctional monomer having two or more vinyl groups in the molecule can be improved relative to 2-chloro-1,3-butadiene and 2,3-dichloro-1,3 - the copolymerization rate of butadiene. The addition of the molecular weight modifier may be carried out by adding 5 to 80% by mass of the total addition amount at the initial stage, and the remaining molecular weight modifier may be added to the polymerization apparatus after the start of the polymerization. Accordingly, it is possible to increase the polyfunctional monomer having two or more vinyl groups in the molecule relative to 2-chloro-1,3-butadiene and 2,3-dichloro-1,3-butadiene. The rate of copolymerization. The gel fraction of the polychloroprene gel (B) is preferably from 5 〇 to 100%, and more preferably from 70 to 95%. By being limited to this range, a polychloroprene elastomer which can obtain a sulfide having excellent workability and mechanical properties can be obtained. 2-Chloro-1,3-butadiene and 2,3-dichloro-1,3-butadiene are typically cooled to prevent polymerization during storage. The temperature of the monomers is preferably added to the polymerization apparatus at -120 to 0 °C. From the economic point of view, it is better -20~0 °C. The polymerization temperature of the polychloroprene sol (A) and the polychloroprene gel (B) is preferably in the range of from 20 ° C to 55 ° C, and more preferably from 30 ° C to 5 (TC or less). The polymerization initiator of the polychloroprene sol (A) and the polychloroprene gel (B) is a conventional potassium persulfate, ammonium persulfate or sodium persulfate which is commonly used in emulsion polymerization of chloroprene. An organic peroxide such as hydrogen peroxide or tert-butyl hydroperoxide. The polymerization initiator is used in an amount of 0.01 to 1 part by mass based on 100 parts by mass of all of the polymerized-14-200940630 monomers. It is preferably 0.05 to 0.5 parts by mass. The final conversion of the polychloroprene sol (A) is preferably from 40 to 95%, more preferably from 50 to 80%, of the polychloroprene gel (B). The final conversion of the polymerization is preferably 80% or more, more preferably 85% or more. To adjust the final conversion ratio, it is preferred to add a polymerization inhibitor which stops the polymerization reaction to stop the polymerization when the desired conversion ratio is obtained. As the agent, a conventional inhibitor can be used, and although it is not particularly limited, 0 has, for example, thiodiphenylamine, 4-tert-butylcatechol, 2,2-methylenebis-4. Methyl-6-tert-butylphenol, etc. The unreacted single system in the polymerization is removed by, for example, steam stripping, followed by the addition of a conventional pH adjuster to adjust the pH of the latex to 5.5 to 7.5. The butadiene sol (A) and the polychloroprene gel (B) may be used in a mass mixing ratio of the polymer solid components of (A) and (B) for every 100 parts by mass of the total polymer solid component ( (A) / (B)) is 〇30/70-80/20, preferably 40/60~70/30, so that the two are mixed in a latex state, and by common freeze-solidification, water washing, hot air Drying or the like to separate the polymer to obtain a polychloroprene elastomer composition having a Mui viscosity of 40 to 110, preferably 45 to 80. If the ratio of the polychloroprene sol (A) exceeds 80% by mass, Then, the workability is deteriorated, and if it is less than 30% by mass, the mechanical properties are insufficient. Therefore, the obtained polychloroprene elastomer composition is difficult to be formed into a wiper, a car coil, a building gasket, Products such as cables. Also, the viscosity of the polychloroprene elastomer composition is less than 40 -15- 200940630 mechanical strength , if not, the processing property is poor. The polychloroprene elastomer composition may contain natural rubber, butyl rubber, BR, NBR, EPDM, etc. as needed. The polychloroprene elastomer composition may be added with conventional chlorine. The vulcanizing agent or the vulcanization accelerator used in the butadiene rubber is kneaded at a temperature lower than the vulcanization temperature, and then formed into various desired shapes, and then vulcanized to form a sulfide. Further, it may be vulcanized before forming, and then formed into a sulfide. The vulcanization temperature can be appropriately set depending on the addition ratio of the polychloroprene elastomer composition and the type of the vulcanizing agent, and is usually preferably in the range of from 140 to 190 ° C, more preferably from 150 to 180 ° C. As the vulcanizing agent, metal monomers such as barium, magnesium, zinc, calcium, strontium, barium, titanium, tin, chromium, strontium, vanadium, niobium, molybdenum, tungsten, bismuth, selenium, iron, nickel, cobalt, and hungry may be used. An oxide of a metal or a hydroxide of such a metal. Among these metal compounds, calcium oxide, zinc oxide, cerium oxide, antimony trioxide, and magnesium oxide are preferred because of their high vulcanization effect. These can also be used in two or more types. The apparatus for kneading, shaping, and vulcanizing the polychloroprene elastomer composition of the present invention, and the apparatus for kneading and shaping the sulfide of the polychlorobutadiene elastomer composition can be used by users in the general rubber industry. The polychloroprene elastomer composition of the present invention may be added with a softener, a chelating agent, a reinforcing agent, a plasticizer, a processing aid, a lubricant, an anti-aging agent, a stabilizer, a decane according to the purpose thereof when it is supplied for practical use. The coupling agent or the like is molded and vulcanized. The chelating agent and the reinforcing agent may be added to the hydrazine used in the general rubber application, such as a reinforcing agent, such as carbon black, cerium oxide, limestone, talc, calcium carbonate-16-200940630, and a reinforcing agent. The total amount of the chelating agent and the reinforcing agent added is preferably from 30 to 100 parts by mass, more preferably from 40 to 70 parts by mass, per 100 parts by mass of the polychloroprene elastomer composition. As the plasticizer, a plasticizer for general rubber use such as dioctyl phthalate, dioctyl adipate or the like can be added. The amount of the plasticizer added is preferably in the range of about 50 φ parts by mass or less, more preferably 30 parts by mass or less, based on 1 part by mass of the rubber composition. The anti-aging agent may be added with an anti-aging agent used in general rubber use, and examples thereof include an amine-based anti-aging agent, an imidazole-based anti-aging agent, a metal urethane, a phenol-based anti-aging agent, a wax, etc., which are not limited to use alone. It can also be used. The anti-aging agent having a large heat-improving effect is exemplified by 4'-bis(?,?-dimethylbenzyl)diphenylamine or octyldiphenylamine which is an amine-based anti-aging agent. As for the softener, a softener used in general rubber use may be added, and φ is a lubricating oil, a process oil, an alkane, a liquid alkane, a petroleum jelly, a petroleum softener, a naphtha, a flax. Plant softeners such as kernel oil, castor oil, and coconut oil. [Examples] Hereinafter, the examples of the invention are described in detail, but the invention is not construed as being limited thereto. <Preparation of polychloroprene sol (A)> -17- 200940630 Into a 4-liter flask containing an internal volume of 5 liters, 130 parts by mass of pure water, 4 parts by mass of potassium rosinate, and 5 masses were fed. Parts of β-naphthalenesulfonic acid formalin, 94 parts by mass of 2-chloro-1,3-butadiene, 4 parts by mass of 2,3-dichloro-1,3-butadiene, 0.3 parts by mass After dodecyl mercaptan and other chemicals, polymerization was carried out for 10 hours at 35 ° C in a nitrogen stream using 〇·1 part by mass of potassium persulfate as a starting agent. When the conversion of the monomer reached 63%, the polymerization was stopped by the addition of thiodiphenylamine. Next, the unreacted monomer was removed by steam stripping to obtain a latex of the polychloroprene sol (A). <Preparation of Polychloroprene Gel (B)> 130 parts by mass of pure water, 5 parts by mass of rosin potassium salt, and 0.5 part by mass of β-naphthylsulfonate were fed into a four-liter four-necked flask Acid formalin, then fed into the monomer and other chemicals according to the polymerization formula and polymerization conditions described in Table 1, using 1 part by mass of potassium persulfate as a promoter, at 35 t and nitrogen flow The polymerization was carried out for 1 hour. When the conversion of the monomer reached 95%, the polymerization was stopped by adding thiodiphenylamine. Next, the unreacted monomer was removed by steam stripping to obtain a latex of the polychloroprene gel (B). <Preparation of Polychloroprene Elastomer Composition> The obtained polychloroprene sol (A) latex and polychloroprene gel (B) were mixed at the ratios shown in Tables 1 and 2. The latex was then obtained by a freeze-solidification drying method to obtain a polychloroprene elastomer composition. The Mooney viscosity of the obtained polychloroprene elastomer composition at 100 ° C was measured in accordance with JIS-K6300, and the results are shown in Tables 1 and 2. 200940630 In addition, in Tables 1 and 2, the addition amount of 2_chloro-1,3-butadiene or the like is a part by mass, and the ratio of the initial monomer to be added (initial addition amount/all addition amount), and the like, and the composition The amount of the polychloroprene sol (A) and the like are all expressed in mass%. <Kneading> Using a 3-liter kneader (32 rpm, cooling water temperature: 30 ° C), 0.5 parts by mass of stearic acid was kneaded with respect to φ of 1 part by mass of the obtained polychloroprene elastomer composition. 1 part by mass of anti-aging agent (NOCRAC PA manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 30 parts by mass of SRF carbon black (manufactured by Asahi Carbon Co., #50), ? ? FEF carbon black (manufactured by Asahi Carbon Co., Ltd., #60), 12 parts by mass of petroleum-based processing oil (DAI ANA treatment oil manufactured by Idemitsu Kogyo Co., Ltd.), 1.5 parts by mass of paraffin wax (manufactured by Nippon Seiko Co., Ltd., paraffin wax) 130 °F), 1.5 parts by mass of petrolatum, and 4 parts by mass of magnesium oxide. Subsequently, the mixture was re-mixed for 1 minute and discharged. 5 parts by mass of zinc oxide and 0.5 parts by mass of ethylenethiourea were added to the compound using a φ 8 吋 roll to prepare a sheet having a thickness of 2.3 mm. <Physical property test> Using the respective examples and comparative examples The above sheet was used to prepare a sample for measuring the Mooney viscosity. The Mooney viscosity was measured using a Mooney viscometer according to JIS K6300. Further, the sheet was pressure-vulcanized under the conditions of being left at 160 ° C for 30 minutes to prepare a sulfide sheet having a thickness of 2 mm. The following sulphide flakes -19- 200940630 The physical property test was carried out using a bell-shaped piece No. 3. The tensile property test was carried out in accordance with JIS K6251, and the hardness measurement was carried out in accordance with JIS K6253. Further, the permanent elongation test and the permanent compression test were carried out in accordance with JIS K6262. The extrusion process was carried out using a 60 Φ extruder, and the extrusion pressure, the die expansion, and the discharge pressure at the time of extrusion were measured using a Garvey die according to the AS method of ASTM D2230-77 at an extrusion temperature of 50 °C. . The measurement results of the respective physical properties of the examples and the comparative examples are shown in Tables 1 and 2. Further, in Tables 1 and 2, Examples 1 to 12, 18 and 19 are Examples. Examples 13 to 17 and 20 are comparative examples. -20- 200940630
(N s ^ ^ 5 〇〇〇〇〇·〇 m 卜cn 卜 cN 卜 ο ο ο ι〇 m \〇 5.8 14.7 209 72 s s s ^ 5 0 0 0 0 0*0 m卜m卜（N卜 ο ο ο 卜 ΓΛ ν〇 53S? 00 o »—< ir> 〇 s ^ 2 Ο Ο Ο Ο Ο V) m卜m卜cn 卜 ο ο ο 寸必ν〇 ON s ^ ^ s OOOOOO m卜m卜cs们 Ο Ο Ο »η »λ ν〇 宕沄 00 s ^ ^ 5 ο ο ο ο o m m 卜 m r- — r-* ο ο ο «η m so os ^ rr ^j- ^ 2 s ^ S - O o (N *T) 卜 g寸^ 2 沄异§ ®宕p ο ο ο »η ν〇 2芽 v〇 S ^ <N ο ο ο ο o tr> m卜cn卜cs卜 ο ο ο 4Γ> V% 'sO ?! K 5! ^ 〇 ο ο ο ο 〇 in m 卜co 卜 （N 卜 ο ο ο »η »η ^ο § ^ 寸 s ^ m 2 Ο Ο Ο Ο Ο V) co卜cn卜（N卜 ο ο Ο Ι〇 »Ti VC 宕T： s ^ °° 2 o o o o o m卜m卜cn卜 ο ο ο νη V-) ό (S 5! ^ 10 5 O O O O O V"> 卜m卜m <N卜 ο ο ο ιη ι〇 ν〇 σ： ^ 5 o 〇 o 〇 〇 v-> m 卜 m 卜 CN t-- ο ο ο Ό ΙΟ ν〇 § ^ 2 ^ 例編號 A氍 應题声 I ^1E S S EO- I «11] 1 賢褰l· ^ ® ^ 1111 Ksb ^ ij ^ 1 | B- 4^ Uln 淚（N CN W H R M 腾_ 蕖呂 11^ g-N^ll SSSS |聽杓+ η杓n ^ ππΐ gg uj j_ <□ if^. ^ anr is nq η- ^ 1〇^ ^ Π3 Dml CL UJ CD 4ία 1 1 ΒΠΓ R -Hi! ^ 1 1 cz \i^, n C3 a 1 )¾ 4=5 )¾ -F=5 -P5 4=5 ^踩膜踩腾贌腾 ΦΑ _ ^ -Ν < m _ Μ g锲薬 §1111 1Η Η-§1« 1# 1巧S ^•fi- Ή-feS 1裊暴ίδ ι βΛ ν.\" Ww yigigDS Is? S_^ f f f ^ ，麵 !! |1§ m ^ ^ ^-N g ^ B- ^ 鹚 M -B- 索濯 酗酗 iff -21 - 200940630 5：寸 〇 O O O O i i Ο Ο 〇 m wn νο m ^ r-H w 2 G卜 Os S寸^ ^ 〇〇〇〇〇»〇 cn卜m卜cn卜 ο ο ο w-> ^ 3 S s F： m »〇 00 ^ ^ ^ s 沄R沄R -> IC 沄沄S ON q 二；寸 β 2 2卜 <N <S CN ^ r- s寸α 5 0 0 0 0 0*0 α 卜 c〇 Γ-* <N Γ-* ο ο ο ίΝ 〇〇 ^Ο ρ 00 J2 r^· od 〇〇·二卜 s § 5； ^ ^ 5 0 0 0 0 0*0 m卜m卜<N卜 S 2 § 4.8 17.5 224 71 s s JO ”2 2 Ο Ο Ο Ο Ο Ό 卜m卜（Ν卜 沄沄§ & s s 寸 5： ^ S 2 Ο Ο Ο Ο 1 1 τ—^ *-Η ο ο ο wn *〇 ν〇 <N m m vo cn s 对·° 2 Ο Ο Ο Ο I 1 y^4 ο ο ο »〇 ν-) so St: 例編號 ^趦 g i| s S Kfr 醴 猢HI 褰1遯 S^Jl 11 fc«b 慇汽卜碑g· 薬？ j q 1 l·碰 C4 (N ω Η M 腾_ gl^ ISi^S iSliia b 杓窣恝诫1攆褂》 匡遯堋与翠 11 sgss Ιϋ-Ν-4-ll g鲥ϋ遐妖 5若酹另Ή韶煺 U滕后賒异异后 £踩籐踩腾腾腾 _运班运游班班 _ _ •Ν ^ S S Μ塵 #铤薬 Ιπ π 卜卜 f-Ν^ ^fr-frfei E1S1SD5 常態物性 (1〇〇%Ϋ莫數（MPa)) (拉伸強度 （MPa)) (破裂伸張（％)) 麵） 11 jlS 雲關 l W W l m 螌旮 =^1 麵酗 0¾¾ Iff 義藏5 录〇 P 糸w w -22- 200940630 如表1及表2中所示，本發明之聚氯丁 成物及硫化物與以以往方法製造之聚氯丁二 物及硫化物相比，押出加工性優異，包含機 伸長之物性均衡亦優異。 [產業上之利用可能性] 本發明之聚氯丁二烯彈性體組成物及由 0 之硫化物押出加工性優異，包含機械特性、 性均衡亦優異，可用於雨刷材、蛇管材、建 、電纜材等產業上。 又，2007年11月7日申請之日本專利 289163之說明書、申請專利範圍及摘要之全 用方式倂入本發明說明書之揭示中供參考。 二烯彈性體組 烯彈性體組成 械特性、永久 該組成物獲得 永久伸長之物 築密封墊片材 申請號2007-部內容均以引 -23-(N s ^ ^ 5 〇〇〇〇〇·〇m 卜 卜 卜 cN 卜 ο ο ο ι〇m \〇5.8 14.7 209 72 sss ^ 5 0 0 0 0 0*0 m Bu m Bu (N Bu ο ο ο 卜ΓΛ ν〇53S? 00 o »—<ir> 〇s ^ 2 Ο Ο Ο Ο Ο V) m 卜 卜 卜 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Ο Ο Ο »η »λ ν〇宕沄00 s ^ ^ 5 ο ο ο ο omm 卜 m r- — r-* ο ο ο «η m so os ^ rr ^j- ^ 2 s ^ S - O o (N *T) 卜 g inch ^ 2 § § ® 宕 p ο ο ο » η ν 〇 2 bud v 〇 S ^ < N ο ο ο ο o tr > m cn 卜 卜 卜 ο ο ο Γ Γ Γ V% 'sO ?! K 5! ^ 〇ο ο ο ο 〇in m 卜 卜 卜 (N οο ο ο »η »η ^ο § ^ 寸 s ^ m 2 Ο Ο Ο Ο Ο V) co Cn卜(N ο ο Ο Ι〇»Ti VC 宕T: s ^ °° 2 ooooom 卜 卜 卜 ο ο ο ο ν ν V S S S S S (S 5! ^ 10 5 OOOOO V"> m <N ο ο ο ιη ι〇ν〇σ: ^ 5 o 〇o 〇〇v-> m 卜 m 卜 CN t-- ο ο ο Ό ΙΟ ν〇§ ^ 2 ^ Example No. A Inscription I ^1E SS EO- I «11] 1贤褰l· ^ ® ^ 1111 Ksb ^ ij ^ 1 | B- 4^ Uln Tears (N CN WHRM 腾_ 蕖吕11^ gN^ll SSSS | 听杓+ η杓n ^ ππΐ gg uj j_ <□ if ^. ^ anr is nq η- ^ 1〇^ ^ Π3 Dml CL UJ CD 4ία 1 1 ΒΠΓ R -Hi! ^ 1 1 cz \i^, n C3 a 1 )3⁄4 4=5 )3⁄4 -F=5 - P5 4=5 ^Treading on the membrane, 贌 贌 Α _ _ ^ -Ν < m _ Μ g锲薬§1111 1Η Η-§1« 1# 1巧 S ^•fi- Ή-feS 1袅 violence ίδ ι βΛ ν.\" Ww yigigDS Is? S_^ fff ^ , face!! |1§ m ^ ^ ^-N g ^ B- ^ 鹚M -B- 索濯酗酗iff -21 - 200940630 5: inch 〇OOOO Ii Ο Ο 〇m wn νο m ^ rH w 2 G 卜 Os S inch ^ ^ 〇〇〇〇〇»〇cn卜 m卜cnοο ο ο w-> ^ 3 S s F: m »〇00 ^ ^ ^ s 沄R沄R -> IC 沄沄S ON q II; inch β 2 2 卜 <N <S CN ^ r- s inch α 5 0 0 0 0 0*0 α 卜c〇Γ- * <N Γ-* ο ο ο ίΝ 〇〇^Ο ρ 00 J2 r^· od 〇〇·二卜s § 5; ^ ^ 5 0 0 0 0 0*0 m b m <N Bu S 2 § 4.8 17.5 224 71 ss JO ”2 2 Ο Ο Ο Ο Ο 卜 卜 卜 卜 Ν Ν : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : 1 τ—^ *-Η ο ο ο wn *〇ν〇<N mm vo cn s 对·° 2 Ο Ο Ο Ο I 1 y^4 ο ο ο »〇ν-) so St: Example number ^趦Gi| s S Kfr 醴猢HI 褰1遁S^Jl 11 fc«b Yin steam monument g· 薬? Jq 1 l·碰C4 (N ω Η M 腾 _ gl^ ISi^S iSliia b 杓窣恝诫1撵褂 匡遁堋 翠 and Cui 11 sgss Ιϋ-Ν-4-ll g鲥ϋ遐妖5若酹Ή韶煺 滕 滕 滕 赊 赊 £ 踩 踩 踩 踩 踩 踩 踩 踩 藤 藤 _ _ _ 运 运 SS SS SS SS SS SS SS SS SS SS SS SS SS SS SS SS ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ (1〇〇%Ϋ莫数(MPa)) (tensile strength (MPa)) (rupture stretch (%)) face) 11 jlS cloud off l WW lm 螌旮=^1 face 酗03⁄43⁄4 Iff 义藏5 Record 〇 P 糸ww -22- 200940630 As shown in Tables 1 and 2, the polychloroprene and the sulfide of the present invention are superior in extrusion workability to the polychloroprene and sulfide produced by the conventional method. The balance of physical properties including machine elongation is also excellent. [Industrial Applicability] The polychloroprene elastomer composition of the present invention and the sulfide of 0 are excellent in workability, and are excellent in mechanical properties and balance, and can be used for wiper materials, serpentine materials, construction, and the like. Cable and other industries. Further, the entire disclosure of the specification, the scope of the application, and the abstract of the Japanese Patent No. 289 163, filed on Nov. 7, 2007, is incorporated herein by reference. Diene elastomer composition, elastomer composition, mechanical properties, permanent, the composition obtained permanent elongation, the gasket material. Application No. 2007-Partial content is quoted -23-