200904849 九、發明說明： 【發明所屬之技術領域】 本發明係有關於聚酯彈性體組成物，係有關於一種聚 酯彈性體組成物及其製法，在前述聚酯彈性體組成物中的 游離二羧酸、游離甘醇、線狀低聚物量及四氫呋喃的含量 極少’該聚酯彈性體組成物係適合於以汽車、家電組件及 包裝材料爲中心之各種用途。 【先前技術】 具有以聚對酞酸乙二酯（PET)或聚對酞酸丁二酯（PBT) 作爲硬部分等的結晶性芳香族聚酯單位、及以聚伸丁二醇 (PTMG)作爲軟部分等的脂肪族聚醚或聚（ε-己內酯）等的脂 肪族聚酯結構單位之聚酯彈性體、因爲耐熱性、機械特性 優良，所以被廣泛地使用於汽車、家電製品及薄膜等的領 域。 以往，製造此種聚酯彈性體之方法，通常係實施使二 羧酸與二醇成分直接酯化，或是使二羧酸的烷酯與二醇成 分進行酯交換來得到羥基酯及/或其低聚物，隨後，使其在 高真空下聚合之方法。 例如，專利文獻1的實施例揭示一種方法，係藉由在 對酞酸二甲酯（DMT)、1，4-丁二醇（BD)、四氫呋喃（THF)及 環氧乙烷（ΕΟ)的無規共聚物、IRGANOX、鈦酸二丁酯（ΤΒΤ) 的存在下，進行酯交換反應，接著進行聚合反應來製造聚 酯彈性體。 又，在專利文獻2、3揭示一種方法，係在DMT、 PTMG、BD、IRGANOX及ΤΒΤ的存在下，進行酯交換反應， 200904849 接著進行聚合反應來製造聚酯彈性體之方法。在專利文獻 4揭示一種方法，係在對酞酸（TPA)、PTMG、BD、IRGANOX 及TBT的存在下，進行酯交換反應，接著進行聚合反應來 製造聚酯彈性體之方法。 專利文獻1 :特開2 0 0 1 - 1 7 2 4 1 1號公報 專利文獻2 :特開平8 -3 02 00 0號公報 專利文獻3 :特開平8- 1 00054號公報 專利文獻4 :特開昭5 7- 1 1 7527號公報 【發明內容】 發明所欲解決之課題 但是，依照上述方法所製造的聚酯彈性體中，會有因 爲大量地殘留游離酸、游離二醇、游離二羧酸甘醇酯等， 而被認爲聚合物的外觀、耐熱性、氣味性變差等之問題。 特別是此種聚酯彈性體使用於微波爐用食品容器本體、食 品容器用層壓薄膜等時，會有內容物的香味變化掉（氣味性 變差）之問題。又，在使用此種方法所製造的聚酯彈性體’ 存在有式（1)所示羥基四亞甲基末端基時，會大量地副生成 起因於加熱熔融時該末端基的閉環反應之四氫呋喃（THF)。 -0(CH2)40H 式（1) 因此，在將含有式（1)之聚酯彈性體的聚合反應製程或 熔融聚合物加以碎片化之鑄塑製程、對聚酯彈性體賦與新 功能之複合製程或成形加工之再熔融製程，因熱分解所副 生成的四氫呋喃揮發會造成臭氣等環境污染。 解決課題之丰段 爲了解決上述課題，本發明者等專心硏討的結果，發 200904849 現藉由使由二羧酸成分、以1，4-丁二醇爲主體之分子量爲 小於25〇的甘醇成分、及數量平均分子量爲4〇〇~7〇〇〇〇的 多元醇所得到的聚酯彈性體中，含有抗氧化劑爲 0.01~5wt%、四氫呋喃爲 2〇〇〇ppm以下、游離二殘酸爲 50ppm以下、游離二醇爲lOppm以下、分子量爲65〇以下 的線狀低聚物爲3 0 0 p p m以下，能夠改善氣味性、耐熱性， 而完成了本發明。 亦即，本發明係如下， [1 ] 一種聚酯彈性體組成物’其特徵係在由二羧酸成分、以 1，4 -丁二醇爲主體之分子量爲小於250的甘醇成分、及數 量平均分子量爲400-700 00的多元醇所得到的聚酯彈性體 中，含有抗氧化劑爲〇·〇1〜5wt%、四氫呋喃爲2000ppm以 下、游離二羧酸爲50ppm以下、游離二醇爲丨〇ppm以下、 分子量爲6 5 0以下的線狀低聚物爲3 0 0 p p m以下。 [2 ]如[1 ]之聚酯彈性體組成物，其中含有前述游離二羧酸爲 15ppm以下，前述游離二醇爲2ppm以下、分子量650以下 的線狀低聚物爲200PPm以下。 [3] —種聚酯彈性體組成物之製法，其係製造[Π或[2]之聚 酯彈性體組成物’該製法係使用二羧酸成分、以1，4 - 丁二 醇爲主體之分子量爲小於250的甘醇成分、及數量平均分 子量爲400〜70000的多元醇作爲原料來熔融聚合聚酯彈性 體，並在聚合反應後期及聚合反應剛完成後之至少一方’ 添加0.0 1〜5 w t %抗氧化劑。 [4] 一種聚酯彈性體組成物之製法，其係製造[2]之聚醋彈性 體組成物，該製法係使用二羧酸成分、以1,4-丁二醇爲主 200904849 體之分子量爲小於250的甘醇成分、及數量平均分子量爲 4 0 0〜7 0 0 0 0的多元醇作爲原料，將預先使對比黏度反應爲 〇. 2 dl/g以上之聚酯彈性體移送至薄膜蒸發器或橫型雙軸反 應罐’並在230~255 °C、2hPa以下更進行聚合反應，且在 聚合反應後期及聚合反應剛完成後之至少一方，添加 0 · 0 1 ~ 5 w t %抗氧化劑。 [5] 如[4]之聚酯彈性體組成物之製法，其係移送至薄膜蒸發 器或橫型雙軸反應罐進行反應，接著移送至雙軸擠壓機並 / 添加抗氧化劑。 [6] 如[4]或[5]之聚酯彈性體組成物之製法，其係加熱混合 由二羧酸成分、以1，4-丁二醇爲主體之分子量爲小於250 的甘醇成分所得到數量平均分子量爲 5 0 00〜5 0000之聚 酯、與數量平均分子量爲400~70000的多元醇，並將預先 使對比黏度反應爲〇.2dl/g以上之聚酯彈性體移送至薄膜 蒸發器或橫型雙軸反應罐。 [7] 如[3]至[6]中任一項之聚酯彈性體組成物之製法’其中 .… 抗氧化劑係選自由受阻酚系、硫系、磷系所組成群組之一 種以上。 [8] 如[6]或[7]之聚酯彈性體組成物之製法’其中前述聚酯 係選自聚對酞酸丁二酯、聚萘二甲酸丁二醋及聚己二酸丁 二酯之至少1種以上’且前述多元醇係選自聚伸丁二醇、 聚碳酸酯二醇、聚丙二醇及聚乙二醇之至少1種以上。 [9] 一種纖維狀物，其特徵係將Π]或[2]之聚酯彈性體組成 物擠壓成形而構成。 [1 0 ] —種薄片狀物，其特徵係將Π ]或[2 ]之聚醋彈性體組成 200904849 物擠壓成形而構成。 [11]一種成形體’其特徵係由[〗]或[2]之聚酯彈性體組成物 所構成。 [1 2 ] —種拉伸薄膜’其特徵係將[丨〇 ]之薄片狀物往至少一方 向拉伸而構成。 發明之效果 本發明的聚酯彈性體之氣味性、耐熱性優良，能夠適 合使用於作爲要求嚴格的纖維、成形體、薄片及拉伸薄膜 之原料。 又’藉由本製造方法來製造聚酯彈性體組成物，含有 會產生的四氫呋喃之具有羥基四亞甲基末端基之化合物 時’能夠降低四氫呋喃的含量，來抑制環境污染或聚合物 品質降低。而且，因爲游離酸、游離二醇及低分子量低聚 物的含量少，聚合物的外觀、耐熱性及氣味性優良。 【實施方式】 實施發明之最佳形態 依照本發明，四氫呋喃之含量的上限在聚酯彈性體組 成物中爲2〇〇Oppm以下。含量係相對於聚酯彈性體組成物 的質量之四氫呋喃的質量。 四氫呋喃的含量以1800ppm以下爲佳，以1500ppm 以下爲更佳，以100 Oppm以下爲最佳。 四氫呋喃大於2000ppm時，由聚酯彈性體組成物所得 到容器等的內容物的風味或香味變有變爲非常差的傾向。 本發明的聚酯彈性體組成物必須在聚合反應後期及 聚合反應剛完成後之至少一方添加抗氧化劑，用以將四氫 200904849 呋喃的含量維持在200〇ppm以下。認爲：藉此，通常在聚 合反應前添加時在聚合反應中會消失掉之抗氧化劑捕集自 由基的功能不會消失’而能夠有助於四氫呋喃末端基的熱 安定性，又’有助於抑制閉環反應。 在此所所稱聚合反應後期係指黏度比規定的對比黏 度低0.01~0.50dl/g之狀態。 四氫呋喃的含量之下限値以〇爲佳，但是爲了小於 40ppm(特別是使用PTMG作爲多元醇時係小於l〇〇ppm)， 必須犧牲生產力來設定製造條件，並非較佳態樣。 在本發明，聚酯彈性體組成物中的游離二羧酸、游離 二醇係各自與構成聚酯彈性體之二羧酸成分、分子量小於 2 5 0的甘醇成分同一化合物。又，分子量6 5 0以下的線狀 低聚物係構成聚酯彈性體之二羧酸分子與分子量小於2 5 0 的甘醇成分鍵結而成的線狀低聚物。 依照本發明，游離的低分子化合物的含量之上限係在 聚酯彈性體組成物中，游離二羧酸爲5 Oppm以下，游離二 醇爲lOppm以下，分子量6 5 0以下的線狀低聚物爲3 00ppm 以下。該等含量係相對於聚酯彈性體組成物的含量之各成 分的質量。 游離二羧酸的含量係以20ppm以下爲佳，以15ppm 以下爲更佳’以1 〇ppm以下爲最佳，游離二醇的含量係以 7ppm以下爲佳’以2ppm以不爲更佳，以lppm以下爲最 佳’分子里6 5 0以下的線狀低聚物的含量係以2 5 0 p p m以下 爲佳’以200Ppm以下爲更佳，以i7〇ppm以下爲最佳。 游離一竣酸的含量大於 5〇ppm，游離二醇小於 -10 - 200904849 lOppm，分子量6 5 0以下的線狀低聚物的含量大於30〇ppm 時，由該聚酯彈性體組成物所得到的容器等的內容物之風 味或香味有變爲非常差的傾向，而且耐熱性有降低的傾向。 游離二竣酸的含量小於15ppm，游離二醇小於2ppm， 分子量65 0以下的線狀低聚物的含量200ppm以下時，由聚 酯彈性體組成物所得到的容器等的內容物之風味或香味能 夠長期間保持，而且耐熱性提升。 爲了使本發明的聚酯彈性體組成物之游離二羧酸的 含量爲5 0ppm以下，游離二醇的含量爲lOppm以下，分子 量65 0以下的線狀低聚物的含量爲3 00ppm，在聚合反應後 期及聚合反應剛完成後之至少一方，必須添加抗氧化劑。 認爲：藉此，通常在聚合反應前添加時在聚合反應中會消 失掉之抗氧化劑捕集自由基的功能不會消失，而能夠有助 於聚合物的熱安定性。 爲了使本發明的聚酯彈性體組成物之游離二羧酸的 含量爲15PPm以下，游離二醇的含量爲2PPm以下，分子 量6 5 0以下的線狀低聚物的含量爲200ppm，必須（1)在聚 合反應後期及聚合反應剛完成後之至少一方，添加抗氧化 劑’並且亦（2)加熱混合由二羧酸成分、以1,4-丁二醇爲主 體之分子量爲小於250的甘醇成分所得到數量平均分子量 爲5000〜50000之聚酯、與數量平均分子量爲400〜70000的 多元醇’並將預先使對比黏度反應爲〇.2dl/g以上之聚酯彈 性體移送至薄膜蒸發器或橫型雙軸反應罐，並且必須在 23 0~2 5 5 °C ' 2hPa以下更進行聚合反應。 在此’在加熱混合時數量平均分子量5000~50000之聚 200904849 酯在溶解之同時會產生一部分解聚’並與多元醇產生反應。 使用二羧酸成分、分子量爲小於250的甘醇成分作爲 原料之先前的DMT法或TPA法時’爲了提高反應率或製程 安定性，必須過剩地添加分子量小於2 5 0的甘醇之緣故， 致使未反應物殘餘而游離物變多。另一方面，藉由實施上 述（1)，因爲通常在聚合反應前添加時在聚合反應中會消失 掉之抗氧化劑捕集自由基的功能可以維持，所以從反應罐 取出時之聚合物的熱分解變少，能夠抑制游離二羧酸、游 離二醇及分子量6 5 0以下的線狀低聚物的生成。又，藉由 實施上述（2)，不必過剩地添加分子量小於2 5 0的甘醇，即 便添加分子量小於2 5 0的甘醇用以調整反應速度時其添加 量亦是少量，所以游離物變少。而且’因爲使用表面更新 性高的薄膜蒸發器或橫型雙軸反應罐來進行聚合反應，所 以反應時間能夠縮短，能夠抑制因熱分解引起之游離二羧 酸、游離二醇及分子量6 5 0以下的線狀低聚物的生成。 又，實施上述（2)時，因爲能夠抑制加熱混合時或聚合 反應時的熱分解所引起之游離二羧酸、游離二醇及分子量 6 5 0以下的線狀低聚物的生成，以預先添加抗氧化劑爲較 佳態樣。 游離二羧酸、游離二醇及分子量65 0以下的線狀低聚 物的含量之下限値係各自以〇爲佳’爲了使游離二羧酸小 於3 ppm、游離二醇小於〇·6 ppm及分子量650以下的線狀 低聚物小於1 2 0 p p m，必須犧牲生產力來設定製造條件’並 非較佳態樣。 在本發明能夠使用之二羧酸可舉出草酸、己二酸、癸 -12- 200904849 二酸、壬二酸、十二烷二酮酸、癸二酸、琥珀酸、戊二酸、 十二烷二酸、二聚酸、加氫二聚酸、丙二酸、戊二酸、環 己烷二羧酸、對酞酸 '異對酞酸' 酞酸、2,6 -萘二羧酸、 2,7-萘二羧酸、雙（對羧苯基）甲烷、蒽二羧酸、4，4，_二苯基 醚二羧酸、4,4，-二苯基二羧酸、二苹氧基乙烷二羧酸、5_ 鈉磺酸基異酞酸及5 -四丁基隣異酞酸等的二竣酸、及該等 的二甲酯體等，以己二酸、對酞酸' 萘二羧酸及該等的二 甲酯體爲佳’以芳香族二羧酸之對酞酸及對酞酸二甲酯爲 特佳。又，該等亦可使用一種或二種以上。 芳香族二羧酸以外的成分以小於5 0莫耳％爲佳，小於 4〇莫耳％爲更佳，小於30莫耳％爲最佳，大於5〇莫耳％時， 聚酯彈性體之結晶性會有降低的傾向，且成形性、耐熱性 有降低的傾向。 分子量小於2 5 0的甘醇成分可舉出例如乙二醇、丨，3 _ 丙二醇、1，4 -丁二醇、庚二醇、己二醇、辛二醇、壬二醇、 癸二醇、1，4-環己烷二甲醇 '新戊二醇、甘醇、新戊四醇、 雙酚A的EO加成物、加氫雙酚A、加氫雙酚F及TCD甘 醇等的甘醇化合物等，該等可使用一種或二種以上。分子 量大於2 5 0時，結晶性降低且成形性耐熱性有降低的傾 向。上述甘醇之中，以乙二醇、1,3 -丙二醇、1，4 -丁二醇爲 佳’以1，4-丁二醇爲特佳。以丨，4-丁二醇作爲主體時，以 含有60莫耳％以上之14-丁二醇爲佳，以含有70莫耳％以 上爲更佳，以含有80莫耳％以上爲最佳，小於60莫耳％時， 會有結晶性降低' 成形性耐熱性降低之傾向。 又’亦可含有乙醇酸、乳酸、羥基丙酸、羥基戊酸、 -13- 200904849 羥基己酸、羥基丁酸、羥基苯甲酸等的羥基羧酸作爲共聚 合成分。 在不損害本發明的內容之範圍，亦可賦予羧酸。導入 羧基之方法，可舉出例如在聚合聚酯彈性體後’加添1，2,4 -苯三甲酸酐、酞酸酐、焦蜜石酸酐、琥珀酸酐、1，8 -萘二 甲酸、1，2 -環己烷二羧酸酐等來後附加酸値’改性聚酯可 舉出使用二羥甲基丙酸、二羥甲基丁酸等進行鏈伸長之方 法。而且，可舉出1,2，4-苯三甲酸、焦蜜石酸等’甘醇成 分可舉出甘油、新戊二醇等。以上共聚合成分的使用量， 係聚酯彈性體實質上必須維持線狀程度。 多元醇可舉出聚乙二醇，聚丙二醇、聚伸丁二醇、聚 伸己二醇、環氧乙烷與四氫呋喃之共聚物、聚丙二醇之環 氧乙烷的加成聚合物、聚碳酸酯二醇、聚新戊二醇、聚3-甲基戊二醇、聚1，5 -戊二醇、雙A環氧乙烷加成物、雙A 環氧丙烷加成物、雙S環氧乙烷加成物等及其衍生物’具 體上，可舉出例如聚新戊二醇與聚乙二醇之共聚物等，其 中以聚伸丁二醇、聚碳酸酯二醇及聚丙二醇爲佳。 多元醇的數量平均分子量爲 4〇〇〜70,〇〇〇，以 600~60,000爲佳，以1,〇〇〇〜50,000爲特佳。數量平均分子 量爲400以上時，耐熱性、彈性性能或成形性優良’數量 平均分子量爲70, 〇〇〇以下時’能夠降低聚合時的相分離’ 且提高反應性。多元醇係聚伸丁二醇時’從降低相分離而 言，數量平均分子量的上限以10,000爲佳，以4,000爲較 佳，以2,0 0 0爲更佳。 在本發明之聚碳酸酯二醇’使用脂肪族聚碳酸酯二醇 -14- 200904849 時調整分子量的方法沒有特別限定，例如因爲市售的脂肪 族聚碳酸酯二醇的分子量係低於本發明之較佳分子量範 圍’以預先使用鏈伸長劑將市售的低分子量脂肪族聚碳酸 酯二醇加以高分子量化來調整分子量之方法爲佳。亦即， 以預先使用鏈伸長劑加以高分子量化使脂肪族聚碳酸酯二 醇的分子量在上述最佳範圍的方式調整後，供給至嵌段化 反應而進行反應爲佳。 使用上述市售的低分子量品之方法，因爲能夠製造任 意分子量的脂肪族聚碳酸酯二醇，且該製造能夠使用本發 明的熱可塑性聚酯彈性體之製造裝置在裝置上進行，其經 濟上的效果大。又’上述方法具有藉由變化鏈伸長劑與脂 肪族聚碳酸酯二醇的加料比之單純的方法，能夠使用市售 之低分子量的脂肪族聚碳酸酯二醇來對應所需要的任意分 子量之優點。 上述鏈伸長劑若是在一分子中含有2個以上具有能夠 與脂肪族聚碳酸酯二醇的末端羥基反應的官能基之多官能 性的活性化合物時’沒有特別限定，官能基數若是2個以 上時沒有特別限定，以2官能基者爲佳。可舉出例如碳酸 二苯酯、二異氰酸酯及二羧酸的酸酐等。亦可少量使用3 官能性以上的多官能性化合物。亦可使用碳酸二甲酯、碳 酸二乙酯、碳酸二丙酯、碳酸二異丙酯、碳酸二丁酯及碳 酸二甲酯等的碳酸酯化合物來代替碳酸二苯酯。又，亦可 以是碳酸乙烯酯等的環狀碳酸酯或二硫代碳酸酯化合物。 又，亦可以是使用咪唑或內醯胺等的含氮化合物殘基來代 替碳酸二苯酯的苯氧基之羰基化合物。 200904849 在上述方法，高分子量化前之低分子量脂肪族聚碳酸 酯二醇係以利用市售品爲佳，但是沒有限定。例如，在必 須特殊的共聚物時等，脂肪族聚碳酸酯二醇亦可使用特別 地調製而成者。 在本發明’導入前述的活性末端基之方法沒有限定， 在使用上述的鏈伸長劑來調整脂肪族聚碳酸酯二醇的分子 量之方法’以藉由在末端加添該鏈伸長劑殘基來調製爲佳。 上述調製方法沒有限定，可舉出調整至比需要的分子 量更低的分子量後’以比添加規定量的鏈伸長劑調整分子 量時更溫和的條件進行反應，來使鏈伸長劑與脂肪族聚碳 酸酯二醇的末端基反應而導入之方法。例如，反應係以在 常壓或加壓下並於100〜200 °c進行爲佳。又，亦可藉由鏈 伸長劑的加料比或反應條件的最佳化，在調整分子量時同 時導入活性末端基來進行。 在上述方法，所得到脂肪族聚碳酸酯二醇之分子量的 調整或導入活性末端基，能夠藉由改變起始原料之脂肪族 聚碳酸酯二醇的分子量及該脂肪族聚碳酸酯二醇與鏈伸長 劑的加料比來進行。又，亦可藉由反應時間來調整。所得 到脂肪族聚碳酸酯二醇之分子量係起始原料之分子量越 高’又，鏈伸長劑的加料比越小時，變爲越高。可配合目 標分子量而適當地設定。 依照上述方法實施時之反應方法，若使分子量比最後 分子量低的脂肪族聚碳酸醋二醇與鏈伸長劑在反應器中進 行混合’反應溫度或反應時間、攪拌條件等反應條件沒有 限定’例如推薦將該分子量調整分割成爲2階段以上的多 -16 - 200904849 階段來進行之方法。亦即’以規定量的加料比反應規定時 間後’測定所得到脂肪族聚碳酸酯二醇的分子量，若該分 子量低於目標分子量時，藉由追加添加鏈伸長劑，相反地， 若分子量太高時，藉由追加添加原料的脂肪族聚碳酸酯二 醇’進而繼續進行反應來調整分子量爲佳。藉由重複該方 法能夠提高分子量或活性末端基濃度的調整精確度。 由二羧酸成分及分子量爲小於250的甘醇成分所構成 的聚酯，可舉出例如聚對酞酸乙二酯、聚對酞酸丁二酯、 聚對酞酸丙二酯、聚對酞酸伸環己基二亞甲酯、聚異酞酸 乙二酯、聚異酞酸丁二酯、聚異酞酸丙二酯、聚萘二甲酸 乙二酯、聚萘二甲酸丁二酯、聚萘二甲酸丙二酯及其他的 共聚物，以聚對酞酸丁二酯、聚萘二甲酸丁二酯、聚己二 酸乙二酯及聚己二酸丁二酯爲佳，以聚對酞酸丁二酯爲特 佳。 本發明所使用的二羧酸成分及以1，4_丁二醇作爲主體 之分子量爲小於250的甘醇成分所得到之數量平均分子量 爲5000〜50000的聚酯，能夠使用上述各聚酯的市售品。 由二羧酸成分及以分子量爲小於2 5 0的甘醇成分所得 到的聚酯，可使用回收的容器或產業廢棄物的聚酯’亦可 使用共聚物聚酯。 聚合反應所使用的觸媒’可舉出例如錫、鋅、船、欽、 鉍、锆、鍺、銻、鋁等的金屬及其衍生物。衍生物係以金 屬烷氧化物、羧酸鹽、碳酸鹽、氧化物及鹵化物爲佳。具 體上，可舉出例如氯化錫、辛酸錫、氯化鋅、乙酸鋅、氧 化鉛、碳酸鉛、氯化鈦、烷氧基鈦、氧化鍺及氧化錯等。 -17- 200904849 此等之中，以鈦化合物、鍺化合物、鋁化合物及銻化合物 爲佳，以鈦化合物爲更佳。 鈦化合物具體上可舉出例如鈦酸四乙酯、欽酸四異丙 酯、鈦酸四正丙酯、鈦酸正四丁酯等的鈦酸四烷酯及該等 的部分水解物、乙酸鈦、草酸氧鈦、草酸氧鈦錢、草酸氧 鈦鈉、草酸氧鈦鉀、草酸氧鈦鈣及草酸氧鈦緦等的草酸氧 鈦化合物、1,2，4_苯三甲酸鈦、硫酸鈦、氯化鈦、欽鹵化物 的水解物、溴化欽、氟化駄、六贏化駄酸鉀、六氣化鈦酸 銨、六氟化鈦酸鈷、六氟化鈦酸錳、乙醯丙酮鈦、由鈦及 矽或錆所構成的複合氧化物、烷氧化鈦與磷化合物之反應 物等。 鍺化合物以使用無定形二氧化鍺、結晶性二氧化鍺、 或將結晶性二氧化鍺溶解在甘醇而成的溶液爲佳。 鋁化合物具體上可舉出甲酸鋁、乙酸鋁、鹼性乙酸 鋁、丙酸鋁、草酸鋁、丙烯酸鋁、月桂酸鋁、硬脂酸鋁、 苯甲酸鋁、三氯乙酸鋁、乳酸鋁、檸檬酸鋁、柳酸鋁等羧 酸鹽、氯化鋁、氫氧化鋁、氫氧化氯化鋁、多氯鋁、硝酸 鋁、硫酸鋁、碳酸鋁、磷酸鋁、膦酸鋁等無機酸鹽、甲醇 鋁、乙醇鋁、正丙醇鋁、異丙醇鋁、正丁醇鋁、第三丁醇 鋁等烷醇鋁、乙醯丙酮鋁、乙醯乙酸鋁、乙基乙醢丙酮鋁、 乙基乙醯乙酸鹽二異丙醇鋁等鋁鉗合化合物、三甲基鋁、 三乙基鋁等有機鋁化合物及此等的部分水解物、氧化鋁 等。此等之中，以羧酸鹽、無機酸鹽及鉗合化合物爲佳， 而且此等之中，以鹼性乙酸鋁、氯化鋁、氫氧化鋁、氫氧 化氯化鋁及乙醯丙酮鋁等爲特佳。 -18- 200904849 又’在本發明聚酯彈性體的製法，亦可並用驗金屬化 口物或驗土類金屬化合物。驗金屬、驗土類金屬以至少選 自 Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr 及 Ba 之至少 l 種爲佳，以使用鹼金屬或其化合物爲更佳。使用鹼金屬或 其化口物時’以使用Li、Na、K爲特佳。驗金屬化合物或 鹼土類金屬化合物可舉出例如該等金屬的甲酸、乙酸、丙 酸、丁酸及草酸等的飽合脂肪族翔酸鹽、丙燦酸、甲基丙 燃酸等的不飽和脂肪族竣酸鹽、苯甲酸等的芳香族竣酸 鹽、三氯乙酸等含有鹵素之羧酸鹽、乳酸、檸檬酸、柳酸 等的經基殘酸鹽、碳酸、硫酸、硝酸、碟酸、膦酸、碳酸 氫、磷酸氫、硫化氫、亞硫酸、硫代硫酸、鹽酸、溴化氫 酸、鹽酸、溴酸等的無機酸鹽、1 -丙磺酸、1 -戊磺酸、萘 磺酸等的有機磺酸鹽、月桂基硫酸等的有機硫酸鹽、甲氧 基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧 基等的烷氧化物、與乙醯丙酮鹽等的鉗合化合物、氫化物、 氧化物及氫氧化物等。 本發明的縮聚觸媒亦能夠並用磷化合物。 能夠與觸媒並用之化合物，以選自由膦酸系化合物、 次膦酸系化合物、氧化膦系化合物、亞膦酸系化合物、卑 膦酸系化合物、膦系化合物所組成群組之至少一種磷化合 物爲佳。聚酯彈性體組成物聚合時，藉由使用該等磷化合 物，能夠觀察到提升觸媒活性的效果及提升聚酯的熱安定 性之效果。該等之中’使用膦酸系化合物，提升觸媒活性 的效果及提升聚酯的熱安定性之效果大’乃是較佳。上述 磷化合物之中，使用具有芳香環結構之化合物時，觸媒活 -19- 200904849 性的提升效果及聚酯彈性體的熱安定性提升效果大，乃是 較佳。 銻化合物可舉出三氧化銻、乙酸銻、酒石酸銻、酒石 酸銻鉀、三氯氧化銻、乙醇酸銻、五氧化銻及三苯基銻等。 熔融聚合本發明所使用聚酯彈性體時所使用的反應 器，能夠使用眾所周知的反應器，可以是批次式或連續式， 可使用縱型反應罐、眼鏡狀翼橫型反應罐、格子翼橫型反 應罐、薄膜蒸發反應罐、攪拌型反應罐、塔型反應罐、短 軸擠壓機及雙軸擠壓機反應罐等。在該等之任一種方式， 熔融縮聚反應能夠以一階段進行，亦可分開成多階段進 行。爲了增加對比黏度，亦能夠進行固相聚合，固相聚合 反應係與熔融縮聚反應同様，能夠使用分批式裝置或連續 式裝置來進行。熔融縮聚與固相聚合可連續進行，亦可分 割而進行。 減壓至2hPa以下而進行聚合反應，在移送至反應罐 之前，以預先使聚酯彈性體對比黏度爲〇.2dl/g以上爲佳。 小於0.2dl/g時，因爲熔融黏度太低，產生暴沸使低黏度的 飛沬積存於罐上部或減壓管路，會成爲污染或減壓管路堵 塞的原因。 抗氧化劑能夠添加眾所周知的受阻酚系抗氧化劑、硫 系抗氧化劑及磷系抗氧化劑之一種類以上。 又，爲了降低四氫呋喃含量之目的，可在聚合反應前 添加上述安定劑一種以上，作爲聚合反應中的熱安定性劑。 相對於聚酯彈性體1 00wt%，抗氧化劑的添加量爲 0_01〜5wt%，以 〇_〇5〜3wt%爲佳，以〇.l~2wt%爲更佳。添 -20- 200904849 加量爲0.01 %以上時，不僅是氣味性、耐熱性或耐水解性， 而且聚合物的機械強度提高。添加量爲5 wt%以下，無法得 到與添加量增加相稱的效果。聚酯彈性體組成物中之抗_ 化劑的含量亦與上述添加量同樣。 此外，能夠添加眾所周知的受阻胺系、三唑系、二苯 基酮系、苯甲酸酯系、鎳系、柳酸系等的光安定劑、防靜 電劑、滑劑、過氧化物等的分子調整劑、金屬鈍化劑、有 機及無機系的核劑、中和劑、抗酸劑、防菌劑、螢光增白 劑、塡料、難燃劑及難燃助劑等一種類以上。 受阻酚系抗氧化劑 在本發明之受阻酚系抗氧化劑可舉出3,5 -二第三丁基 -4-羥基-甲苯、正十八烷基- β- (4’-羥基-3’，5’ -二-第三丁基 苯基）丙酸酯、新戊四醇肆[3-(3,5-二-第三丁基-4-羥苯基） 丙酸酯]、硫二伸乙基雙[3-(3,5 -二-第三丁基-4-羥苯基）丙 酸酿、十八烷基雙[3-(3,5-二-第三丁基-4-羥苯基）丙酸酯、 肆[亞甲基-3-(3’，5’·二-第三丁基-4’-羥苯基）丙酸酯]甲 烷、1，3,5-三甲基-2,4,6，-參（3,5-二-第三丁基-4-羥苄基） 苯、（3,5-二-第三丁基-4-羥基-苄基-單乙基-磷酸）鈣、三乙 二醇-雙[3-(3-第三丁基-5-甲基-4-羥苯基）丙酸酯]、3,9-雙 [1,1-二甲基-2-{/3 -(3 -第三丁基-4-羥基-5 -甲基苯基）丙嫌 醯氧基}乙基]2,4,8, 10-四氧雜螺[5,5]十一烷、雙[3 ,3-雙（4’ -羥基_3’-第三丁基苯基）丁酸]甘醇酯、生育酚、2，2’-亞乙 基雙（4,6 -二-第三丁基苯酚）、Ν,Ν’-己烷-1,6 -二基雙 [3-(3,5-二-第三丁基-4-羥苯基丙醯胺）、1,3,5-雙[2,4_雙 (1，1-二甲基乙）-6-甲基苯基]乙基酯亞磷酸、肆（2,4-二-第三 -21 - 200904849 丁基苯基）[1,1-聯苯基]_4,4’-二基雙亞膦酸酯、雙（2,4-二_ 第三丁基苯基）新戊四醇二亞磷酸酯、N，N’-雙[3-(3,5-二_ 第三丁基-4-羥苯基）丙醯基]肼、2,2’-草醯胺基雙[乙基 -3-(3，5-二-第三丁基-4-羥苯基）丙酸酯]、1，1，3-參（2-甲基 -4-羥基-5-第三丁基苯基）丁烷、l，3,5-參（3’，5，·二·第三丁 基-4’-羥苄基）_S-三畊-2,4,6(111，311，515)-三酮、三聚異氰酸 1，3,5 -參（4-第三丁基-3-羥基-2,6-二甲基苄基）酯、3,5 -二-第三丁基-4-羥基氫化肉桂三酯和（with)-1，3,5-參（2-羥乙 (: 基）-S-三阱-2,4,6(1H，3H，5H；^。 硫系抗氧化劑 ' 在本發明之硫系抗氧化劑可舉出二月桂基-3,3，-硫代 二丙酸酯、二肉豆蔻基-3，3，-硫代二丙酸酯 '二硬脂醯基 _3，3硫代二丙酸酯、月桂基硬脂醯基-3，3’·硫代二丙酸 醋、二-十八烷基硫醚、新戊四醇-肆（/3 -月桂基-硫代丙酸 酯）等。 憐系抗氧化劑 C., 磷系抗氧化劑可舉出例如參（混合、單及二聚苯醚苯 基）亞磷酸酯、參（2,3 -二-第三丁基苯基）亞磷酸酯、4,4，-亞丁基-雙（3-甲基-6-第三丁基苯基-二-十三烷基）亞磷酸 醋、1，1，3-參（2-甲基-4-二-十三烷基亞磷酸酯-5-第三丁基 苯基）丁烷、雙（2,4-二-第三丁基苯基）新戊四醇-二-亞磷酸 酷、肆（2,4-二-第三丁基苯基）-4,4’-伸聯苯基膦酸酯、雙 (2’6 -二-第三丁基-仁甲基苯基）新戊四醇-二-亞磷酸酯、 2，2’_亞乙基-雙（4,6-二-第三丁基苯基）-2-乙基己基-亞磷 酸酯、雙（2,4,6-二-第三丁基苯基）新戊四醇-二-亞磷酸酯、 -22- 200904849 亞磷酸三苯酯、亞磷酸二苯基癸酯、亞磷酸二癸基苯酯、· 亞磷酸十三烷酯、亞磷酸三辛酯、亞磷酸三-十二烷酯、亞 磷酸三-十八烷酯、亞磷酸三壬酯及三硫代亞磷酸三-十二 烷酯等。 受阻胺系光安定劑 在本發明之受阻胺可舉出琥珀酸二甲酯與1-(2-經乙 基）-4 -羥基- 2,2,6,6 -四甲基哌咯啶（piperodine)之縮聚物、 聚[[6-(1,1,3,3-四甲基）亞胺基-1，3, 5-三阱-2,4-二基]六亞 甲[(2,2,6,6-四甲基-4-哌啶基）亞胺]]、2_正丁基丙二酸的雙 (1，2,2,6,6-四甲基-4-哌啶基）-1，2,3,4-丁烷四羧酸酯、癸二 酸雙（2,2,6,6-四甲基-4-哌啶基）酯、N，N’-雙（2,2,6,6-四甲基 -4-哌啶基）六亞甲二胺與1，2-二溴乙烷之縮聚物、聚 [(N，N，-雙（2，2,6,6-四甲基-4-哌啶基）六亞甲二胺）-(4 -味啉 -1,3,5-三阱-2,6-二基）-雙（3,3,5,5-四甲基哌畊酮）、參 (2,2,6,6-四甲基-4-哌啶基）-十二烷基-1，2,3,4-丁烷四竣酸 酯、參（1,2,2,6，6-五甲基-4-哌啶基）-十二烷基-1,2,3,4-丁院 四羧酸酯、雙（1，2,2,6,6_五甲基-4-哌啶基）癸二酸醋、 1，6,11-參[{4,6-雙（1丁基-；^-(1，2,2,6,6-五甲基哌啶-4-基） 胺基-1，3,5-三阱-2-基}胺基]十一烷、卜[2-[3-5-二-第三丁 基-4-羥苯基）丙烯醯氧基]-2,2,6，6 -四甲基哌啶、8-节基 -7,7,9,9-四甲基-3·辛基-1,3,8-三氮螺[4,5]十一烷-2，4-二 酮、4-苯甲醯氧基-2,2,6,6-四甲基哌啶、N，N，-雙（3-胺基苯 基）伸乙二胺-2,4-雙[1丁基-1^-(1，2,2,6,6-五甲基-4-脈陡 基）胺基]-6-氯-1,3,5-三畊縮合物等。 在本發明之三阱系、二苯基酮系、苯甲酸酯系、鎳系、 -23- 200904849 柳酸系等的光安定劑可舉出例如2,2’-二羥基-4-甲氧基二 苯基酮、2-羥基-4-正辛氧基二苯基酮、對第三丁基苯基柳 酸酯、2,4 -二-第三丁基苯基-3, 5-二-第三丁基-4-羥基苯甲 酸酯、2-(2’-羥基- 5’-甲基苯基）苯并三唑、2-(2’-羥基- 3’，5，-二-第三戊基-苯基）苯并三唑、2-(2’-羥基-3’-第三丁基-5’-甲基苯基）-5-氯苯并三唑、2-(2’-羥基-3’，5’_二·第三丁基苯 基）-5·氯苯并三唑、2,5-雙-[5，-第三丁基苯并噚嗖基-(2)]-噻酧、[雙（3, 5-二-第三丁基-4-羥苄基磷酸一乙酯]鎳鹽、2-乙氧基-5-第三丁基-2’-乙基草酸-雙-醯替苯胺85〜90%與2-乙氧基-5-第三丁基- 2’-乙基-4’-第三丁基草酸-雙-醯替苯 胺10〜15%之混合物、2-(3,5-二-第三丁基-2-羥苯基）苯并三 唑、2-[2-羥基-3,5-雙（α，α-二甲基苄基）苯基]-2H-苯并三 唑、2-乙氧基-2’-乙基草酸-雙醯替苯胺、2-[2’-羥基-5’-甲 基-3’-(3”，4”，5”，6”-四氫酞醯亞胺-甲基）苯基]苯并三唑、雙 (5-苯甲醯基-4-羥基-2-甲氧基苯基）甲烷、2-(2’-羥基-5’-第三辛基苯基）苯并三唑、2-羥基-4-異辛氧基二苯基酮、2-羥基-4-十二烷氧基二苯基酮及2-羥基-十八烷氧基二苯基 酮等。 防靜電劑 在本發明之防靜電劑，可舉出甘油脂肪酸（C8〜C22) 酯、山梨糖醇酐脂肪酸（C 8〜C 22)酯、丙二醇脂肪酸（C 8〜C22) 酯、蔗糖酸脂肪酸（C 8〜C 22)酯、檸檬酸一（二或三）硬脂酸 酯、新戊四醇脂肪酸（C 8〜C 18)酯、三羥甲基丙烷脂肪酸 (C8〜C18)酯、聚甘油脂肪酸（C8-C22)酯、聚氧乙烯（20莫耳） 甘油脂肪酸（C 1 2〜C 1 8 )酯、聚氧乙烯（2 0莫耳）山梨糖醇酐脂 -24- 200904849 肪酸（C12〜C18)酯、聚乙二醇脂肪酸（C8〜C22)酯、聚氧乙稀 脂肪醇（C12〜C20)醚、聚氧乙烯（4~50莫耳）烷基（C4以上） 苯基醚、Ν,Ν-雙（2-羥乙基）脂肪（C8~C18)胺、脂肪酸與二 乙醇胺之縮合生成物、聚氧丙烯聚氧乙烯嵌段聚合物、聚 乙二醇、聚丙二醇等的非離子性界面活性劑；烷基（c丨〇〜C2〇) 磺酸鹽（Na、K、NH4)、烷基萘磺酸鹽（Na)、二烷基（C4〜C16) 砸琥珀酸鈉、烷基（C8〜C20)硫酸鹽（Na、K、NH4)、脂肪酸 (C8〜C22)鹽（Na、K、NH4)等的陰離子界面活性劑；N_醯基 (C 8〜C 1 8 )肌胺酸酯等的兩性界面活性劑；聚丙烯酸及其鈉 鹽等其他的助劑等。 滑劑 在本發明的樹脂組成物中能夠調配的滑劑，可舉出己 醯胺、辛醯胺、硬脂醯胺、油醯胺、順二十二碳烯醯胺伸 乙基雙硬脂醯胺、月桂醯胺、二十二烷醯胺、亞甲雙硬脂 醯胺、蓖麻醇醯胺等的碳數3~30的飽和或不飽和脂肪族醯 胺及其衍生物；硬脂酸丁酯、硬脂酸異丁酯等的碳數3〜30 的飽和或不飽和脂肪族酯及其衍生物；市售的矽脫模劑矽 油、矽膠等的矽化合物；市售的氟系脫模劑 '四氟化乙烯 等的氟系化合物等。 金屬鈍化劑 在本發明的樹脂組成物中能夠調配的金屬鈍化劑可 舉出3-1^’-柳醯基胺基-1，2,4-三唑、柳醛、柳醯肼、：^，>>1，-雙-[3-(3,5-二-第三丁基-4-羥苯基）丙醯基]醯肼、草醯基_ 雙[亞苄基醯肼]、9,10-二氫-9-氧雜_10-磷菲-ίο-氧化物、 3，4,5,6-二苯并- I，2 -氧雜氯化錢-2-氧化物、參[2 -第三丁基 -25- 200904849 -4-硫（2，-甲基_4’-羥基-5-第三丁基）苯基-5-甲基]苯基亞磷 酸酯、2,2’·草醯胺-雙-[乙基- 3(3,5-二-第三丁基·4-羥苯基） 丙酸酯]等。 核劑 在本發明的樹脂組成物中能夠調配的核劑可舉出 1，3,2,4-二-亞苄基-山梨糖醇、；ι，3,2,4-二-二-(對甲基-二-亞苄基）山梨糖醇、1，3,2,4-二-(對乙基-亞苄基）山梨糖醇、 1，3,2,4-二-(2’，4，-二-甲基-亞苄基）山梨糖醇、1，3-對氯-亞 ί ' 苄基-2,4-對甲基-亞苄基-山梨糖醇、1,3,2,4-二-(對丙基- \ 亞苄基）山梨糖醇、單羥基-二-對第三丁基苯甲酸鋁、雙（4-第三丁基苯基）磷酸鈉、2,2，-亞甲基-雙-(4,6-二-第三丁基-苯基）磷酸鈉、滑石、苯甲酸鈉及2,2’-亞甲基-雙-(4,6-二-第三丁基苯基）磷酸鋰等。 中和劑及抗酸劑 在本發明的樹脂組成物中能夠調配的中和劑及抗酸 劑可舉出硬脂酸鋰、硬脂酸1,2-羥基鋰、硬脂醯乳酸鈉、 ( 硬脂酸鈉、硬脂酸鉀、蘿酸鋰、二十八酸鋰 '蘿酸鈉、二 十八酸鈉、硬脂醯乳酸鈣、蘿酸鈣、二十八酸鈣 '硬脂醯 乳酸鎘、月桂酸鎘、蓖麻醇酸鎘、環烷酸鋇、2-乙基己糖 酸鋇、硬脂酸鋇、2-乙基己糖酸鋇、硬脂酸鈣、月桂酸鈣、 蓖麻醇酸鈣、硬脂酸緦、硬脂酸綷、月桂酸鋅、蓖麻醇酸 鋅、2 -乙基己糖酸鋅、硬脂酸鋅、二元硬脂酸鉛、環烷酸 鉛、硬脂酸錫、硬脂酸鋁及硬脂酸鎂等高級脂肪酸、烷基 乳酸的或鹼土類金屬鹽：鹼性鎂-鋁-羥基-碳酸鹽-水滑石 (hydrotalcite)、鹼性沸石、表氯醇與雙酚Α聚合物類、環 -26- 200904849 氧化大豆油類、環氧化脂肪化單酯類、環氧化脂環狀脂肪 酸類、聚碳化二亞胺類及異氰酸酯系化合物等。 塡料 在本發明的樹脂組成物中能夠調配的塡料可舉出氧 化鎂、氧化鋁、氧化矽、氧化鈣、氧化鈦、氧化鉻（3價）、 氧化鐵、氧化鋅、二氧化矽、矽藻土、氧化鋁纖維、氧化 銻、鋇肥粒鐵、緦肥粒鐵、氧化鈹、浮石、浮石氣球等的 氧化物；氫氧化鎂、氫氧化鋁、鹼性碳酸鎂等的鹼性物或 氫氧化物；碳酸鎂、碳酸鈣、硫酸鋇、硫酸銨、亞硫酸鈣、 白雲石、碳鈉鋁石（Dawsonite)等的碳酸鹽；硫酸鈣、硫酸 鋇、硫醯銨、亞硫酸鈣、鹼性硫酸鎂等的（亞）硫酸鹽；矽 酸鈉、矽酸鎂、矽酸鋁、矽酸鉀、矽酸鈣、滑石、黏土、 雲母、石棉、玻璃纖維、蒙脫石、玻璃氣球、玻璃珠、膨 土等的矽酸鹽；高嶺土（陶土）、珠層鐵、鐵粉、銅粉、鉛 粉、鋁粉、硫化鉬、硼纖維、碳化矽纖維、黃銅纖維、鈦 酸鉀、鈦酸銷酸鉛、硼酸鋅、硼酸鋁、偏硼酸、硼酸鈣及 硼酸鈉等。 難燃劑 本發明的難燃劑沒有限定，可舉出在銻系添加鹵素系 之類型，非鹵素系有多磷酸系、金屬氫氧化物系等。 具體上，銻化合物可舉出三氧化銻、四氧化銻及五氧 化銻作爲代表。 鹵素系有溴系難燃劑、氯系難燃劑等，溴系難燃劑的 具體代表例可舉出十溴二苯基醚、六溴苯、六溴環十二烷、 四溴雙酚A、四溴雙酚A -四溴雙酚A -二環氧丙基醚共聚 -27- 200904849 物。氯系難燃劑的具體代表例有氯化石蠟、全氯環癸焼。 多磷酸系的具體代表例可舉出多磷酸銨、多磷酸三聚 氰胺。 金屬氫氧化物系（亦有稱爲金屬水合物之情況）可舉出 氫氧化鎂、氫氧化鋁等。 如此進行所得到的聚酯彈性體與先前的酯交換聚合 法或酯化聚合法所得到的聚合物比較，游離物較少、不會 損害氣味性、耐熱性且副生成的四氫呋喃量較少’而且與 先前的酯交換聚合法、酯化聚合法比較時生產力較佳’在 製造成本面係有利的。 在本發明所製造的聚酯彈性體能夠以作爲單體或樹 脂組成物的方式而利用於纖維、薄膜、薄片、電氣電子組 件、汽車組件及家電組件等各種用途。 實施例 以下，藉由實施例來具體地說明本發明。 (1) 對比黏度 將〇.〇5克試料溶解於25毫升的混合溶劑（苯酚/四氯 乙烷= 6 0/4 0)，並使用奧士瓦黏度計在30°C測定。 (2) 熱特性測定 所得到聚酯彈性體的熱特性係使用 TA Instruments(股）製DSC，試樣量爲10毫克，在氮氣環境下 且測定溫度條件係依照所得到聚酯彈性體來適當地設定。 升溫、降溫速度條件係以20°C /分鐘從室溫升溫到25 0°C以 下，以20°C /分鐘冷卻至室溫，並重複施行2次，將第2 次升溫時所得到的融點（Tm)作爲測定結果。 -28 - 200904849 (3) 游離物含量、線狀低聚物含量 將試樣溶解於溶劑（六氟異丙醇/氯仿=2/3 (v/v))3毫％ 混合液，並添加2 0毫升氯仿來稀釋。對其添加1 〇毫升甲 醇並使聚合物沈澱後，過濾。將濾液蒸發乾涸並使用10毫 升二甲基甲醯胺再溶解。將離心過濾後的溶液供給至液相 層析法質量分析裝置（LC-MS)來定量各成分。測定條件係如 下述。 [LC條件] f 裝置：Agilent 1100 柱：Imtakt Cadenza CD-C18 2x150 毫米 移動相：A 0.1 %甲酸、B 乙腈 〇 分鐘（10%B)-40(98)-60(98) 流速：0.2毫升/分鐘 柱溫度：4 (TC 植入量：5微升 檢測波長：2 5 8奈米 , [MS條件] 裝置：BRUKER DALTONICS esquire 3 0 0 0 Plus 離子化法：E S I (陽性） (4) 耐熱性 使聚合物在空氣環境下於250 °C熔融5分鐘，使用目 視熔融前後的著色差異之方法來實施。 〇：幾乎未著色 △:稍黃色著色、或是灰色 X :明顯黃色著色 -29- 200904849 (5) 官能試驗（氣味性） 使用YAM ΑΤΟ科學製真空乾燥器DP6i型並使用預先 減壓乾燥的聚酯彈性體碎片，在成形材料料斗內進行乾燥 惰性氣體（氮氣）吹塡，用以防止在成形中碎片的吸濕。 M-l5〇C(DM)射出成形機之可塑化條件係給料螺桿轉 數=70%、螺桿轉數= i20rpm、背壓爲〇.5MPa、圓筒溫度係 從料斗正下方依照順序設定爲45 °C、240它、以下包含噴 嘴爲24 5 °C ’成形帶階段成形板並切取3毫米板，將其放 入70 °C的離子交換水保持30分鐘後，冷卻至室溫並放置i 個月後’進行風味、臭味等的試驗。比較用空白試驗係使 用離子交換水。官能試驗係由參加者1 0人，依照以下基準 來實施，並以平均値比較。 〇:未感覺異味、臭味。1:感覺與空白試驗稍有差異。2: 感覺與空白試驗有差異。3:感覺與空白試驗有相當的差 異。4:感覺與空白試驗有非常大的差異。 (6) 四氫呋喃含量的測定、算出方法 將2 0克鑄塑而成的碎片放入能夠密閉的容器，並重 複減壓氮氣取代3次後，在氮氣密封下密閉。將密、@^ 保持在設定於245 °C的油浴中30分鐘後，選取碎片狀的，溶 融樹脂（長徑爲3〜5毫米、短徑2~4毫米、高度2〜4毫米、 粒重爲20〜30毫克/個）。選取5克碎片後，在1〇分鐘以內 計量放入試樣瓶中並添加5 0克的純水，以試樣瓶內無空隙 的方式關閉蓋子並以四氫呋喃不會揮發的方式加以密K。 因爲若從碎片計量至試樣瓶密閉爲止花費時間胃，HD夫 喃會從碎片揮發，會無法正確地進行分析。接著，將密閉 -30- 200904849 後的試樣瓶放入溫風乾燥器，於50 °C 24小時以上’並在純 水中萃取在聚酯彈性體中的四氫呋喃。被萃取的四氫卩夫喃 濃度之測定係相對於1毫升萃取液，添加20微升1，4_二曙 烷標準原液5180微克/毫升並注入氣體層析儀（Agilent公 司製6850系列II)來進行。將該四氫呋喃濃度乘以10倍， 來算出聚酯彈性體中的四氫呋喃含量。 以下，使用實施例來詳細地說明本發明，但是只要未 超過本發明的要旨，本發明未限定於以下的實施例。 f 實施例1 在縱型反應罐加入36.9公斤DMT(對酞酸二甲酯）、 25.8公斤BD( 丁二醇）、36.5公斤PTMG(聚伸丁二醇、數量 平均分子量1 000)、150克抗氧化劑IRGANOX 1 3 3 0(曰本 CIBA-GEIGY公司製）、60克TBT(四氫呋喃），並以2小時 從130°C升溫至220°C，來進行常壓酯交換反應。接著，以 1小時從220°C升溫至245°C，並減壓至2hPa以下在245 t進行聚合反應至規定的熔融黏度。聚合反應後，在同一 / 反應槽添加3 7 5克IRG AN OX 1 3 3 0作爲四氫呋喃含量降低 用的抗氧化劑，並減壓至2hPa以下而混合5分鐘。混合後， 鑄塑而使聚合物碎片化。 所得到的聚酯彈性體之對比黏度爲1.94 dl/ g、Tm 1 8 7 °C、四氫呋喃（THF)含量爲60 0ppm、游離對酞酸爲9ppm、 游離丁二醇爲8ppm、線狀低聚物200ppm，耐熱性、官能 性試驗良好。又，因爲四氫呋喃的含量少，在鑄塑製程等 亦無臭氣的問題。在此，線狀低聚物量係如 TPA-BD-TPA-BD-TPA鍵結而成之分子量爲606的低聚物及 -31- 200904849 分子量比其小之低聚物的合計。 實施例2 至聚合反應完成爲止係與實施例1同樣地進行。聚合 反應後，在同一反應槽添加 150 克 SANDSTAB P-EPQ(CLARIANT JAPAN公司製）作爲抗氧化劑，並減壓至 2hPa以下而混合5分鐘。混合後，鑄塑而使聚合物碎片化。 所得到的聚酯彈性體之對比黏度爲2.(Hdl/g、Tml87 °C、THF含量爲440ppm、游離對酞酸爲8ppm、游離丁二 醇爲7ppm、線狀低聚物1 95ppm，耐熱性、官能性試驗良 好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦無臭氣 的問題。 實施例3 至聚合反應完成爲止係與實施例1同樣地進行。聚合 反應後，在同一反應槽添加 150克IRGANOX 1 098(曰本 CIBA-GEIGY公司製）作爲抗氧化劑，並減壓至2hPa以下而 混合5分鐘。混合後，鑄塑而使聚合物碎片化。 所得到的聚酯彈性體之對比黏度爲2.00 dl/g、Tm 186 °C、THF含量爲8 3 0ppm、游離對酞酸爲8ppm、游離丁二 醇爲5ppm、線狀低聚物1 84ppm，耐熱性、官能性試驗良 好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦無臭氣 的問題。 實施例4 至聚合反應完成爲止係與實施例1同樣地進行。聚合 反應後，在同一反應槽添加、3 7 5克IRGANOX1010(日本 CIBA-GEIGY公司製）、150克IRGANOX 1 0 9 8作爲抗氧化 -32- 200904849 劑，並減壓至2hPa以下而混合1 〇分鐘。混合後，減壓至 2hPa以下並進行聚合反應至規定的熔融黏度後，鑄塑而使 聚合物碎片化。 所得到的聚酯彈性體之對比黏度爲1 . 9 5 d 1 / g、T m 1 8 5 °C、THF含量爲5 00Ppm、游離對酞酸爲9ppm、游離丁二 醇爲9 p p m、線狀低聚物2 Ο 2 p p m，耐熱性、官能性試驗良 好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦無臭氣 的問題。 實施例5 在縱型反應罐加入4 1 .8公斤PBT、36.5公斤PTMG (數 量平均分子量 1〇〇〇)、150 克 IRGANOX1330、41 克 TBT， 並以1小時從1 30°c升溫至245 °c且同時減壓至2hPa以 下。隨後，在245 °C下，進行聚合反應至規定的熔融黏度。 聚合反應後，添加150克IRGANOX 1330、150克SANDSTA BP-EPQ ,並實施減少混合，隨後，鑄塑而使聚合物碎片化。 所得到的聚酯彈性體之對比黏度爲2.00dl/g、Tml84 ◦C、THF含量爲5 5 0ppm、游離對酞酸爲7ppm、游離丁二 醇爲1 .Oppm、線狀低聚物205ppm，耐熱性、官能性試驗 良好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦無臭 氣的問題。 實施例6 將PBT(數量平均分子量20000)以 4.2公斤/小時、 PTMG(數量平均分子量 1000)以 3.7 公斤/小時、 IRGANOX 1 3 3 0以15克/小時、TBT以4.1克/小時連續地供 給至雙軸擠壓機，並在2 4 5 °C下混合而得到對比黏度爲 -33- 200904849 0.3 dl/g的聚酯彈性體後，移送至薄膜蒸發反應機並在245 °C減壓至2hPa以下。隨後，進行聚合反應至規定的熔融黏 度。聚合反應完成後，在熔融狀態移送至雙軸擠壓機，並 以15克/小時供給IRGANOX 1 098並混合後，鑄塑而使聚合 物碎片化。所得到的聚酯彈性體之對比黏度爲1 .90dl/g、 Tml85°C、THF含量爲400PPm、游離對酞酸爲5ppm、游離 丁二醇爲 0.8 p p m、線狀低聚物1 4 0 p p m，耐熱性、官能性 試驗良好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦 無臭氣的問題。 實施例7 將 PBT(數量平均分子量 20000)以 4.2公斤/小時、 PTMG(數量平均分子量 1 000)以 3.7 公斤/小時、 IRGANOX 1 3 3 0以1 5克/小時、T B T以4.1克/小時連續地供 給至縱型反應罐，並在24 5 °C下混合後，在24 5 °C減壓至 2hPa以下並進行聚合反應至聚酯彈性體的對比黏度爲 0.4dl/g。隨後，移送至薄膜蒸發反應機並在24 5 °C、2hPa 以下進行聚合反應至規定的熔融黏度。聚合反應完成後， 在熔融狀態移送至抗氧化劑添加用雙軸擠壓機，並以1 5克 M、時供給 IRGANOX 1 3 3 0、15 克 /小時供給 SANDSTAB P-EP Q並混合後，鑄塑而使聚合物碎片化。所得到的聚酯 彈性體之對比黏度爲1.90dl/g、Tml87°C 、THF含量爲 3 5 0ppm、游離對酞酸爲3ppm、游離丁二醇爲〇.9ppm、線 狀低聚物1 30ppm，耐熱性、官能性試驗良好。又，因爲四 氫呋喃的含量少，在鑄塑製程等亦無臭氣的問題。 實施例8 -34- 200904849 將PBT(數量平均分子量20000)以4.2公斤/小時、 PTMG(數量平均分子量 1〇〇〇)以 3.7 公斤/小時、 IRGANOX 1 3 3 0以15克/小時、TBT以4」克/小時連續地供 給至雙軸擠壓機’並在2 3 0〜2 9 0 °C的料筒加熱器下加熱混 合，且反應至對比黏度爲0.2〜0.5dl/g。接著，連續地移送 至橫型雙軸擠壓機並在245 °C減壓至2hPa以下，且進行聚 合反應至規定的熔融黏度。聚合反應完成後，在熔融狀態 移送至抗氧化劑添加用雙軸擠壓機，並以1 5克/小時供給 IRGANOX 1 09 8、以 1 5 克 / 小時供給 s AN D S T A B P - E P Q 並混 合後，鑄塑而使聚合物碎片化。所得到的聚酯彈性體之對 比黏度爲2.45dl/g、Tml90°C、THF含量爲150ppm、游離 對酞酸爲 5ppm、游離丁二醇爲 〇.7ppm '線狀低聚物 1 4 2 p p m，耐熱性、官能性試驗良好。又，因爲四氫呋喃的 含量少，在鑄塑製程等亦無臭氣的問題。 實施例9 將PBT(數量平均分子量20000)以27.4公斤/小時、 PTMG(數量平均分子量 1 000)以 2.8 公斤/小時、 IRGANOX 1 3 3 0以60克/小時、TBT以12克/小時連續地供 給至雙軸擠壓機，並在23 0〜290°C的料筒加熱器下加熱混 合，且反應至對比黏度爲0.2〜0.5dl/g。接著，連續地移送 至橫型雙軸擠壓機並在24 5 °C減壓至2hPa以下，且進行聚 合反應至規定的溶融黏度。聚合反應完成後，在熔融狀態 移送至抗氧化劑添加用雙軸擠壓機，並以1 5克/小時供給 IRGANOX 1 3 3 0、以 1 5 克 / 小時供給 IR G ΑΝ Ο X 1 0 9 8、以 1 5 克/小時供給SANDS TAB P-EPQ並混合後，鑄塑而使聚合物 -35- 200904849 碎片化。所得到的聚酯彈性體之對比黏度爲1 . 1 5 dl/g、 Tm222〇C、THF含量爲90ppm、游離對酞酸爲5ppm、游離 丁二醇爲0.7 p p m、線狀低聚物1 6 5 p p m，耐熱性、官能性 試驗良好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦 無臭氣的問題。 實施例1 〇 將 PBT(數量平均分子量 20000)以 6.9公斤/小時、 PTMG(數量平均分子量1 000)以0.7公斤/小時、丁二醇（BD) f 以1 〇克/小時、IRGANOX 1 3 3 0以1 5克/小時、TBT以3.0 克/小時連續地供給至雙軸擠壓機，並在2 3 0〜290°C的料筒 加熱器下加熱混合，且反應至對比黏度爲〇.2~0.5dl/g。接 著，連續地移送至橫型雙軸擠壓機並在245 °C減壓至2hPa 以下，且進行聚合反應至規定的熔融黏度。聚合反應完成 後，在熔融狀態移送至抗氧化劑添加用雙軸擠壓機，並以 15 克/小時供給 IRGANOX 1 3 3 0、以 15 克/小時供給 IRGANOX 1 09 8並混合後，鑄塑而使聚合物碎片化。所得到 I. 的聚酯彈性體之對比黏度爲1.10dl/g、Tm223 °C、THF含量 爲5 0ppm、游離對酞酸爲4ppm、游離丁二醇爲〇.6ppm、線 狀低聚物168ppm，耐熱性、官能性試驗良好。又，因爲四 氫呋喃的含量少，在鑄塑製程等亦無臭氣的問題。 實施例1 1 將 PBT(數量平均分子量20000)以 5.8公斤/小時、 PTMG(數量平均分子量1〇〇〇)以1.9公斤/小時、丁二醇（BD) 以2 0克/小時、IR G ΑΝ Ο X 1 3 3 0以1 5克/小時、T B T以3 · 0 克/小時連續地供給至雙軸擠壓機，並在2 3 0〜29 0°C的料筒 -36- 200904849 加熱器下加熱混合，且反應至對比黏度爲0.2〜0.5 dl/g。接 著，連續地移送至橫型雙軸擠壓機並在24 5 °C減壓至2hP a 以下，且進行聚合反應至規定的熔融黏度。聚合反應完成 後，在熔融狀態移送至抗氧化劑添加用雙軸擠壓機，並以 15 克/小時供給 IRG AN 0X1010、以 15 克/小時供給 IRGANOX 1 098並混合後，鑄塑而使聚合物碎片化。所得到 的聚酯彈性體之對比黏度爲1.60dl/g、Tm210°C、THF含量 爲60ppm、游離對酞酸爲5ppm'游離丁二醇爲0.8ppm、線 狀低聚物1 60ppm，耐熱性、官能性試驗良好。又，因爲四 氫呋喃的含量少，在鑄塑製程等亦無臭氣的問題。 實施例1 2 將PBT(數量平均分子量20000)以3.6公斤/小時、 PTMG(數量平均分子量 2000)以 4.1 公斤/小時、 IRGANOX 1 3 3 0以1 5克/小時、T B T以5 · 0克/小時連續地供 給至雙軸擠壓機，並在2 3 0〜29 0 °C的料筒加熱器下加熱混 合，且反應至對比黏度爲0.2〜〇.5dl/g。接著，連續地移送 至橫型雙軸擠壓機並在24 5 °C減壓至2hPa以下，且進行聚 合反應至規定的熔融黏度。聚合反應完成後，在熔融狀態 移送至抗氧化劑添加用雙軸擠壓機，並以1 5克/小時供給 IRGANOX 1 3 3 0、以 15 克 / 小時供給 IRG ANOX 1 0 1 0、以 15 克/小時供給SAND STAB P-EPQ並混合後，鑄塑而使聚合物 碎片化。所得到的聚酯彈性體之對比黏度爲2.30dl/g、 Tm205 °C、THF含量爲l〇〇ppm、游離對酞酸爲5ppm、游離 丁二醇爲0_6ppm、線狀低聚物120Ppm，耐熱性、官能性 試驗良好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦 無臭氣的問題。 -37- 200904849 實施例1 3 將PBT(數量平均分子量20000)以3.6公斤/小時、聚 碳酸酯二醇（PCD)以1.4公斤/小時、IRGANOX 1 3 3 0以15 克/小時，並在22 5〜290 °C的料筒加熱器下加熱混合。接著， 連續地移送至橫型雙軸擠壓機並在22 5~245 °C減壓至2hPa 以下，且進行聚合反應至規定的熔融黏度。聚合反應完成 後，在熔融狀態移送至抗氧化劑添加用雙軸擠壓機，並以 15 克/小時供給 IRGANOX 1 3 3 0、以 15 克/小時供給 IRGANOX1010、以 15 克 /小時供給 IRGANOX1098、以 15 克/小時供給SAND STAB P-EPQ並混合後，鑄塑而使聚合物 碎片化。所得到的聚酯彈性體之對比黏度爲1.25dl/g、 Tm214°C、THF含量爲5 0PPm、游離對酞酸爲6ppm、游離 丁二醇爲〇.9ppm、線狀低聚物125ppm，耐熱性、官能性 試驗良好。又，因爲四氫呋喃的含量少，在鑄塑製程等亦 無臭氣的問題。 實施例1 4 將PBT(數量平均分子量2 000 0)以3.6公斤/小時、PCD 以 1.4公斤/小時、IRGANOX 1 3 3 0以 15克/小時，並在 22 5〜2 9 0 °C的料筒加熱器下加熱混合。接著，連續地移送至 橫型雙軸擠壓機並在22 5〜245 °C減壓至2hPa以下，且進行 聚合反應至規定的熔融黏度。聚合反應完成後，在熔融狀 態移送至抗氧化劑添加用雙軸擠壓機，並以1 5克/小時供 給SAND STAB P-EPQ並混合後，鑄塑而使聚合物碎片化。 所得到的聚酯彈性體之對比黏度爲1.15dl/g、Tm212°C、THF 含量爲 40Ppm、游離對酞酸爲 5PPm、游離丁二醇爲 〇-8ppm、線狀低聚物122ppm，耐熱性、官能性試驗良好。 又’因爲四氫呋喃的含量少，在鑄塑製程等亦無臭氣的問 -38- 200904849 題。 實施例1 5 將PBT(數量平均分子量20000)以 4.2公斤/小時、 PTMG(數量平均分子量 1 000)以 3.7 公斤/小時、 IRGANOX 1 3 3 0以15克/小時、TBT以4.1克/小時連續地供 給至雙軸擠壓機，並在2 3 0〜2 9 (TC的料筒加熱器下加熱混 合，且反應至對比黏度爲0.2〜0.5dl/g。接著，連續地移送 至橫型雙軸擠壓機並在24 5 °C減壓至2hPa以下，在對比黏 度比規定黏度低〇.2dl/g之聚合反應後期，以15克/小時供 給IRGANOX10 10、以15克/小時供給IRGANOX 1 09 8並混 合後，鑄塑而使聚合物碎片化。所得到的聚酯彈性體之對 比黏度爲 2.05dl/g、Tml89°C、THF 含量爲 ΐ00ρρπι、游離 對酞酸爲 6 p p m、游離丁二醇爲 0.7 p p m、線狀低聚物 1 3 0 p p m ’耐熱性、官能性試驗良好。又，因爲四氫肤喃的 含量少，在鑄塑製程等亦無臭氣的問題。 實施例1 6 將PBT(數量平均分子量20000)以4_2公斤/小時、 PTMG(數量平均分子量 1 000)以 3.7 公斤/小時、 IRGANOX 1 3 3 0以1 5克/小時、T B T以4.1克/小時連續地供 給至雙軸擠壓機，並在2 3 0〜2 9 0 °C的料筒加熱器下加熱混 合’且反應至對比黏度爲0.2〜0.5dl/g。接著，連續地移送 至橫型雙軸擠壓機並在245 °C減壓至2hPa以下，在對比黏 度比規定黏度低〇」dl/g之聚合反應後期，以15克/小時供 給IRGANOX1098並混合’來進行聚合反應至規定的熔融 黏度。聚合反應完成後’移送至抗氧化劑添加用雙軸擠壓 機，並以15克/小時供給SANDSTAB P-EPQ並混合後，鑄 塑而使聚合物碎片化。所得到的聚酯彈性體之對比黏度爲 -39- 200904849 1.90dl/g、Tml86°C、THF含量爲125PPm、游離對酞酸爲 6ppm、游離丁二醇爲〇.7ppm、線狀低聚物140ppm，耐熱 性、官能性試驗良好。又，因爲四氫呋喃的含量少，在鑄 塑製程等亦無臭氣的問題。 比較例1 至聚合反應完成係與實施例1同樣地進行，聚合反應 完成後，立即鑄塑而使聚合物碎片化。所得到的聚酯彈性 體之對比黏度爲2.04(11/经、1'111184°(3、111?含量爲9000卩卩〇1、 游離對酞酸爲20ppm、游離丁二醇爲15ppm、線狀低聚物 255ppm，耐熱性、官能性試驗不良。 比較例2 在縱型反應罐，添加51.1公斤DMT、38.7公斤BD、 18.7 公斤 PTMG(數量平均分子量 1 000)、150 克 IRGANOX1330、60克TBT，並以與實施例1同樣的反應條 件來完成聚合反應。聚合反應完成後，立即鑄塑而使聚合 物碎片化。所得到的聚酯彈性體之對比黏度爲1.50dl/g、 Tm212〇C、THF含量爲5700ppm、游離對酞酸爲15ppm、游 離丁二醇爲20PPm、線狀低聚物280ppm，耐熱性、官能性 試驗不良。 比較例3 在縱型反應罐，添加31.7公斤DMT、23.2公斤BD、 40.8 公斤 PTMG(數量平均分子量 2000)、150 克 IRGANOX1330、62.3克TBT，並以與實施例1同樣的反應 條件來完成聚合反應。聚合反應完成後，立即鑄塑而使聚 合物碎片化。所得到的聚酯彈性體之對比黏度爲2.20 dl/g、 Tm203 〇C、THF含量爲6200ppm、游離對酞酸爲17ppm、游 離丁二醇爲16ppm、線狀低聚物2 5 8ppm，耐熱性、官能性 -40- 200904849 試驗不良。 比較例4 在縱型反應罐，添加60.4公斤DMT、47.0公斤BD、 7.1 公斤 PTMG(數量平均分子量 1 00 0)、 150 克 IRGANOX1330、60 克 TBT，以 2 小時從 130 °C 升溫至 220 t，來進行常壓酯交換反應。接著，以1小時從22 0 °C升 溫至245 °C，並減壓至2hPa以下，在24 5 °C進行聚合反應 至規定的熔融黏度。聚合反應完成後，立即鑄塑而使聚合 物碎片化。所得到的聚酯彈性體之對比黏度爲1 . 1 4dl/g、 Γ Tm22 3 〇C、THF含量爲5 000ppm、游離對酞酸爲20ppm、游 離丁二醇爲25ppm、線狀低聚物3 05 ppm，耐熱性、官能性 試驗不良。 比較例5 在縱型反應罐，添加3 1 .6公斤對酞酸（TPA)、25.8公 斤BD、36.5公斤PTMG(數量平均分子量1 000)、150克 IRGANOX1330、60 克 TBT，以 2 小時從 130〇C 升溫至 220 °C，來進行常壓酯交換反應。接著，以1小時從220°C升 溫至245 °C ’並減壓至2hPa以下，在245 °C進行聚合反應 〃 至規定的熔融黏度。聚合反應完成後，立即鑄塑而使聚合 物碎片化。所得到的聚酯彈性體之對比黏度爲2.00dl/g、 Tml86°C、THF含量爲i〇〇〇〇ppm、游離對酞酸爲30ppm、 游離丁二醇爲28ppm、線狀低聚物260ppm，耐熱性、官能 性試驗不良。 以上的結果係如表1、表2所示。 41 - 200904849 [表l] 原料組成 二羧酸 成分 甘醇 成分 多元醇 聚酯 觸媒 抗氧化劑的添加時期 IRGANOX 1330 IRGANOX 1010 IRGANOX 1098 SANDOSTAB P-EPQ 實施例1 DMT BD PTMG - TBT 聚合反應前/ 聚合剛完成後 - - - 實施例2 DMT BD PTMG - TBT 聚合反應前 墨 - 聚合反應剛 完成後 實施例3 DMT BD PTMG - TBT 聚合反應前 - 聚合反應剛 完成後 - 實施例4 DMT BD PTMG - TBT 聚合反應前 聚合反應剛 完成後 聚合反應剛 完成後 - 實施例5 - - PTMG PBT TBT 聚合反應前/ 聚合剛完成後 - - 聚合反應剛 完成後 實施例6 - - PTMG PBT TBT 聚合反應前 - 聚合反應剛 完成後 - 實施例7 - - PTMG PBT TBT 聚合反應前/ 聚合剛完成後 - - 聚合反應剛 完成後 實施例8 - - PTMG PBT TBT 聚合反應前 - 聚合反應剛 完成後 聚合反應剛 完成後 實施例9 - PTMG PBT TBT 聚合反應前/ 聚合剛完成後 - 聚合反應剛 完成後 聚合反應剛 完成後 實施例10 - - PTMG PBT TBT 聚合反應前/ 聚合剛完成後 - 聚合反應剛 完成後 實施例11 - BD PTMG PBT TBT 聚合反應前 聚合反應剛 完成後 聚合反應剛 完成後 - 實施例12 PTMG PBT TBT 聚合反應前/ 聚合剛完成後 聚合反應剛 完成後 - 聚合反應剛 完成後 實施例13 PCD PBT TBT 聚合反應前/ 聚合剛完成後 聚合反應剛 完成後 聚合反應剛 完成後 - 實施例14 PCD PBT TBT 聚合反應前 - - 聚合反應剛 完成後 實施例15 PTMG PBT TBT 聚合反應前 聚合反應後期 聚合反應後期 - 實施例16 - PTMG PBT TBT 聚合反應前 - 聚合反應後期 聚合反應剛 完成後 比較例1 DMT BD PTMG TBT 聚合反應前 _ . 比較例2 DMT BD PTMG TBT 聚合反應前 _ • • 比較例3 DMT BD PTMG - TBT 聚合反應前 • • 比較例4 DMT BD PTMG - TBT 聚合反應前 - - 比較例5 TPA BD PTMG - TBT 聚合反應前 - - - -42- 200904849 [表2] 聚酯彈性體特性 線狀低聚物 對比黏度 Tm THF含量 耐熱性 官能試驗 游離酸 游離二醇 合計量 (dl/g) (°c) (ppm) (色調） (氣味性） (ppm) (ppm) (ppm) 實施例1 1.94 187 600 △~〇 1 9 8 200 實施例2 2.04 187 440 △〜ο 1 8 7 195 實施例3 2.00 186 830 △~〇 1 8 5 184 實施例4 1.95 185 500 △〜〇 1 9 9 202 實施例5 2.00 184 550 △〜ο 0 7 1.0 205 實施例6 1.90 185 400 〇 0 5 0.8 140 實施例7 1.90 187 350 〇 0 3 0.9 130 實施例8 2.45 190 150 〇 0 5 0.7 142 實施例9 1.15 222 90 〇 0 5 0.7 165 實施例10 1.10 223 50 〇 0 4 0.6 168 實施例11 1,60 210 60 〇 0 5 0.8 160 實施例12 2.30 205 100 〇 0 5 0.6 120 實施例13 1.25 214 50 〇 0 6 0.9 125 實施例14 1.15 212 40 〇 0 5 0.8 122 實施例15 2.05 189 100 〇 0 6 0.7 130 實施例16 1.90 186 125 〇 0 6 0.7 140 比較例1 2.04 184 9000 X 4 20 15 255 比較例2 1.50 212 5700 X 4 15 20 280 比較例3 2.20 203 6200 X 4 17 16 258 比較例4 1.14 223 5000 X 4 20 25 305 比較例5 2.00 186 10000 X 4 30 28 260 -43- 200904849 產業上之可利 在由二拜 於2 5 0的甘醇 元醇所得到 〇 · 0 1 〜5 w t %、| 50ppm以下、 的線狀低聚物 性而成的聚酯 的纖維、成形 【圖式簡單說 【主要元件符 4rni 撕0 用性 丨酸成分、以1，4-丁二醇爲主體之分子量爲小 成分、及數量平均分子量爲400〜70000的多 的聚酯彈性體中’藉由使抗氧化劑爲 3氫呋喃爲2〇00ppm以下、游離二羧酸爲 游離一醇爲l0ppm以下、分子量爲65〇以下 爲30〇PPm以下，能夠得到改善氣味性、耐熱 彈性體組成物，能夠適合使用作爲要求嚴格 體及拉伸薄膜之原料。 明】 號說明】 -44-200904849 IX. Description of the Invention: [Technical Field] The present invention relates to a polyester elastomer composition, relating to a polyester elastomer composition and a process for the preparation thereof, which are free in the aforementioned polyester elastomer composition The amount of dicarboxylic acid, free glycol, linear oligomer, and tetrahydrofuran is extremely small. The polyester elastomer composition is suitable for various applications centered on automobiles, home appliance components, and packaging materials. [Prior Art] A crystalline aromatic polyester unit having polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) as a hard portion, and polybutanediol (PTMG) A polyester elastomer which is an aliphatic polyester structural unit such as an aliphatic polyether or a poly(ε-caprolactone) such as a soft portion, is excellent in heat resistance and mechanical properties, and is widely used in automobiles and home electric appliances. And fields such as films. Conventionally, a method for producing such a polyester elastomer is usually carried out by directly esterifying a dicarboxylic acid with a diol component, or transesterifying a dicarboxylic acid alkyl ester with a diol component to obtain a hydroxy ester and/or Its oligomer, followed by a method of polymerizing it under high vacuum. For example, the embodiment of Patent Document 1 discloses a method by using dimethyl phthalate (DMT), 1,4-butanediol (BD), tetrahydrofuran (THF), and ethylene oxide (oxime). A polyester elastomer is produced by performing a transesterification reaction in the presence of a random copolymer, IRGANOX, and dibutyl titanate (ΤΒΤ), followed by polymerization. Further, Patent Documents 2 and 3 disclose a method of performing a transesterification reaction in the presence of DMT, PTMG, BD, IRGANOX, and hydrazine, and then performing a polymerization reaction to produce a polyester elastomer in 200904849. Patent Document 4 discloses a method of producing a polyester elastomer by performing a transesterification reaction in the presence of phthalic acid (TPA), PTMG, BD, IRGANOX, and TBT, followed by polymerization. [Patent Document 1] JP-A-20001 - 1 2 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Japanese Patent Publication No. 5-71-1750. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, in the polyester elastomer produced by the above method, free acid, free diol, free dicarboxylic acid may remain in a large amount. The acid glycol ester or the like is considered to have problems such as deterioration in appearance, heat resistance, and odor of the polymer. In particular, when the polyester elastomer is used for a food container main body for a microwave oven or a laminate film for a food container, the flavor of the content is changed (the odor is deteriorated). Further, when the polyester elastomer produced by such a method has a hydroxytetramethylene terminal group represented by the formula (1), a large amount of a tetrahydrofuran which is caused by a ring-closing reaction of the terminal group upon heating and melting is generated in a large amount. (THF). -0(CH2)40H Formula (1) Therefore, in a casting process in which a polymerization process containing a polyester elastomer of the formula (1) or a molten polymer is fragmented, a new function is imparted to the polyester elastomer. In the remelting process of the composite process or the forming process, the tetrahydrofuran generated by the thermal decomposition may cause environmental pollution such as odor. In order to solve the above problems, the inventors of the present invention have focused on the results of the discussion, and have made the use of a dicarboxylic acid component and a molecular weight of 1,4-butanediol having a molecular weight of less than 25 Å. The polyester elastomer obtained by the alcohol component and the polyol having a number average molecular weight of 4 〇〇 7 〇〇〇〇 contains an antioxidant of 0. 01~5wt%, tetrahydrofuran is 2〇〇〇ppm or less, free diunsaturated acid is 50ppm or less, free diol is 10ppm or less, and linear oligomer having a molecular weight of 65〇 or less is 300 ppm or less, which can improve odor. The present invention has been completed in terms of properties and heat resistance. That is, the present invention is as follows, [1] a polyester elastomer composition characterized by a glycol component having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol; The polyester elastomer obtained by the polyol having a number average molecular weight of 400 to 700 00 contains 1 to 5 wt% of an antimony agent, 2000 ppm or less of tetrahydrofuran, 50 ppm or less of a free dicarboxylic acid, and a free diol of ruthenium. The linear oligomer having a molecular weight of 650 or less and having a molecular weight of 650 or less is 300 ppm or less. [2] The polyester elastomer composition according to [1], wherein the free dicarboxylic acid is 15 ppm or less, the free diol is 2 ppm or less, and the linear oligomer having a molecular weight of 650 or less is 200 ppm or less. [3] A method for producing a polyester elastomer composition, which is a polyester elastomer composition of [Π or [2], which uses a dicarboxylic acid component and 1,4-butanediol as a main component The glycol component having a molecular weight of less than 250 and a polyol having a number average molecular weight of 400 to 70,000 are used as a raw material to melt-polymerize the polyester elastomer, and at least one of the late stage of the polymerization reaction and the completion of the polymerization reaction is added. 0 1~5 w t % antioxidant. [4] A method for producing a polyester elastomer composition, which comprises the polyacetal elastomer composition of [2], which is a molecular weight of a dicarboxylic acid component and a molecular weight of 1,4-butanediol of 200,904,849. For the glycol component of less than 250, and the polyol having a number average molecular weight of 4 0 0 to 7 0 0 0 as a raw material, the comparative viscosity is previously reacted to 〇. 2 dl/g or more of the polyester elastomer is transferred to a thin film evaporator or a horizontal biaxial reaction tank' and polymerized at 230 to 255 ° C, 2 hPa or less, and at the end of the polymerization reaction and immediately after the completion of the polymerization reaction Add at least one of 0 · 0 1 ~ 5 wt % antioxidant. [5] The polyester elastomer composition of [4] is prepared by transferring it to a thin film evaporator or a horizontal biaxial reaction tank for reaction, followed by transfer to a twin screw extruder and / adding an antioxidant. [6] The method for producing a polyester elastomer composition according to [4] or [5], which comprises heating and mixing a glycol component having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol. The obtained polyester having a number average molecular weight of 500 to 50,000, and a polyol having a number average molecular weight of 400 to 70,000, and reacting the comparative viscosity to 〇 in advance. The polyester elastomer above 2 dl/g is transferred to a film evaporator or a horizontal biaxial reaction tank. [7] A method of producing a polyester elastomer composition according to any one of [3] to [6]. The antioxidant is selected from the group consisting of hindered phenol, sulfur, and phosphorus. [8] The method for producing a polyester elastomer composition according to [6] or [7] wherein the polyester is selected from the group consisting of polybutylene terephthalate, polybutylene naphthalate, and polybutylene adipate. At least one or more of the esters are selected, and the polyol is at least one selected from the group consisting of polytetramethylene glycol, polycarbonate diol, polypropylene glycol, and polyethylene glycol. [9] A fibrous material characterized by extrusion molding a polyester elastomer composition of Π] or [2]. [1 0 ] A sheet-like material characterized in that the vinegar elastomer composition of Π or [2] is formed by extrusion molding. [11] A molded body 'characteristics consisting of a polyester elastomer composition of [〗] or [2]. [1 2 ] A stretched film ‘ is characterized in that the sheet of [丨〇] is stretched in at least one direction. Advantageous Effects of Invention The polyester elastomer of the present invention is excellent in odor and heat resistance, and can be suitably used as a raw material of a fiber, a molded article, a sheet, and a stretched film which are required to be strict. Further, when the polyester elastomer composition is produced by the production method and the compound having a hydroxytetramethylene terminal group of tetrahydrofuran is produced, the content of tetrahydrofuran can be lowered to suppress environmental pollution or deterioration of polymer quality. Further, since the content of the free acid, the free diol, and the low molecular weight oligomer is small, the appearance, heat resistance, and odor of the polymer are excellent. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, the upper limit of the content of tetrahydrofuran is 2 〇〇 O ppm or less in the polyester elastomer composition. The content is the mass of tetrahydrofuran relative to the mass of the polyester elastomer composition. The content of tetrahydrofuran is preferably 1800 ppm or less, more preferably 1500 ppm or less, and most preferably 100 Oppm or less. When the tetrahydrofuran is more than 2,000 ppm, the flavor or flavor of the contents obtained from the polyester elastomer composition to the container or the like tends to be extremely poor. The polyester elastomer composition of the present invention must be added with at least one of a late stage of the polymerization reaction and immediately after the completion of the polymerization reaction to maintain the content of tetrahydrogen 200904849 furan at 200 〇 ppm or less. It is considered that, by this, the function of trapping the free radicals which will disappear in the polymerization reaction, which is usually added before the polymerization reaction, does not disappear, and it can contribute to the thermal stability of the terminal group of the tetrahydrofuran, and it is helpful. Inhibition of the closed loop reaction. In the term "polymerization" as used herein, the viscosity is lower than the specified contrast viscosity. 01~0. The state of 50dl/g. The lower limit of the content of tetrahydrofuran is preferably 〇, but in order to be less than 40 ppm (particularly less than 10 〇〇 ppm when PTMG is used as the polyol), it is necessary to set the production conditions at the expense of productivity, which is not preferable. In the present invention, the free dicarboxylic acid and the free diol in the polyester elastomer composition are each the same compound as the dicarboxylic acid component constituting the polyester elastomer and the glycol component having a molecular weight of less than 250. Further, the linear oligomer having a molecular weight of 650 or less is a linear oligomer in which a dicarboxylic acid molecule of a polyester elastomer and a glycol component having a molecular weight of less than 250 are bonded. According to the present invention, the upper limit of the content of the free low molecular compound is in the polyester elastomer composition, the free dicarboxylic acid is 5 ppm or less, the free diol is 10 ppm or less, and the linear oligomer having a molecular weight of 65 or less. It is below 00ppm. These contents are the mass of each component relative to the content of the polyester elastomer composition. The content of the free dicarboxylic acid is preferably 20 ppm or less, more preferably 15 ppm or less, and most preferably 1 〇 ppm or less, and the content of the free diol is preferably 7 ppm or less, preferably 2 ppm or less. The content of the linear oligomer of not more than 1 ppm is preferably 650 ppm or less in the molecule, and is preferably 200 ppm or less, and more preferably i7 〇 ppm or less. When the content of the free monodecanoic acid is more than 5 〇 ppm, the free diol is less than -10 - 200904849 lOppm, and the content of the linear oligomer having a molecular weight of 650 or less is more than 30 〇 ppm, the polyester elastomer composition is obtained. The flavor or flavor of the contents of the container or the like tends to be extremely poor, and the heat resistance tends to be lowered. When the content of the free diterpene acid is less than 15 ppm, the free diol is less than 2 ppm, and the content of the linear oligomer having a molecular weight of 65 or less is 200 ppm or less, the flavor or flavor of the contents of the container obtained from the polyester elastomer composition It can be maintained for a long period of time and the heat resistance is improved. In order to make the content of the free dicarboxylic acid of the polyester elastomer composition of the present invention 50 ppm or less, the content of the free diol is 10 ppm or less, and the content of the linear oligomer having a molecular weight of 65 0 or less is 300 ppm, in polymerization. At least one of the late stage of the reaction and the completion of the polymerization reaction must be added with an antioxidant. It is considered that the function of trapping the radicals by the antioxidant which is usually lost in the polymerization reaction when it is added before the polymerization reaction does not disappear, and the thermal stability of the polymer can be facilitated. In order to make the content of the free dicarboxylic acid of the polyester elastomer composition of the present invention 15 ppm or less, the content of the free diol is 2 ppm or less, and the content of the linear oligomer having a molecular weight of 650 or less is 200 ppm, which is necessary (1) Adding an antioxidant to at least one of the late stage of the polymerization reaction and the completion of the polymerization reaction, and (2) heating and mixing the glycol having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol. The component obtains a polyester having a number average molecular weight of 5,000 to 50,000, and a polyol having a number average molecular weight of 400 to 70,000 and reacts the comparative viscosity to 〇 in advance. The polyester elastomer of 2 dl/g or more is transferred to a thin film evaporator or a horizontal biaxial reaction tank, and polymerization must be carried out at 23 0 to 2 5 5 ° C '2 hPa or less. Here, the number average molecular weight of 5,000 to 50,000 in the heating and mixing of the 200904849 ester dissolves while generating a part of the depolymerization and reacts with the polyol. When a dicarboxylic acid component or a glycol component having a molecular weight of less than 250 is used as a raw material in the prior DMT method or the TPA method, in order to increase the reaction rate or process stability, it is necessary to excessively add a glycol having a molecular weight of less than 250. The unreacted material remains and the free matter is increased. On the other hand, by carrying out the above (1), since the function of trapping the radicals by the antioxidant which is usually lost in the polymerization reaction when it is added before the polymerization reaction can be maintained, the heat of the polymer when taken out from the reaction tank is maintained. The decomposition is reduced, and the formation of a free dicarboxylic acid, a free diol, and a linear oligomer having a molecular weight of 65 or less can be suppressed. Further, by carrying out the above (2), it is not necessary to excessively add a glycol having a molecular weight of less than 250, and even if a glycol having a molecular weight of less than 250 is added to adjust the reaction rate, the amount of addition is small, so the free matter becomes less. Moreover, since the polymerization reaction is carried out using a thin film evaporator having a high surface renewability or a horizontal biaxial reaction tank, the reaction time can be shortened, and the free dicarboxylic acid, the free diol and the molecular weight of the molecular weight of 6 5 0 due to thermal decomposition can be suppressed. The formation of the following linear oligomers. In addition, when the above (2) is carried out, it is possible to suppress the formation of a free dicarboxylic acid, a free diol, and a linear oligomer having a molecular weight of 65 or less due to thermal decomposition during heating or polymerization or during polymerization. The addition of an antioxidant is a preferred aspect. The lower limit of the content of the free dicarboxylic acid, the free diol, and the linear oligomer having a molecular weight of 65 or less is preferably 〇, in order to make the free dicarboxylic acid less than 3 ppm and the free diol less than 〇·6 ppm and A linear oligomer having a molecular weight of 650 or less is less than 120 ppm, and it is not preferable to set the production conditions at the expense of productivity. Examples of the dicarboxylic acid which can be used in the present invention include oxalic acid, adipic acid, cesium-12-200904849 diacid, sebacic acid, dodecanedioic acid, sebacic acid, succinic acid, glutaric acid, and twelve. Alkanoic acid, dimer acid, hydrogenated dimer acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, p-citric acid 'iso-p-citric acid' tannic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4,-diphenyl ether dicarboxylic acid, 4,4,-diphenyldicarboxylic acid, two apples Dioxalic acid such as oxyethane dicarboxylic acid, 5-sodium sulfonate isophthalic acid and 5-tetrabutyl ortho-isophthalic acid, and the like, and the like, and adipic acid, p-citric acid 'Naphthalene dicarboxylic acid and these dimethyl esters are preferred'. It is particularly preferred to use para-acids of aromatic dicarboxylic acids and dimethyl phthalate. Further, these may be used alone or in combination of two or more. The component other than the aromatic dicarboxylic acid is preferably less than 50% by mole, more preferably less than 4% by mole, more preferably less than 30% by mole, and more than 5 % by mole of the polyester elastomer. The crystallinity tends to decrease, and the moldability and heat resistance tend to be lowered. Examples of the glycol component having a molecular weight of less than 250 include ethylene glycol, hydrazine, 3 - propylene glycol, 1,4-butanediol, heptanediol, hexanediol, octanediol, decanediol, and decanediol. 1,4-cyclohexanedimethanol 'nepentanediol, glycol, pentaerythritol, EO adduct of bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F and TCD glycol A glycol compound or the like may be used alone or in combination of two or more. When the molecular weight is more than 25,000, the crystallinity is lowered and the formability heat resistance is lowered. Among the above glycols, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferred, and 1,4-butanediol is particularly preferred. When 丨, 4-butanediol is used as the main component, it is preferably 60 mol% or more of 14-butanediol, more preferably 70 mol% or more, and most preferably 80 mol% or more. When the amount is less than 60% by mole, the crystallinity is lowered, and the heat resistance of the moldability tends to decrease. Further, a hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxyvaleric acid, -13-200904849 hydroxycaproic acid, hydroxybutyric acid or hydroxybenzoic acid may be contained as a copolymerization component. The carboxylic acid can also be imparted without departing from the scope of the invention. The method of introducing a carboxyl group may be, for example, adding 1,2,4-benzenetricarboxylic anhydride, phthalic anhydride, pyrogallic anhydride, succinic anhydride, 1,8-naphthalenedicarboxylic acid, 1, after polymerizing the polyester elastomer. The addition of the acid hydrazone-modified polyester after the addition of 2-cyclohexanedicarboxylic anhydride or the like may be carried out by chain extension using dimethylolpropionic acid or dimethylolbutanoic acid. Further, examples of the 'glycol component such as 1,2,4-benzenetricarboxylic acid and pyromic acid include glycerin and neopentyl glycol. The amount of the above copolymerized component used is such that the polyester elastomer must be substantially linear. Examples of the polyhydric alcohol include polyethylene glycol, polypropylene glycol, polybutanediol, polyhexamethylene glycol, a copolymer of ethylene oxide and tetrahydrofuran, an addition polymer of ethylene oxide of polypropylene glycol, and polycarbonate. Ester diol, poly neopentyl glycol, poly 3-methyl pentane diol, poly 1,5-pentanediol, bis-A ethylene oxide adduct, double A propylene oxide adduct, double S ring Specific examples of the oxyethylene adduct and the like thereof include a copolymer of polyneopentyl glycol and polyethylene glycol, among which polybutanediol, polycarbonate diol, and polypropylene glycol are polymerized. It is better. The number average molecular weight of the polyol is 4 〇〇 to 70, 〇〇〇, preferably 600 to 60,000, and particularly preferably 1, 〇〇〇 to 50,000. When the number average molecular weight is 400 or more, heat resistance, elastic properties, or moldability are excellent. The number average molecular weight is 70. When 〇〇〇 or less, the phase separation at the time of polymerization can be lowered, and the reactivity can be improved. When the polyol is polycondensed in the butanediol, the upper limit of the number average molecular weight is preferably 10,000, more preferably 4,000, and most preferably 2,0 0. The method for adjusting the molecular weight in the polycarbonate diol of the present invention using aliphatic polycarbonate diol-14-200904849 is not particularly limited, for example, because the molecular weight of the commercially available aliphatic polycarbonate diol is lower than the present invention. The preferred molecular weight range is preferably a method of adjusting the molecular weight by mass-quantifying a commercially available low molecular weight aliphatic polycarbonate diol in advance using a chain extender. In other words, it is preferred to adjust the molecular weight of the aliphatic polycarbonate diol by a high molecular weight in advance using a chain extender in an optimum range as described above, and then supply it to a block reaction to carry out a reaction. The method of using the commercially available low molecular weight product described above is capable of producing an aliphatic polycarbonate diol of any molecular weight, and the production can be carried out on a device using the manufacturing apparatus of the thermoplastic polyester elastomer of the present invention, which is economical. The effect is great. Further, the above method has a simple method of changing the ratio of the chain extender to the aliphatic polycarbonate diol, and a commercially available low molecular weight aliphatic polycarbonate diol can be used to correspond to any desired molecular weight. advantage. When the chain extender is a polyfunctional active compound having two or more functional groups capable of reacting with a terminal hydroxyl group of an aliphatic polycarbonate diol in one molecule, it is not particularly limited, and when the number of functional groups is two or more It is not particularly limited, and a 2-functional group is preferred. Examples thereof include diphenyl carbonate, diisocyanate, and an acid anhydride of a dicarboxylic acid. A trifunctional or higher polyfunctional compound can also be used in a small amount. Instead of diphenyl carbonate, a carbonate compound such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate or dimethyl carbonate may be used. Further, it may be a cyclic carbonate such as ethylene carbonate or a dithiocarbonate compound. Further, a carbonyl compound of a phenoxy group of diphenyl carbonate may be used instead of a nitrogen-containing compound residue such as imidazole or indoleamine. In the above method, the low molecular weight aliphatic polycarbonate diol before the high molecular weight is preferably a commercially available product, but is not limited. For example, when a special copolymer is necessary, the aliphatic polycarbonate diol can be specifically prepared by using it. In the present invention, the method of introducing the above-mentioned active terminal group is not limited, and the method of adjusting the molecular weight of the aliphatic polycarbonate diol by using the above chain extender is to add the chain extender residue at the end. Modulation is better. The preparation method is not limited, and after adjusting to a molecular weight lower than a desired molecular weight, the reaction is carried out under milder conditions than when a predetermined amount of chain extender is added to adjust the molecular weight, thereby causing the chain extender and the aliphatic polycarbonate. A method in which a terminal group of an ester diol is reacted and introduced. For example, the reaction is preferably carried out at 100 to 200 ° C under normal pressure or under pressure. Further, it is also possible to carry out the simultaneous introduction of the active terminal group at the same time of adjusting the molecular weight by optimizing the feed ratio of the chain extender or the reaction conditions. In the above method, the molecular weight of the obtained aliphatic polycarbonate diol is adjusted or introduced into the active terminal group, and the molecular weight of the aliphatic polycarbonate diol of the starting material and the aliphatic polycarbonate diol can be changed. The feed ratio of the chain extender is carried out. Also, it can be adjusted by the reaction time. The molecular weight of the aliphatic polycarbonate diol obtained is the higher the molecular weight of the starting material. In addition, the smaller the feed ratio of the chain extender, the higher the ratio. It can be appropriately set in accordance with the molecular weight of the target. According to the reaction method in the above-mentioned method, if the aliphatic polycarbonate diol having a molecular weight lower than the final molecular weight is mixed with the chain extender in the reactor, the reaction conditions such as the reaction temperature, the reaction time, and the stirring conditions are not limited, for example. It is recommended to divide the molecular weight adjustment into a multi-stage 16 - 200904849 stage of two or more stages. That is, the 'molecular weight of the obtained aliphatic polycarbonate diol is measured after reacting for a predetermined amount of the feed ratio for a predetermined period of time. If the molecular weight is lower than the target molecular weight, the chain extender is additionally added, and conversely, if the molecular weight is too large When it is high, it is preferable to adjust the molecular weight by further adding the aliphatic polycarbonate diol of the raw material to further carry out the reaction. By repeating this method, the adjustment accuracy of the molecular weight or the concentration of the active terminal group can be improved. The polyester composed of a dicarboxylic acid component and a glycol component having a molecular weight of less than 250 may, for example, be polyethylene terephthalate, polybutylene terephthalate, propylene terephthalate or polypair. Cyclodecyl dimethylene phthalate, polyisophthalic acid ethylene glycol ester, polyisophthalic acid butyl diester, polyisophthalic acid propylene glycol ester, polyethylene naphthalate, polyethylene naphthalate, Polypropylene naphthalate and other copolymers, preferably polybutylene terephthalate, polybutylene naphthalate, polyethylene adipate and polybutylene adipate, It is especially good for butylene phthalate. The dicarboxylic acid component used in the present invention and a polyester having a number average molecular weight of 5,000 to 50,000 obtained by using a glycerol component having a molecular weight of less than 250 as a main component of 1,4-butanediol, and a polyester having the above-mentioned respective polyesters can be used. Commercial products. As the polyester obtained from the dicarboxylic acid component and the glycol component having a molecular weight of less than 250, a recycled container or a polyester of industrial waste can be used. A copolymer polyester can also be used. The catalyst used in the polymerization reaction may, for example, be a metal such as tin, zinc, ship, yttrium, lanthanum, zirconium, hafnium, yttrium or aluminum, or a derivative thereof. The derivatives are preferably metal alkoxides, carboxylates, carbonates, oxides and halides. Specifically, for example, tin chloride, tin octylate, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, titanium alkoxide, ruthenium oxide, and oxidization may be mentioned. -17- 200904849 Among these, a titanium compound, a ruthenium compound, an aluminum compound, and a ruthenium compound are preferred, and a titanium compound is more preferable. Specific examples of the titanium compound include tetraalkyl titanate such as tetraethyl titanate, tetraisopropyl phthalate, tetra-n-propyl titanate, and n-tetrabutyl titanate, and partial hydrolyzates thereof, titanium acetate. , titanium oxalate, titanium oxalate, sodium oxalate titanate, potassium oxalate titanate, calcium oxalate titanate and oxytitanium oxalate, such as titanium oxalate compound, titanium 1,2,4-benzenetricarboxylate, titanium sulfate, Titanium chloride, hydrolyzate of chlorinated halide, bromide, barium fluoride, hexa-sodium citrate, ammonium hexa-titanate, cobalt hexafluoride, manganese hexa-nitride, acetonitrile Titanium, a composite oxide composed of titanium and ruthenium or osmium, a reaction product of a titanium alkoxide and a phosphorus compound, and the like. The ruthenium compound is preferably a solution obtained by using amorphous cerium oxide, crystalline cerium oxide, or dissolving crystalline cerium oxide in glycol. Specific examples of the aluminum compound include aluminum formate, aluminum acetate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, and lemon. a mineral acid salt such as aluminophosphate or aluminum sulphate, aluminum chloride, aluminum hydroxide, aluminum chloride hydroxide, polyaluminum chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate, etc., methanol Aluminum, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum alkoxide such as aluminum butoxide, aluminum acetonitrile, aluminum acetate, aluminum ethyl acetoacetate, ethyl ethyl An aluminum alloy compound such as acetonitrile acetate aluminum diisopropoxide, an organoaluminum compound such as trimethyl aluminum or triethyl aluminum, or a partial hydrolyzate or alumina. Among these, a carboxylate, a mineral acid salt, and a chelating compound are preferred, and among these, alkaline aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum oxychloride, and aluminum acetonate are used. It is especially good. -18- 200904849 Further, in the method for producing the polyester elastomer of the present invention, a metallization or a soil-like metal compound may be used in combination. The metal for the metal examination and the soil test is preferably at least one selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba, and it is more preferable to use an alkali metal or a compound thereof. When an alkali metal or a chemical substance thereof is used, it is particularly preferable to use Li, Na, and K. Examples of the metal compound or the alkaline earth metal compound include unsaturated fatty acid salts such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated acids such as acrylic acid and methyl propylene acid. An aliphatic citrate such as an aliphatic citrate or a benzoic acid, a carboxylate containing a halogen such as trichloroacetic acid, a residual acid salt such as lactic acid, citric acid or salicylic acid, carbonic acid, sulfuric acid, nitric acid or a dish acid. , mineral acid salts of phosphonic acid, hydrogencarbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, hydrochloric acid, bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, naphthalene Alkylation of organic sulfonates such as sulfonic acid, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy a compound, a hydride compound, a hydride, an oxide, a hydroxide, or the like. The polycondensation catalyst of the present invention can also be used in combination with a phosphorus compound. The compound which can be used in combination with a catalyst is at least one phosphorus selected from the group consisting of a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphinic acid compound, a phosphinic acid compound, and a phosphine compound. The compound is preferred. When the polyester elastomer composition is polymerized, by using these phosphorous compounds, the effect of enhancing the activity of the catalyst and the effect of improving the thermal stability of the polyester can be observed. Among these, it is preferable to use a phosphonic acid compound to enhance the activity of the catalyst and to increase the thermal stability of the polyester. Among the above-mentioned phosphorus compounds, when a compound having an aromatic ring structure is used, the effect of improving the catalytic activity of -19-200904849 and the thermal stability of the polyester elastomer are preferable. Examples of the cerium compound include antimony trioxide, cerium acetate, cerium tartrate, cerium potassium tartrate, cerium trichloride, cerium glycolate, cerium pentoxide, and triphenyl sulfonium. For the reactor used in the melt polymerization of the polyester elastomer used in the present invention, a well-known reactor can be used, and it can be a batch type or a continuous type, and a vertical reaction tank, an spectacles-like horizontal reaction tank, and a lattice wing can be used. Horizontal reaction tank, thin film evaporation reaction tank, stirred reaction tank, tower type reaction tank, short shaft extruder and twin shaft extruder reaction tank. In either of these modes, the melt polycondensation reaction can be carried out in one stage or in multiple stages. In order to increase the comparative viscosity, solid phase polymerization can also be carried out, and the solid phase polymerization reaction can be carried out in the same manner as the melt polycondensation reaction, and can be carried out using a batch type apparatus or a continuous apparatus. The melt polycondensation and solid phase polymerization can be carried out continuously or by division. The polymerization reaction was carried out under reduced pressure to 2 hPa or less, and the polyester elastomer was previously made to have a viscosity of 〇 before being transferred to the reaction tank. More than 2 dl / g is preferred. Less than 0. At 2 dl/g, because the melt viscosity is too low, bumping occurs so that low-viscosity fly hoppers accumulate in the upper part of the tank or in the decompression line, which may cause contamination or decompression pipeline clogging. The antioxidant can be added to one or more types of well-known hindered phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Further, in order to reduce the content of tetrahydrofuran, one or more of the above stabilizers may be added before the polymerization reaction as a thermal stabilizer in the polymerization reaction. The antioxidant is added in an amount of 0_01 to 5 wt%, preferably 〇_〇 5 to 3 wt%, based on 100% by weight of the polyester elastomer. l~2wt% is better. Tim -20- 200904849 The added amount is 0. When it is 0.01% or more, it is not only odor, heat resistance or hydrolysis resistance, but also the mechanical strength of the polymer is improved. The addition amount is 5 wt% or less, and the effect corresponding to the increase in the addition amount cannot be obtained. The content of the anti-chemical agent in the polyester elastomer composition is also the same as the above-mentioned addition amount. Further, it is possible to add a known light stabilizer such as a hindered amine-based, triazole-based, diphenylketone-based, benzoic acid-based, nickel-based, or citric acid-based, antistatic agent, a lubricant, a peroxide, or the like. Molecular modifiers, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent whitening agents, tanning materials, flame retardants, and flame retardant auxiliaries. Hindered Phenolic Antioxidant The hindered phenol antioxidant in the present invention may, for example, be 3,5-di-t-butyl-4-hydroxy-toluene or n-octadecyl-β-(4'-hydroxy-3'. 5'-di-t-butylphenyl)propionate, neopentyl pentoxide [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], sulphur diene Ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid, octadecylbis[3-(3,5-di-t-butyl-4- Hydroxyphenyl)propionate, hydrazine [methylene-3-(3',5'.di-t-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-three Methyl-2,4,6,-paraxyl (3,5-di-t-butyl-4-hydroxybenzyl)benzene, (3,5-di-t-butyl-4-hydroxy-benzyl- Monoethyl-phosphoric acid) calcium, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-bis[1,1 -Dimethyl-2-{/3-(3 -th-butyl-4-hydroxy-5-methylphenyl)-propyl oxime-oxy}ethyl]2,4,8, 10-tetraoxa Spiro[5,5]undecane, bis[3,3-bis(4'-hydroxy-3'-t-butylphenyl)butanoic acid]glycolate, tocopherol, 2,2'-Asian Bis(4,6-di-t-butylphenol), hydrazine, Ν'-hexane-1,6 -diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide), 1,3,5-bis[2,4-bis(1,1-dimethyl) B)-6-methylphenyl]ethyl phosphite, ruthenium (2,4-di-third-21 - 200904849 butylphenyl)[1,1-biphenyl]_4,4'- Bisphosphonate, bis(2,4-di-t-butylphenyl)neopentitol diphosphite, N,N'-bis[3-(3,5-di-third) 4-hydroxyphenyl)propanyl]anthracene, 2,2'-oxalylamine bis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Ester], 1,1,3-glycol(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-para (3',5,·di·third Butyl-4'-hydroxybenzyl)_S-three tillage-2,4,6(111,311,515)-trione, isocyanuric acid 1,3,5-gin (4-tert-butyl 3-hydroxy-2,6-dimethylbenzyl)ester, 3,5-di-t-butyl-4-hydroxyhydrocinnamate, and (with)-1,3,5-para (2- Hydroxyethyl (:)-S-tripper-2, 4, 6 (1H, 3H, 5H; ^. Sulfur-based antioxidants] The sulfur-based antioxidant of the present invention may be dilauryl-3,3. - thiodipropionate, dimyristyl-3,3,-thiodipropionate di-diestil Base_3,3 thiodipropionate, lauryl stearyl-3,3'-thiodipropionate, di-octadecyl sulfide, neopentyl alcohol-肆 (/3 - Lauryl-thiopropionate) and the like. Pity is an antioxidant C. Examples of the phosphorus-based antioxidants include ginseng (mixed, mono- and di-phenylene ether phenyl) phosphites, ginseng (2,3-di-t-butylphenyl) phosphite, 4, 4,- Butylene-bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite lactic acid, 1,1,3-gin (2-methyl-4-di-tridecane) Lithophosphate-5-t-butylphenyl)butane, bis(2,4-di-t-butylphenyl)neopentanol-di-phosphite cool, bismuth (2,4-di -T-butylphenyl)-4,4'-extended biphenylphosphonate, bis(2'6-di-t-butyl-enmethylphenyl)neopentanol-di-phosphite Ester, 2,2'-ethylene-bis(4,6-di-t-butylphenyl)-2-ethylhexyl-phosphite, bis(2,4,6-di-third Phenyl phenyl) pentaerythritol-di-phosphite, -22- 200904849 Triphenyl phosphite, diphenyl decyl phosphite, dinonyl phenyl phosphite, · tridecyl phosphite, sub Trioctyl phosphate, tri-dodecyl phosphite, tri-octadecyl phosphite, tridecyl phosphite, tri-dodecyl trithiophosphate, and the like. Hindered Amine Light stabilizers In the hindered amines of the present invention, dimethyl succinate and 1-(2-ethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine ( Piperodine) polycondensate, poly[[6-(1,1,3,3-tetramethyl)imino-1,3,5-tri-trap-2,4-diyl]hexamethylene [2 , 2,6,6-tetramethyl-4-piperidinyl)imide]], 2_n-butylmalonic acid bis(1,2,2,6,6-tetramethyl-4-piperidin Pyridyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, N,N'-double Polycondensate of (2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 1,2-dibromoethane, poly[(N,N,-bis(2,2) ,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine)-(4-nornaline-1,3,5-tri-trap-2,6-diyl)-bis (3,3 ,5,5-tetramethylpipecolone), ginseng (2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl-1,2,3,4-butane IV Phthalate, ginseng (1,2,2,6,6-pentamethyl-4-piperidinyl)-dodecyl-1,2,3,4-butane tetracarboxylic acid ester, double (1 , 2,2,6,6-pentamethyl-4-piperidinyl) succinic acid vinegar, 1,6,11-gin[{4,6-bis(1 butyl-;^-(1,2) ,2,6,6-pentamethylpiperidin-4-yl)amino-1,3 , 5-triacyl-2-yl}amino]undecane, [2-[3-5-di-t-butyl-4-hydroxyphenyl)propenyloxy]-2,2,6 ,6-tetramethylpiperidine, 8-memberyl-7,7,9,9-tetramethyl-3.octyl-1,3,8-triaziro[4,5]undecane-2 ,4-dione, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, N,N,-bis(3-aminophenyl)ethylenediamine-2,4 - bis[1butyl-1^-(1,2,2,6,6-pentamethyl-4-p-stiryl)amino]-6-chloro-1,3,5-three-till condensate, etc. . The light stabilizer of the triple well type, the diphenyl ketone type, the benzoate type, the nickel type, and the -23-200904849 citric acid type of the present invention may, for example, be 2,2'-dihydroxy-4-methyl. Oxydiphenyl ketone, 2-hydroxy-4-n-octyloxydiphenyl ketone, p-tert-butylphenyl lysate, 2,4-di-t-butylphenyl-3, 5- Di-tert-butyl-4-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5,- Di-t-pentyl-phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2,5-bis-[5,-tert-butylbenzofluorenyl- (2)]-thiazide, [bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel salt, 2-ethoxy-5-tert-butyl-2' -ethyl oxalic acid-bis-indoleaniline 85~90% with 2-ethoxy-5-tert-butyl-2'-ethyl-4'-tert-butyl oxalic acid-bis-indoleani 10~ 15% mixture, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethyl Benzyl)phenyl]-2H- Benzotriazole, 2-ethoxy-2'-ethyloxalic acid-biguanide, 2-[2'-hydroxy-5'-methyl-3'-(3",4",5", 6"-tetrahydrofurfurimide-methyl)phenyl]benzotriazole, bis(5-benzylidene-4-hydroxy-2-methoxyphenyl)methane, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 2-hydroxy-4-isooctyloxydiphenyl ketone, 2-hydroxy-4-dodecyloxydiphenyl ketone and 2- Hydroxy-octadecyloxydiphenyl ketone, etc. Antistatic agent The antistatic agent of the present invention may, for example, be a glycerin fatty acid (C8 to C22) ester or a sorbitan fatty acid (C 8 to C 22 ) ester. Propylene glycol fatty acid (C 8~C22) ester, sucrose fatty acid (C 8~C 22) ester, citric acid mono (di or tri) stearate, neopentyl glycol fatty acid (C 8~C 18) ester, three Hydroxymethylpropane fatty acid (C8~C18) ester, polyglycerol fatty acid (C8-C22) ester, polyoxyethylene (20 mol) glycerol fatty acid (C 1 2~C 1 8 ) ester, polyoxyethylene (20 0 Mo Ear) sorbitan ester-24- 200904849 fatty acid (C12~C18) ester, polyethylene glycol fatty acid (C8~C22) ester, polyoxyethylene fatty alcohol (C12 C20) Ether, polyoxyethylene (4~50 mol) alkyl (C4 or higher) phenyl ether, hydrazine, bismuth(2-hydroxyethyl) fat (C8~C18) amine, condensation of fatty acid with diethanolamine a nonionic surfactant such as a product, a polyoxypropylene polyoxyethylene block polymer, polyethylene glycol or polypropylene glycol; an alkyl group (c丨〇~C2〇) sulfonate (Na, K, NH4) , alkylnaphthalene sulfonate (Na), dialkyl (C4~C16) sodium succinate, alkyl (C8~C20) sulfate (Na, K, NH4), fatty acid (C8~C22) salt (Na An anionic surfactant such as K, NH4); an amphoteric surfactant such as N_mercapto (C 8~C 1 8 ) sarcosinate; and other auxiliary agents such as polyacrylic acid and its sodium salt. The slip agent which can be formulated in the resin composition of the present invention may, for example, be hexylamine, octylamine, stearylamine, decylamine, cis-docosa carbamide, ethyl bis-stearyl a saturated or unsaturated aliphatic decylamine having 3 to 30 carbon atoms and a derivative thereof, such as decylamine, laurylamine, behenylamine, methylenebisstearylamine, ricinoleamide or the like; a saturated or unsaturated aliphatic ester having a carbon number of 3 to 30, such as butyl acrylate or isobutyl stearate, and a derivative thereof; a commercially available hydrazine compound, an antimony compound such as eucalyptus oil or bismuth rubber; and a commercially available fluorine-based compound The release agent is a fluorine-based compound such as tetrafluoroethylene. Metal Deactivator The metal deactivator which can be formulated in the resin composition of the present invention may be exemplified by 3-1^'-carbanylamino-1,2,4-triazole, salicylaldehyde, sorghum, :^,> ;>1,-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene, oxalidyl _bis[benzylidene fluorene], 9 ,10-Dihydro-9-oxa-10-phosphonium-ίο-oxide, 3,4,5,6-dibenzo-I,2-oxachlorinated -2-oxide, ginseng 2 - tert-butyl-25- 200904849 -4-sulfur (2,-methyl-4'-hydroxy-5-t-butyl)phenyl-5-methyl]phenylphosphite, 2,2 '· Grassamine-bis-[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like. Nucleating agent The nucleating agent which can be formulated in the resin composition of the present invention may be 1,3,2,4-di-benzylidene-sorbitol, iota, 3,2,4-di-di-( p-Methyl-di-benzylidene) sorbitol, 1,3,2,4-di-(p-ethyl-benzylidene) sorbitol, 1,3,2,4-di-(2' ,4,-di-methyl-benzylidene) sorbitol, 1,3-p-chloro-ylidene benzyl-2,4-p-methyl-benzylidene-sorbitol, 1,3, 2,4-di-(p-propyl- \benzylidene) sorbitol, monohydroxy-di-p-butyl butyl benzoate, sodium bis(4-t-butylphenyl)phosphate, 2, 2,-methylene-bis-(4,6-di-t-butyl-phenyl)phosphate, sodium talc, sodium benzoate and 2,2'-methylene-bis-(4,6-di- Third butyl phenyl) lithium phosphate or the like. Neutralizing agent and antacid agent The neutralizing agent and the antacid agent which can be blended in the resin composition of the present invention include lithium stearate, 1,2-hydroxylithium stearate, sodium stearate, and (hard). Sodium oleate, potassium stearate, lithium citrate, lithium octadecanoate, sodium laurate, sodium octadecyl citrate, calcium sulphate, calcium citrate, calcium octadecanoate , cadmium laurate, cadmium citrate, barium naphthenate, barium 2-ethylhexanoate, barium stearate, barium 2-ethylhexanoate, calcium stearate, calcium laurate, castor Calcium alkyd, barium stearate, barium stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexanoate, zinc stearate, lead dibasic stearate, lead naphthenate, Higher fatty acids such as tin stearate, aluminum stearate and magnesium stearate, alkyl lactic acid or alkaline earth metal salts: basic magnesium-aluminum-hydroxy-carbonate-hydrotalcite, basic zeolite, table Chlorohydrin and bisphenol fluorene polymer, -26-200904849 Oxidized soybean oil, epoxidized fatty monoester, epoxidized lipid cyclic fatty acid, polycarbodiimide, and isocyanate compound. Examples of the tanning material which can be formulated in the resin composition of the present invention include magnesium oxide, aluminum oxide, cerium oxide, calcium oxide, titanium oxide, chromium oxide (trivalent), iron oxide, zinc oxide, cerium oxide, and alfalfa. Oxides of earth, alumina fiber, cerium oxide, strontium ferrite, strontium ferrite, strontium oxide, pumice, pumice balloon, etc.; basic substance such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate or hydrogen Oxide; carbonates such as magnesium carbonate, calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite, dolomite, Dawsonite, etc.; calcium sulfate, barium sulfate, ammonium thiocyanate, calcium sulfite, alkaline (Sub)sulfate such as magnesium sulfate; sodium citrate, magnesium citrate, aluminum citrate, potassium citrate, calcium citrate, talc, clay, mica, asbestos, fiberglass, montmorillonite, glass balloon, glass beads Citrate such as bentonite; kaolin (ceramic), bead iron, iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, boron fiber, tantalum carbide fiber, brass fiber, potassium titanate, titanic acid Lead pinacid, zinc borate, aluminum borate, metaboric acid, calcium borate and boric acid The flame retardant of the present invention is not limited, and examples thereof include a halogen-based type, a non-halogen type polyphosphoric acid type, a metal hydroxide type, etc. Specifically, the ruthenium compound may be exemplified. Oxidation of ruthenium oxide, osmium tetroxide and ruthenium pentoxide. Halogen is a bromine-based flame retardant or a chlorine-based flame retardant. Specific examples of the bromine-based flame retardant include decabromodiphenyl ether and hexabromo. Benzene, hexabromocyclododecane, tetrabromobisphenol A, tetrabromobisphenol A - tetrabromobisphenol A - diepoxypropyl ether copolymerization -27- 200904849. Specific examples of chlorine-based flame retardants are Chlorinated paraffin and perchlorocyclohexane. Specific examples of the polyphosphoric acid system include ammonium polyphosphate and melamine polyphosphate. Metal hydroxide systems (also referred to as metal hydrates) include magnesium hydroxide. Aluminum hydroxide, etc. The polyester elastomer obtained in this manner is less free, does not impair odor, heat resistance and is produced by the polyester obtained by the conventional transesterification polymerization method or the esterification polymerization method. The amount of tetrahydrofuran is less' and compared with the previous transesterification polymerization method, When the comparison of the polymerization productivity preferred 'system is advantageous in the manufacturing cost of the surface. The polyester elastomer produced by the present invention can be used in various applications such as fibers, films, sheets, electrical and electronic components, automobile parts, and home electric appliances, as a monomer or a resin composition. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. (1) Contrast viscosity will be 〇. 5 g of the sample was dissolved in 25 ml of a mixed solvent (phenol/tetrachloroethane = 60/40) and measured at 30 ° C using an Oswald viscometer. (2) Measurement of thermal characteristics The thermal properties of the obtained polyester elastomer were determined by using DSC manufactured by TA Instruments, and the sample amount was 10 mg, and the temperature conditions were determined in accordance with the obtained polyester elastomer under a nitrogen atmosphere. Ground setting. The temperature rise and temperature drop conditions were raised from room temperature to 25 ° C below 20 ° C / min, cooled to room temperature at 20 ° C / min, and repeated twice, to obtain the melt at the second temperature rise. Point (Tm) was used as the measurement result. -28 - 200904849 (3) Free matter content, linear oligomer content Dissolve the sample in a solvent (hexafluoroisopropanol / chloroform = 2 / 3 (v / v)) 3 m% mixture, and add 2 Dilute with 0 ml of chloroform. After adding 1 mM of methanol and precipitating the polymer, it was filtered. The filtrate was evaporated to dryness and redissolved using 10 mL of dimethylformamide. The centrifugally filtered solution was supplied to a liquid chromatography mass spectrometer (LC-MS) to quantify each component. The measurement conditions are as follows. [LC condition] f Unit: Agilent 1100 Column: Imtakt Cadenza CD-C18 2x150 mm Mobile phase: A 0. 1% formic acid, B acetonitrile 〇 minutes (10% B) -40 (98) -60 (98) Flow rate: 0. 2 ml/min column temperature: 4 (TC implant volume: 5 μl detection wavelength: 2 5 8 nm, [MS condition] Device: BRUKER DALTONICS esquire 3 0 0 0 Plus Ionization method: ESI (positive) (4 Heat resistance The polymer was melted in an air atmosphere at 250 ° C for 5 minutes, and was carried out by a method of color difference before and after visual melting. 〇: Almost uncolored Δ: slightly yellow colored, or gray X: marked yellow coloring - 29- 200904849 (5) Functional test (odor) The dry inert gas (nitrogen) was blown in a hopper of a forming material using a YAM ΑΤΟScientific Vacuum Dryer DP6i type and using polyester elastomer pieces which were dried under reduced pressure in advance. It is used to prevent the moisture absorption of the chips during forming. The plasticizing conditions of the M-l5〇C (DM) injection molding machine are the feed screw rotation number=70%, the screw rotation number=i20rpm, and the back pressure is 〇. 5MPa, cylinder temperature is set from the bottom of the hopper in order to 45 °C, 240 it, below the nozzle is 24 5 °C 'forming belt stage forming plate and cutting 3 mm plate, put it into the ion at 70 °C After the exchange of water was kept for 30 minutes, it was cooled to room temperature and left for 1 month, and then tests for flavor, odor, and the like were performed. Ion exchange water was used for comparison with the blank test system. The functional test was performed by 10 participants, according to the following criteria, and compared by the average 値. 〇: No odor or odor. 1: The feeling is slightly different from the blank test. 2: The feeling is different from the blank test. 3: The feeling is quite different from the blank test. 4: There is a big difference between the feeling and the blank test. (6) Measurement and calculation method of tetrahydrofuran content 20 g of the cast pieces were placed in a container which can be sealed, and the pressure was replaced with nitrogen under reduced pressure three times, and then sealed under a nitrogen atmosphere. Hold the dense, @^ in an oil bath set at 245 °C for 30 minutes, and then select a fragmented, molten resin (long diameter 3 to 5 mm, short diameter 2 to 4 mm, height 2 to 4 mm, grain) The weight is 20~30 mg / piece). After selecting 5 g of the chips, the sample was placed in a sample bottle within 1 minute and 50 g of pure water was added, and the lid was closed without voids in the sample bottle and densely K was obtained in such a manner that tetrahydrofuran did not volatilize. Because it takes time for the stomach to be measured from the measurement of the debris to the closure of the sample vial, the HD will evaporate from the debris and will not be analyzed correctly. Next, the sample vial sealed after -30-200904849 was placed in a warm air dryer at 50 ° C for 24 hours or more and the tetrahydrofuran in the polyester elastomer was extracted in pure water. The concentration of the extracted tetrahydrofurfuran was determined by adding 20 μl of a standard stock solution of 1,4-dioxane to 5180 μg/ml with respect to 1 ml of the extract and injecting it into a gas chromatograph (6850 Series II manufactured by Agilent). Come on. The tetrahydrofuran content was multiplied by 10 times to calculate the tetrahydrofuran content in the polyester elastomer. Hereinafter, the present invention will be described in detail by way of examples. However, the invention is not limited to the following examples unless the gist of the invention is exceeded. f Example 1 was added to the vertical reactor. 9 kg of DMT (dimethyl phthalate), 25. 8 kg BD (butanediol), 36. 5 kg of PTMG (polybutanediol, number average molecular weight of 1 000), 150 g of antioxidant IRGANOX 1 3 3 0 (manufactured by Sakamoto CIBA-GEIGY Co., Ltd.), 60 g of TBT (tetrahydrofuran), and from 130 ° for 2 hours C was heated to 220 ° C to carry out an atmospheric pressure transesterification reaction. Subsequently, the temperature was raised from 220 ° C to 245 ° C over 1 hour, and the polymerization reaction was carried out at 245 t under reduced pressure to 2 hPa or less to a predetermined melt viscosity. After the polymerization, 375 g of IRG AN OX 1 3 3 0 was added as an antioxidant for lowering the tetrahydrofuran content in the same/reaction tank, and the mixture was mixed under reduced pressure to 2 hPa for 5 minutes. After mixing, the polymer is cast to fragment. The comparative viscosity of the obtained polyester elastomer is 1. 94 dl / g, Tm 1 8 7 ° C, tetrahydrofuran (THF) content of 60 0 ppm, free paraic acid of 9 ppm, free butanediol of 8 ppm, linear oligomer 200 ppm, and good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Here, the linear oligomer amount is an oligomer having a molecular weight of 606 bonded by TPA-BD-TPA-BD-TPA and a total of oligomers having a molecular weight smaller than that of -31-200904849. Example 2 The same procedure as in Example 1 was carried out until the completion of the polymerization reaction. After the polymerization, 150 g of SANDSTAB P-EPQ (manufactured by CLARIANT JAPAN Co., Ltd.) was added as an antioxidant in the same reaction vessel, and the mixture was mixed under reduced pressure to 2 hPa or less for 5 minutes. After mixing, the polymer is cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 2. (Hdl/g, Tml87 °C, THF content: 440 ppm, free paraic acid of 8 ppm, free butanediol of 7 ppm, linear oligomer of 1 95 ppm, good heat resistance and functionality test. Also, because of tetrahydrofuran content There is no problem of odor in the casting process, etc. Example 3 The polymerization was carried out in the same manner as in Example 1. After the polymerization reaction, 150 g of IRGANOX 1 098 (Sakamoto CIBA-GEIGY) was added to the same reaction tank. As a antioxidant, it was mixed for 5 minutes under reduced pressure to 2 hPa. After mixing, the polymer was broken by casting. The comparative viscosity of the obtained polyester elastomer was 2. 00 dl/g, Tm 186 °C, THF content of 830 ppm, free paraic acid of 8 ppm, free butanol of 5 ppm, linear oligomer of 84 ppm, and good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 4 The same procedure as in Example 1 was carried out until the completion of the polymerization reaction. After the polymerization reaction, 751 g of IRGANOX 1010 (manufactured by CIBA-GEIGY Co., Ltd., Japan, 150 g of IRGANOX 1 0 9 8) was added as an antioxidant-32-200904849 agent in the same reaction tank, and the pressure was reduced to 2 hPa or less and mixed 1 〇. minute. After mixing, the pressure was reduced to 2 hPa or less, and polymerization was carried out until a predetermined melt viscosity, followed by casting to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 1. 9 5 d 1 / g, T m 1 8 5 °C, THF content 500 pm, free paraic acid 9 ppm, free butanediol 9 ppm, linear oligomer 2 Ο 2 ppm, heat resistance, functional The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 5 Adding 4 1 to a vertical reaction tank. 8 kg PBT, 36. 5 kg of PTMG (number average molecular weight 1 〇〇〇), 150 g of IRGANOX 1330, 41 g of TBT, and the temperature was raised from 1 30 ° C to 245 ° C in 1 hour while reducing the pressure to below 2 hPa. Subsequently, the polymerization reaction was carried out at 245 ° C to a prescribed melt viscosity. After the polymerization, 150 g of IRGANOX 1330, 150 g of SANDSTA BP-EPQ was added, and mixing was reduced, followed by casting to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 2. 00 dl / g, Tml84 ◦ C, THF content of 550 ppm, free paraic acid of 7 ppm, free butyl diol is 1. Oppm, linear oligomer 205 ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 6 PBT (number average molecular weight 20000) was 4. 2 kg / hour, PTMG (number average molecular weight 1000) to 3. 7 kg / h, IRGANOX 1 3 3 0 at 15 g / h, TBT at 4. 1 g/hr was continuously supplied to a twin-screw extruder and mixed at 2 4 5 ° C to obtain a comparative viscosity of -33 - 200904849 0. After 3 dl/g of the polyester elastomer, it was transferred to a thin film evaporation reactor and decompressed at 245 ° C to below 2 hPa. Subsequently, the polymerization reaction is carried out to a prescribed melt viscosity. After completion of the polymerization, the mixture was transferred to a twin-screw extruder in a molten state, and IRGANOX 1 098 was supplied at 15 g/hr and mixed, followed by casting to pelletize the polymer. The comparative viscosity of the obtained polyester elastomer was 1. 90dl/g, Tml85°C, THF content is 400PPm, free p-citric acid is 5ppm, free butanediol is 0. 8 p p m, linear oligomer 1 40 p p m, heat resistance, and functionality were tested well. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 7 PBT (number average molecular weight 20000) was 4. 2 kg / hour, PTMG (number average molecular weight 1 000) to 3. 7 kg / h, IRGANOX 1 3 3 0 at 15 g / h, T B T at 4. 1 g/hr was continuously supplied to the vertical reaction tank, and after mixing at 24 5 ° C, the pressure was reduced to below 2 hPa at 24 5 ° C and polymerization was carried out until the comparative viscosity of the polyester elastomer was 0. 4dl/g. Subsequently, the mixture was transferred to a thin film evaporation reactor and subjected to polymerization at a temperature of 24 ° C and 2 hPa to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to SANDSTAB P-EP Q at a supply of IRGANOX 1 3 3 0, 15 g/hr at 15 gm, and mixed, and then cast. Molding causes the polymer to fragment. The comparative viscosity of the obtained polyester elastomer was 1. 90dl / g, Tml87 ° C, THF content of 305 ppm, free paraic acid of 3ppm, free butanediol is 〇. 9 ppm, linear oligomer 1 30 ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 8 -34- 200904849 PBT (number average molecular weight 20000) was 4. 2 kg / hour, PTMG (number average molecular weight 1 〇〇〇) to 3. 7 kg / h, IRGANOX 1 3 3 0 at 15 g / h, TBT continuously supplied to the twin-screw extruder at 4" g / h ' and under the barrel heater at 2 3 0 ~ 2 90 ° C Heating and mixing, and the reaction to a comparative viscosity of 0. 2~0. 5dl/g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed at 245 ° C to 2 hPa or less, and a polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1 09 8 at 15 g/hr, and supplied to s AN DSTABP-EPQ at 15 g/hr and mixed, and then cast. Molding causes the polymer to fragment. The comparative viscosity of the obtained polyester elastomer was 2. 45dl/g, Tml90°C, THF content 150ppm, free p-citric acid 5ppm, free butanediol 〇. 7 ppm 'linear oligomer 1 4 2 p p m, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 9 PBT (number average molecular weight 20000) was 27. 4 kg / h, PTMG (number average molecular weight 1 000) to 2. 8 kg / h, IRGANOX 1 3 3 0 at 60 g / h, TBT continuously fed to a twin-screw extruder at 12 g / h, and heated and mixed under a cylinder heater at 23 0 to 290 ° C, and The reaction to a comparative viscosity of 0. 2~0. 5dl/g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to a temperature below 2 hPa at 24 5 ° C, and a polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1 3 3 0 at 15 g/hr, and supplied to IR G ΑΝ Ο X 1 0 9 8 at 15 g/hr. The SANDS TAB P-EPQ was supplied at 15 g/hr and mixed, and cast to fragment the polymer-35-200904849. The comparative viscosity of the obtained polyester elastomer was 1. 1 5 dl / g, Tm222 〇 C, THF content of 90ppm, free paraic acid of 5ppm, free butanediol of 0. 7 p p m, linear oligomer 1 6 5 p p m, heat resistance, and functionality were tested well. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 1 〇 PBT (number average molecular weight 20000) was 6. 9 kg / hour, PTMG (number average molecular weight 1 000) to 0. 7 kg / h, butanediol (BD) f at 1 g / h, IRGANOX 1 3 3 0 at 15 g / h, TBT at 3. 0 g / hr was continuously supplied to a twin-screw extruder, and heated and mixed under a barrel heater of 2 30 0 to 290 ° C, and reacted until the comparative viscosity was 〇. 2~0. 5dl/g. Subsequently, it was continuously transferred to a horizontal twin-screw extruder and decompressed at 245 ° C to 2 hPa or less, and polymerization was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1 3 3 0 at 15 g/hr, and supplied to IRGANOX 1 09 8 at 15 g/hr, and mixed, and cast. The polymer is fragmented. I got it. The comparative viscosity of the polyester elastomer is 1. 10 dl / g, Tm 223 ° C, THF content of 50 ppm, free paraic acid of 4 ppm, free butanediol is 〇. 6 ppm, linear oligomer 168 ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 1 1 PBT (number average molecular weight 20000) was 5. 8 kg / hour, PTMG (number average molecular weight 1 〇〇〇) to 1. 9 kg/hr, butanediol (BD) was continuously supplied to the biaxial extrusion at 20 g/hr, IR G ΑΝ Ο X 1 3 3 0 at 15 g/hr, and TBT at 3 · 0 g/hr. Machine, and mix and mix under the heater of -3 - 30 - 29 0 °C -36 - 200904849 heater, and the reaction to a comparative viscosity of 0. 2~0. 5 dl/g. Subsequently, it was continuously transferred to a horizontal twin-screw extruder and depressurized to 2 hPa or less at 24 5 ° C, and polymerization was carried out to a predetermined melt viscosity. After completion of the polymerization, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRG AN 0X1010 at 15 g/hr, and supplied to IRGANOX 1 098 at 15 g/hr, and mixed to cast a polymer. fragmentization. The comparative viscosity of the obtained polyester elastomer was 1. 60 dl / g, Tm 210 ° C, THF content of 60ppm, free paraic acid is 5ppm 'free butanediol is 0. 8 ppm, linear oligomer 1 60 ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 1 2 PBT (number average molecular weight 20000) was 3. 6 kg / h, PTMG (quantitative average molecular weight 2000) to 4. 1 kg/hr, IRGANOX 1 3 3 0 at 15 g/hr, TBT at 5 · 0 g/hr continuously supplied to the twin-screw extruder, and at 2 3 0 to 29 ° C barrel heater The mixture was heated under heating, and the reaction was carried out until the comparative viscosity was 0. 2 ~ 〇. 5dl/g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to a temperature below 2 hPa at 24 5 ° C, and a polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1 3 3 0 at 15 g/hr, and supplied to IRG ANOX 1 0 1 0 at 15 g/hr, at 15 g. After the SAND STAB P-EPQ was supplied and mixed, it was cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 2. 30 dl/g, Tm 205 ° C, THF content of l〇〇ppm, free p-iconic acid of 5 ppm, free butanediol of 0-6 ppm, linear oligomer of 120 Ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. -37- 200904849 Example 1 3 PBT (number average molecular weight 20000) was 3. 6 kg / h, polycarbonate diol (PCD) to 1. 4 kg / h, IRGANOX 1 3 3 0 at 15 g / h, and heated under a barrel heater at 22 5 ~ 290 °C. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and depressurized to 2 hPa or less at 22 to 245 ° C, and polymerization was carried out to a predetermined melt viscosity. After completion of the polymerization, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1 3 3 0 at 15 g/hr, IRGANOX 1010 at 15 g/hr, and IRGANOX 1098 at 15 g/hr. After 15 g/hr of SAND STAB P-EPQ was supplied and mixed, it was cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer is 1. 25dl/g, Tm214°C, THF content is 50 ppm, free paraic acid is 6 ppm, free butanediol is 〇. 9 ppm, linear oligomer 125 ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Example 1 4 PBT (number average molecular weight 2 000 0) was 3. 6 kg / hour, PCD to 1. 4 kg / h, IRGANOX 1 3 3 0 at 15 g / h, and heated at 22 5 ~ 2 90 ° C barrel heater. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and depressurized to 2 hPa or less at 22 5 to 245 ° C, and polymerization was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a dual-axis extruder for addition of an antioxidant in a molten state, and supplied to SAND STAB P-EPQ at 15 g/hr, and mixed, followed by casting to pellet the polymer. The comparative viscosity of the obtained polyester elastomer is 1. 15 dl / g, Tm 212 ° C, THF content of 40 Ppm, free paraic acid of 5PPm, free butanediol of 〇-8ppm, linear oligomer 122ppm, heat resistance, functional test is good. Also, because the content of tetrahydrofuran is small, there is no odor in the casting process, etc. -38-200904849. Example 1 5 PBT (number average molecular weight 20000) was 4. 2 kg / hour, PTMG (number average molecular weight 1 000) to 3. 7 kg / h, IRGANOX 1 3 3 0 at 15 g / h, TBT at 4. 1 g/hr was continuously supplied to the twin-screw extruder, and heated and mixed at 2 3 0 to 2 9 (TC barrel heater, and reacted to a comparative viscosity of 0. 2~0. 5dl/g. Then, it is continuously transferred to a horizontal twin-screw extruder and depressurized to below 2 hPa at 24 5 °C, at a comparative viscosity lower than the specified viscosity. At the later stage of the polymerization of 2 dl/g, IRGANOX 10 10 was supplied at 15 g/hr, and IRGANOX 1 09 8 was supplied at 15 g/hr, and after mixing, casting was carried out to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 2. 05dl/g, Tml89°C, THF content is ΐ00ρρπι, free p-citric acid is 6 p p m, free butanediol is 0. 7 p p m, linear oligomer 1 3 0 p p m 'The heat resistance and the functionality test were good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process. Example 1 6 PBT (number average molecular weight 20000) was 4_2 kg/hr, PTMG (number average molecular weight 1 000) was 3. 7 kg / h, IRGANOX 1 3 3 0 at 15 g / h, T B T at 4. 1 g/hr was continuously supplied to a twin-screw extruder, and heated under a barrel heater of 2 30 0 to 2 0 ° C and reacted to a comparative viscosity of 0. 2~0. 5dl/g. Then, it was continuously transferred to a horizontal twin-screw extruder and depressurized to 245 ° C to 2 hPa or less. At a later stage of the polymerization reaction in which the comparative viscosity was lower than the specified viscosity dl dl / g, IRGANOX 1098 was supplied at 15 g / h and mixed. 'To carry out the polymerization reaction to the specified melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a biaxial extruder for antioxidant addition, and supplied to SANDSTAB P-EPQ at 15 g/hr and mixed, followed by casting to pellet the polymer. The comparative viscosity of the obtained polyester elastomer is -39- 200904849. 90dl/g, Tml86°C, THF content is 125ppm, free paraic acid is 6ppm, free butanediol is 〇. 7 ppm, linear oligomer 140 ppm, good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Comparative Example 1 The completion of the polymerization reaction was carried out in the same manner as in Example 1. Immediately after completion of the polymerization reaction, the polymer was cast and the polymer was fragmented. The comparative viscosity of the obtained polyester elastomer was 2. 04(11/经, 1'111184° (3, 111? content is 9000 卩卩〇1, free paraic acid is 20 ppm, free butane diol is 15 ppm, linear oligomer 255 ppm, heat resistance, functional test) Poor. Comparative Example 2 In the vertical reaction tank, add 51. 1 kg DMT, 38. 7 kg BD, 18. 7 kg of PTMG (number average molecular weight 1 000), 150 g of IRGANOX 1330, and 60 g of TBT were used, and the polymerization was carried out under the same reaction conditions as in Example 1. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer is 1. 50 dl/g, Tm212 〇C, THF content: 5700 ppm, free paraic acid 15 ppm, free butanediol 20 ppm, linear oligomer 280 ppm, poor heat resistance and functionality test. Comparative Example 3 In a vertical reaction tank, 31. 7 kg DMT, 23. 2 kg BD, 40. 8 kg PTMG (quantitative average molecular weight 2000), 150 g IRGANOX 1330, 62. 3 g of TBT was used, and the polymerization reaction was carried out under the same reaction conditions as in Example 1. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 2. 20 dl/g, Tm203 〇C, THF content 6200 ppm, free paraic acid 17 ppm, free butanediol 16 ppm, linear oligomer 258 ppm, heat resistance, functionality -40-200904849 Poor test. Comparative Example 4 In a vertical reaction tank, 60. 4 kg DMT, 47. 0 kg BD, 7. 1 kg PTMG (quantitative molecular weight 1 00 0), 150 g IRGANOX 1330, 60 g TBT, heated from 130 ° C to 220 t in 2 hours for atmospheric pressure transesterification. Subsequently, the temperature was raised from 22 ° C to 245 ° C over 1 hour, and the pressure was reduced to 2 hPa or less, and polymerization was carried out at 24 5 ° C to a predetermined melt viscosity. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 1. 1 4 dl / g, Γ Tm22 3 〇 C, THF content 5 000 ppm, free paraic acid 20 ppm, free butanediol 25 ppm, linear oligomer 3 05 ppm, poor heat resistance and functionality test. Comparative Example 5 In a vertical reaction tank, 3 1 was added. 6 kg of citric acid (TPA), 25. 8 kg BD, 36. 5 kg of PTMG (quantitative molecular weight of 1 000), 150 g of IRGANOX 1330, and 60 g of TBT were heated from 130 ° C to 220 ° C for 2 hours to carry out atmospheric pressure transesterification. Subsequently, the temperature was raised from 220 ° C to 245 ° C ' in 1 hour, and the pressure was reduced to 2 hPa or less, and polymerization was carried out at 245 ° C to a predetermined melt viscosity. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The comparative viscosity of the obtained polyester elastomer was 2. 00 dl/g, Tml 86 ° C, THF content: i 〇〇〇〇 ppm, free paraic acid 30 ppm, free butane diol 28 ppm, linear oligomer 260 ppm, poor heat resistance and functionality test. The above results are shown in Tables 1 and 2. 41 - 200904849 [Table l] Raw material composition Dicarboxylic acid component Glycol component Polyol polyester catalyst Antioxidant addition period IRGANOX 1330 IRGANOX 1010 IRGANOX 1098 SANDOSTAB P-EPQ Example 1 DMT BD PTMG - TBT Prepolymerization / Polymerization Immediately after completion - - - Example 2 DMT BD PTMG - TBT Pre-polymerization ink - just after completion of polymerization Example 3 DMT BD PTMG - TBT Pre-polymerization - just after completion of polymerization - Example 4 DMT BD PTMG - TBT Immediately after the polymerization reaction After the completion of the polymerization reaction - Example 5 - - PTMG PBT TBT Before the polymerization / After the completion of the polymerization - - Immediately after the completion of the polymerization Example 6 - - PTMG PBT TBT Prepolymerization - Polymerization Immediately after the completion of the reaction - Example 7 - - PTMG PBT TBT Before the polymerization / just after the completion of the polymerization - - After the completion of the polymerization Example 8 - - PTMG PBT TBT Before the polymerization - Immediately after the completion of the polymerization Example 9 - PTMG PBT TBT Before Polymerization / After Polymerization Just After - After Polymerization Just After Polymerization Just After Completion Example 10 - - PTMG PBT TBT Before Polymerization / Immediately after Polymerization - Immediately after Polymerization Example 11 - BD PTMG PBT TBT Polymerization Just After Polymerization Just After Polymerization - Example 12 PTMG PBT TBT Prepolymerization / Polymerization Immediately after the completion of the polymerization reaction - just after the completion of the polymerization, Example 13 PCD PBT TBT before the polymerization / just after the completion of the polymerization, just after the completion of the polymerization reaction - Example 14 PCD PBT TBT before the polymerization - Immediately after the polymerization reaction Example 15 PTMG PBT TBT Polymerization reaction Polymerization reaction late stage Polymerization reaction - Example 16 - PTMG PBT TBT Before polymerization - Polymerization reaction After the polymerization reaction was completed, Comparative Example 1 DMT BD PTMG TBT Before polymerization _ . Comparative Example 2 DMT BD PTMG TBT Before Polymerization _ • • Comparative Example 3 DMT BD PTMG - TBT Before Polymerization • • Comparative Example 4 DMT BD PTMG - TBT Before Polymerization - - Comparative Example 5 TPA BD PTMG - TBT Before Polymerization - - - -42- 200904849 [Table 2] Polyester Elastomer Properties Linear Oligomer Comparative Viscosity Tm THF Content Heat Resistance Functional Test Free Acid Free Glycol Total (dl/g) (°c) (ppm) ( Hue) (odor) (ppm) (ppm) (ppm) Example 1 1. 94 187 600 △~〇 1 9 8 200 Example 2 2. 04 187 440 △~ο 1 8 7 195 Example 3 2. 00 186 830 △~〇 1 8 5 184 Example 4 1. 95 185 500 △ ~ 〇 1 9 9 202 Example 5 2. 00 184 550 △~ο 0 7 1. 0 205 Example 6 1. 90 185 400 〇 0 5 0. 8 140 Example 7 1. 90 187 350 〇 0 3 0. 9 130 Example 8 2. 45 190 150 〇 0 5 0. 7 142 Example 9 1. 15 222 90 〇 0 5 0. 7 165 Example 10 1. 10 223 50 〇 0 4 0. 6 168 Example 11 1,60 210 60 〇 0 5 0. 8 160 Example 12 2. 30 205 100 〇 0 5 0. 6 120 Example 13 1. 25 214 50 〇 0 6 0. 9 125 Example 14 1. 15 212 40 〇 0 5 0. 8 122 Example 15 2. 05 189 100 〇 0 6 0. 7 130 Example 16 1. 90 186 125 〇 0 6 0. 7 140 Comparative Example 1 2. 04 184 9000 X 4 20 15 255 Comparative Example 2 1. 50 212 5700 X 4 15 20 280 Comparative Example 3 2. 20 203 6200 X 4 17 16 258 Comparative Example 4 1. 14 223 5000 X 4 20 25 305 Comparative Example 5 2. 00 186 10000 X 4 30 28 260 -43- 200904849 The industrially profitable linear oligomerization of 〇· 0 1 ～5 wt %, | 50 ppm or less obtained from the glycol alcohol of 2 500 The fiber of the polyester is formed into a physical property. [The figure is simple [the main component is 4rni tearing 0 phthalic acid component, the molecular weight of 1,4-butanediol is small component, and the number average molecular weight is 400. In the polyester elastomer of more than 70000, the antioxidant is 3 〇 00 ppm or less, the free dicarboxylic acid is 10 ppm by weight of the free monool, and the molecular weight is 65 Å or less and 30 〇 PPm or less. A composition for improving the odor and the heat-resistant elastomer can be suitably used as a raw material for a strict body and a stretched film. Ming] No. Description] -44-