TW202118828A - 高分子組成及用其所製之纖維或無紡布 - Google Patents

高分子組成及用其所製之纖維或無紡布 Download PDF

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TW202118828A
TW202118828A TW109138977A TW109138977A TW202118828A TW 202118828 A TW202118828 A TW 202118828A TW 109138977 A TW109138977 A TW 109138977A TW 109138977 A TW109138977 A TW 109138977A TW 202118828 A TW202118828 A TW 202118828A
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polymer composition
polymer
vinyl aromatic
block
copolymer
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徐泰易
楊豐瑜
蔡祐銓
孫得凱
丁晴
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台橡股份有限公司
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Abstract

本發明提供一種用於纖維或無紡布的高分子組成，包含一乙烯芳香族系共聚物，以及以該高分子組成之總重量為基準之0至30 wt%的烯烴系高分子。該乙烯芳香族系共聚物以式A1-B-A2表示，其中嵌段A1與嵌段A2為相同或不同的乙烯芳香族嵌段，嵌段A1或嵌段A2具有峰分子量為3,800~4,800，嵌段B為氫化共軛二烯嵌段。該乙烯芳香族系共聚物之共軛二烯單體含量中乙烯基(Vinyl)結構含量為32 wt%~50 wt%，且該乙烯芳香族系共聚物的熔流指數(melt flow index, MFI)為20 g/10min ~ 60 g/10min (230℃, 2.16 kg)。本發明亦提供高分子組成所製之纖維或無紡布。

Description

高分子組成及用其所製之纖維或無紡布
本發明關於一種高分子組成，特別是關於包含乙烯芳香族系共聚物的高分子組成以及其纖維或無紡布的應用。
無紡布是乙烯芳香族系共聚物的一種可行的應用。一般無紡布是用聚丙烯為原料，藉由紡黏與熔噴設備進行加工而成無紡布，但此種無紡布並無彈性或伸縮性可言。近年來，由於衛生用品的高透氣性及彈性性能發展需求，因此開發彈性無紡布便可滿足此應用需求。US 9,963,585號專利，揭露一種可用於纖維擠塑的熱可塑性苯乙烯彈性體，其具有優良的彈性性能。此彈性體在加工過程中，由於彈性體流動特性不佳，難以加工成型，因此需要添加高流動性聚烯烴高分子或提高加工溫度才能順利加工成形。但加入高流動性聚烯烴高分子會使無紡布/纖維上喪失其優越彈性性能；在升高加工溫度下，擠出纖維容易互黏造成無紡布品質不佳，難以順利加工。
US7,910,208及US8,003,209專利提出使用高流動性苯乙烯共聚物及其配方，其材料需搭配雙組分紡黏設備可進行高速生產彈性無紡布。但雙組分紡黏設備稀少，非普遍被應用於一般無紡布製造。另一方面，此等專利提及彈性體具有70~85 wt%的高乙烯基Vinyl結構，而高乙烯基Vinyl結構會犧牲彈性回復力(卸載應力)的性能，導致彈性性能不優越。此外，TWI641636專利也揭露可應用於纖維的含乙烯芳香族系共聚物高分子組成，惟其仍有流動性不足之缺點。
於一方面，本發明提供一種用於纖維及無紡布的高分子組成，包含一乙烯芳香族系共聚物以及以該高分子組成之總重量為基準之0至30 wt%的烯烴系高分子，該乙烯芳香族系共聚物為具有良好之流動特性的乙烯芳香族系共聚物。
於另一方面，本發明提供如前述之用於纖維及無紡布的高分子組成，其中該乙烯芳香族系共聚物以式A1-B-A2表示，嵌段A1與嵌段A2為相同或不同的乙烯芳香族嵌段，嵌段A1或嵌段A2具有峰分子量為3,800~4,800，嵌段B為氫化共軛二烯嵌段。該乙烯芳香族系共聚物之共軛二烯單體含量中乙烯基(Vinyl)結構含量為32 wt%~50 wt%，且該乙烯芳香族系共聚物的熔流指數(melt flow index, MFI)為20 g/10min ~ 60 g/10min (230℃, 2.16 kg)。
於另一方面，本發明提供由該高分子組成所形成的纖維及無紡布，特別是具有彈性的纖維及無紡布，以供衛生材料與織物的應用。
本發明尚包含其他各方面以解決其他問題並合併上述之各方面詳細揭露於以下實施方式中。
以下將示範本發明之較佳實施例以更進一步說明本發明之方法、特徵及優點，但並非用來限制本發明之範圍，本發明之範圍應以所附之申請專利範圍為準。為避免模糊本發明之內容，以下說明亦省略習知之元件、相關材料、及其相關處理技術。
本發明各種特性的量測方法
乙烯芳香族系共聚物的乙烯芳香族單體含量：使用核磁共振分析儀量測，為本領域技術人士熟知的量測方法。
乙烯芳香族系共聚物之共軛二烯單體含量中乙烯基(Vinyl)結構含量：使用核磁共振分析儀量測，為本領域技術人士熟知的量測方法。
乙烯芳香族系共聚物之乙烯芳香族嵌段之峰分子量/重均分子量、乙烯芳香族系共聚物之峰分子量/重均分子量：採用膠體滲透層析儀量測，為本領域技術人士熟知的量測方法。
乙烯芳香族系共聚物之乙烯芳香族嵌段之真實分子量、乙烯芳香族系共聚物之真實分子量：採用膠體滲透層析-光散射儀量測，為本領域技術人士熟知的量測方法。
乙烯芳香族系共聚物的共軛二烯嵌段的氫化率：使用核磁共振分析儀量測，為本領域技術人士熟知的量測方法。
乙烯芳香族系共聚物之雙嵌段含量：使用核磁共振分析儀量測，為本領域技術人士熟知的量測方法。
有序–無序相轉化溫度(order-disorder transition temperature, ODT)：使用TA  Instruments  ARES-II儀器以動態力學分析(DMA)進行量測，為本領域技術人士熟知的量測方法。
熔流指數(melt flow index, MFI)：依據ASTM D1238標準量測。
200 % 峰值應力(peak stress)：依據ASTM D882 標準量測。
50% 彈性回復力，或稱為50%卸載應力(unload stress, MPa)：依據ASTM D882 標準量測。彈性回復力代表樣品在回復過程中，所維持的力量值，因此彈性回復力值越高者彈性越佳。
永久變形率(permanent set)：依據ASTM D882 標準量測。永久變形率越低代表彈性較佳。
乙烯芳香族系共聚物
本發明提供具有優良的流動特性的乙烯芳香族系共聚物。該乙烯芳香族系共聚物以式A1-B-A2表示，其中嵌段A1與嵌段A2為相同或不同的乙烯芳香族嵌段，嵌段A1或嵌段A2之峰分子量為3,800~4,800，嵌段B為氫化共軛二烯嵌段。該乙烯芳香族系共聚物之共軛二烯單體含量中乙烯基(Vinyl)結構含量為 32 wt%~50 wt%，較佳小於等於45 wt%，例如為32 wt%~45 wt%，更佳為32 wt%~42 wt%，特佳為36 wt%~40 wt%。該乙烯芳香族系共聚物的熔流指數(melt flow index, MFI)為 20g/10min ~ 60 g/10min (230℃, 2.16 kg)，較佳為30 g/10min ~ 50 g/10min (230℃, 2.16 kg)，特佳為35 g/10min ~45 g/10min (230℃, 2.16 kg)。該乙烯芳香族系共聚物的50% 卸載應力大於或等於0.49 MPa。該乙烯芳香族系共聚物的永久變形率小於或等於25%。於較佳實例，該乙烯芳香族系共聚物的乙烯芳香族單體含量為16 wt%~28 wt%，較佳為18 wt%~26 wt%，或更佳為20 wt%~24 wt%。於較佳實例，嵌段B為氫化率至少為90%的氫化共軛二烯嵌段，更佳為氫化率大於95%的氫化共軛二烯嵌段。依據較佳實例，該乙烯芳香族系共聚物之有序–無序相轉化溫度(order-disorder transition temperature, ODT)為200℃~220℃。於較佳實例，該乙烯芳香族系共聚物之峰分子量的較佳範圍為62,000~74,000，更佳範圍為64,000~72,000；與上述峰分子量對應之真實分子量的較佳範圍為38,000~46,000，更佳範圍為40,000~44,000；其中，該乙烯芳香族系共聚物之峰分子量與重均分子量的較佳範圍與更佳範圍相同。依據較佳實例，嵌段A1或嵌段A2之峰分子量的較佳範圍為3,800~4,800，更佳範圍為4,400~4,700；其中，嵌段A1或嵌段A2之峰分子量、真實分子量及重均分子量的範圍相同。
嵌段A1或嵌段A2為乙烯芳香族嵌段其可衍生自一乙烯芳香族單體，此乙烯芳香族單體舉例而言可為選自以下項目：苯乙烯、甲基苯乙烯、乙基苯乙烯、叔丁基苯乙烯、二甲基苯乙烯、甲氧基苯乙烯、環己基苯乙烯、乙烯基聯苯、1-乙烯基-5-己基萘、乙烯基萘、乙烯基蒽、2, 4-二異丙基苯乙烯、5-叔丁基-2-甲基苯乙烯、二乙烯基苯、三乙烯基苯、二乙烯基萘、叔丁氧基苯乙烯、4-丙基苯乙烯、4-十二烷基苯乙烯、2-乙基-4-苄基苯乙烯(2-ethyl-4-benzylstyrene)、4-(苯基丁基)苯乙烯、N-4-乙烯基苯基-N,N-二甲胺、(4-乙烯基苯基)二甲基氨基乙基醚、N,N-二甲基氨基甲基苯乙烯、N,N-二甲基氨基乙基苯乙烯、N,N-二乙基氨基甲基苯乙烯、N,N-二乙基氨基乙基苯乙烯、乙烯基二甲苯、乙烯基吡啶、二苯基乙烯、2,4,6-三甲基苯乙烯、α-甲基-2,6-二甲基苯乙烯、α-甲基-2,4-二甲基苯乙烯、β-甲基-2,6-二甲基苯乙烯、β-甲基-2,4-二甲基苯乙烯、茚、含有叔氨基的二苯基乙烯及其上述各項之任何組合。嵌段A1與嵌段A2為相同或不同的乙烯芳香族嵌段。嵌段B較佳為氫化率至少為90%之氫化共軛二烯嵌段，其單體舉例而言可衍生自以下項目：1,3-丁二烯、1,3-戊二烯、1,3-己二烯、1,3-庚二烯、2-甲基-1,3-丁二烯(異戊二烯)、2-甲基-1,3-戊二烯、2-己基-1,3-丁二烯、2-苯基-1,3-丁二烯、2-苯基-1,3-戊二烯、2-對甲苯基-1,3-丁二烯、2-苄基-1,3-丁二烯(2-benzyl-1,3-butadiene)、3-甲基-1,3-戊二烯、3-甲基-1,3-己二烯、3-丁基-1,3-辛二烯、3-苯基-1,3-戊二烯、4-甲基-1,3-戊二烯、1,4-二苯基-1,3-丁二烯(1,4-diphenyl-1,3-butadiene)、2,3-二甲基-1,3-丁二烯、2,3-二甲基-1,3-戊二烯、2,3-二苄基-1,3-丁二烯(2,3-dibenzyl-1,3-butadiene)、4,5-二乙基-1,3-辛二烯、月桂烯(myrcene)及其上述各項之任何組合。
由上述可知該乙烯芳香族系共聚物為線性嵌段共聚物，其結構中未含偶合劑殘基。於較佳實例，基於該乙烯芳香族系共聚物之總重量該乙烯芳香族系共聚物之雙嵌段含量低於3wt%，更佳低於1wt%。
生產前述乙烯芳香族系共聚物的方法包含陰離子聚合與氫化。有關陰離子聚合製程，較佳的作法選項為使用含有機鋰的有機鹼金屬化合物作為觸媒起始劑，如此即可於合適溶劑並在0℃至100℃的溫度下加入所選定的單體後獲得活性聚合物。由於分子鏈的尾端包含一碳-鋰離子，所以當單體加入後分子鏈會成長使聚合持續進行。有機鋰起始劑的具體例子包含正丙基鋰、異丙基鋰、正丁基鋰、仲丁基鋰、叔丁基鋰、正戊基鋰、苯基鋰、甲苯基鋰等，較佳者為正丁基鋰或仲丁基鋰。聚合時有機鋰起始劑的用量取決於所想要獲得之聚合物的分子量，其通常視整體單體的實際消耗量而定。有關陰離子聚合的方法可參考如美國專利US 4,039,593等類似文獻。聚合反應合適的溶劑包含鈍性有機溶劑，其意為在聚合反應中不會參與反應的溶劑。此類溶劑的實例包含丁烷、異丁烷、戊烷、正戊烷、異戊烷、2,2,4-三甲基戊烷、異己烷、正己烷、異庚烷、正庚烷、異辛烷、正辛烷的脂肪族碳氫化合物；或者像環己烷、甲基環己烷、乙基環己烷、環戊烷、環庚烷、甲基環戊烷的環烷族；或者苯、甲苯、二甲苯、乙苯、二乙苯及丙苯等芳香烴化合物，適用於本發明較佳者為環己烷。
氫化在聚合反應之後進行。已知的方法中用來製備本發明氫化嵌段共聚物的係涉及合適催化劑或催化前驅物其包含鈦基的催化系統以及合適的還原劑如烷基鋁及合適的觸媒穩定劑例如磷酸鹽族群等。氫化通常在0℃~ 200℃的溫度範圍下進行且氫氣壓力範圍為1~90 kg/cm2 。觸媒濃度之使用範圍通常為鈦基觸媒重量占聚合物總固含量的約10ppm 到約200ppm。有關製備氫化嵌段共聚物的方法可參考如美國專利US 7,612,148等類似文獻。
乙烯芳香族系共聚物的實施例-聚合物A
聚合物A為前述乙烯芳香族系共聚物之示範實例，其係以下述方法製備。在100升的反應器中加入48 kg 的環己烷及120 g的THF(四氫呋喃)。加入9.50 g的NBL(正丁基鋰)後接著加入690 g的苯乙烯單體以起始反應。待苯乙烯聚合完成後，加入4.89 kg的丁二烯。待丁二烯聚合完成後，再加入690 g的苯乙烯。待苯乙烯聚合完成後即形成SBS三嵌段共聚物，以甲醇來中止此聚合物的聚合。取1000g上述所製備之SBS三嵌段共聚物的聚合物溶液將其置於耐壓氫化反應器中並維持在氮氣環境中。在室溫下將0.11 毫莫耳的穩定劑溶入10 ml的環己烷中；0.055 毫莫耳的雙(環戊二烯基)二氯化鈦(bis(cyclopentadienyl)titanium dichloride) 分散在10ml的環己烷中；0.33 毫莫耳的三異丁基鋁 (triisobutylaluminum) 溶入10ml的環己烷中。將上述溶液加入SBS三嵌段共聚物。注入氫氣壓力25 kg/cm2 在 80℃下進行氫化。SBS三嵌段共聚物將接著被氫化直到大於95%的丁二烯雙鍵飽和為止。所產出的聚合物進入水中沉澱形成膠粒然後進行乾燥。
乙烯芳香族系共聚物的實施例-聚合物B及聚合物C
聚合物B及聚合物C之製備方法與聚合物A的製備方法類似，相較於聚合物A的製備方法，差別僅在於聚合物B及聚合物C的製備方法調整了NBL(正丁基鋰)的使用量，進而改變聚合物B及聚合物C之苯乙烯嵌段的峰分子量（式A1-B-A2之嵌段A1或嵌段A2之峰分子量），其餘製備流程並無太大差異，於此不再贅述。
非本發明的乙烯芳香族系共聚物-T-6014、聚合物D、聚合物E及聚合物F。
T-6014、聚合物D、聚合物E及聚合物F之製備方法與聚合物A的製備方法類似，相較於聚合物A的製備方法，主要差異在於上述聚合物的製備方法調整了NBL(正丁基鋰)的使用量，以及調整了苯乙烯與丁二烯的使用比例，進而改變上述聚合物之峰分子量、苯乙烯含量及苯乙烯嵌段的峰分子量，其餘製備流程並無太大差異，於此不再贅述。
有關聚合物A、聚合物B、聚合物C及其他用於比較例之非本發明的乙烯芳香族系聚合物(T-6014、聚合物D、聚合物E、聚合物F，MD-1648(Kraton 公司產品))其特性如表一所示。相較於T-6014、聚合物D、聚合物E及聚合物F(苯乙烯嵌段的峰分子量在5000以上)，聚合物A、聚合物B及聚合物C明顯有較優的熔流指數(MFI)。MD-1648雖有更高的熔流指數，但因具高量的乙烯基Vinyl結構，導致彈性性能不足。
表一
乙烯芳香族系共聚物 T-6014 聚合物A 聚合物B 聚合物C 聚合物D 聚合物E 聚合物F MD-1648 Kraton
MFI (230 ˚C, 2.16 kg) (g/10min) 7.2 44.4 50.4 40.4 10.7 12.5 6.4 191
峰分子量 (Mp, K) 87 68 67 66 73 65 87 70
苯乙烯含量 (wt %) 18.5 23.6 23.5 23.7 27.9 31.8 23.6 19.5
SM1(Mp) 5230 4671 4493 3806 5503 5993 5430  -
乙烯基含量 (wt%) 37.8 40.4 40 37.1 39.8 36.3 39.7 76
共軛二烯嵌段氫化率 (%) ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 ＞95
SM1：代表苯乙烯嵌段的峰分子量（式A1-B-A2之嵌段A1之峰分子量）
高分子組成
本發明提供一種高分子組成，其可用於製造具有優越彈性/作業流動性的纖維/彈性無紡布。依據一實施例，本發明之高分子組成包含至少一乙烯芳香族系共聚物，以及以該高分子組成之總重量為基準之0至30 wt%（不大於30 wt%）烯烴系高分子。
該乙烯芳香族系共聚物可為前述之以聚合物A、聚合物B或聚合物C為範例的乙烯芳香族系共聚物。又於其他實施例，舉例而言，該乙烯芳香族系共聚物可為苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、苯乙烯-乙烯-(乙烯-丙烯)-苯乙烯嵌段共聚物(SEEPS)、或上述之組合，其中SEBS為較佳實例。
烯烴系高分子係烯烴系均聚物、烯烴系共聚物、或其組合。舉例而言，烯烴系高分子之單體較佳為碳數2~10的烯烴，更佳為碳數2~8的烯烴，再更佳為碳數2~5的烯烴，特佳為碳數2~4的烯烴。烯烴系高分子之單體例如可舉出：乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、異丁烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、異戊二烯、四氟乙烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、1-二十烯、環丁烯、環戊烯、環己烯、環辛烯、1,3－丁二烯、1,3－戊二烯、3,4-二甲基環戊烯、3-甲基環己烯、2-(2-甲基丁基)-1-環己烯、1,4-己二烯、4-甲基-1,4-己二烯、5-甲基-1,4-己二烯、7-甲基-1,6-辛二烯、3,7-二甲基-1,6-辛二烯、5,7-二甲基-1,6-辛二烯、1,7-辛二烯、3,7,11-三甲基-1,6,10-辛三烯、6-甲基-1,5-庚二烯、1,6-庚二烯、1,8-壬二烯、1,9-癸二烯、或1,10-十一烷二烯等。
於較佳實施例，烯烴系高分子係選自乙烯系聚合物或丙烯系聚合物。乙烯系聚合物為含有乙烯作為單體的任何均聚物或共聚物，如聚乙烯、乙烯/乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸丁酯共聚物(EBA)、乙烯-丙烯酸酯、乙烯-丙烯酸離子聚合物、乙烯-降冰片烯共聚物等環狀烯烴系聚合物、乙烯-α-烯烴共聚物(嵌段或無規)，其中乙烯-α-烯烴共聚物是較佳的選擇。以聚乙烯(PE)為例，可列舉：高密度聚乙烯、超高分子量高密度聚乙烯、低密度聚乙烯、線狀低密度聚乙烯、超低密度聚乙烯等。以乙烯-α-烯烴共聚物為例，可列舉：乙烯-丙烯共聚物、乙烯-1-丁烯共聚物、乙烯-1-己烯共聚物、乙烯-1-庚烯共聚物、乙烯-1-辛烯共聚物、乙烯-4-甲基-1-戊烯共聚物、乙烯-1-壬烯共聚物、乙烯-1-癸烯共聚物、氯化聚乙烯丙烯-丁烯共聚物或它們的改性物等。丙烯系聚合物為含有丙烯作為單體的任何均聚物或共聚物，如聚丙烯、氯化聚丙烯、丙烯-α-烯烴共聚物(嵌段或無規)。以丙烯-α-烯烴共聚物為例，可列舉：丙烯-乙烯共聚物、丙烯-1-丁烯共聚物、丙烯-1-己烯共聚物、丙烯-1-庚烯共聚物、丙烯-1-辛烯共聚物、丙烯-4-甲基-1-戊烯共聚物、丙烯-1-壬烯共聚物、丙烯-1-癸烯共聚物、丙烯-戊烯無規共聚物、丙烯-乙烯-戊烯無規共聚物、丙烯-乙烯-己烯無規共聚物等、或它們的改性物等。
於較佳實施例，烯烴系高分子係選自高密度聚乙烯(HDPE)、等規聚丙烯(isotactic PP)、乙烯-α-烯烴共聚物(POE)或上述之組合。
於較佳實施例，以該高分子組成之總重量為基準，該烯烴系高分子之含量不大於20 wt% 或較佳不大於15 wt%。本發明也包含不添加烯烴系高分子之實施例。另外，當該烯烴系高分子之含量大於以該高分子組成之總重量為基準之0 wt%時，亦即該高分子組成包含該烯烴系高分子時，該高分子組成的熔流指數(melt flow index, MFI)為 20 g/10min ~ 60 g/10min (230℃, 2.16 kg)，較佳為30 g/10min ~ 50 g/10min (230℃, 2.16 kg)。該高分子組成的50% 卸載應力大於或等於0.49 MPa。該高分子組成的永久變形率小於或等於25%。
依據某些實例，為進一步增加應用性、或加強其物理或化學性質，以該高分子組成之總重量為基準高分子組成可進一步包含小於7 wt%的加工助劑。該加工助劑可包含增塑劑、熔融強度增強劑、抗氧化劑、抗黏劑、滑劑、柔軟劑、相容劑或抗靜電劑、或上述之組合。
高分子組成的應用
本發明提供由前述之高分子組成所形成的纖維及無紡布，特別是具有彈性的纖維及無紡布，以供衛生材料與織物的應用。本發明提供了具有優越彈性及作業流動性的纖維及無紡布。本發明之纖維係由前述之高分子組成所製成。本發明之無紡布具有包含至少一無紡纖維層的多層結構，該無紡纖維層係由前述高分子組成所製成，其中該無紡纖維層為以紡黏(Spun bond, S)或熔噴(Meltblown, M)方式形成。紡黏法係將熔融的高分子組成擠出、拉伸而形成連續長絲後，長絲鋪設成網，纖網再經過自身粘合、熱粘合、化學粘合或機械加固方法，使纖網變成無紡布。熔噴法係將將熔融的高分子組成藉由押出機擠入高速熱氣流中，以形成超細纖維並吹向收集器堆積成超細纖維網狀結構。
具體而言，本發明之高分子組成可在單螺旋或雙螺旋擠壓機中配混以形成一混合物。此混合物可以視需要進行造粒。以下為本發明之高分子組成造粒後製成薄片以檢測機械物性的實例。
實例1
實例1的高分子組成：聚合物B 100 wt%。將此高分子組成投入雙螺桿押出機以160~220℃混煉及造粒。將造粒物於射出機射出2mm厚度試片(長寬:12cm x12cm)，隨後將射出試片運用模壓機熱壓成薄片(厚度=200~300um)，加工溫度160℃，預熱三分鐘排氣二次、實際熱壓四分鐘。將熱壓片利用薄膜裁切器切割出標準試片(長寬:1 inch x12 inch) ，後續進行各種性質測試，結果顯示於表二。
比較例 PP
比較例 PP的高分子組成：等規聚丙烯(Isotactic PP: Yungsox PP-1352F，台塑公司) 100 wt%。其餘步驟與實例1同，結果顯示於表二。
表二
　高分子組成 比較例PP 實例1
等規聚丙烯 (wt%) 100  
聚合物B (wt%) 100
高分子組成/薄片物性
MFI at 230o C & 2.16kg(g/10min) 33.3 50.4
200%峰值應力(MPa) - 2.61
50%卸載應力 (MPa) - 1
永久變形率(%) - 11
本發明之各表中所示MFI可視為高分子組成的流動性指標，MFI越高代表流動性與加工性越好。本發明之各表中所示50%卸載應力及永久變形率可視為薄片的彈性指標，50%卸載應力越高或永久變形率越低代表彈性越好。表二顯示比較例PP之等規聚丙烯薄片無法量得永久變形率及50%卸載應力。相較於比較例PP，實例1之聚合物B的薄片顯然有較佳的彈性。
有關本發明所示範實例2至8及比較例1至9之薄片的作法，除其高分子組成與實例1不同外，其餘均與實例1同。
表三
 高分子組成　 比較例 1 實例 1 比較例 2 實例2 比較例 3 實例3 比較例 4 實例4
T-6014 (wt%) 100% - 85% - 70% - 50% -
聚合物B (wt%) - 100% - 85% - 70% - 50%
等規聚丙烯 (wt%) - - 15% 15% 30% 30% 50% 50%
高分子組成/薄片物性
MFI at 230o C & 2.16kg(g/10min) 7.2 50.4 8.8 42.4 11.3 40.7 17.1 38.3
200% 峰值應力 (MPa) 2.37 2.61 4.24 4.98 6.99 9.48 13.17 16.3
50% 卸載應力 (MPa) 0.86 1 0.82 0.94 0.43 0.49 0 0
永久變形率  (%) 11 11 15 14 27 25 80 78
從表三之實例1至實例4可知，隨著高分子組成中等規聚丙烯成分的增加，薄片的彈性逐漸變差。於不含等規聚丙烯之高分子組成狀況下，相較於比較例1之聚合物T-6014薄片，實例1之聚合物B的薄片具有較好的彈性。於含15 wt%/30 wt%等規聚丙烯之高分子組成狀況下，相較於比較例2/比較例3之聚合物T-6014薄片，實例2/實例3之聚合物B的薄片具有較好的彈性。於含50 wt% 之等規聚丙烯之高分子組成狀況下，比較例4之聚合物T-6014薄片與實例4之聚合物B的薄片之彈性都顯然不好。另，T-6014在添加與未添加等規聚丙烯的情況下，MFI都偏低，顯然有較差的流動性；而聚合物B即使添加等規聚丙烯，仍能維持較高的MFI。由此可知，聚合物B在添加適量之等規聚丙烯的情況下，仍有同時具備高流動性與高彈性的優點。
表四
高分子組成 比較例 5 實例5 比較例6 實例6 實例7
聚合物A (wt%) - 100% - 70% 70%
MD-1648 (wt%) 100% - 70% -    -
等規聚丙烯 (wt%) - - 30% 30%    -
Engage-8407(POE)** (wt%)      -     -     -     - 30%
高分子組成/薄片物性
MFI at 230o C & 2.16kg(g/10min) 191 44.4 142.2 45.3 54
200% 峰值應力 (MPa) 2.08 2.94 9.2 9.54 3.32
50% 卸載應力 (MPa) 0.56 1.06 0.16 0.5 0.78
永久變形率 (%) 14 11 40 25 13
參見表四，於不含等規聚丙烯之高分子組成狀況下，相較於比較例5之聚合物MD-1648薄片，實例5之聚合物A的薄片具有較好的彈性。於含30 wt%等規聚丙烯之高分子組成狀況下，相較於比較例6之聚合物MD-1648薄片，實例6之聚合物A的薄片具有較好的彈性。詳言之，聚合物MD-1648因為具有高乙烯基含量，導致聚合物MD-1648在加入等規聚丙烯後，彈性性能嚴重衰退且不符合應用需求；而聚合物A因為乙烯基含量低，即使添加等規聚丙烯，仍具有較佳的彈性表現。由此可知，聚合物A在添加適量之等規聚丙烯的情況下，仍有同時具備高流動性與高彈性的優點。至於實例7，則是改於高分子組成中添加30% Engage-8407(POE)以取代等規聚丙烯，結果顯示比起添加等規聚丙烯的實例6，改用POE實例7更可提高其薄片的彈性性能，獲得較低的永久變形率與較高的彈性回復力。Engage-8407為陶氏公司出產的乙烯-α-烯烴共聚物。
表五
　高分子組成 實例5 實例1 實例8 比較例7 比較例8 比較例9
聚合物A (wt%) 100    
聚合物B (wt%)   100        
聚合物C (wt%)     100      
聚合物D (wt%)       100    
聚合物E (wt%)         100  
聚合物F (wt%)           100
峰分子量(Mp, K) 68 67 66 73 65 87
SM1(Mp) 4671 4493 3806 5503 5993 5430
MFI at 230o C & 2.16kg (g/10min) 44.4 50.4 40.4 10.7 12.5 6.4
200% 峰值應力 (MPa) 2.94 2.61 2.86 2.1 2.72 2.12
50% 卸載應力 (MPa) 1.06 1 0.58 0.75 0.68 0.86
永久變形率 (%) 11 11 22 15 19 12
如前述，相較於聚合物D、聚合物E及聚合物F，聚合物A、聚合物B及聚合物C明顯有較優的熔流指數(MFI)。表五顯示相較於以聚合物D、聚合物E或聚合物F為主之高分子組成或由上述高分子組成所得之薄片(比較例7、比較例8及比較例9)，以聚合物A、聚合物B或聚合物C為主之高分子組成或由上述高分子組成所得之薄片(實例5、實例1及實例8)同時具備高流動性與高彈性的優點。由上述實驗結果可知，由於本發明之高分子組成具有高流動性之優點，當本發明之高分子組成用於纖維或無紡布材料時，即可提升加工性以順利製作纖維或無紡布材料；此外，經檢視本發明之高分子組成的薄片之50%卸載應力及永久變形率等測試結果，可知本發明之高分子組成具有高彈性之優點，當本發明之高分子組成用於纖維或無紡布材料時，亦可提升纖維或無紡布材料之彈性，以符合產品的性能需求。
雖然本發明已以較佳實施例揭露如上，然其並非用以限制本發明，任何熟習此項技藝者，在不脫離本發明之精神和範圍內，當可做更動與潤飾，因此本發明之保護範圍當以後附之申請專利範圍所界定者為準。
無。

Claims (22)

  1. 一種用於纖維或無紡布材料的高分子組成，包含： 一乙烯芳香族系共聚物，該乙烯芳香族系共聚物以式A1-B-A2表示，其中嵌段A1與嵌段A2為相同或不同的乙烯芳香族嵌段，嵌段A1或嵌段A2之峰分子量為3,800~4,800，嵌段B為氫化共軛二烯嵌段，該乙烯芳香族系共聚物之共軛二烯單體含量中乙烯基(Vinyl)結構含量為32 wt%~50 wt%，且該乙烯芳香族系共聚物的熔流指數(melt flow index, MFI)為20 g/10min ~ 60 g/10min (230℃, 2.16 kg)；以及以該高分子組成之總重量為基準之0至30 wt%之一烯烴系高分子。
  2. 如請求項1所述之高分子組成，其中該乙烯芳香族系共聚物的乙烯芳香族單體含量為16 wt%~28 wt%。
  3. 如請求項1所述之高分子組成，其中該乙烯芳香族系共聚物之該共軛二烯單體含量中該乙烯基(Vinyl)結構含量為32 wt%~45wt%。
  4. 如請求項1所述之高分子組成，其中該乙烯芳香族系共聚物的該熔流指數為30 g/10min ~ 50 g/10min (230℃, 2.16 kg)。
  5. 如請求項1所述之高分子組成，其中該乙烯芳香族系共聚物之有序–無序相轉化溫度(order-disorder transition temperature, ODT)為200℃~220℃。
  6. 如請求項1所述之高分子組成，其中該乙烯芳香族系共聚物之峰分子量的範圍為62,000~74,000。
  7. 如請求項1所述之高分子組成，其中嵌段A1或嵌段A2之該峰分子量為4,400~4,700。
  8. 如請求項1所述之高分子組成，其中嵌段B之氫化率大於或等於90%。
  9. 如請求項1所述之高分子組成，其中該高分子組成的50%卸載應力大於或等於0.49 MPa。
  10. 如請求項1所述之高分子組成，其中該高分子組成的永久變形率小於或等於25%。
  11. 如請求項1所述之高分子組成，其中該乙烯芳香族系共聚物為苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、苯乙烯-乙烯-(乙烯-丙烯)-苯乙烯嵌段共聚物(SEEPS)、或上述之組合。
  12. 如請求項1所述之高分子組成，其中該烯烴系高分子係烯烴系均聚物、烯烴系共聚物、或其組合。
  13. 如請求項1所述之高分子組成，其中該烯烴系高分子係選自乙烯系聚合物或丙烯系聚合物。
  14. 如請求項1所述之高分子組成，其中烯烴系高分子係選自高密度聚乙烯(HDPE)、等規聚丙烯(isotactic PP)、乙烯-α-烯烴共聚物(POE)或上述之組合。
  15. 如請求項1所述之高分子組成，其中該烯烴系高分子之含量不大於以該高分子組成之總重量為基準之20 wt%。
  16. 如請求項1所述之高分子組成，其中該高分子組成不包含該烯烴系高分子。
  17. 如請求項1所述之高分子組成，其中該烯烴系高分子之含量大於以該高分子組成之總重量為基準之0 wt%，該高分子組成的該熔流指數為20 g/10min ~ 60 g/10min (230℃, 2.16 kg)。
  18. 如請求項1所述之高分子組成，更包含加工助劑。
  19. 如請求項18所述之高分子組成，該加工助劑係為增塑劑、熔融強度增強劑、抗氧化劑、抗黏劑、滑劑、柔軟劑、相容劑、抗靜電劑、或上述之組合。
  20. 一種纖維，係由請求項1至19中任一項之高分子組成所製成。
  21. 一種無紡布，具有包含至少一無紡纖維層的多層結構，該無紡纖維層係由請求項1至19中任一項之高分子組成所製成。
  22. 如請求項21所述之無紡布，其中該無紡纖維層為以紡黏或熔噴方式形成。
TW109138977A 2019-11-08 2020-11-09 高分子組成及用其所製之纖維或無紡布 TWI776272B (zh)

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