CN1818162A - 聚氨酯弹性体纤维和制备该纤维的方法 - Google Patents
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Abstract
本发明由热塑性聚氨酯弹性体纤维组成,通过熔体纺丝回弹率为60%或更大的聚氨酯和异氰酸酯封端的聚醚或聚酯添加剂而获得该纤维。弹性纤维具有低收缩率、高耐热性、低拉伸变形、和高伸长率。
Description
本发明是申请号为02805408.3、申请日为2002年2月5日、发明名称为“聚氨酯弹性体纤维和制备该纤维的方法”的中国专利申请的分案申请。
发明背景
本发明涉及通过熔体纺丝回弹率为60%或更大的聚氨酯和异氰酸酯封端的聚醚或聚酯获得的聚氨酯弹性体纤维,以得到具有低收缩率、高耐热性、低拉伸变形和高伸长率的弹性纤维。具有改进弹性体性能的聚氨酯具有许多实际应用,如生活消费品中的织物,如袜子和服装,医疗应用、娱乐应用、汽车应用、或工业应用,如传送带、电缆护套等。
用于服装工业的通常弹性纤维是斯潘德克斯(spandex)。它是具有高弹性回复率的可拉伸纤维。斯潘德克斯用于许多商业纱线和织物以向服装添加弹性。
斯潘德克斯由联邦商业委员会定义为包括至少85%嵌段聚氨酯的长链合成聚合物。它通过反应高分子量二羟基化合物与有机二异氰酸酯和扩链剂以形成弹性体纤维而制备。由于它在聚合物结构中由交替软和硬区域组成,它是嵌段的。硬链段用作将聚合物链结合在一起的物理交联。聚合物链的软链段由包含长、卷曲链段的聚合物组成,该长、卷曲链段可在拉伸材料时取向。交联防止聚合物链显著通过彼此移动。在拉伸之后,线性软链段回复到卷曲形式,使得纤维返回到它的原始形状。
尽管湿纺和熔体纺丝方法是已知的,它优选由干纺方法制备。DuPont首先在1959年使用干纺方法,引入了斯潘德克斯弹性聚氨酯(脲)纤维。在1937年,Bayer引入了由熔体纺丝方法制备的聚氨酯弹性纤维。
干纺方法是一种这样的工艺,其中将长链二元醇与芳族二异氰酸酯(通常是4,4’-亚甲基二苯基二异氰酸酯,MDI)以生产异氰酸酯封端的预聚物。在极性溶剂存在下,通过反应预聚物与二胺而完成扩链以制备纺丝原液。然后将原液以多长丝形式从喷嘴挤出。通过在纺丝塔中与热空气或热N2接触而蒸发溶剂。然后将纺成的纱线假捻,油处理和卷绕在线轴上。干纺纤维有在老化时损失强度的趋势。
熔体纺丝方法的不同在于在溶剂不存在下进行预聚物制备和扩链两者。为达到性能可比于由干纺达到的那些纤维,必须将纺成的纤维进行热老化处理,以促进通过剩余异氰酸酯基团的交联。
由Bayer在二十世纪三十年代后期和二十世纪四十年代早期开发的聚氨酯热塑性弹性体的熔体纺丝方法并没得到令人满意的性能。聚氨酯的其它熔体纺丝方法是已知的。U.S.专利No.3,503,933公开了熔体纺丝的斯潘德克斯,它使用不对称二异氰酸酯,该二异氰酸酯在两个异氰酸酯基团的反应性中具有五倍的差异。这些二异氰酸酯导致具有差加工品质如高粘性,差的织物性能如低卸荷力,在如染色、整理、和洗涤等领域中具有差的织物加工性能的斯潘德克斯。Foss等人的U.S.专利No.5,840,223教导了从包括二异氰酸酯封端的多元醇预聚物的可熔体纺丝弹性体组合物,制备熔体纺丝弹性体纤维的方法,采用芳族二羟基化合物将该预聚物扩链。可以将生产的纤维编织或织造成纺织品制品,如袜子或连裤袜。
U.S.专利No.6,127,506,Green教导了熔体纺丝斯潘德克斯的方法,其中从精制的封端多元醇,线性脂族二胺和单胺链终止剂制备聚氨酯(脲)聚合物。在该方法期间,将二异氰酸酯与聚合二元醇接触以得到封端的二元醇。在Green中该方法的重点在于在聚氨酯(脲)的形成之前精制封端的二元醇。用于该方法的聚合二元醇包括聚醚二元醇、聚酯二元醇、聚碳酸酯二元醇、和二元醇的共聚物。二异氰酸酯基本具有与聚合物多元醇相同的对羟基的反应性。优选的二异氰酸酯是MDI。在Green中,将单体聚合和然后熔体纺丝以得到斯潘德克斯或聚氨酯(脲)。
传统上,斯潘德克斯由干纺或湿纺制备。由于熔体纺丝并不涉及使用有机溶剂,其在健康、安全和环境考虑方面是最有利的方法。但,干纺斯潘德克斯生产了具有与由其它工艺制备的那些相比,最好性能平衡的纤维。因此,需要具有斯潘德克斯的性能但可以熔体纺丝而不是干纺的纤维材料。尽管热塑性聚氨酯一般具有关于耐磨性的所需性能,它们一般并不显示出如高熔点,低拉伸变形,低压缩变形,良好的回弹性,和低滞后的性能。
聚醚聚氨酯是已知的,例如,Vedula等人的U.S专利No.5,959,059教导了聚醚尿烷,该聚醚尿烷当从如下物质的熔体聚合制备时,具有良好的物理性能:包含2-6个碳原子的烯化氧重复单元的、羟基封端聚醚中间体,和扩链剂与二异氰酸酯。Vedula等人,使用芳族二异氰酸酯,优选是MDI。此外,热塑性聚醚尿烷由“一步法工艺”生产,其中将羟基封端的聚醚中间体,扩链剂,和二异氰酸酯加入在一起,混合,和聚合。由此“一步法工艺”生产的聚氨酯是这样的聚氨酯,其中扩链剂包括具有更高熔点的芳族部分。获得的聚醚尿烷显示170℃-230℃的高熔点,1.10或更小的低密度,和至少15或20的肖氏D硬度。另外,该聚醚尿烷显示良好的耐撕裂性,良好的耐磨性,和水解稳定性。
聚氨酯聚合物的熔体纺丝也是已知的,包括在熔体中结合聚氨酯聚合物与另外的材料,以达到各种益处。例如,日本专利公开JP58098421(1983)(Yasuhiro等人)教导了向聚氨酯弹性体中加入来自多异氰酸酯和封端剂的反应产物,以生产在高温下具有高变形回复率的弹性纱线。在Yasuhiro公开文献中的反应,是在两个端部上的分子量为400或更大的多异氰酸酯,优选p,p’-二苯基甲烷二异氰酸酯(MDI)和聚四亚甲基二醇与封端剂之间的反应。Yamakawa等人的日本专利公开60048617(2000)教导了熔体纺线对苯二甲酸丁二醇酯类结晶聚酯和热塑性聚氨酯,以制备光泽度为70或更小的弹性纤维。Yoshimoto等人的日本专利公开No.JPl282387(1989)教导了通过捏合作为交联剂的多异氰酸酯预聚物而生产弹性聚氨酯纱线,其中将纱线随后采用矿物油、聚硅氧烷、和二胺混合物处理,以防止纤维的附着。Ogawa等人的日本专利公开No.JP58186609(1983)教导了通过向熔融聚氨酯弹性体中,加入多异氰酸酯化合物和颜料制备的具有改进耐热性的纤维。Ogawa等人的日本专利公开No.JP57112409(1982)教导了通过向熔融聚氨酯弹性体中,加入来自分子量为300-2,500的聚醚和二苯基甲烷二异氰酸酯的含封端NCO端基的多异氰酸酯反应产物,而制备在高温下具有高变形回复率的弹性纱线。
发明概述
本发明是如下发现的结果:可以通过回弹率为60%或更高的聚氨酯,和扩链或交联异氰酸酯封端的聚醚或聚酯添加剂的本体熔体纺丝聚合,获得聚氨酯弹性体纤维。聚氨酯优选衍生自与羟基封端的聚醚反应的二异氰酸酯和二醇扩链剂。聚醚尿烷优选来自羟基封端的聚醚中间体和扩链剂与二异氰酸酯的聚合,其中羟基封端的聚醚含有包含2-6个碳原子的烯化氧重复单元且重均分子量至少为1,500。扩链剂基本是含有2-16个碳原子的非支化二醇,且扩链剂的数量是从0.7至小于1.0摩尔每摩尔该羟基封端的聚醚。
在本发明中,当将聚氨酯聚合物熔体纺丝以生产纤维时,其通过引入异氰酸酯封端的预聚物而扩链或交联。与干纺的斯潘德克斯相比,获得的纤维具有改进的耐热性和降低的滞后损失,同时仍然保持干纺斯潘德克斯的所有有利性能。
发明详述
本发明涉及聚氨酯弹性体纤维,该纤维可以由聚氨酯和异氰酸酯封端的聚醚或聚酯添加剂的本体熔体纺丝聚合而获得。该聚氨酯衍生自与羟基封端的聚醚反应的二异氰酸酯和二醇扩链剂。
具体而言,在本发明的一个方面,提供了一种由如下物质本体熔体聚合获得的热塑性聚氨酯弹性体:
A.聚氨酯,该聚氨酯衍生自与羟基封端的聚醚中间体反应的二异氰酸酯和二醇扩链剂,其中扩链剂的数量是从0.7至小于1.0摩尔每摩尔该羟基封端的中间体;和
B.异氰酸酯封端的聚醚添加剂,其中该添加剂能交联(A)中所述的聚氨酯。
在本发明的另一方面,提供了一种熔体纺丝的弹性体纤维的制备方法,包括熔融具有根据ASTM D2632测量的回弹率为60%或更大的聚氨酯和异氰酸酯封端的聚醚,熔体纺丝以提供纤维,和回收该纤维;其中该聚氨酯衍生自与羟基封端的聚醚中间体反应的二异氰酸酯和二醇扩链剂,其中该扩链剂的数量是从0.7至小于1.0摩尔每摩尔该羟基封端的中间体。
在本发明的再一方面,提供了由上述热塑性聚氨酯弹性体制备的弹性纤维。优选,该弹性体纤维在100℃下在水中30分钟的收缩率小于10%。更优选,该弹性体纤维在100℃下在水中30分钟,它的断裂伸长率百分比为300-700%,和收缩率小于10%,重均分子量为300,000-500,000,和在30分钟、130℃、和200%伸长率下的回复率大于70%。
用于本发明的聚氨酯可以是回弹率为60%或更高的聚醚聚氨酯或聚酯聚氨酯。可以采用的一种聚氨酯是描述于Ravi Vedula的USPat.No.5,959,059中的聚醚聚氨酯,尽管本发明并不限于描述于Vedula专利的聚醚尿烷,该文献的公开内容引入作为参考。例如,Muller的U.S.专利No.3,016,364,该文献也引入作为参考,也教导了可以采用的聚醚尿烷。可通过羟基封端的聚醚中间体和扩链剂与二异氰酸酯的熔体聚合,制备具有良好物理性能的聚醚尿烷。羟基封端的聚醚含有包含2-6个碳原子的烯化氧重复单元且重均分子量至少为1,500。扩链剂基本是含有2-16个碳原子的非支化二醇。扩链剂的数量是从0.7至小于1.0摩尔每摩尔该羟基封端的聚醚。尽管软化点可用于表征聚氨酯,但优选聚醚聚氨酯的熔点为约160℃或更大(如160℃-230℃),优选是175℃或更大。此外,优选尿烷的回弹率为60%或更大,进一步优选是65%或更大。
添加剂是异氰酸酯封端的聚醚或聚酯添加剂,如异氰酸酯封端的多元醇预聚物,它优选由芳族二羟基化合物扩链。术语“异氰酸酯封端的聚醚或聚酯添加剂”一般表示包括多元醇的预聚物,该多元醇已经与二异氰酸酯化合物(即包含至少两个异氰酸酯(-NCO)基团的化合物)反应。在优选的形式中,预聚物的官能度为2.0或更大,平均分子量为约250-10,000,制备该预聚物以基本不包含未反应的单体异氰酸酯化合物。术语“未反应的异氰酸酯化合物”表示含游离的单体异氰酸酯的化合物,即二异氰酸酯化合物,该二异氰酸酯化合物用作与预聚物制备相关的起始材料和在预聚物组合物中保持未反应。在此使用的术语“多元醇”一般表示含有多于一个羟基(-OH)的聚合物,优选每个末端被羟基封端的脂族聚合物。很多种多元醇化合物可用于预聚物的制备。在优选的实施方案中,多元醇可包括聚合二元醇,聚合二元醇包括,例如,聚醚二元醇和聚酯二元醇及其混合物或共聚物。优选的聚合二元醇是聚醚二元醇,更优选是聚亚烷基醚二元醇。示例性聚亚烷基聚醚二元醇包括,例如,聚亚乙基醚二醇、聚亚丙基醚二醇、聚四亚甲基醚二醇(PTMEG)和聚六亚甲基醚二醇及其混合物或共聚物。在这些聚亚烷基醚二元醇中优选是PTMEG。在聚酯二元醇中优选是,例如,聚己二酸丁二醇酯二醇和聚己二酸乙二醇酯二醇及其混合物或共聚物。一旦了解了本发明的公开内容,除以上例举的那些以外,其它多元醇化合物对于本领域技术人员是很显然的。
可以从其衍生预聚物的多元醇的数均分子量可为约800-约3500,和其中所有范围的结合和子结合。更优选,多元醇的数均分子量可为约1500-约2500,甚至更优选是约2000的数均分子量。
采用异氰酸酯化合物封端预聚物中的多元醇。很多种二异氰酸酯化合物可用于本发明预聚物的制备。一般来说,二异氰酸酯化合物可以是芳族或脂族的,优选是芳族二异氰酸酯化合物。合适芳族二异氰酸酯化合物的例子包括二苯基甲烷二异氰酸酯、二甲苯二异氰酸酯、甲苯二异氰酸酯、亚苯基二异氰酸酯、和萘二异氰酸酯及其混合物。合适脂族二异氰酸酯的例子包括二环己基甲烷异氰酸酯和六亚甲基二异氰酸酯及其混合物。至少部分由于它的通用可获得性和高安全程度,以及它与扩链剂(以下更详细讨论)的一般所需反应性,在二异氰酸酯化合物中优选是MDI。一旦了解了本发明的公开内容,除以上例举的那些以外,其它二异氰酸酯化合物对于本领域技术人员是很显然的。
优选的添加剂是二苯基甲烷二异氰酸酯封端的聚醚预聚物或二苯基甲烷二异氰酸酯封端的聚酯预聚物。这些物质是聚醚或聚酯多元醇,其中将羟基转化成异氰酸酯基团,以提供异氰酸酯封端。前者组合物以Hyperlast5130购自Hyperlast Limited,UK,而后者组合物以Diprane5128和Diprane5184也购自HyperlastLimited,Diprane5128衍生自官能己二酸乙二醇酯和MDI,和Diprane5184衍生自己二酸丁二醇酯/己二醇酯和MDI。优选的添加剂是Hyperlast5130,它是衍生自如下物质的二苯基甲烷二异氰酸酯封端的聚醚预聚物:MW为约2000的聚(四亚甲基醚)二醇和MDI。
通过熔体纺丝聚醚尿烷和添加剂制备纤维。熔体纺丝是公知的方法,其中将聚合物由挤出熔融,通过纺丝喷嘴进入空气,由冷却固化,和通过在收集设备上卷绕纤维而收集。典型地在约150℃-约300℃的聚合物温度下熔体纺丝纤维。
最好可通过参考以下的实施例理解本发明,其中更详细地呈现了本发明。然而,实施例并不解释为在此以任何方式限制本发明,本发明的范围在所附的权利要求中确定。
可以通过将它们的性能与Lycra斯潘德克斯纤维(购自E.I.duPont)进行比较而示例根据本发明制备的纤维性能,该斯潘德克斯纤维是市购的和由干纺工艺制备。根据本发明的纤维通过如下方式制备:将Estane58280聚醚聚氨酯(它的熔点为约170℃-约230℃,购自The BF Goodrich Company)和Hyperlast二苯基甲烷二异氰酸酯封端的聚醚交联添加剂,以如下所示的数量加入,在12MPa的压力、20-22rpm的螺杆速度、和219℃的聚合物温度下通过挤出机,以反应聚氨酯和交联剂,和随后将熔融聚合物通过在195℃下操作的熔体纺丝设备。将获得的纤维冷却和回收,和进行物理评价。评价结果见表I。
表I
试验 | Lycra斯潘德克斯 | Estane58280聚氨酯 | Estane58280与10wt%的Hyperlast5130 | Estane58280与15wt%的Hyperlast5130 |
第1循环变形(%) | 21.54 | 31.03 | 22.92 | 18.76 |
第5循环变形(%) | 26.3 | 47.11 | 28.0 | 26.30 |
300%Mod.(N)第一循环 | 0.129 | 0.136 | 0.264 | 0.117 |
滞后(一个点)(%) | 41 | 50 | 47 | 37 |
Kofler软化点1min(℃) | 226 | 185 | 190 | 190 |
Kofler软化点3min(℃) | 226 | 185 | 190 | 190 |
表I显示了在如下物质之间的性能差异:Lycra,聚氨酯,聚氨酯与10wt%交联剂Hyperlast5130,和聚氨酯与15wt%交联剂Hyperlast5130。表I也显示,当通过引入异氰酸酯封端的预聚物,如Hyperlast 5130,将聚合物扩链和一定程度上交联时,耐热性得到进一步改进。
滞后是在弹性材料拉伸和收缩期间能量损失的量度。将此能量损失转换为纤维弹性的损失。大的能量损失表示生热的增加和因此不舒适度的增加。表I显示与Lycra相比,15%Hyperlast的加入可显著降低滞后。
在表II和III中给出了在Lycra斯潘德克斯纤维和采用和不采用Hyperlast5130的Estane58280聚氨酯之间的另外比较。
表II
样品 | Lycra斯潘德克斯 | Estane58280(在70℃下4天烘箱老化) | Estane58280(在70℃下4天烘箱老化) |
%交联剂 | 无 | 10 | 无 |
添加剂类型 | 无 | Hyperlast 5130 | 无 |
旦 | 41.1 | 36.6 | 39.3 |
熔融指数(g/10min)(@210℃3800g) | - | 6 | 6 |
Mw | 390849 | 420620 | 232641 |
Mn | 90735 | 118748 | 87935 |
Mw/Mn | 4.31 | 3.54 | 2.65 |
热变形数据 | |||
%变形(30min,130℃,200%伸长) | 24.0 | 20.0 | 28.4 |
%回复率(30min,130℃,200%伸长) | 76.0 | 80.0 | 71.6 |
%变形(90sec,185℃,100%伸长) | 16.7 | 21.2 | 破坏/无测试 |
%回复率(90sec,185℃,100%伸长) | 83.3 | 78.8 | 破坏/无测试 |
%变形(90sec,185℃,50%伸长) | 11.4 | 13.2 | 破坏/无测试 |
%回复率(90sec,185℃,50%伸长) | 88.6 | 86.8 | 破坏/无测试 |
收缩率(%)(在沸水中) | 8.0 | 0.0 | 6.0 |
表III
旦 | 韧度(g/d) | 伸长率(%) | 100%应力(g/d) | 300%应力(g/d) | 从200%伸长的回复率(%)温度/曝露时间 | ||||
室温5min | 室温24hr | 130℃干燥空气30min | 100℃热水30min | ||||||
58280与10wt%的Hyperlast5130 | 40.1 | 1.45 | 537.4 | 0.12 | 0.41 | 98.8 | 95.0 | 73.5 | 77.0 |
Lycra | 40.1 | 1.02 | 575.2 | 0.10 | 0.38 | 98.8 | 98.3 | 69.0 | 68.5 |
如可以从表II和III看出的那样,从聚氨酯和二异氰酸酯封端的聚醚添加剂制备的熔体纺丝纤维,具有可比于Lycra斯潘德克斯的热定形数据回复率,和韧度(拉伸强度)。
给出本发明的以上实施方案用于说明和描述的目的。这些描述和实施方案并不是穷举的和不限制本发明到公开的精确形式,和显然地根据以上公开内容很多改进和变化是可能的。选择和描述实施方案,以最好解释本发明的原则和它的实际应用,以因此使本领域其它技术人员能最好地以其各种实施方案和采用适于设想的特定用途的各种改进来使用本发明。希望本发明由如下权利要求限定。
Claims (2)
1.一种熔体纺丝的弹性体纤维的制备方法,包括熔融具有根据ASTM D2632测量的回弹率为60%或更大的聚氨酯和异氰酸酯封端的聚醚,熔体纺丝以提供纤维,和回收该纤维;其中该聚氨酯衍生自与羟基封端的聚醚中间体反应的二异氰酸酯和二醇扩链剂,其中该扩链剂的数量是从0.7至小于1.0摩尔每摩尔该羟基封端的中间体。
2.一种熔体纺丝纤维的制备方法,包括可熔体纺丝的热塑性聚氨酯弹性体组合物,该组合物包括
A.衍生自与羟基封端的聚醚中间体反应的二异氰酸酯和二醇扩链剂的聚醚尿烷,
-该羟基封端的聚醚中间体含有包含2-6个碳原子的烯化氧重复单元且重均分子量至少为1,500,
-该扩链剂为含有2-16个碳原子的非支化二醇,
-其中该扩链剂的数量是从0.7至小于1.0摩尔每摩尔该羟基封端的聚醚中间体,和其中当根据ASTM D2632测量时,该聚醚尿烷的回弹率至少为60%;
B.二苯基甲烷二异氰酸封端的聚醚添加剂,其中该添加剂能交联(A)中的聚醚尿烷;和
熔体纺丝该弹性体组合物以提供纤维。
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Application Number | Title | Priority Date | Filing Date |
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CNB028054083A Expired - Lifetime CN1249165C (zh) | 2001-02-23 | 2002-02-05 | 聚氨酯弹性体纤维和制备该纤维的方法 |
CNB2006100090323A Expired - Lifetime CN100535211C (zh) | 2001-02-23 | 2002-02-05 | 聚氨酯弹性体纤维的制备方法 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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CNB028054083A Expired - Lifetime CN1249165C (zh) | 2001-02-23 | 2002-02-05 | 聚氨酯弹性体纤维和制备该纤维的方法 |
Country Status (13)
Country | Link |
---|---|
US (1) | US6911502B2 (zh) |
EP (1) | EP1379591B1 (zh) |
KR (1) | KR100855435B1 (zh) |
CN (2) | CN1249165C (zh) |
AR (1) | AR032713A1 (zh) |
AT (1) | ATE382661T1 (zh) |
BR (1) | BR0207300B1 (zh) |
DE (1) | DE60224376T2 (zh) |
ES (1) | ES2298354T3 (zh) |
MX (1) | MXPA03007524A (zh) |
MY (1) | MY128216A (zh) |
TW (1) | TWI226392B (zh) |
WO (1) | WO2002068534A1 (zh) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030092848A1 (en) * | 2001-09-11 | 2003-05-15 | Ashok Sengupta | Sprayable liner for supporting the rock surface of a mine |
US7357889B2 (en) | 2003-04-09 | 2008-04-15 | Lubrizol Advanced Materials, Inc. | Melt spun TPU fibers and process |
US8148475B2 (en) * | 2003-06-30 | 2012-04-03 | Lubrizol Advanced Materials, Inc. | Melt spun polyether TPU fibers having mixed polyols and process |
US7799255B2 (en) * | 2003-06-30 | 2010-09-21 | Lubrizol Advanced Materials, Inc. | Melt spun elastic tape and process |
CN101918046B (zh) * | 2008-02-15 | 2014-09-24 | 东丽奥培隆特士株式会社 | 除臭材料 |
US20090311529A1 (en) | 2008-06-16 | 2009-12-17 | Voith Patent Gmbh | High tenacity thermoplastic polyurethane monofilament and process for manufacturing the same |
BRPI1015425B1 (pt) * | 2009-06-25 | 2020-10-27 | Lubrizol Advanced Materials, Inc. | fibra elástica fiada por fusão feita a partir de poliuretano termoplástico reticulado, tecido, artigo de vestuário, e, processo para produzir uma fibra elástica |
ES2870853T3 (es) * | 2010-01-25 | 2021-10-27 | Lubrizol Advanced Mat Inc | Telas elásticas no tejidas de alta resistencia |
MX351314B (es) * | 2010-06-15 | 2017-10-10 | Lubrizol Advanced Mat Inc | Fibras elasticas hiladas en estado fundido que tienen modulo plano. |
CN102251316B (zh) * | 2011-06-14 | 2012-11-28 | 吴中虎 | 一种利用氨纶废丝回收生产氨纶丝的方法 |
US20130255103A1 (en) | 2012-04-03 | 2013-10-03 | Nike, Inc. | Apparel And Other Products Incorporating A Thermoplastic Polymer Material |
CN102677213A (zh) * | 2012-06-13 | 2012-09-19 | 浙江华峰氨纶股份有限公司 | 一种简便的氨纶废丝回收再纺丝的方法 |
WO2015055459A1 (en) * | 2013-10-14 | 2015-04-23 | Basf Se | Disposable hygiene article comprising a melt-spun elastic fiber |
CN104911723A (zh) * | 2015-05-21 | 2015-09-16 | 苏州富莱克斯氨纶有限公司 | 一种双组分氨纶制备工艺 |
WO2018146192A1 (en) * | 2017-02-10 | 2018-08-16 | Basf Se | Process for producing elastic fiber, process for producing elastic fiber article, elastic fiber and elastic fiber article |
EP3724248B1 (en) * | 2017-12-15 | 2022-08-10 | The LYCRA Company UK Limited | Polymers with engineered segment molecular weights |
CN108084400B (zh) * | 2017-12-29 | 2020-08-04 | 美瑞新材料股份有限公司 | 一种高性能热塑性聚氨酯弹性体的制备方法 |
US11560647B1 (en) * | 2018-05-07 | 2023-01-24 | David Lewis Kitchen Trumbull | Elastomeric yarn for safety applications |
EP4039118A1 (en) | 2019-08-02 | 2022-08-10 | NIKE Innovate C.V. | An outsole for an article of footwear |
CN112962171B (zh) * | 2021-02-04 | 2022-10-11 | 泉州市成意纺织科技有限公司 | 一种防紫外线弹力健康针织布料及其制造方法 |
Family Cites Families (13)
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DE1029559B (de) | 1956-11-16 | 1958-05-08 | Bayer Ag | Verfahren zur Herstellung hochmolekularer vernetzter Kunststoffe unter Formgebung |
US3503933A (en) | 1966-08-16 | 1970-03-31 | American Cyanamid Co | Low melting polyurethane urea and method for manufacture |
US3494894A (en) | 1966-08-20 | 1970-02-10 | Federico Urgesi | Process for producing elastic fibers from polyurethan polymers having a crosslinked structure |
JPS5846573B2 (ja) | 1980-12-27 | 1983-10-17 | カネボウ合繊株式会社 | ポリウレタン弾性糸の製造方法 |
JPS6043445B2 (ja) | 1981-12-07 | 1985-09-28 | カネボウ株式会社 | ポリウレタン弾性糸の製造方法 |
JPS6044406B2 (ja) | 1982-04-24 | 1985-10-03 | カネボウ株式会社 | 着色したポリウレタン弾性糸の製造方法 |
JPS6048617A (ja) | 1983-08-29 | 1985-03-16 | Matsushita Electric Ind Co Ltd | 信号選択回路 |
JPH01282387A (ja) | 1988-05-10 | 1989-11-14 | Kanebo Ltd | ポリウレタン弾性糸の製造方法 |
DE3930838A1 (de) * | 1989-09-15 | 1991-03-28 | Bayer Ag | Verfahren zur herstellung von tpu-enthaltenden chemiewerkstoffen |
EP0548364A4 (en) | 1991-05-14 | 1994-06-22 | Kanebo Ltd | Potentially elastic conjugate fiber, production thereof, and production of fibrous structure with elasticity in expansion and contraction |
US5959059A (en) | 1997-06-10 | 1999-09-28 | The B.F. Goodrich Company | Thermoplastic polyether urethane |
US5840233A (en) | 1997-09-16 | 1998-11-24 | Optimer, Inc. | Process of making melt-spun elastomeric fibers |
US6127506A (en) | 1999-02-19 | 2000-10-03 | E. I. Du Pont De Nemours And Company | Process for melt spinning spandex |
-
2001
- 2001-02-23 US US09/792,604 patent/US6911502B2/en not_active Expired - Lifetime
-
2002
- 2002-02-05 CN CNB028054083A patent/CN1249165C/zh not_active Expired - Lifetime
- 2002-02-05 BR BRPI0207300-5A patent/BR0207300B1/pt not_active IP Right Cessation
- 2002-02-05 WO PCT/US2002/003477 patent/WO2002068534A1/en active IP Right Grant
- 2002-02-05 EP EP02709371A patent/EP1379591B1/en not_active Revoked
- 2002-02-05 MX MXPA03007524A patent/MXPA03007524A/es active IP Right Grant
- 2002-02-05 CN CNB2006100090323A patent/CN100535211C/zh not_active Expired - Lifetime
- 2002-02-05 AT AT02709371T patent/ATE382661T1/de not_active IP Right Cessation
- 2002-02-05 ES ES02709371T patent/ES2298354T3/es not_active Expired - Lifetime
- 2002-02-05 DE DE60224376T patent/DE60224376T2/de not_active Expired - Lifetime
- 2002-02-05 KR KR1020037011055A patent/KR100855435B1/ko active IP Right Grant
- 2002-02-18 AR ARP020100549A patent/AR032713A1/es unknown
- 2002-02-20 TW TW091102889A patent/TWI226392B/zh not_active IP Right Cessation
- 2002-02-22 MY MYPI20020612A patent/MY128216A/en unknown
Also Published As
Publication number | Publication date |
---|---|
MXPA03007524A (es) | 2003-12-04 |
DE60224376T2 (de) | 2008-12-18 |
KR20030078081A (ko) | 2003-10-04 |
MY128216A (en) | 2007-01-31 |
EP1379591B1 (en) | 2008-01-02 |
CN1249165C (zh) | 2006-04-05 |
ATE382661T1 (de) | 2008-01-15 |
US6911502B2 (en) | 2005-06-28 |
TWI226392B (en) | 2005-01-11 |
US20020161159A1 (en) | 2002-10-31 |
EP1379591A1 (en) | 2004-01-14 |
WO2002068534A1 (en) | 2002-09-06 |
CN1511180A (zh) | 2004-07-07 |
AR032713A1 (es) | 2003-11-19 |
DE60224376D1 (de) | 2008-02-14 |
ES2298354T3 (es) | 2008-05-16 |
KR100855435B1 (ko) | 2008-09-01 |
CN100535211C (zh) | 2009-09-02 |
BR0207300B1 (pt) | 2012-02-07 |
BR0207300A (pt) | 2004-02-10 |
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