CN1711384B - 多组分熔喷纤网 - Google Patents

多组分熔喷纤网 Download PDF

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CN1711384B
CN1711384B CN2003801033021A CN200380103302A CN1711384B CN 1711384 B CN1711384 B CN 1711384B CN 2003801033021 A CN2003801033021 A CN 2003801033021A CN 200380103302 A CN200380103302 A CN 200380103302A CN 1711384 B CN1711384 B CN 1711384B
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fibre web
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web
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CN1711384A (zh
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V·班萨尔
S·L·萨米尔斯
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3M Innovative Properties Co
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Abstract

公开一种多组分熔喷纤网，其中熔喷纤维包括在其周边表面至少一部分上的离聚物。该熔喷纤网尤其适用于灰尘收集之用。

Description

多组分熔喷纤网
技术领域
本发明涉及含有离聚物组分的多组分熔喷纤网。该多组分熔喷纤网特别适合用于灰尘抹布。
背景技术
单组分熔喷离聚物微纤维及其制成的纤网(web)在技术上是公知的。例如，Chou等人，美国专利5,817,415，在此收作参考，描述由乙烯/羧酸离聚物制备滤材用微纤维熔喷纤网的技术。Allan等人，欧洲专利申请号EP 351318描述熔喷可包括离聚物的不相容热塑性树脂聚合物分散体。该熔喷纤网适合用作抹布、餐巾和个人护理制品。Boettcher等人，美国专利5,409,765描述一种其纤维系通过不掺混聚烯烃、单体或溶剂的离聚物树脂挤出而形成的纤维的非织造纤网，以及通过离聚物与相容共聚物或三元共聚物的混合物的挤出成形的非织造布。该非织造纤网可采用熔喷方法成形并且可用于提供对超吸收剂粉末的廉价替代物。
迄今，一直需要一种适合作为高集尘量灰尘抹布以及其它最终用途使用的较低成本非织造布材料。
发明内容
在一种实施方案中，本发明涉及一种包含多组分熔喷纤维的熔喷纤网，该纤维包含含有离聚物的第一聚合物组分和第二聚合物组分，其中第一和第二聚合物组分包含沿纤维长度基本上连续延伸的界线分明的区，且其中多组分纤维的至少一部分周边表面含有第一聚合物组分。
发明详述
本发明涉及包含多组分熔喷纤维的熔喷纤网，该纤维含有位于其至少一部分周边表面上的离聚物。
术语“离聚物”在这里被用来指一种乙烯共聚物的盐，它包括多种由烯属不饱和羧酸或烯属不饱和羧酸的酸酐前体衍生的共聚单体。至少一部分该羧酸基团或酸酐基团被中和生成一价或多价金属阳离子的盐。术语“共聚物”在这里被用来包括通过2或更多种共聚单体的聚合制备的无规、嵌段、交替和接枝共聚物，因此包括二元共聚物、三元共聚物等。
术语“聚烯烃”在这里被用来指由至少50wt％不饱和烃类单体制备的均聚物、共聚物和共混物。聚烯烃的例子包括聚乙烯、聚丙烯、聚4-甲基戊烯-1、聚苯乙烯及其共聚物。
术语“聚乙烯”(PE)在这里被用来涵盖不仅乙烯的均聚物，而且还包括那些至少85％重复单元是乙烯单元的共聚物。
术语“聚丙烯”(PP)在这里被用来涵盖不仅丙烯的均聚物，而且还包括那些至少85％重复单元是丙烯单元的共聚物。
术语“线型低密度聚乙烯”(LLDPE)在这里被用来指密度小于约0.955g/cm3，优选0.91g/cm3～0.95g/cm3，更优选0.92g/cm3～0.95g/cm3的线型乙烯/α-烯烃共聚物。线型低密度聚乙烯通过乙烯与少量α-、β-烯属不饱和烯烃共聚单体(α-烯烃)的共聚制备，其中α-烯烃共聚单体具有3～12个碳原子/每个α-烯烃分子，优选4～8个碳原子/每个α-烯烃分子。能与乙烯共聚生成LLDPE的α-烯烃包括丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯或其混合物。优选的是，该α-烯烃是1-己烯或1-辛烯。
术语“高密度聚乙烯”(HDPE)在这里被用来指密度至少为约0.94g/cm3，优选约0.94g/cm3～约0.965g/cm3的聚乙烯均聚物。
术语“聚酯”在这里被用来涵盖这样的聚合物，其至少85％重复单元是二羧酸与二羟基醇的缩合产物，其中的键是通过酯单元的生成而产生的。这包括芳族、脂族、饱和及不饱和二-酸和二-醇。术语“聚酯”在这里也用来包括共聚物(例如，嵌段、接枝、无规和交替共聚物)、共混物及其改性物。聚酯的例子是聚对苯二甲酸乙二醇酯(PET)，它是乙二醇和对苯二甲酸的缩合产物。
术语“非织造布、片材或纤网”在这里被用来指由单根纤维、长丝或线构成的结构，它们以无规方式铺置而形成一种平面材料，不形成可辨认的图案，这与针织或机织织物不同。非织造布的例子包括熔喷纤网、纺粘连续长丝纤网、梳理纤网、(air-laid webs)气流铺网和湿法铺网(wet-laid webs)。
这里所使用的术语“熔喷纤维”是指通过熔喷方法成形的纤维，该方法包括将可熔融加工聚合物通过大量纺丝孔以熔融流股的方式挤出到高速气体(例如，空气)流中。高速气流将熔融热塑性聚合物材料的流股拉细，缩小其直径并形成直径介于约0.5～10μm的熔喷纤维。熔喷纤维一般为不连续纤维但也可以是连续的。熔喷纤网通常被高速气流夹带着沉积在收集表面上形成由无规散乱分布的纤维组成的熔喷纤网。
这里所使用的术语“纺粘”长丝是指通过将熔融热塑性聚合物材料经大量细小，通常为圆形的纺丝孔挤出为丝束而成形的长丝，随后，该挤出长丝的直径借助牵伸而迅速缩小，然后对长丝实施骤冷。其它长丝断面形状，例如，椭圆、多叶等，也可采用。纺粘长丝一般为连续的并具有大于约5μm的平均直径。纺粘非织造布或纤网是通过令纺粘长丝散乱地铺置在收集表面如多孔网或带上而形成的。纺粘纤网通常采用技术上公知的方法，例如通过热辊压光或通过将纤网送过高压下的饱和水蒸气室达到粘合。例如，纤网可沿着遍布整个纺粘织物的大量热粘合点进行热粘合。
本文所使用的术语“多组分纤维”是指任何由至少2种截然不同的聚合物组分在一起纺丝形成单根纤维所组成的纤维。这里所使用的术语“纤维”既指不连续也指连续纤维。该至少两种聚合物组分优选排列在多组分纤维断面上的界线鲜明、位置基本固定并基本上沿着纤维的长度连续延伸的各自区内。优选的是，多组分纤维是由2种明显不同的聚合物组成的双组分纤维。多组分纤维与由聚合物材料的单一均匀或不均匀共混物挤出的纤维截然不同。然而，用来构成多组分纤维的截然不同聚合物组分之一或多种却可包含聚合物的共混物。这里所使用的术语“多组分纤网”是指含有多组分纤维的非织造纤网。这里使用的术语“双组分纤网”是指含有双组分纤维的非织造纤网。
本发明熔喷纤网包含多组分熔喷纤维，该纤维由舍有一种或多种离聚物的第一聚合物组分和第二聚合物组分构成。该多组分熔喷纤维的至少一部分周边表面包含第一聚合物组分。例如，这两种聚合物组分可按照并列构型或按照皮芯构型，其中第一聚合物组分构成皮，的方式纺丝。在优选的实施方案中，多组分熔喷纤网包含并列双组分熔喷纤维。多组分熔喷纤网可采用技术上公知的方法制备。例如，双组分熔喷纤网可通过分别熔融挤出第一和第二聚合物组分，并且或者令两种聚合物组分在出纺丝板(die)之前在双组分熔喷纺丝板中彼此接触(预-聚结方法)，或者令这两种聚合物组分在出熔喷纺丝板以后彼此接触(后-聚结方法)，来制备。例如，Krueger电容，美国专利6,057,256，在此收作参考，描述一种预聚结双组分熔喷方法。
适合作为本发明多组分熔喷纤网中第一聚合物组分的离聚物包括金属离子中和的乙烯与丙烯酸、甲基丙烯酸或其组合的共聚物。该离聚物优选含有5～25wt％，乙烯8～20wt％，最优选8～15wt％丙烯酸、甲基丙烯酸或其组合。优选介于约5～70％，更优选约25～60％酸基团被金属离子中和。合适的金属离子包括钠、锌、锂、镁及其组合。任选地，离聚物可以是一种三元共聚物，其中第三单体，包含丙烯酸烷基酯，其中烷基基团具有1～8个碳原子，与乙烯和丙烯酸(或甲基丙烯酸或其与丙烯酸的组合)进行共聚。该单体被称作“软化”单体并代表高达约40wt％的比例，以全部单体为基准计。适合用于本发明的离聚物可由许多商业来源获得，包括Surlyn离聚物树脂，由杜邦公司(Wilmington，DE)供应。
第一聚合物组分可主要由一种或多种离聚物组成并可含有一种或多种离聚物与一种或多种非离聚物的共混物。共混物包括的附加聚合物优选地构成一种相容(可混溶)或接近-相容(基本可混溶)共混物。例如，Surlyn离聚物可与LLDPE、HDPE或LDPE构成接近-相容共混物。该共混物优选被制成含有5～25wt％中和的酸单体单元，以聚合物共混物的总重量为基准计。例如，舍有25wt％中和的酸单体单元的离聚物以50∶50重量比与另一种聚合物掺混将提供一种含有12.5wt％中和的酸单体单元(以共混物中聚合物总重量为基准计)的共混物。
第二聚合物组分可选择用来提供要求的成本或其它性能如集尘、温度稳定性等。例如，聚烯烃、聚酯和聚酰胺适合用作第二聚合物组分。适合作为第二聚合物组分的具体聚合物包括聚丙烯、聚乙烯、聚苯乙烯、聚对苯二甲酸1，3-丙二醇酯、聚对苯二甲酸乙二醇酯、聚己二酰己二胺(尼龙6，6)和聚己内酰胺(尼龙6)。合适的聚乙烯包括线型低密度聚乙烯和高密度聚乙烯。含有聚对苯二甲酸乙二醇酯作为其第二聚合物组分的纤网，据发现，能提供灰尘收集性能优异的低成本多组分熔喷纤网。替代地，聚丙烯可选作第二聚合物组分以提供低成本多组分熔喷织物。
多组分熔喷纤维优选地含有约10～90wt％第一聚合物组分和约90～10wt％第二聚合物组分。双组分并列熔喷纤网，其中第一聚合物组分含有乙烯和丙烯酸、甲基丙烯酸或其组合的离聚物共聚物，而其第二聚合物组分含有PET，据发现，当熔喷纤维含有约20～30wt％离聚物时以及当熔喷纤维含有约70～80wt％离聚物时作为灰尘抹布表现得令人吃惊。例如当熔喷纤维中的离聚物∶PET的重量比是75∶25时以及还有当它是25∶75时，熔喷纤网的灰尘收集性能比当离聚物∶PET的重量比是50∶50时令人惊奇地好。
本发明熔喷纤网优选具有约10～100g/m2的基重并且适合用作灰尘抹布，颗粒过滤器和防护服。熔喷纤网尤其优选用作灰尘抹布。据信，小纤维大小与离聚物纤维表面的组合提供一种具有极佳灰尘收集性能的织物。本发明某些熔喷纤网具有比由非离聚物如聚丙烯、聚乙烯或聚对苯二甲酸乙二醇酯制成的单组分熔喷纤网更好的灰尘收集性能。
多层复合片材可通过将多组分熔喷纤维聚集在第二层，例如，另一非织造纤网、机织织物或针织织物上来制成。适合作为第二层的非织造纤网的例子包括纺粘、水刺(hydroentangled)和针刺纤网。替代地，以前成形的多组分熔喷纤网可粘合到某一材料片材上或粘合到聚合物薄膜上。诸层可采用技术上公知的方法例如水刺力针(hydraulic needling)或通过热、超声和/或粘合剂粘合结合在一起。当复合片材被用作灰尘抹布时，该熔喷纤网优选地构成复合片材的(两个)外表面之一或其两个表面。例如，复合片材可通过将一片本发明熔喷纤网粘合到纺粘纤网(S-M)或者通过将熔喷纤网粘合到纺粘纤网的两面(M-S-M)而制成。多组分熔喷纤网和其它片材层优选地每一层包括相容的聚合物组分，以便使各个层能够热粘合，例如，通过热点粘合。例如，在一种实施方案中，复合片材可制成包含本发明多组分熔喷纤网和多组分纺粘纤网如含有皮芯或并列纤维的纺粘纤网。纺粘纤网的聚合物组分优选地被选择，以使纺粘纤维的周边表面(例如，皮芯纤维中的皮)含有聚合物，其与离聚物或者，在熔喷纤网舍有并列熔喷纤维的情况下，与第二聚合物组分相容，就是说能热粘合。例如，纺粘纤维的周边表面含有选自聚烯烃、聚酰胺和聚酯的聚合物。线型低密度聚乙烯是与离聚物相容或接近相容的聚合物的例子。可将相容剂加入到聚合物之一中以促进热粘合。合适的相容剂的例子是Fusabond
Figure DEST_PATH_G200380103302101D00021
E MB 226D，由杜邦公司(Wilmington，DE)供应。该材料可按照约5～7wt％的数量加入到LLDPE中以达到热粘合到PET上去的目的。杜邦的Fusabond
Figure DEST_PATH_G200380103302101D00022
产品系列中的树脂是官能化过的，通常采用马来酐接枝改性的聚合物。合适的Fusabond
Figure DEST_PATH_G200380103302101D00023
树脂包括改性的乙烯-丙烯酸酯-一氧化碳三元共聚物、乙烯-醋酸乙烯、聚乙烯、金属茂聚乙烯、乙丙橡胶和聚丙烯。
具体实施方式
试验方法
在上面的描述以及在下面的实例中，下面的试验方法被用来确定各种不同报告的特性和性能。ASTM指的是美国材料试验学会。
基重是单位面积织物或片材的质量的度量，按照ASTM D-3776确定，在此将其收作参考，并以g/m2为单位。
灰尘收集性能采用市售供应的Swiffer
Figure DEST_PATH_G200380103302101D00024
mop(拖把)(由Procter &Gamble，Cincinnati，OH销售)来评估。拖把的一半表面覆盖以市售供应的Swiffer
Figure DEST_PATH_G200380103302101D00025
干灰尘抹布(15.2cmx15.2cm)。另一半则覆盖以待测样品，其尺寸与Swiffer
Figure DEST_PATH_G200380103302101D00026
抹布一样。在作为轻工业环境的合格仓库中，实施50次地板面积的猛拖动作。Swiffer
Figure DEST_PATH_G200380103302101D00027
抹布和试验样品在50次猛拖前后分别称重。通过重量差计算出灰尘收集量。集尘性能系数被定义为试验样品拾起的灰尘重量与Swiffer灰尘抹布拾起的灰尘重量之比。
实例
熔喷双组分纤网由离聚物组分和聚酯组分制成。离聚物是乙烯与甲基丙烯酸的共聚物，其熔体指数为280g/10min(按照ASTM D-1238测定；在190℃、2.16kg条件下)并含有10wt％羧酸，其中25％酸基团被镁离子中和。聚酯组分是特性粘度据说是0.53dl/g的聚对苯二甲酸乙二醇酯，由杜邦公司作为Crystar聚酯(代号4449)供应。该聚对苯二甲酸乙二醇酯在放入到挤出机时的含湿量是1500ppm。在各自的挤出机中，离聚物加热到260℃，同时聚对苯二甲酸乙二醇酯加热到305℃，并作为分开的聚合物流股计量加入到加热到305℃的熔喷纺丝组件中。两股聚合物流独立地在纺丝组件中进行过滤，然后合并成为并列纤维构型。聚合物通过每个纺丝孔以0.8g/min(30孔每英寸)的每孔聚合物通量纺成丝，借助加压热空气(5psig(34.5kPa)，305℃)喷嘴被牵伸从而成形为熔喷纤维，后者随后被收集在位于纺丝板下方的多孔移动网上成为双组分熔喷纤网。从纺丝板到收集表面的距离是12.7cm。离聚物和聚对苯二甲酸乙二醇酯的百分率，通过改变这两种聚合物的聚合物通量比例来变化从而制成不同的样品。片材按照聚对苯二甲酸乙二醇酯占75％、50％和25wt％的比例收集。对于每一种聚合物比例，收集基重为12g/m2和36g/m2的样品。按如上所述试验样品的灰尘收集性能。也试验了对比样品：实例A：双组分聚对苯二甲酸乙二醇酯熔喷纤网，其中纤维由80wt％聚对苯二甲酸乙二醇酯(特性粘度0.53dl/g，杜邦公司供应的Crystar 4449)和20wt％线型低密度聚乙烯(熔体指数135g/10min，由Equistar化学公司供应的商品名GA 594)制成；实例B：单组分熔喷纤网，其纤维由聚丙烯形成(熔流速率1200g/10min，由埃克森化学公司供应的3546G)；实例C：单组分熔喷纤网，其纤维由crystar
Figure 10003_12
 4449聚对苯二甲酸乙二醇酯制成，实例D：单组分熔喷纤网，其纤维由Equistar GA594线型低密度聚乙烯制成。集尘性能系数载于下表1：
                 表1.熔喷纤网的集尘性能系数
  EX   熔喷纤网说明   基重  (g/m<sup>2</sup>)   集尘性能系数
  1   75wt％PET/25wt％  离聚物   12   1.16
  2   50wt％PET/50wt％  离聚物   12   0.22
  3   25wt％PET/75wt％  离聚物   12   0.81
  4   75wt％PET/25wt％  离聚物   36   1.43
  A   80wt％PET/25wt％  LLDPE   17   0.51
  B   100％PP   17   0.36
  C   100％PET   17   0.61
  D   100％LLDPE   17   0.52
结果显示，由含75wt％PET和25wt％离聚物的并列纤维制成的熔喷纤网表现出提供相对于市售供应Swiffer
Figure 10003_13
灰尘捧布而言在灰尘收集性能方面明显的改进。比较实例4的结果与实例1的结果，可以看出，较高基重导致集尘性能的改进。上面的结果也显示，两种聚合物之间的比例对于决定集尘性能起一定作用。例如，当PET或者Surlyn
Figure 10003_14
组分是主要组分时，如同实例1、3和4，可以看到比实例2有明显改善，在后者中，PET和Surlyn
Figure 10003_15
以相同重量百分率存在。实例1、3和4还表现出在集尘性能方面相对于对比例A～D的显著改善。对比例与本发明的抹布的表现比较相差甚远。

Claims (13)

1.一种用于作为灰尘抹布的熔喷纤网，其包含双组分熔喷纤维，其中熔喷纤维直径介于0.5～10μm，该纤维包含第一聚合物组分和第二聚合物组分，其中第一和第二聚合物组分排列成并列构型，该第一聚合物组分由离聚物组成，其中第一和第二聚合物组分包含沿纤维长度基本上连续延伸的界线分明的区，且其中多组分纤维的至少一部分周边表面含有第一聚合物组分，
其中离聚物是金属离子中和的乙烯与选自丙烯酸、甲基丙烯酸及其组合的烯属不饱和羧酸或其酸酐前体的共聚物，
其中第二聚合物组分是聚对苯二甲酸乙二醇酯，
其中双组分纤维包含70～80wt％聚对苯二甲酸乙二醇酯和20～30wt％第一聚合物组分，或
其中双组分纤维包含70～80wt％第一聚合物组分和20～30wt％聚对苯二甲酸乙二醇酯。
2.权利要求1的熔喷纤网，其中烯属不饱和羧酸占离聚物的5～25wt％。
3.权利要求2的熔喷纤网，其中5～70％羧酸基团被金属离子中和。
4.权利要求3的熔喷纤网，其中金属离子选自钠、锌、锂、镁及其组合。
5.权利要求1的熔喷纤网，其中该纤维包含25wt％的第一聚合物组分。
6.一种用作灰尘抹布的多层复合片材，它包含第一层和第二层，其中第一层是权利要求1的熔喷纤网，且该熔喷纤网包含复合片材的外表面。
7.权利要求6的复合片材，其中第二层选自非织造纤网、薄膜、机织织物和针织织物。
8.权利要求7的复合片材，其中第二层是纺粘非织造纤网。
9.权利要求8的复合片材，其中纺粘纤网是双组分纺粘纤网。
10.权利要求9的复合片材，其中双组分纺粘纤网包含皮芯纺粘纤维。
11.权利要求10的复合片材，其中皮包含选自聚烯烃、聚酰胺和聚酯的聚合物。
12.权利要求11的复合片材，其中皮包含聚乙烯。
13.抹布，其包含权利要求1或权利要求5的熔喷纤网。
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DE60327235D1 (de) 2009-05-28
US20040092191A1 (en) 2004-05-13
WO2004044297A2 (en) 2004-05-27
EP1560969B1 (en) 2009-04-15
JP2006506544A (ja) 2006-02-23
JP4603363B2 (ja) 2010-12-22
US7049254B2 (en) 2006-05-23
WO2004044297A3 (en) 2004-07-22
EP1560969A2 (en) 2005-08-10

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