CN102300883B - 聚丙烯非织造纤维和织物及其制造方法 - Google Patents
聚丙烯非织造纤维和织物及其制造方法 Download PDFInfo
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- CN102300883B CN102300883B CN200980155668.0A CN200980155668A CN102300883B CN 102300883 B CN102300883 B CN 102300883B CN 200980155668 A CN200980155668 A CN 200980155668A CN 102300883 B CN102300883 B CN 102300883B
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Abstract
纤维的非织造织物包含一种或多种具有小于3.5的分子量分布和5-500dg/min的熔体流动速率的主聚丙烯，所述纤维具有小于20μm的平均直径或小于2.0的旦尼尔(g/9000m)，从而形成基于丙烯的织物。所述主聚丙烯优选是使用单中心催化剂制得的反应器等级聚合物。在某些实施方案中，本文公开的基于丙烯的织物当在110-150℃的温度下压延时具有大于20N/5cm的MD拉伸强度(WSP 110.4(05))。此外，在某些实施方案中，所述织物当在110-150℃的温度下压延时具有大于10N/5cm的CD拉伸强度(WSP 110.4(05))。所述织物优选是熔纺织物，在特定的实施方案中，是纺粘织物。
Description
优先权声明
本申请要求于2009年1月29日提交的在前美国临时申请序列号61/148,253的权益，该文献全文引入本文供参考。
技术领域
本公开内容涉及基于丙烯的纤维和由其得到的非织造织物，更尤其涉及具有低旦尼尔的基于丙烯的纤维，所述织物具有低的单位重量(basis weight)和小的孔隙尺寸。
背景技术
制备具有比当前聚丙烯等级可能的直径更小的直径的熔纺纤维将是合乎需要的。包括更细纤维的熔纺织物，例如，通过纺粘技术制备的那些将比用更大直径纤维制备的可比单位重量(单位面积的质量)熔纺织物每单位体积(或面积)具有更多纤维。此类熔纺织物的更小直径的纤维将提供一些优点。每单位面积增加数目的纤维将提高织物的不透明性，从而提高它的视觉美感。小直径纤维也提供更均匀、一致的纤维层，比用更大直径纤维制备的织物出现更少″细斑″。改进的均匀性(或″覆盖度″)为熔纺织物和含这些熔纺织物的层压体提供额外的性能优点。具体的性能增强包括，但不限于，减小非织造织物的平均孔隙尺寸。
减小熔纺织物的孔隙尺寸将提高固体材料(例如可以存在于卫生制品例如婴儿尿布、成人失禁产品或其它吸收产品中的超吸收聚合物)的容积。减小的纤维直径，和伴随的每单位体积/面积纤维数目的增加将导致织物具有比由更大直径纤维制备的相似单位重量的织物更高的拉伸强度。增加的织物强度可能是合乎需要的，例如，以提高防护衣的耐久性，但是或许更令人感兴趣的是能够减小织物单位重量和维持拉伸强度。希望的是，用于制备熔纺织物和其层压体的聚合物在宽的加工条件范围内，特别是在宽的压延机粘结温度(calender bondingtemperature)范围内显示好的拉伸性能。进一步希望的是在尽可能低的压延机温度下获得高拉伸强度。低压延温度提供潜在节能(例如，减少要求的加热)。低压延温度还减少压延操作″烧穿″低单位重量织物而在熔纺织物或层压体中产生不可接受的″针眼(pin-holes)″和/或硬点的可能性。
发明人已经发现使用具有较高熔体流动速率、窄分子量分布并具有使得减少峰平均结晶熔点的区域缺陷(regio-defect)结构的聚丙烯制备熔纺纤维和包含所述纤维的织物将解决这些及其它问题。
相关的公开内容包括US 2009/0022956、US 6,583,076、US5,723,217和US 5,726,103。
发明内容
发明概述
本文公开了纤维的非织造织物，所述纤维包含一种或多种具有小于3.5的分子量分布和5-500dg/min的熔体流动速率的主聚丙烯(primary polypropylene)，所述纤维具有小于20μm的平均直径或小于2.0的旦尼尔(g/9000m)，从而形成基于丙烯的织物。所述主聚丙烯优选是使用单中心催化剂制得的反应器等级聚合物。
在某些实施方案中，本文公开的基于丙烯的织物当在110-150℃的温度下压延时具有大于20N/5cm的MD拉伸强度(WSP 110.4(05))。此外，在某些实施方案中，所述织物当在110-150℃的温度下压延时具有大于10N/5cm的CD拉伸强度(WSP 110.4(05))。所述织物优选是熔纺织物，在特定的实施方案中，是纺粘织物。
本文还公开了形成基于丙烯的织物的方法，包括在熔纺方法中以大于3000m/min的成纤速度熔纺一种或多种具有小于3.5的分子量分布和5-500dg/min的熔体流动速率的主聚丙烯以制备具有小于20μm的平均直径，或小于2.0的旦尼尔(g/9000m)的纤维。在一个特定的实施方案中，将挤出纤维暴露到大于2000Pa的变细用空气压力(attenuating air pressure)中。
本文公开的各种描述性元素和数值范围可以与其它描述性元素和数值范围结合以描述基于丙烯的纤维、包含所述纤维的织物和层压体的优选实施方案；此外，可以将元素的任何数值上限与同样元素的任何数值下限结合以描述优选的实施方案。在这方面，短语″在X-Y的范围内″旨在包括在″X″和″Y″值的范围内。
附图简述
图1是本发明纤维和对比纤维的纤维直径随用于以示例性的纺粘方法制备纤维的变细用空气压力(″料仓压力(cabin pressure)″)变化的图解表示。
发明详述
某些聚丙烯(本文称作″第一聚丙烯″)用来制备与诸如尿布、绷带等的应用当前所用的织物相比具有改进的性能的非织造纤维和织物(″基于丙烯的织物″)。在某些实施方案中，这些第一聚丙烯由单中心催化剂例如金属茂制成，并且是反应器等级聚合物，这是指它们没有经历改变它们的分子量例如通过受控流变性的任何制备后方法。第一聚丙烯尤其适合于以熔纺方法例如熔喷、纺粘和/或共成型(coform)方法制造纤维和织物。所述纤维较细，具有小于20μm的平均直径，或小于2.0的旦尼尔(g/9000m)，或这两者。这些属性为由其制得的织物赋予合乎需要的性能，例如小的平均孔隙体积和制备维持它们的强度的较轻(较低的单位重量)织物的能力。此外，第一聚丙烯使得它们可以用于使用较高生产量和高的变细用力或压力制备细纤维。
本文所使用的″族″是指如HAWLEY′S CONDENSED CHEMICALDICTIONARY(RJ.Lewis，Sr.Wiley &Sons，Inc.1997)中那样采用元素周期表对族的新编号方案。
本文所使用的″熔纺″是指通过形成纤维的网幅(″织物″)的方法制得的织物，其中经过喷丝头挤出聚合物熔体或溶液而形成长丝，然后通过适当手段使该长丝变细并放下在移动筛、鼓或其它适合的设备上。熔纺方法包括，但不限于，纺粘、闪蒸纺丝、共成型和熔喷。熔纺纤维通常具有小于250或150或60或40μm的平均直径。用于制备熔纺纤维的适合的聚合物的非限制性实例是聚丙烯(例如，均聚物、共聚物、抗冲共聚物)、聚酯(例如，PET)、聚酰胺、聚氨酯(例如，LycraTM)、聚乙烯(例如，LDPE、LLDPE、HDPE、塑性体)、聚碳酸酯和它们的共混物。
本文所使用的″纺粘″是指形成织物的熔纺方法，其中经过喷丝头挤出聚合物熔体或溶液以形成长丝，将该长丝冷却，然后通过合适的手段例如通过静电荷或高速空气变细，然后将这些变细的长丝(″纤维″)放下在移动筛上以形成织物。由纺粘方法产生的纤维通常具有其中赋予的某种分子取向度。本文所使用的″熔喷″是指形成织物的方法，其中经过喷丝头挤出聚合物熔体或溶液以形成长丝，通过合适的手段例如通过静电荷或高速空气使该长丝变细，然后将这些变细的长丝(″纤维″)放下在移动筛上以形成织物。纤维本身可以称为″纺粘″或″熔喷″纤维。纺粘和熔喷纤维可以具有任何合乎需要的平均直径，在某些实施方案中，在0.1或1或4至15或20或40或50或150或250μm的范围内，或以另一种方式表示，小于2.0或1.9或1.8或1.6或1.4或1.2或1.0的旦尼尔(g/9000m)。
本文所使用的术语″共成型″是指另一种熔纺方法，其中靠近斜槽安排至少一个熔纺模头，经过该斜槽在形成织物的同时将其它材料添加到该织物中。此类其它材料可以是例如，纸浆、超吸收颗粒、纤维素或短纤维。共成型方法示于US 4,818,464和US 4,100,324中。对本公开内容来说，共成型方法认为是熔纺方法的一个特定的实施方案。在某些实施方案中，本文描述的基于丙烯的织物是共成型织物。
本文所使用的″纤维″是其长度远大于其直径或宽度的结构；平均直径的数量级为0.1-250μm，并包括天然和/或合成材料。纤维可以是″单组分″或″双组分″的。双组分纤维包含由单独挤出机，但是由相同喷丝头挤出的具有不同化学和/或物理性能的两种或更多种聚合物，其中这两种聚合物在相同长丝内，而导致纤维具有不同的域。此种双组分纤维的构型可以是，例如，鞘/核配置，其中一种聚合物被另一种聚合物包围，或可以是并列型布置的，如US 5,108,820中那样，或″天星状(islands-in-the-sea)″的，例如US 7,413,803中那样。纤维也可以是″单成分″或″双成分″的，这是指它们由单一聚合物或两种或更多种聚合物的共混物制成。在一个特定的实施方案中，本文描述的基于丙烯的纤维是单组分和单成分的。
本文所使用的″层压体″包括至少两个织物和/或膜层。层压体可以通过在本领域中已知的任何手段形成。此种层压体可以例如如下制得：首先将熔纺织物层顺序沉积到活动成型带上，然后在所述第一熔纺织物层的上面沉积另一个熔纺织物层或添加干法成网织物，然后在那些层的上面添加熔纺织物层，接着是层压体的某种粘结，例如通过热点粘结(thermal point bonding)或各层彼此粘附的固有倾向、水力缠绕(hydroentangling)等。或者，可以单独地形成织物层，在辊中收集，并在单独的一个或多个粘结步骤中结合。多层层压体也可以具有呈许多不同构型的各种数目的层并可以包括其它材料如膜或共成型材料、熔喷和纺粘材料、气流成网材料等。
本文所使用的称为是″弹性″或″弹性体″的材料和/或织物是在施加偏压力(biasing force)后可以伸展到其松弛的原始长度的至少110％的伸长长度而不会破裂或断裂的那些，但是在释放该偏压力后该材料显示其伸长率的至少40％或更多的恢复。适合的弹性体材料将在本文进一步描述。如果材料，例如织物在施加偏压力后可以伸展到其松弛的原始长度的至少110％的伸长长度而不会破裂或断裂，但是在释放该偏压力后该材料显示其伸长率的少于40％的恢复，则该材料是″可延伸的″。可延伸的织物通常伴随层压体的弹性体织物或膜层并由可延伸材料(例如，聚氨酯、苯乙烯类嵌段共聚物、乙烯-乙酸乙烯酯、某些聚丙烯共聚物、聚乙烯和它们的共混物)形成，或通过织物(天然或合成织物)的机械扭曲或扭转形成。
本文所使用的″膜″是塑料和/或弹性体材料的平的未经担载的部分，其厚度相对于其宽度和长度非常窄并在其整个结构中具有连续或几乎连续的宏观形态，而允许空气按扩散受限的速率或更低速率通过。本文描述的层压体可以包括一个或多个膜层并且可以包含本文对于织物描述的任何材料。在某些实施方案中，膜不存在于本文描述的层压体中。本文描述的膜可以含有添加剂，该添加剂在处理后促进穿孔和允许空气和/或流体通过该膜。添加剂例如粘土等是在本领域中熟知的并尤其描述在US 6,632,212中。
本文所使用的″主聚丙烯″是指丙烯均聚物、或丙烯的共聚物、或丙烯均聚物和共聚物的某种混合物。在某些实施方案中，本文描述的主聚丙烯是主要结晶的，因此该主聚丙烯可以具有小于165或160或155或150℃的熔点(Tm)。本文所使用的术语″结晶″表征具有高度的分子间和分子内有序的那些聚合物。在某些实施方案中，主聚丙烯具有通过DSC分析测定的大于40J/g或60J/g或70J/g，在某些实施方案中，在40或50至70或80或100或140或150J/g的范围内的熔化热(Hf)。熔化热依赖于主聚丙烯的组成；主聚丙烯的最高阶热能估算在189J/g，即100％结晶度等于189J/g的熔化热。聚丙烯均聚物将具有比共聚物或均聚物和共聚物的共混物更高的熔化热。
在某些实施方案中，主聚丙烯(一种或多种)是全同立构的。主聚丙烯中的丙烯序列的全同立构规整度可以通过选择合乎需要的催化剂组合物的聚合达到。主聚丙烯的通过13C NMR测量的并表示为内消旋二单元组含量的全同立构规整度在90％(内消旋二单元组[m]＞0.90)或95％或97％至98％或99％的范围内，如US 4,950,720中那样通过13CNMR测定。按另一种方式表示，主聚丙烯的通过13C NMR测量并表示为五单元组含量的全同立构规整度在某些实施方案中在60％或70％至97％或98％或99％的范围内。也可以描述，适合的主聚丙烯具有通过13C NMR测量的在0.1或0.5至1摩尔％至2或3或4或5或8或15摩尔％范围内的区域缺陷。本文所使用的″区域缺陷″是指单体单元相对于占优势的插入方向按相反方向插入。用丙烯作为实例，亚甲基碳标记为″1″且亚乙基碳标记为″2″，则误插入将是与正常的1，2-插入相对的2，1-插入。
主聚丙烯在组成上可以广泛地改变。例如，可以使用基本上全同立构的主聚丙烯均聚物或丙烯共聚物，其含有等于或小于10wt％的其它单体，即含至少90wt％的丙烯。此外主聚丙烯可以以接枝或嵌段共聚物的形式存在，其中主聚丙烯的嵌段具有与丙烯-α-烯烃共聚物基本上相同的立构规整性，只要接枝或嵌段共聚物具有高于110℃或115℃或130℃的尖锐熔点就行，这是立构规整丙烯序列的特征。主聚丙烯可以是本文所述的均聚聚丙烯，和/或无规和/或嵌段共聚物的组合。当主聚丙烯是无规共聚物时，一般而言，该共聚物中α-烯烃衍生的单元的百分率是该主聚丙烯的至多5wt％，在另一个实施方案中，0.5wt％-5wt％，在又一个实施方案中，1wt％-4wt％。优选的共聚单体衍生自乙烯或含4-12个碳原子的α-烯烃。一种、两种或更多种共聚单体可以与丙烯共聚合。示例性的α-烯烃可以选自乙烯；1-丁烯；1-戊烯-2-甲基-1-戊烯-3-甲基-1-丁烯；1-己烯-3-甲基-1-戊烯-4-甲基-1-戊烯-3，3-二甲基-1-丁烯；1-庚烯；1-己烯；1-甲基-1-己烯；二甲基-1-戊烯；三甲基-1-丁烯；乙基-1-戊烯；1-辛烯；甲基-1-戊烯；二甲基-1-己烯；三甲基-1-戊烯；乙基-1-己烯；1-甲基乙基-1-戊烯；1-二乙基-1-丁烯；丙基-1-戊烯；1-癸烯；甲基-1-壬烯；1-壬烯；二甲基-1-辛烯；三甲基-1-庚烯；乙基-1-辛烯；甲基乙基-1-丁烯；二乙基-1-己烯；1-十二碳烯和1-十六碳烯。
在反应器中(″反应器等级″)通过在本领域中熟知的技术制备的同时原位调节主聚丙烯的分子量，例如通过向反应器添加链终止剂，例如氢气。主聚丙烯优选是反应器等级聚丙烯。主聚丙烯的重均分子量(Mw)在一个实施方案中，在50,000-800,000g/mol的范围内，或在另一个实施方案中，在60,000-600,000g/mol的范围内。主聚丙烯具有在一个实施方案中，25,000-60,000，在又一个实施方案中30,000-100,000的数均分子量(Mn)值。主聚丙烯的分子量分布(MWD，Mw/Mn)在某些实施方案中，在1.5至2.5或3.0或4.0或5.0的范围内，在还有的其它实施方案中，小于3.5或3.0或2.5。主聚丙烯具有在一个实施方案中，200,000-600,000，在又一个实施方案中，300,000-550,000，在某些实施方案中，大于200,000或300,000或400,000或500,000的z-均分子量(Mz)值。在其它实施方案中，主聚丙烯具有大于2.0，在另一个实施方案中，大于2.1，在又一个实施方案中，大于2.2的Mz/Mw，在还有的其它实施方案中，Mz/Mw在2.0或2.1或2.2或2.3至2.8或3.0或3.5或3.8或4.0或4.5或5.0或6.0或7.0的范围内。主聚丙烯具有在某些实施方案中小于100或80或70或60或55dg/min的MFR(2.16kg/230℃)；MFR在其它实施方案中在5或10或20或30至100或150或200或300或500dg/min的范围内。
对本文描述的主聚丙烯的制备方法不存在特别限制。例如，所述聚丙烯可以通过齐格勒-纳塔催化形成，或优选通过单中心催化形成。适合的单中心催化剂包括，但不限于，第4-10族金属茂，第4-10族约束几何结构催化剂，和第4-10族胺或二亚胺-配位化合物，各自与适合的活化剂联用。在一个特定的实施方案中，将第4族金属茂与合适的活化剂联合用来催化主聚丙烯。金属茂描述在例如，1&2METALLOCENE-BASED POLYOLEFINS(John Scheirs &W.Kaminskyeds.，John Wiley &Sons，Ltd.2000)中。在任何情况下，主聚丙烯可以通过丙烯在单阶段或多阶段反应器中的均聚获得。可以通过在单阶段或多阶段反应器中将丙烯和乙烯或含4-20个碳原子的α-烯烃共聚合获得共聚物。聚合方法包括，但不限于，高压、淤浆、气体、本体、或溶液相聚合方法或它们的组合。
示例性的商业主聚丙烯包括AchieveTM聚合物家族(ExxonMobilChemical Company，Baytown，TX)。所述Achieve聚合物是基于金属茂催化剂体系制备的。在某些实施方案中，这种金属茂催化剂体系制备窄分子量分布聚合物。MWD在某些实施方案中在1.5-3.0的范围内，在另一个实施方案中，在1.5-2.5的范围内。然而，在有多个反应器的方法中可以制备出较宽MWD的聚合物。在各反应器中制备不同MW的聚合物以增宽MWD。也可使用其它主聚丙烯无规共聚物和抗冲共聚物。
虽然纤维和织物组合物的″主聚丙烯″组分有时论述为单一聚合物，但是该术语还考虑两种或更多种不同聚丙烯的共混物，它们当结合时得到具有在本文描述范围内的性能的聚合物组合物。在某些实施方案中，主聚丙烯可以按75或70至80或90或95或99或99.9wt％存在于织物中，按织物层/组合物的重量计。所述共混物可以包括，但不限于，其它聚丙烯(抗冲共聚物、无规共聚物、弹性体聚丙烯)、聚酯、聚酰胺、聚氨酯、聚乙烯、弹性体(如本文所述)和它们的共混物。这些及其它适合的材料是在本领域中熟知的并在本文进一步阐明。用此类共混物制成的纤维称作″双成分″纤维，并不限于仅具有共混在一起的两种不同聚合物。此外，此种共混物不受聚合物的混溶性水平限制并且事实上在某些实施方案中可以形成两相共混物。
本文特别公开了使用主聚丙烯或包括此种主聚丙烯的组合物制备的非织造织物(″基于丙烯的织物″)。所述非织造织物在某些实施方案中是熔纺织物，在一个特定的实施方案中是纺粘织物。在某些实施方案中，纺粘方法包括经过一个或多个喷丝头将所需材料熔体挤出的方法，该喷丝头包括至少一个具有小直径孔的模头，然后通过加压空气使熔融材料流变细(拉伸)，从而产生文丘里效应。所述材料可以作为具有合乎需要的添加剂的粒料添加到熔体挤出机中，或添加剂可以在这一步骤中结合。
特别地，主聚丙烯长丝的形成如下达到：经过在本领域中已知的包括多个喷丝头(毛细管、孔)的合适的模头挤出熔融材料，接着用其温度可以被控制的骤冷空气系统将熔融材料(在模头内具有合乎需要的熔体温度)骤冷。常用的骤冷空气系统包括以交叉流动方向输送温度受控空气的那些。然后从一个或多个喷丝头拉离长丝并因此变细。为了达到这一点，通过让长丝穿过其中由于加压空气流动而使长丝加速和/或变细的文丘里设备将长丝变细。提高文丘里设备内的空气速度可以通过在本领域中描述的各种方法进行，包括提高文丘里设备内的空气压力。通常，提高这种空气速度(例如通过提高空气压力)导致提高的长丝速度和更大的长丝变细。空气压力越高，使主聚丙烯加速并因此变细更多，就由其形成的纤维的速度和旦尼尔而言。为了获得更细的纤维，高空气压力是合乎需要的。然而，这必须通过长丝由于过度压力而断裂的倾向加以平衡。可以使用比其它纺粘方法中典型的空气压力更高的空气压力使本文描述的主聚丙烯变细。在一个实施方案中，用于纺粘方法的变细用空气压力大于2000或3000或4000或6000Pa，且在其它实施方案中，小于600或500或400kPa；并在其它实施方案中在2000或3000或4000至8000或10,000或15,000Pa的范围内。此种空气压力可以在其中将纤维变细的封闭区域例如″料仓″中产生，并且其中的空气压力有时称为″料仓压力″。
如何可以实现空气变细是在本领域中熟知的并且该方法不限于使长丝变细的任何特定的方法。在一个实施方案中，通过使用吸气器狭槽拉伸主聚丙烯的长丝(狭槽拉伸)获得文丘里效应，其沿着所述机器的宽度运行。在另一个实施方案中，通过经由喷嘴或吸气枪拉伸长丝获得文丘里效应。可以使用多个枪，因为可以改变开口尺寸来获得所需效果。将如此形成的主聚丙烯的长丝在一个实施方案中，收集到筛网(″线网″)上，或在另一个实施方案中，收集到多孔成型带上，以形成长丝的织物。通常，在该带子的下侧上保持真空以促进均匀织物的形成和除去用来使长丝变细和产生空气压力的空气。空气变细的实际方法不是关键性的，只要获得合乎需要的加速空气速度(通常由空气压力反映)，和因此的文丘里效应以使主聚丙烯长丝变细。
在一个实施方案中，通过齿轮泵产生模块(die block)中的压力。模块中的压力的形成方法不是关键性的，但是模块内部的压力在一个实施方案中，为35-50巴(3500-5000kPa)，在另一个实施方案中，为36-48巴(3600-4800kPa)，在又一个实施方案中，为37-46巴(3700-4600kPa)。
模头中的主聚丙烯熔体的熔体温度在一个实施方案中，为200-260℃，在又一个实施方案中，为200-250℃，在又一个实施方案中，为210-245℃。
可以使用包括任意数目模头的任意数目喷丝头。在一个实施方案中，使用含有4000-9000个孔/米，在另一个实施方案中，4500-8500个孔/米，在又一个实施方案中，5000-8000个孔/米的模头，其中任何模头孔上限可以与任何模头孔下限组合以获得合乎需要的模头孔范围。
在某些实施方案中，纺粘生产线生产量在150或170至200或270至300kg/hr的范围内。在某些其它实施方案中，纺粘生产线生产量/孔在0.20或0.30或0.40至0.60或0.70或0.90ghm的范围内。
在形成基于丙烯的织物时，存在许多将长丝分散或分布以形成均匀织物的方法。在一个实施方案中，使用固定或移动的偏转器。在另一个实施方案中，使用静电或空气湍流改进织物均匀性。如在本领域中已知的那样，也可以使用其它手段。在任何情况下，形成的织物通常穿过压缩辊以改进织物完整性。在一个实施方案中，然后让织物在加热的压延辊之间通过，在那里，在一个辊上的增加的地区(land)在某些点处将织物粘结以进一步提高纺粘织物完整性。在一个实施方案中，可以使该压缩和加热的压延机与形成长丝的区域隔离。
在不脱离本发明精神和范围的情况下可以进行在本领域中已知的各种额外可能的加工和/或整理步骤，例如切割、处理、印刷图形等。例如，织物或包含织物的层压体可以任选地沿横向和/或纵向机械地拉伸以提高延伸性。在一个实施方案中，让织物或层压体经过沿CD和/或MD方向有槽的两个或更多个辊。此种有槽的satellite/anvil辊配置描述在US 2004/0110442和US 2006/0151914和US 5,914,084中。例如，可以让织物或层压体经过沿CD和/或MD方向有槽的两个或更多个辊。所述有槽的辊可以由钢或其它硬质材料(例如硬质橡胶)构成。如果需要的话，可以通过在本领域中已知的任何适合的方法施加热，例如加热的空气、红外线加热器、加热的夹辊或织物或层压体围绕着一个或多个加热的辊或蒸汽罐部分包裹等。还可以将热施加于有槽辊本身上。还应该理解，其它有槽辊配置是同样适合的，例如彼此紧密相邻布置的两个有槽辊。除有槽辊之外，其它技术也可以用来沿一个或多个方向机械地拉伸复合材料。例如，可以让复合材料穿过拉伸复合材料的拉幅机。此种拉幅机是在本领域中熟知的并描述在例如，US2004/0121687中。
不管如何形成和压延，基于丙烯的织物包含在某些实施方案中具有小于20或17或15或12μm的平均直径，在某些实施方案中，具有小于2.0或1.9或1.8或1.6或1.4或1.2或1.0的旦尼尔(g/9000m)或这两者的纤维。当110-150℃的温度(压延机设定温度)下压延时，此种织物在某些实施方案中具有大于20或25N/5cm的MD拉伸强度(WSP 110.4(05))。在其它实施方案中，所述织物当在110-150℃的温度(压延机设定温度)下压延时具有大于10或15N/5cm的CD拉伸强度(WSP 110.4(05))。
在某些实施方案中，基于丙烯的织物具有由显微照片研究测定的10或25或50至100或200μm的平均孔隙尺寸。在还有的其它实施方案中，所述织物具有小于14或13或12或11g/m2，在其它实施方案中，在0.1或1或2至11或14g/m2范围内的单位重量。
在某些实施方案中，用来形成基于丙烯的织物的纤维是双组分或″共轭″纤维。这些包括是并列型、分节(segmented)、鞘/芯、天星状结构(″基体原纤维″)的结构和本领域中已知的其它的结构。在这些结构中，用来制备所述纤维的聚合物中的至少一种是主聚丙烯。共轭纤维的第二、第三等组分可以由任何适合的材料制成，所述材料例如聚丙烯、聚乙烯(例如，LDPE、LLDPE、HDPE)、塑性体(乙烯-α-烯烃共聚物)、聚氨酯、聚酯例如聚对苯二甲酸乙二醇酯、聚乳酸、聚氯乙烯、聚四氟乙烯、苯乙烯类嵌段共聚物、丙烯-α-烯烃弹性体(例如，Vistmaxx)乙烯-乙酸乙烯酯共聚物、聚酰胺、聚碳酸酯、纤维素材料(例如，棉、RayonTM、LyocellTM、TencilTM)、木材、粘胶纤维(viscose)和这些材料中任何两种或更多种的共混物。尤其优选的第二(或第三等)组分是聚乙烯。制备双组分纤维的主要目的是开发任一单独的聚合物本身不存在的能力。通过这一技术，可以制备可以想到的任何横截面形状或几何结构的纤维。并列型纤维一般用作自卷曲纤维。存在用来获得自卷曲纤维的数种体系。它们中之一基于每种组分的不同收缩特性。已有基于各组分的不同电测量性能制备自卷曲纤维的尝试。一些类型的并列型纤维随着牵引张力移除而自发地卷曲并且其它具有″潜在卷曲″，这在某些环境条件获得时出现。在一些实施方案中，当将纤维沉浸在水中可以消除可逆卷曲并当干燥纤维时再出现时，使用″可逆″和″不可逆″卷曲。这种现象基于组分的溶胀特性。当纤维用作热粘结的非织造网幅中的粘结纤维时，利用在纤维侧面上的不同熔点。鞘-芯双组分纤维是其中组分之一(芯)完全被第二组分(鞘)包围的那些纤维。粘附对于纤维完整性并不总是重要的。制备鞘-芯纤维的最常用的方法是这样一种技术，其中将两种聚合物液体分开地引导至非常接近于喷丝孔的位置，然后以鞘-芯形式挤出。在同心纤维的情况下，提供″芯″聚合物的孔在纺丝孔出口的中心并且芯聚合物流体的流动条件被严格地控制以当纺丝时维持这两种组分的同心度。偏心纤维制备基于数种途径：偏心布置内部聚合物孔道并控制两种组分聚合物的供应速率；接近鞘组分熔体的供应引入不同元素；恰恰在从所述孔出来时与同心鞘-芯组分合并引入单组分的料流；和通过让纺丝同心纤维在热边缘上通过而使该纤维变形。由两种聚合物的混合物以所要求的比例纺丝基体原纤维；其中一种聚合物以小液滴形式悬浮在第二熔体中。基体原纤维制备中的重要的特征为必需在喷丝孔下面立即地人工冷却纤维。两种组分的不同的可纺性将几乎禁止该混合物的可纺性，除低浓度混合物(小于20％)之外。双组分纤维用来制备进入如下产品的织物：尿布、女性护理品和成人失禁产品(作为顶片、后片、腿袖带、弹性腰带、转移层)；气流成网非织造结构用作湿巾中的吸收性芯；并用于纺丝花边非织造产品如医疗一次性织物、过滤产品。
此外，在某些实施方案中，基于丙烯的织物可以是包含基于丙烯的纤维的混合纤维织物。混合纤维织物公开在例如，US 2008/0038982中。可以有一种、两种或更多种与所述基于丙烯的纤维一起的其它类型的纤维，包括由以下物质制造的纤维：聚丙烯、聚乙烯、塑性体、聚氨酯、聚酯例如聚对苯二甲酸乙二醇酯、聚乳酸、聚氯乙烯、聚四氟乙烯、苯乙烯类嵌段共聚物、丙烯-α-烯烃弹性体(例如，VistamaxxTM)或本文所述的其它弹性体，乙烯-乙酸乙烯酯共聚物、聚酰胺、聚碳酸酯、纤维素材料(例如，棉、RayonTM、LyocellTM、TencilTM)、木材、粘胶纤维和这些材料中任何两种或更多种的共混物。
在某些实施方案中，一种或多种基于丙烯的织物可以与其本身或与其它副层形成层压体。各种层的层压可以进行以致CD和/或MD取向被赋予织物或层压体，特别是在层压体包括至少一个弹性体层的情况下。可以采取许多方法形成包括弹性体膜和/或织物层的层压体，该弹性体膜和/或织物层在一旦层压体层被粘结在一起时仍保持弹性体性质。一种方法是在将织物层粘结到弹性体膜上之前折叠，弄皱，弄绉或以其它方式聚集织物层。在规定点或线处将聚集的织物粘结到所述膜上，而不连续地横穿所述膜的表面。在所述膜/织物处于松弛状态时，所述织物在所述膜上保持弄皱或起皱；一旦拉伸所述弹性体膜，织物层变平直到起皱材料基本上平坦，此时弹性体拉伸停止。
另一种方法是拉伸弹性体膜/织物，然后在拉伸所述膜的同时将所述织物粘结到所述膜上。同样，在规定的点或线处将所述织物与所述膜粘结，而不是连续地横穿所述膜的表面。当允许拉伸膜松弛时，所述织物在未拉伸弹性体膜上弄皱或起皱。
另一种方法是在将织物粘结到弹性体层上之前″颈缩(neck)″织物，如US 5,336,545、US 5,226,992、US 4,981,747和US 4,965,122中所述。颈缩是这样一种方法，通过该方法，沿一个方向牵引织物，这使织物中的纤维紧密滑动在一起，并且织物沿垂直于牵引方向的方向的宽度减小。如果颈缩织物与弹性体层点粘结(point-bonded)，则所得的层压体将稍微沿垂直于在颈缩过程中牵引织物的方向的方向拉伸，因为颈缩织物的纤维可以当层压体拉伸时彼此滑离。
又一种方法是弹性体层压体一旦形成时将该弹性体层压体活化。活化是使弹性体层压体变得易于拉伸的方法。最通常，活化是弹性体层压体的物理处理、改性或变形，所述活化通过机械手段进行。例如，弹性体层压体可以通过使用啮合辊逐渐拉伸，如US 5,422,172或US2007/0197117中所述，以使该层压体变得可拉伸和可恢复。最后，弹性体膜或织物可以使得它不需要活化并且简单地形成到和/或粘结到副层上而形成弹性层压体。此种方法还可以用于非弹性体层压体以改进其它性能例如褶皱和软度。
在任何情况下，本文描述的层压体包括一个或多个副层，所述副层包含其它织物、网、共成型织物(coformfabric)、纱布(scrim)和/或膜，它们中的任何材料由天然材料、合成材料或其共混物制备。在某些实施方案中，该材料可以是可延伸的、弹性或塑性的。在特定的实施方案中，一个或多个副层包含选自以下的材料：聚丙烯、聚乙烯、塑性体、聚氨酯、聚酯例如聚对苯二甲酸乙二醇酯、聚乳酸、聚氯乙烯、聚四氟乙烯、苯乙烯类嵌段共聚物、乙烯-乙酸乙烯酯共聚物、聚酰胺、聚碳酸酯、纤维素材料(例如，棉、RayonTM、LyocellTM、TencilTM)、木材、粘胶纤维和这些材料中任何两种或更多种的共混物。任何副层还可以包含(或基本上由其组成)任何弹性材料，其实例包括丙烯-α-烯烃弹性体(例如，由ExxonMobil Chemical销售的VistamaxxTM基于丙烯的弹性体)、天然橡胶(NR)、合成聚异戊二烯(IR)、丁基橡胶(异丁烯和异戊二烯的共聚物，IIR)、卤化丁基橡胶(氯化丁基橡胶：CIIR；溴-丁基橡胶：BIIR)、聚丁二烯(BR)、苯乙烯-丁二烯橡胶(SBR)、丁腈橡胶、氢化丁腈橡胶、氯丁二烯橡胶(CR)、聚氯丁二烯、氯丁橡胶、EPM(乙烯-丙烯橡胶)和EPDM橡胶(乙烯-丙烯-二烯橡胶)、表氯醇橡胶(ECO)、聚丙烯酸类橡胶(ACM，ABR)、硅氧烷橡胶、氟硅氧烷橡胶、含氟弹性体、全氟弹性体、聚醚嵌段酰胺(PEBA)、氯磺化聚乙烯(CSM)、乙烯-乙酸乙烯酯(EVA)、热塑性弹性体(TPE)、热塑性硫化橡胶(TPV)、热塑性聚氨酯(TPU)、热塑性烯烃(TPO)、聚硫化物橡胶或这些弹性体中任何两种或更多种的共混物。在某些实施方案中，一个或多个弹性层包含丙烯-α-烯烃弹性体、苯乙烯-丁二烯橡胶或它们的共混物。在还有的其它实施方案中，一个或多个弹性层基本上由丙烯-α-烯烃弹性体(一种或多种)组成。在一个特定的实施方案中，基于苯乙烯类的弹性体(包含至少10wt％苯乙烯或取代的苯乙烯衍生的单元的聚合物)不存在于所述多层织物中。
所述副层(一个或多个)可以呈膜、织物或这两种形式。膜可以是流延、吹塑膜，或通过任何其它适合的手段制得。当所述副层是织物时，所述副层可以是熔纺、干法成网或湿法成网织物。干法成网方法包括机械手段，例如如何制备梳理织物，和空气动力学手段，例如气流成网方法。干法成网非织造织物是用短纤维加工机械例如梳理机和回丝机(garnett)制成的，所述加工机械设计用来操作干燥状态下的短纤维。还包括在这种类别中的是由呈丝束形式的纤维制造的非织造织物和由短纤维和缝合长丝或纱线，即缝合非织造织物构成的织物。通过湿法成网方法制得的织物用与纸浆纤维化例如锤式研磨机和纸形成相联系的机械设备制成。网幅粘结方法可以描述为化学方法或物理方法。在任何情况下，干法和湿法成网织物可以射流和/或水力缠绕而形成射流喷网法(spunlace)织物，如本领域中已知的那样。化学粘结是指使用水基和溶剂基聚合物将纤维网幅粘结在一起。这些粘结剂可以通过饱和(浸渍)、喷雾、印刷施加或作为泡沫施加来施加。物理粘结方法包括热力方法例如压延和热空气粘结，和机械法例如针刺和水力缠绕。Spunlaid非织造织物由一个连续方法制造：通过熔体挤出纺丝纤维，然后通过偏转器直接分散到网幅中或可以用空气流引导。
更具体地说，″梳理″是解缠结、清洁和掺合纤维以制备用于进一步加工成非织造织物的网幅的方法并且是本领域中熟知的。当使用这些方法制备时，织物称作″梳理″织物。目的是取得大量纤维簇绒并制备均匀、清洁网幅。梳理方法的实例描述在US 4,105,381中。该方法主要排列通过机械缠结和纤维-纤维摩擦维持在一起作为网幅的纤维。主要类型梳理是辊梳理。梳理作用是纤维在一系列互相配合的梳理辊上在锯齿线布的点之间的梳理或工作。移除短纤维和不相干体，打开纤维簇绒，并近乎平行排列纤维。当表面之一按大于其它表面的速度移动时，发生纤维的梳理或平行化。当所述点沿相同方向排列并且更迅速移动的表面从更缓慢移动的表面移除或转移时，纤维被移除或″剥离″。
设计用来制备非织造网幅的高速梳理机可以配备有一个或多个主机筒、辊或固定顶端、一个或两个落纱机或这些主要部件的不同组合。单机筒梳理机通常用于要求纵向或平行纤维取向的产品。双机筒梳理机(或″串连″梳理机)基本上是通过剥除机的部分和进给辊连接在一起的两个单机筒梳理机以从第一工作区输送和进料网幅到第二工作区。两个梳理单元一前一后地连接分布工作区并允许按与较慢单机筒机器相当的网幅质量水平达到更大纤维生产量。辊-顶梳理机具有五至七组劳动者和剥除机以混合和梳理机筒上携带的纤维。新组纤维到梳理区的多次转移行为和再引入提供提高网幅均匀性的加倍作用。固定顶端梳理机具有安装在板上的金属布条，该板围绕着机筒的上边缘凹入地布置。如此建立的额外的梳理表面提供扩展的纤维排列而具有最小纤维提取。
在某些实施方案中，基于丙烯的聚合物可以形成共成型织物。形成此种织物的方法描述在例如，US 4,818,464和US 5,720,832中。一般而言，可以形成两种或更多种不同热塑性和/或弹性体材料的织物。例如，本文描述的共成型织物可以包含1或5或10或20或40或50至60或70或80或90或99wt％的主聚丙烯和99或90或80或70或60至50或40或20或10或5或1wt％的其它热塑性材料例如其它聚丙烯、聚乙烯、聚氨酯等，或弹性体例如基于丙烯的弹性体或苯乙烯类嵌段共聚物。因此，在一个方面中，规定熔融挤出的主聚丙烯和任选地，一种或多种其它材料(弹性、吸附、热塑性材料等)引入到惰性气体的至少一个迅速移动料流或射流的剪切层上，所述惰性气体来自围绕高速气体输送喷嘴的交替侧或相对侧布置或在所述交替侧或相对侧上的两个或更多个挤出开口或开口组。从这些开口挤出的热塑性材料可以是相同材料或，也可以是化学和/或物理性能方面彼此不同的材料。命名为第一、第二等热塑性、吸收或弹性材料，所述材料可以具有相同或不同的化学组成或分子结构并且，当具有相同分子结构时，可以在分子量或导致物理性能差异的其它特性方面不同。在其中使用在某些方面，例如物理性能方面彼此不同的热塑性材料的那些情况下，挤出头或模头将配备有多个室，一个室用于所述热塑性材料中的每一种，例如第一、第二等热塑性材料。即，模头配备有用于第一热塑性材料的第一室和用于第二热塑性材料的第二室等。相对照而言，此种配置，其中单一室配备有为所述单一室和第一和第二热塑性挤出出口开口中的每一个之间提供连通的导管或通道，当第一室和第二室分别用于第一和第二热塑性材料时，每个室配备有到仅一个挤出出口开口或开口组的通道。因此，第一热塑性材料室利用第一热塑性材料通道与第一挤出出口开口连通，而第二热塑性材料室经由第二热塑性材料通道与第二热塑性挤出开口连通。
构成本文所述层压体的两个或更多个各种织物或纤维层可以按某种方式粘结。本文所使用的″粘结″(或″结合″或″粘附″)是指两个或更多个织物，或多个纤维经由以下彼此固定：i)熔融或非熔融材料能够经由化学相互作用粘附的固有倾向和/或ii)熔融或非熔融纤维和/或织物与包含另一种材料的纤维缠绕以在纤维或织物之间产生键的能力。本文描述的层压体的层可以通过已知的方法彼此层压(粘结)，包括热粘结方法例如热轧花、点粘结、压延和超声波粘结；机械缠绕方法例如针刺和水冲；使用粘合剂例如热熔粘合剂和氨基甲酸酯粘合剂；和挤出层压。粘合剂可用来促进织物层的粘结，但是在一个特定的实施方案中，粘合剂不存在于本文描述的织物层(不用来粘结织物的纤维)中；在另一个实施方案中，不存在于本文描述的层压体(不用来粘结相邻的织物层)中。粘合剂的实例包括包含低重均分子量(＜80,000g/mol)聚烯烃、聚乙酸乙烯酯聚酰胺，烃树脂、天然沥青、苯乙烯类橡胶和它们的共混物的那些粘合剂。
本文描述的层压体的基于丙烯的织物或任何其它膜和/或织物层可以包括其它添加剂。添加剂可以按任何合乎需要的水平存在，所述水平的实例包括0.1至3或4或5或10wt％，按纤维或织物的重量计。本文所使用的″添加剂″包括，例如，稳定剂、表面活性剂、抗氧化剂、抗臭氧剂(例如硫脲)、填料、迁移(预防)剂、着色剂、成核剂、抗粘连剂、UV阻滞剂/吸收剂、烃树脂(例如，OpperaTM树脂、PicolyteTM增粘剂、聚异丁烯等)及其它增粘剂、油(例如，链烷、无机、芳族、合成油)、滑爽添加剂和它们的组合。主和副抗氧化剂包括，例如，位阻酚、位阻胺和磷酸酯。滑动剂包括，例如，油酰胺和芥酰胺。填料的实例包括炭黑，粘土、滑石、碳酸钙、云母、二氧化硅、硅酸盐和它们的组合。其它添加剂包括分散剂和催化剂钝化剂例如硬脂酸钙、水滑石和氧化钙，和/或本领域中已知的其它酸中和剂。
在某些实施方案中，本文描述的层压体(包含一种或多种以名称″P″表征的基于丙烯的织物)选自由以下示例的结构：MP、MPM、PP、PPP、PPPP、PPM、PMP、PMMP、PPMPP、PMMPP、PMPPP、PPMMPP、PMPMP、PPPMPP、SP、SPS、PP、PPP、PPPP、DPPPP、MPPPP、SPPPP、PPS、PSP、PSSP、PPSPP、PSSPP、PSPPP、PPSSPP、PSPSP、PPPSPP、DP、DDP、DPD、DPP、DDDDP、PPD、PDP、PDDP、PPDPP、PDDPP、PPDDPP、DMP、DDMPP、PDMDP、DPMPD、DDPMPD、DDPMPDD、DDPMMPDD、DPMMPD、PDMDMD、PMDMP、PDMMDD、PPDMDPP、DDDDMP、PPDMMDPP、FP、MPF、FPP、FPPP、FPPPP、FPPF、FPFPF、FPPM、PFP、PMFP、PPFPP、PFFPP、PMFPP、PPMFPP、PFD、SPFD、SPMD、PDFD、PDDFFD、PDFDD、DPF、DFP、DDDFP、FDP、PDDF、PFDPP、FPDDPP、PFDDPP、DMPF、DFMPP、PDFDP、DPFPD、DDPFPD、DDPFPDD、DDPFFPDD、DPFFPD、PFDFD、PFDFP、SFMP、SSFMP、PFMFP和PFFP，其中″M″表示熔喷织物层，″S″表示纺粘织物层，″F″表示膜层，″D″表示干法成网(梳理或气流成网)织物层，每个层彼此邻接。在一个优选的实施方案中，基于丙烯的织物是熔纺的，在一个特定的实施方案中是纺粘的。织物和/或层压体可用来形成吸收或阻隔产品例如，但不限于，个人护理品、婴儿尿布、训练罩、吸收底垫、游泳衣、擦拭物、女性卫生产品、绷带、伤口护理品、医用衣服、手术长袍、过滤器、成人失禁产品、手术单、覆盖物、衣服和清洁制品和设备。
在一个实施方案中，吸收制品是一次性尿布，例如，US2008/0119102A1中公开的那样，该文献大体上限定了前腰部分、后腰部分和将所述前和后腰部分互联的中部。所述前和后腰部分包括尿布的一般部分，它们经构造在使用过程中分别大体上在穿戴者的前和后腹部上延伸。该尿布的中部包括尿布的一般部分，其经构造延伸经过穿戴者腿之间的胯部。因此，中部是其中尿布中通常发生重复液体浪涌的区域。例如，这些结构中的任一个或多个可以包含本文描述的基于丙烯的织物和层压体。
尿布包括，但不限于，外覆盖物或背片、透液体侧衬垫或顶片(与所述背片呈面对关系布置)和吸收性芯体或液体保持结构，例如吸收垫，其设置在所述背片和顶片之间。例如，这些结构中的任一个或多个可以包含本文描述的基于丙烯的织物和层压体。所述背片限定长度，或纵向，和宽度或横向，它们与尿布的长度和宽度重合。液体保持结构一般具有分别小于背片的长度和宽度的长度和宽度。因此，尿布的边缘部，例如背片的边缘部可以延伸穿过液体保持结构的端边缘。在某些实施方案中，背片向外延伸穿过液体保持结构的端边缘以形成尿布的侧边缘和末端边缘。顶片一般与背片作同等延伸，但是根据需要可以任选地覆盖比背片的面积更大或更小的面积。
为了提供改进的配合和帮助减少身体分泌液从尿布的渗漏，尿布侧边缘和末端边缘可以用适合的弹性构件加以弹性化。例如，尿布可以包括腿弹性物，该腿弹性物经构造可操作地拉紧尿布的侧边缘以提供加以弹性化的腿带，该带子可以围绕着穿戴者的腿紧密地配合以减少渗漏和提供改进的舒适和外观。腰弹性物用来使尿布的末端边缘弹性化以提供加以弹性化的腰带。该腰弹性物配置用来提供围绕着穿戴者的腰的弹性、舒适紧密的配合。可以与本文描述的基于丙烯的织物形成层压体的潜在弹性材料，例如VistamaxxTM弹性体适合于用作腿弹性物和腰弹性物。此类材料的示例是包括背片或与背片粘附的层压片，以致弹性压缩力被施加于背片上。
众所周知，紧固件，例如钩和环紧固件可以用来将尿布固定在穿戴者上。或者，可以采用其它紧固件，例如按钮、插销、固定杆、粘合带紧固件、粘聚性物、织物和环紧固件等。在所示实施方案中，尿布包括与紧固件连接的一对侧板(或耳)，表示为钩和环紧固件的钩部分。一般而言，所述侧板与尿布的在腰部分之一中的侧边连接并从那里向外横向地延伸。所述侧板可以使用潜弹性材料加以弹性化或赋予弹性。
尿布还可以包括设置在顶片和液体保持结构之间的浪涌控制层以迅速地接受流体分泌液和将该流体分泌液分布到尿布内的液体保持结构中。尿布还可以包括设置在液体保持结构和背片之间的透气层，也称作间隔物，或间隔层，以隔离背片与液体保持结构而减少衣服在透气性外覆盖物或背片的外表面处的潮湿。这些结构中的任一种可以包含本文描述的基于丙烯的织物和层压体。
一次性尿布还可以包括一对容器挡板，其配置用来提供对身体分泌液的侧向流动的屏障。该容器挡板可以沿着邻接液体保持结构侧边的尿布的横向相对侧边设置。每个容器挡板通常限定不连接的边缘，其配置用来在至少尿布的中部维持直立、垂直构型以形成相对穿戴者身体的密封。该容器挡板可以沿着液体保持结构的整个长度纵向地延伸或可以仅沿着液体保持结构的长度部分延伸。当容器挡板长度比液体保持结构短时，容器挡板可以选择性地沿着尿布在中部中的侧边布置在任何地方。此种容器挡板是本领域技术人员公知的。
实施例
在Reicofil 4生产线上纺粘三个本发明样品和三个对比实施例(一个金属茂等级hPP和两个齐格勒-纳塔等级hPP)。三个本发明″构思″聚丙烯均聚物如下制备：将标称22熔体流动速率金属茂催化的丙烯聚合物颗粒(用于ExxonMobil AchieveTM 3854的基础颗粒)过氧化物裂化到标称40、55和70(都±5dg/min)dg/min熔体流动速率(″MFR″，ASTM D 1238，2.16kg，230℃)。因为按所制备时(″反应器等级″)的Achieve聚丙烯颗粒具有窄分子量分布(Mw/Mn接近2，其为理论最小值)，所以预期过氧化物裂化将降低平均分子量，但是不会显著地改变(减小)分子量分布(Mw/Mn)和因此用于低分子量反应器等级金属茂催化的聚合物的峰态(model)。这些构思聚合物结合了窄分子量分布与低于典型分子量的分子量。存在于金属茂催化的聚合物中的区域缺陷结构有助于减小峰平均结晶熔点，并将有助于减小压延粘结纺粘非织造织物所需要的温度。窄分子量分布、低分子量和mPP-特异性区域缺陷的组合提供了流变性能和熔融/结晶性能的平衡。
样品如下描述：
·本发明实施例1是40dg/min的标称MFR，Mw/Mn小于3.0；
·本发明实施例2是55dg/min的标称MFR，Mw/Mn小于3.0；
·本发明实施例3是70dg/min的标称MFR，Mw/Mn小于3.0；
·对比金属茂催化的AchieveTM 3854，24dg/min的MFR，Mw/Mn小于3.0；
·对比齐格勒-纳塔催化的ExxonMobil PP 3155，36dg/min的MFR，Mw/Mn小于4.0；和
·对比齐格勒-纳塔催化的ExxonMobil PP 3885E1，65dg/min的MFR。
本发明″构思″聚丙烯还含有0.06wt％IrganoxTM3114、0.02wt％硬脂酸钙、0.06wt％IrgafosTM168和0.04wt％DHT4V。聚合物输送固定在0.47克/孔/分钟。
Reicofil生产线中的某些条件如表1-6中那样维持。冷却空气温度固定在20℃，SAS间隙(变细用单元)在20和23之间。在某些实验中，逐步提高料仓压力(或一般而言，″空气压力″)并收集纤维用于直径测量。料仓压力的最高制表(和图解)值表示能维持长丝连续性时的最大值。在更高料仓压力下运行的尝试导致断裂的长丝(不可接受的工艺连续性)。制表为最大料仓压力的值反映在至少20分钟连续操作期间工艺稳定时的值(即，没有看见断裂的长丝)。图1显示了本发明聚合物能在比常规聚合物PP3155或PP3885E1更高的料仓压力下加工。通过比较PP3885E1(标称65MFR)与本发明实施例2(标称55MFR)可以观察到该影响不简单地归因于熔体流动速率。本发明实施例2在更高的料仓压力下运行，产生更细纤维，即使标称更低的MFR也暗示本发明实施例2的聚合物设计特征的组合允许产生更细纤维。除了本发明实施例之外没有聚合物允许在本研究中使用的条件下制备旦尼尔小于1.0的纤维。应指出，本发明实施例3(标称70MFR)没有运行到最大料仓压力，这归因于有限的材料可获得性。结果表明更高的料仓压力(可能接近8000Pa或更高)是可能的，纤维尺寸小于1旦尼尔/长丝同样可能。还应当指出，计算的长丝速度(基于质量生产量0.47克/分钟的组合)和测得的纤维尺寸(使用本发明实施例2制备的样品的0.9旦尼尔/长丝)接近4700m/min。这对于使用丙烯聚合物的纺粘操作是非常快速的。
参照US 5,891,814中公开的催化剂合成方法公开了这一预期实施例，将二氯·二甲基亚甲硅烷基·双(2-甲基-4-苯基茚基)合锆在甲苯中与甲基铝氧烷结合，接着与二氧化硅氧化物载体结合以形成负载型金属茂催化剂体系。然后干燥该金属茂催化剂并在添加到聚合体系中之前预聚合或不预聚合。该聚合体系包括用N2吹洗同时加热的2升高压釜反应器。然后将冷的三乙基铝(大约0.25mL的在己烷中的1M溶液)和所需的mM氢气加入高压釜，随后加入大约1000mL丙烯。调节氢气水平以致达到聚丙烯均聚物的55dg/min的熔体流动速率。将反应器加热到50-80℃的温度。将催化剂样品(大约0.075克裸露催化剂)装入注射管并在大约2mL己烷中制浆。将该催化剂加入反应器同时用大约200mL丙烯吹洗以启动反应。在大约20分钟之后，将反应器冷却，排气，用N2吹扫并打开。允许回收的聚合物在空气中干燥至少4小时，然后在真空中在75℃下最少干燥大约2小时。在回收之后，将该干燥的反应器等级聚丙烯均聚物用于纤维/织物形成步骤。该聚丙烯具有大约55dg/min的MFR，大约155-145℃的Tm和小于3.0的Mw/Mn。
在Reicofil 4生产线上进行该金属茂反应器等级均聚物的纺粘。该55dg/min反应器等级均聚物输送固定在0.47克/孔/分钟以形成单一纺粘织物层。冷却空气温度固定在20℃；轧花辊温度固定在大约137℃且光滑的压延辊(″S-辊″)温度固定在大约135℃；压延机温度设定是130-145℃。料仓压力为大约7000Pa，生产线速度为大约240kg/hr。由此，这样制备的纤维具有大约0.9-1.2g/9000m的旦尼尔且由其制得的织物具有8-12g/m2的单位重量和20-30N/5cm的MD拉伸强度和10-15N/5cm的CD拉伸强度。
虽然已经描述了阐明基于丙烯的纤维、包含该纤维的织物和层压体的优选实施方案的各种描述性元素和数值范围，但是在此以编号实施方案描述的是：
纤维的非织造织物，所述纤维包含一种或多种具有小于3.5的分子量分布和5-500dg/min的熔体流动速率的主聚丙烯，所述纤维具有小于20μm的平均直径或小于2.0的旦尼尔(g/9000m)或这两者。
1.编号实施方案1的基于丙烯的织物，其中所述织物当在110-150℃的温度下压延时具有大于20N/5cm的MD拉伸强度(WSP 110.4(05))。
2.编号实施方案1或2的基于丙烯的织物，其中所述织物当在110-150℃的温度下压延时具有大于10N/5cm的CD拉伸强度(WSP110.4(05))。
3.前述编号实施方案中任一项的基于丙烯的织物，其中所述主聚丙烯包含0-5wt％的选自乙烯和C4-C12α-烯烃的共聚单体衍生的单元。
4.前述编号实施方案中任一项的基于丙烯的织物，其中所述主聚丙烯是反应器等级的。
5.前述编号实施方案中任一项的基于丙烯的织物，其中所述主聚丙烯具有小于165℃的熔点。
6.前述编号实施方案中任一项的基于丙烯的织物，其中所述主聚丙烯是通过单中心催化剂体系制备的。
7.前述编号实施方案中任一项的基于丙烯的织物，其中所述主聚丙烯具有0.1-15摩尔％的区域缺陷(13C NMR)。
8.前述编号实施方案中任一项的基于丙烯的织物，其中所述织物是纺粘织物。
9.前述编号实施方案中任一项的基于丙烯的织物，其中所述织物具有10-200μm的平均孔隙尺寸。
10.前述编号实施方案中任一项的基于丙烯的织物，其中所述织物具有小于14g/m2的单位重量。
11.包括前述编号实施方案中任一项的基于丙烯的织物的一个或多个层的层压体。
12.实施方案12的层压体，其中所述层压体包括一个或多个副层，所述副层包含由天然和/或合成材料制备的其它织物、网、共成型织物、纱布和/或膜。
13.实施方案13的层压体，其中所述一个或多个副层包含选自以下的材料：主聚丙烯、聚乙烯、塑性体、聚氨酯、聚酯、苯乙烯类嵌段共聚物、乙烯-乙酸乙烯酯共聚物、聚酰胺、聚碳酸酯、纤维素材料(例如，棉、RayonTM、LyocellTM、TencilTM)、木材、粘胶纤维和这些材料中任何两种或更多种的共混物。
14.实施方案12的层压体，其中所述基于丙烯的非织造织物由名称″P″表征，所述层压体选自由以下组成的结构：MP、MPM、PP、PPP、PPPP、PPM、PMP、PMMP、PPMPP、PMMPP、PMPPP、PPMMPP、PMPMP、PPPMPP、SP、SPS、PP、PPP、PPPP、DPPPP、MPPPP、SPPPP、PPS、PSP、PSSP、PPSPP、PSSPP、PSPPP、PPSSPP、PSPSP、PPPSPP、DP、DDP、DPD、DPP、DDDDP、PPD、PDP、PDDP、PPDPP、PDDPP、PPDDPP、DMP、DDMPP、PDMDP、DPMPD、DDPMPD、DDPMPDD、DDPMMPDD、DPMMPD、PDMDMD、PMDMP、PDMMDD、PPDMDPP、DDDDMP、PPDMMDPP、FP、MPF、FPP、FPPP、FPPPP、FPPF、FPFPF、FPPM、PFP、PMFP、PPFPP、PFFPP、PMFPP、PPMFPP、PFD、PDFD、PDDFFD、PDFDD、DPF、DFP、DDDFP、FDP、PDDF、PFDPP、FPDDPP、PFDDPP、DMPF、DFMPP、PDFDP、DPFPD、DDPFPD、DDPFPDD、DDPFFPDD、DPFFPD、PFDFD、PFDFP、SFMP、SSFMP和PFFP，其中″M″表示熔喷织物层，″S″表示纺粘织物层，″F″表示膜层，″D″表示干法成网(梳理或气流成网)织物层。
15.由前述编号实施方案中任一项的织物制成的吸收或阻隔产品，所述制品包括个人护理品、婴儿尿布、训练罩、吸收底垫、游泳衣、擦拭物、女性卫生产品、绷带、伤口护理品、医用衣服、手术长袍、过滤器、成人失禁产品、手术单、覆盖物、衣服和清洁制品和设备。
16.形成织物的方法，包括按大于3000m/min的成纤速度将一种或多种前述编号实施方案中任一项的主聚丙烯熔纺以制备具有小于20μm的平均直径或小于2.0的旦尼尔(g/9000m)的纤维。
17.实施方案17的方法，其中所述熔纺方法是纺粘方法且将所述挤出纤维暴露到大于2000Pa的变细用空气压力中。
18.实施方案17-18中任一项的方法，其中所述织物是在110-150℃的温度下压延的并具有大于20N/5cm的MD拉伸强度(WSP110.4(05))。
19.实施方案17-19中任一项的方法，其中所述织物是在110-150℃的温度下压延的并具有大于10N/5cm的CD拉伸强度(WSP110.4(05))。
20.实施方案17-20中任一项的方法，其中所述主聚丙烯是通过单中心催化剂体系制备的。
21.实施方案17-21中任一项的方法，其中所述纺粘生产线生产量在150-300kg/hr的范围内。
22.实施方案17-22中任一项的方法，其中所述纺粘生产线生产量/孔在0.30-0.90ghm的范围内。
Claims (32)
1.纤维的非织造织物，所述纤维包含一种或多种具有小于3.5的分子量分布和5-500dg/min的熔体流动速率的主聚丙烯，所述主聚丙烯为丙烯均聚物、丙烯的共聚物、或丙烯均聚物和共聚物的混合物，且具有0.1-15摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量；所述纤维具有小于20μm的平均直径和小于2.0的旦尼尔，其中所述旦尼尔具有g/9000m的单位；和所述织物具有在0.1至14g/m2范围内的单位重量。
2.权利要求1的非织造织物，其中所述织物当在110-150℃的温度下压延时具有大于20N/5cm的MD拉伸强度，其中所述MD拉伸强度根据WSP 110.4，05测量。
3.权利要求1或2的非织造织物，其中所述织物当在110-150℃的温度下压延时具有大于10N/5cm的CD拉伸强度，其中所述CD拉伸强度根据WSP 110.4，05测量。
4.权利要求1或2的非织造织物，其中所述主聚丙烯包含0-5wt％的选自乙烯和C4-C12α-烯烃的共聚单体衍生的单元。
5.权利要求1或2的非织造织物，其中所述主聚丙烯是反应器等级的。
6.权利要求1或2的非织造织物，其中所述主聚丙烯具有小于165℃的熔点。
7.权利要求1或2的非织造织物，其中所述主聚丙烯是通过单中心催化剂体系制备的。
8.权利要求1或2的非织造织物，其中所述主聚丙烯具有0.1-8摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量。
9.权利要求1或2的非织造织物，其中所述主聚丙烯具有0.1-5摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量。
10.权利要求1或2的非织造织物，其中所述主聚丙烯具有0.1-4摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量。
11.权利要求1或2的非织造织物，其中所述主聚丙烯具有0.1-3摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量。
12.权利要求1或2的非织造织物，其中所述主聚丙烯具有0.1-2摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量。
13.权利要求1或2的非织造织物，其中所述主聚丙烯具有0.1-1摩尔％的区域缺陷，其中所述区域缺陷根据13C NMR测量。
14.权利要求1或2的非织造织物，其中所述织物是纺粘织物。
15.权利要求1或2的非织造织物，其中所述织物具有10-200μm的平均孔隙尺寸。
16.包括前述权利要求中任一项的非织造织物的一个或多个层的层压体。
17.权利要求16的层压体，其中所述层压体包括一个或多个副层，所述副层包含由天然和/或合成材料制备的其它织物和/或膜。
18.权利要求17的层压体，其中所述其它织物选自网、共成型织物和纱布。
19.权利要求17的层压体，其中所述一个或多个副层包含选自以下的材料：主聚丙烯、聚乙烯、聚氨酯、聚酯、苯乙烯类嵌段共聚物、乙烯-乙酸乙烯酯共聚物、聚酰胺、聚碳酸酯、纤维素材料、木材、粘胶纤维和这些材料中任何两种或更多种的共混物；其中所述主聚丙烯为丙烯均聚物、丙烯的共聚物、或丙烯均聚物和共聚物的混合物。
20.权利要求19的层压体，其中所述纤维素材料选自棉、RayonTM、LyocellTM、TencilTM。
21.权利要求16的层压体，其中所述非织造织物由名称″P″表征，所述层压体选自由以下组成的结构：MP、MPM、PP、PPP、PPPP、PPM、PMP、PMMP、PPMPP、PMMPP、PMPPP、PPMMPP、PMPMP、PPPMPP、SP、SPS、DPPPP、MPPPP、SPPPP、PPS、PSP、PSSP、PPSPP、PSSPP、PSPPP、PPSSPP、PSPSP、PPPSPP、DP、DDP、DPD、DPP、DDDDP、PPD、PDP、PDDP、PPDPP、PDDPP、PPDDPP、DMP、DDMPP、PDMDP、DPMPD、DDPMPD、DDPMPDD、DDPMMPDD、DPMMPD、PDMDMD、PMDMP、PDMMDD、PPDMDPP、DDDDMP、PPDMMDPP、FP、MPF、FPP、FPPP、FPPPP、FPPF、FPFPF、FPPM、PFP、PMFP、PPFPP、PFFPP、PMFPP、PPMFPP、PFD、PDFD、PDDFFD、PDFDD、DPF、DFP、DDDFP、FDP、PDDF、PFDPP、FPDDPP、PFDDPP、DMPF、DFMPP、PDFDP、DPFPD、DDPFPD、DDPFPDD、DDPFFPDD、DPFFPD、PFDFD、PFDFP、SFMP、SSFMP和PFFP，其中″M″表示熔喷织物层，″S″表示纺粘织物层，"F″表示膜层，″D″表示干法成网织物层。
22.权利要求21的层压体，其中所述干法成网织物层是梳理织物层或气流成网织物层。
23.由权利要求1-15中任一项的非织造织物制成的吸收或阻隔产品，所述产品包括个人护理品、训练罩、擦拭物、伤口护理品、过滤器、覆盖物、衣服和清洁制品和设备。
24.权利要求23的吸收或阻隔产品，所述产品包括婴儿尿布、吸收底垫、游泳衣、女性卫生产品、绷带、手术长袍、成人失禁产品、和手术单。
25.权利要求23的吸收或阻隔产品，所述产品包括医用衣服。
26.形成织物的方法，包括按大于3000m/min的成纤速度将一种或多种权利要求1-15中任一项的非织造织物中的主聚丙烯熔纺以制备具有小于20μm的平均直径和小于2.0的旦尼尔的纤维，其中所述旦尼尔具有g/9000m的单位。
27.权利要求26的方法，其中所述熔纺方法是纺粘方法且将所述挤出纤维暴露到大于2000Pa的变细用空气压力中。
28.权利要求26-27中任一项的方法，其中所述织物是在110-150℃的温度下压延的并具有大于20N/5cm的MD拉伸强度，其中所述MD拉伸强度根据WSP 110.4，05测量。
29.权利要求26-27中任一项的方法，其中所述织物是在110-150℃的温度下压延的并具有大于10N/5cm的CD拉伸强度，其中所述CD拉伸强度根据WSP 110.4，05测量。
30.权利要求26-27中任一项的方法，其中所述主聚丙烯是通过单中心催化剂体系制备的。
31.权利要求27的方法，其中纺粘方法的纺粘生产线生产量在150-300kg/hr的范围内。
32.权利要求27的方法，其中纺粘方法的纺粘生产线生产量/孔在0.30-0.90ghm的范围内。
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- 2009-12-21 WO PCT/US2009/069042 patent/WO2010087921A1/en active Application Filing
- 2009-12-21 US US13/140,654 patent/US20120116338A1/en not_active Abandoned
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| EP2382243A1 (en) | 2011-11-02 |
| US20120116338A1 (en) | 2012-05-10 |
| CN102300883A (zh) | 2011-12-28 |
| US20140378017A1 (en) | 2014-12-25 |
| WO2010087921A8 (en) | 2011-03-17 |
| WO2010087921A1 (en) | 2010-08-05 |
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