CN1973070A - 裂膜纤维的集合体 - Google Patents

裂膜纤维的集合体 Download PDF

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CN1973070A
CN1973070A CNA2005800209340A CN200580020934A CN1973070A CN 1973070 A CN1973070 A CN 1973070A CN A2005800209340 A CNA2005800209340 A CN A2005800209340A CN 200580020934 A CN200580020934 A CN 200580020934A CN 1973070 A CN1973070 A CN 1973070A
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fiber
multicomponent
polymers
multicomponent fibre
fibre
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V·班萨尔
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EIDP Inc
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EI Du Pont de Nemours and Co
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Abstract

由不同相容性聚合物组分形成的裂膜纤维所形成的纤维集合体，其中这些可相容聚合物组分中的至少一种包括液晶聚合物，而这些可相容聚合物组分中的另一种包括热塑性各向同性聚合物，并且尽管是可相容的，但是液晶聚合物组分容易与热塑性各向同性聚合物组分分离，且不需要为裂膜进行单独的机械或化学处理步骤。

Description

裂膜纤维的集合体
发明背景
1.发明领域
本发明涉及使多组分纤维开裂而制备的裂膜纤维，该多组分纤维包括至少两种不同相容性的聚合物组分。
2.相关技术描述
将两种或更多种不同的聚合物组分共纺丝成为多组分纤维使得这些聚合物组分形成横跨沿着纤维长度伸展的纤维的横截面的非互锁的可分离片段(segments)从而形成可开裂纤维。本技术领域众所周知含细纤维的非织造织物是使较大的多组分纤维开裂成纤维状网而形成的。多组分纤维中的纤维片段通过机械力，例如高压水喷射(例如液压缠结)、击打、梳理或其它纤维的机械加工而分离。可开裂纤维也可以在热处理中或者在拉伸过程中被分裂。选择不相容的不同聚合物组分使得聚合物组分易于在开裂过程中分离。
Haggard等人的国际公开号WO 99/19131描述了一种在纺粘工艺中使纤维在线开裂的方法，其中通过多组分纤维中两种或更多种组分的不同热收缩率而实现开裂。
Gillespie等人的美国专利5,783,503描述了从热塑性可开裂连续多组分纤维制备产品的方法。这些纤维在没有机械处理或不使用高压水喷射装置的条件下，至少部分开裂成更细小的纤维。聚合物组分的不同结晶行为可促进裂膜。
Polanco等人的美国专利申请2003/0203695描述了可开裂多组分纤维，其中至少一种聚合物组分包括约10-95重量％的填料。这些聚合物本身可相容或可不相容，并且采用一种分离处理，例如与刮刀接触，以便施加机械力使多组分纤维开裂。
Sasse等人的美国专利5,895,710描述了通过在热的含水条件下拉伸纤维而由至少两种不相容组分形成的多组分纤维的在线裂膜方法。
仍然存在不借助于使用不相容聚合物和/或处理以诱导开裂而获得细纤维非织造物和其它细旦尼尔纤维材料的需要。
附图简述
图1和2为穿过具有并列截面的纤维的横截面草图。
图3和4为穿过具有组合截面的纤维的横截面草图。
图5和6为穿过具有分块饼(segmented-pie)截面的纤维的横截面草图。
图7为穿过具有菊花截面的纤维的横截面草图。
图8为穿过具有镶尖三叶形截面的纤维的横截面草图。
图9显示了适合制备双组分纺粘网的常规纺粘设备的侧视图。
发明详述
本发明涉及包括小有效直径裂膜纤维的纤维的集合体，其中这些裂膜纤维是通过使包含至少两种相容性不同的聚合物组分的多组分纤维开裂而获得的。在相容性聚合物组分的相邻片段间发生这种开裂。在一个实施方案中，这种纤维集合体包括非织造网。例如，这种纤维集合体可包括纺粘非织造网，该网包含以纺粘工艺制备的连续裂膜纤维，该工艺过程中，在纺粘网铺网之前，不需要加热或另外加工，就可将这些多组分纤维开裂。
在此使用的术语“共聚物”包括无规、嵌段、交替和接枝的共聚物，其通过将两种或多种共聚单体聚合而制备，并因此包括二元聚物、三元聚合物等。
在此使用的术语“液晶聚合物”(LCP)囊括了显示液晶性能同时在熔融时显示流动性的聚合物。LCP在熔融时是各向异性的，即它们在熔融态下显示分子取向性。分子取向由双折射度量，其用第一方向和与第一方向垂直的第二方向上的折射率之差来表征。双折射可使用本领域已知的方法以偏光显微镜测定。非LCP在熔融态下是各向同性的。在此使用的术语“热塑性各向同性聚合物”是指在熔融态下各向同性的热塑性聚合物，这可由熔体相中缺少分子取向表征，即它的折射率基本上与熔体中的方向无关。
在此使用的术语“聚酯”拟包括其中至少85％的重复单元是二羧酸与二羟基醇的缩聚产物的聚合物，二者通过形成酯单元而键合。
在此使用的术语“非织造织物、片材、层或网”是指独立的纤维、长丝或细线结构，它们被以无规的方式定位以形成没有一致图案的平面材料，与编织或织造织物相反。非织造织物的实例包括熔喷网、纺粘网、梳理网、气流成网、湿法成网和射流喷网以及包含多于一层非织造层的复合网。
在此使用的术语“纺粘纤维”是指通过从多个具有挤出纤维直径的细的通常为圆形的喷丝板毛细孔中挤出纤维状的熔融热塑性聚合物材料，然后通过拉伸使挤出纤维的直径快速减小，接着骤冷纤维而熔纺的纤维。纺粘纤维通常是连续的纤维。
在此使用的术语“熔喷纤维”是指通过熔喷法熔纺的纤维，其包括使可熔融加工的聚合物经过多个毛细孔挤出成为熔融细流，进入到高速气体中(如空气)气流中。熔喷纤维直径通常为约0.5至10微米，而且通常是不连续的，但也可以是连续的。
在此使用的术语“纺粘-熔喷-纺粘非织造织物”(SMS)是指在两个纺粘层之间夹合一层与两个纺粘层粘着的熔喷纤维层的多层复合片材。可在SMS织物中引入另外的纺粘和/或熔喷层，例如纺粘-熔喷-熔喷-纺粘(SMMS)等等。
在此使用的术语“多组分纤维”是指由至少两种不同的聚合物组分制造的纤维，所述的多个组分已经一起纺丝形成单根纤维。该至少两种聚合物组分排列在横跨多组分纤维截面的不同的基本上固定的区域或片段中，这些区域沿着纤维长度方向基本上连续地延伸。在此使用的多组分纤维包括在纺丝工艺中开裂前作为中间纤维存在的可开裂的多组分纤维。这种开裂对应由不同的聚合物区域所形成的多组分纤维中的片段形成裂膜纤维片段。这种可开裂纤维在本申请中也称作“母体”纤维。这种多组分母体纤维在从其被纺出的喷丝板孔出来时基本上立刻开裂。多组分纤维的一种特定类型是由两种不同的聚合物组分制备的一种双组分纤维。多组分纤维与从聚合材料的均质或非均质的单一共混物挤出的纤维是不同的。在此使用的术语“多组分非织造网”是指含有多组分纤维的非织造网。在此使用的术语“双组分非织造网”是指含有双组分纤维的非织造网。多组分网可包括多组分纤维和单组分纤维两者。为了形成可开裂纤维，这些聚合物组分按照非咬合的构型配置，从而不同的聚合物片段在开裂时容易开裂。至少一个含一种不同聚合物组分的可分离片段形成纤维外围表面的一部分，并且其具有不被其邻近片段包封的，从而与相邻的一个或多个片段的分离不受到物理性阻碍。本领域公知可裂膜纤维的横截面。
在此使用的术语“裂膜纤维”是指在多组分纤维通过在多组分纤维的不同聚合物组分的相邻片段之间分离而使多组分纤维分离或开裂成两根或更多根纤维片段时所获得的纤维。裂膜纤维包括已部分地从多组分母体纤维上裂离出来的纤维。术语裂膜纤维还包括在其中从喷丝孔挤出前不同聚合物组分进行接触并在出喷丝孔时自发分开的方法中所纺制的纤维。
在此使用的术语“相容性聚合物”是指可形成可溶混的共混物的聚合物，即这些聚合物在熔融共混在一起时是可溶混的。
可使用聚合物溶解度参数选择适用于本发明的相容性聚合物。在本领域各种聚合物的溶解度参数是公知的。例如，在1973年International Textbook Co.，Ltd.，出版的J.M.G.Cowie的《聚合物：现代材料的化学和物理(Polymer：Chemistry and Physics ofModern Materials)》第142-145页发表了有关溶解度参数的讨论，在此将其内容引入本申请作为参考。多组分纤维中相邻排列的可相容的不同聚合物组分理想地具有小于约3(cal/cm3)1/2的溶解度参数差异。更优选，相邻聚合物组分存在的溶解度参数差异小于约2(cal/cm3)1/2。当不同聚合物组分中的一种或多种包含两种或多种聚合物的共混物时，体积加权平均值用于计算溶解度参数。例如，如果一种聚合物组分是25体积％的聚合物A与75体积％的聚合物B的共混物，则这种共混物的溶解度参数如下计算：0.25(聚合物A的溶解度参数)+0.75(聚合物B的溶解度参数)。
合适的非咬合的纤维的横截面示于图1-图8。图1和图2例示了双组分并列的横截面，其中第一聚合物组分的片段1与第二聚合物组分的片段3相邻，第一聚合物组分与第二聚合物组分是相容的。每个片段在纤维长度方向上基本上连续，两种聚合物组分均被暴露在纤维表面上。这些片段之间的界面5′和5″可以分别如图1所示是直的，或者如图2所示是弯曲的。图3和图4例示的截面构型中，至少一种聚合物组分形成与第二聚合物组分的一个或更多个片段9交替排列的两个或更多个片段7，类似于并列织物置。图5例示了一种分块饼形纤维的横截面，包括第一聚合物组分和第二聚合物组分的交替楔形片段11和13。图6例示了与图5类似的一种中空分块饼形纤维横截面，不同的是图6的母体纤维具有穿过纤维中心延伸的孔隙15。图7例示了本领域中有时称为菊花横截面的一种横截面，其中一种聚合物组分的片段17为花瓣形的，而且其被第二聚合物组分的相邻片段19部分覆盖。尽管花瓣形片段由于相邻片段的覆盖而存在某些部分的咬合，但是这些片段能够容易地分开形成裂膜纤维。图8例示了一种镶尖三叶形的横截面，其中一种不同聚合物组分在叶的尖部形成片段21。适于形成可裂膜纤维的其它横截面是本领域公知的。这些纤维横截面可对称或不对称。这些纤维可为圆形横截面的，或者为诸如椭圆或多叶横截面等其它横截面形状的。不同聚合物组分可等量或不等量地存在。优选对纺丝条件和设备进行选择，使得单根裂膜纤维片段具有小于0.04-50微米的有效直径。例如，裂膜纤维片段可具有不大于约10微米的有效纤维直径，优选其在约1微米至10微米的范围内。在此使用的具有不规则横截面的纤维(例如由本发明的至少部分开裂纤维而获得的裂膜片段或裂膜片段的组合)的“有效直径”等于具有相同横截面面积的假想圆纤维的直径。
本发明的材料优选由可开裂母体纤维形成，该母体纤维含有第一聚合物组分和第二聚合物组分，该第一聚合物组分包括液晶聚合物，该第二聚合物组分包括热塑性各向同性聚合物。第一和第二聚合物组分以相邻片段排列在非咬合横截面中，例如上述的横截面中。合适的LCP包括液晶聚酯，例如美国专利5,525,700中描述的那些液晶聚酯，其在此引入本申请作为参考。液晶聚酯可为全芳香(基于芳香二醇和芳香二羧酸)的，或者可为部分芳香(基于一种或多种含2至10个碳原子的脂肪二醇和芳香二羧酸)的。母体纤维中的第二聚合物组分经过选择以便其与第一聚合物组分相容。当第一聚合物组分含有液晶聚酯时，第二聚合物组分可选自热塑性各向同性聚酯，例如聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸-1，3-丙二醇酯)、聚(对苯二甲酸-1，4-丁二醇酯)、聚(萘二甲酸乙二醇酯)和聚(对苯二甲酸环己二甲酯)及其共聚物或共混物。可使用其它聚酯共聚物，包括其中基于二酸组分约5-30摩尔％由间苯二甲酸酯基(例如源于二甲基间苯二甲酸)形成的聚(对苯二甲酸乙二醇酯)共聚物，和其中基于二醇组分约5-60摩尔％由-1，4-环己烷二甲醇形成的聚(对苯二甲酸乙二醇酯)共聚物。可从Eastman Chemicals(Kingsport，TN)以PETG共聚物获得的经过-1，4-环己烷二甲醇改性的聚(对苯二甲酸乙二醇酯)共聚物。
令人惊讶的是，母体多组分纤维的相容性聚合物片段是容易开裂的。这与现有技术情形相反，现有技术教导，为了取得明显开裂效果，使用不相容的聚合物片段或者在至少一种聚合物组分中要求高填料加入量的相容聚合物片段。通常，这种多组分纤维在纺丝过程中至少部分开裂，并且因此一般不分离出“未开裂”的纤维。本发明的裂膜纤维材料不要求为了引起母体纤维开裂而分开进行加热、机械处理、液压处理或化学处理。在多组分进行纺丝过程中，母体纤维能自发开裂。
在一个实施方案中，本发明的纤维集合体包含复丝纱或丝束。在本发明的一个优选实施方案中，由多组分纤维开裂形成的纤维集合体包括非织造织物或非织造网。非织造网可包括纺粘非织造网，其包含基本上连续的纺粘裂膜纤维。可替换地，非织造网可包括熔喷网，其包含裂膜熔喷纤维。纤维集合体可包含第二纤维，这种第二纤维包括单组分和/或多组分纤维，其可为连续纤维或不连续纤维。第二纤维可与裂膜连续纤维共混，或者它们可作为单独的层沉积在裂膜连续纤维的网上。可替换地，纤维集合体可基本上由裂膜连续纤维组成。
在一个实施方案中，纤维集合体含有多层非织造网，其中至少一层包含裂膜纤维集合体。例如，这种纤维集合体可为含至少一个纺粘层和至少一个熔喷层的多层网，其中该纺粘层和/或熔喷层包含由多组分纤维开裂形成的裂膜纤维，这些多组分纤维包含一种或多种LCP片段和一种或多种热塑性各向同性聚合物片段。在一个这样的实施方案中，纤维集合体包含熔喷层和纺粘层的组合，例如SMS、SMMS等非织造织物，其中至少一个纺粘层包含本发明裂膜连续纤维的集合体。在另一个这样的实施方案中，纤维集合体是SMS、SMMS等非织造织物，其中该熔喷层包含按照本发明制备的裂膜纤维。可替换地，纺粘层和熔喷层可各自含有本发明的裂膜纤维。一种或全部聚合物组分可包含本领域已知的非聚合物添加剂，包括抗氧化剂、颜料、填料等等。这些添加剂不是为了获得组分开裂而要求添加的。通常，在使用了颜料和/或微粒填料时，它们的存在量为少于约5重量％，基于含这种添加剂和/或填料的聚合物组分。术语“微粒”用于本申请是指颜料和其它固体填料。例如，基于包含这种微粒的聚合物组分，微粒可总共添加约2重量％或更少。
图9显示了用于由两种不同聚合物组分制备纺粘网的常规纺粘设备的侧视图。将液晶聚合物喂入加料斗40而热塑性各向同性聚合物喂入加料斗42。将加料斗40和42中的聚合物分别进料到挤出机44和46，它们各自对其中所含的聚合物进行熔融和加压，并迫使其分别通过过滤器48和50以及计量泵52和54。两股聚合物流在纺丝头组合体56中按照已知方法组合，从而产生需要的非咬合纤维横截面。可以选择这些聚合物组分以便热塑性各向同性聚合物比LCP组分的熔点更低，以便于纺粘织物的热粘结。例如，热塑性各向同性聚合物的熔点可比LCP的熔点低至少10℃，并更优选其熔点比LCP的熔点低至少20℃。可替换地，LCP的熔点可更低。如果热粘合法未被用于粘结纺粘织物，则聚合物组分可具有类似的熔点。例如，如果通过使用高压水喷射装置(液力缠结)缠结使非织造网结合，则熔点差异就不重要了。熔融的聚合物经过许多位于喷丝板58表面上的毛细孔或开孔离开喷丝头组合体56，形成纤维帘幕60。这些毛细开孔可以按照常规样式排列在喷丝板板面上，例如矩形排列的、交错排列的或者一些其它构型。用骤冷空气62冷却这些纤维，然后在铺放形成非织造网之前通过一个气流拉伸喷嘴64。由一个或多个引导空气吹向纤维的常规骤冷箱(未示出)提供骤冷空气，其速率通常为约0.3至2.5米/秒且温度在5℃至25℃范围内。可替换地，可使用双侧骤冷系统，其中从两侧引导骤冷空气到达纤维帘幕上，以便获得更均匀的骤冷效果。在骤冷步骤中，纤维的温度被充分地降低，使得纤维在通过喷嘴时不再彼此粘住，或者粘在喷嘴的内壁上。将空气66馈入拉伸喷嘴并对纤维提供拉伸张力，引起纤维在喷丝板板面附近被拉伸。馈入拉伸喷嘴中的空气可以是热的或不热的。离开拉伸喷嘴的纤维67被沉积在铺网输送带或成网筛网68上，形成连续纤维的网70。网70可任选地从热粘合辊72和74之间通过，然后收集在辊78上。
不希望受理论的约束，认为在骤冷步骤中聚合物固化时，这些纤维至少部分开裂。当出自骤冷区的纤维在铺网形成纺粘网之前经过气流拉伸喷嘴时，可能发生了进一步的开裂。
测试方法
在以上描述中，采用下列测试方法确定各种报告的特征和性能。
有效纤维直径是用光学显微镜测定的，并且以微米为单位报告平均值。对于包含本发明裂膜纤维集合体的每个样品，测量并平均约100根纤维的直径。
聚合物的熔点根据ASTM D 3418-99使用差示扫描量热法(DSC)测定。

Claims (18)

1.一种纤维集合体，其包含第一聚合物组分的许多第一纤维片段和第二聚合物组分的许多第二纤维片段，该第一聚合物组分包含第一液晶聚合物，该第二聚合物组分包含第一热塑性各向同性聚合物，其中第一和第二聚合物组分是相容的，并且第一和第二纤维片段通过包含第一和第二纤维片段的多组分纤维的至少部分开裂形成，该第一和第二纤维片段排列在横跨多组分纤维横截面的不同非咬合区域中，并且沿着多组分纤维长度基本上连续地延伸，其中在第一和第二纤维片段之间发生开裂。
2.一种非织造网，其包含权利要求1的纤维集合体。
3.权利要求2的非织造网，其中第一和第二纤维片段包括连续纤维。
4.权利要求3的非织造网，其中非织造网是纺粘网。
5.权利要求2或4任一项的非织造网，其中第一和第二纤维片段具有非圆形的横截面形状。
6.权利要求5的非织造网，其中第一和第二纤维片段是楔形的。
7.权利要求4的非织造网，其中第一和第二纤维片段的有效纤维直径介于约0.04微米和50微米之间。
8.权利要求7的非织造网，其中第一和第二纤维片段的有效纤维直径不超过约10微米。
9.权利要求4的非织造网，进一步包含粘着到纺粘网第一侧上的一个熔喷纤维层。
10.权利要求9的非织造网，其中熔喷纤维是多组分纤维。
11.权利要求9的非织造网，其中熔喷纤维层包含许多第三和第四纤维片段，其中第三纤维片段包含第二液晶聚合物，而第四纤维片段包含与第二液晶聚合物相容的第二热塑性各向同性聚合物，第三和第四纤维片段通过多组分熔喷纤维的开裂形成，该多组分熔喷纤维包含排列在横跨多组分熔喷纤维横截面的不同非咬合区域中的第三和第四纤维片段，并且沿着多组分熔喷纤维长度方向基本上连续地延伸，其中在第三和第四纤维片段之间发生开裂。
12.权利要求2的非织造网，其中第一和第二纤维片段包括熔喷纤维片段。
13.权利要求2或4任一项的非织造网，其中液晶聚合物选自全芳香聚酯和部分芳香聚酯，而热塑性各向同性聚合物是聚酯，其选自：聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸-1，3-丙二醇酯)、聚(对苯二甲酸-1，4-丁二醇酯)、聚(萘二甲酸乙二醇酯)和聚(对苯二甲酸环己二甲酯)、聚酯共聚物以及它们的共混物。
14.权利要求13的非织造网，其中热塑性各向同性聚合物是聚酯共聚物，其选自其中基于二酸组分约5-30摩尔％由间苯二甲酸酯基团形成的聚(对苯二甲酸乙二醇酯)共聚物，和其中基于二醇组分约5-60摩尔％由-1，4-环己烷二甲醇形成的聚(对苯二甲酸乙二醇酯)共聚物。
15.一种纺粘非织造织物，其包含第一聚合物组分的许多第一连续纤维片段和第二聚合物组分的许多第二连续纤维片段，该第一聚合物组分包含液晶聚合物，该第二聚合物组分包含热塑性各向同性聚合物，其中第一和第二纤维片段通过许多包含第一和第二聚合物组分的片段的多组分纤维的开裂形成，第一和第二聚合物组分排列在横跨多组分纤维横截面的不同非咬合区域中，并且沿着多组分纤维长度基本上连续地延伸，其中在第一和第二聚合物组分的片段之间发生开裂。
16.权利要求15的纺粘织物，其中多组分纤维的横截面选自分块饼形和中空分块饼形的横截面。
17.包含裂膜纤维的纺粘非织造织物的制备方法，包括以下步骤：
(a)从喷丝板熔纺许多可开裂的连续多组分纤维，这些多组分纤维包含第一聚合物组分和第二聚合物组分，第一和第二聚合物组分排列在横跨多组分纤维横截面的不同非咬合区域中，并且沿着多组分纤维长度基本上连续地延伸，第一和第二聚合物组分各自构成多组分纤维外围表面的至少一部分，其中第一和第二聚合物组分是相容的，并且第一和第二聚合物组分各含少于5重量％的微粒；
(b)在第一和第二聚合物熔融时，在多组分纤维离开喷丝板后拉伸它们；
(c)骤冷多组分纤维，其中多组分纤维在完成骤冷步骤之前，至少部分地自发开裂；和
(d)在收集表面上沉积至少部分开裂的纤维，以形成纺粘非织造网。
18.纺粘织物的制备方法，包括以下步骤：
(a)从喷丝板熔纺许多可开裂的连续多组分纤维，这些多组分纤维包含第一聚合物组分和第二聚合物组分，该第一聚合物组分含一种液晶聚合物，而该第二聚合物组分包含热塑性各向同性聚合物，第一和第二聚合物组分排列在横跨多组分纤维横截面的不同非咬合区域中，并且沿着多组分纤维长度基本上连续地延伸，第一和第二聚合物组分各自构成多组分纤维外围表面的至少一部分，其中第一和第二聚合物组分是相容的；
(b)在第一和第二聚合物仍然熔融时，在多组分纤维离开喷丝板后拉伸它们；
(c)骤冷多组分纤维，其中多组分纤维在完成骤冷步骤之前，至少部分地自发开裂；和
(d)在收集表面上沉积裂膜纤维，以形成纺粘非织造网。
CNA2005800209340A 2004-06-24 2005-06-24 裂膜纤维的集合体 Pending CN1973070A (zh)

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