CN1446275A - 熔喷纤网 - Google Patents

熔喷纤网 Download PDF

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Publication number
CN1446275A
CN1446275A CN01812708A CN01812708A CN1446275A CN 1446275 A CN1446275 A CN 1446275A CN 01812708 A CN01812708 A CN 01812708A CN 01812708 A CN01812708 A CN 01812708A CN 1446275 A CN1446275 A CN 1446275A
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China
Prior art keywords
weight
polyester
inherent viscosity
meltblown fibers
fibre web
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Granted
Application number
CN01812708A
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English (en)
Other versions
CN1190535C (zh
Inventor
E·N·鲁迪西尔
V·班索
M·C·戴维斯
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of CN1446275A publication Critical patent/CN1446275A/zh
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Publication of CN1190535C publication Critical patent/CN1190535C/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • D04H1/435—Polyesters
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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  • Engineering & Computer Science (AREA)
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Abstract

提供了一种熔喷纤维，其包含至少20％重量的聚酯，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯。所述熔喷纤维以纤网收集，该纤网可以引入复合片材结构。

Description

熔喷纤网
发明背景
发明领域
本发明涉及熔喷纤维、熔喷纤维纤网和包含熔喷纤维的复合非织造织物。本发明的熔喷纤网可以引入复合材料织物，其适合用于服装、抹布、卫生产品和医药包装材料。
相关技术描述
在熔喷方法中，非织造纤网通过挤出熔融聚合物通过模头，然后用热的高速气流拉细和断裂得到的长丝而形成。该方法产生短的、非常细的纤维，其可以被收集在运送带上，其中它们在冷却期间互相粘合。熔喷纤网可以具有很好的阻隔性能。
熔喷纤维最通常由聚丙烯纺丝。其他已经作为熔喷纤维纺丝的聚合物包括聚乙烯、聚酰胺、聚酯和聚氨酯。聚酯聚合物，例如聚对苯二甲酸乙二醇酯(“PET”)和聚对苯二甲酸丙二醇酯(“PTT”)，不太适合于生产细的熔喷纤维。此外，由于聚酯在熔喷纤网中形成低的结晶度和由于聚酯低的结晶温度，热粘合熔喷聚酯纤网倾向于是脆性的和它们具有较差的流体阻隔性能，特别是当经过机械应力时。美国专利号5,364,694公开了PET与另一热塑性聚合物、例如聚乙烯的共混物的熔喷方法，该热塑性聚合物与PET不相容并且具有高的结晶速率和低的熔体粘度。第二聚合物产生“粘度-降低效果”，其减小总的共混物的熔体粘度，以致促进PET熔喷时的拉细。美国专利号4,795,668公开了双组分纤维的熔喷，其中一个组分是PET和另一个组分是更加热稳定的聚合物例如聚丙烯或者聚苯乙烯。
熔喷纤维已经引入各种非织造织物，包括复合层压制品，例如纺粘-熔喷-纺粘(“SMS”)复合片材。在SMS复合材料中，外部层是纺粘纤维层，其为整个复合材料提供强度，而芯层是熔喷纤维层，其提供阻隔性能。传统上，SMS复合材料的纺粘和熔喷层一直是由聚丙烯纤维制成。对于某些最终用途，例如医用长袍，需要SMS复合片材具有好的强度和阻隔性能，同时尽可能柔软和悬垂。虽然聚丙烯基SMS织物提供优良的强度和阻隔性能，但是它们不易于被制成如服装产品所需要的那样柔软和悬垂。聚丙烯基SMS织物还具有这样的局限性，即它们不能用γ辐射灭菌，因为这类织物在用γ辐射灭菌时变色和弱化，而且聚丙烯基SMS织物的γ辐射灭菌产生不良气味。当织物用γ辐射灭菌导致纤维或者织物强度的明显降低、纤维或者织物外观的显著变化或者产生不良的气味时，聚合物纤维或者织物一般地被认为是不能幅射灭菌的。对于聚丙烯基SMS织物，不能经受γ辐射灭菌带来很大问题，因为辐射灭菌在整个医药工业中被普遍使用。
对形成纤网时具有优良阻隔性能的较细的聚酯熔喷纤维存在需求。此外，对柔韧的和在受到机械应力时不显著损失阻隔性能的熔喷聚酯纤网存在需求。
发明内容
本发明涉及熔喷纤维和熔喷纤维纤网。本发明的熔喷纤维包含至少20％重量的聚酯，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯。本发明的熔喷纤维的平均有效直径低于10微米。优选，聚对苯二甲酸乙二醇酯的特性粘度在0.20到0.50dl/g范围之内和聚对苯二甲酸丙二醇酯的特性粘度在0.45到0.75dl/g范围之内。更优选，聚对苯二甲酸乙二醇酯的特性粘度在0.25到0.45dl/g范围之内和聚对苯二甲酸丙二醇酯的特性粘度在0.50到0.70dl/g范围之内。本发明的熔喷纤维优选形成熔喷纤网。
按照本发明的一个优选的实施方案，熔喷纤维是多组分纤维，其由20％和98％重量之间的聚对苯二甲酸乙二醇酯和80％和2％重量之间的第二聚合物组分组成，该第二聚合物组分由至少10％聚乙烯聚合物组成。本发明的熔喷纤维优选形成多组分熔喷纤网，其由20％和98％重量之间的聚对苯二甲酸乙二醇酯和80％和2％重量之间的第二聚合物组分组成，该第二聚合物组分由至少10％重量聚乙烯聚合物组成。
本发明还涉及复合片材，其具有第一纤维层，该第一纤维层具有第一侧和相反的第二侧，和第二纤维层，该第二纤维层粘合到第一纤维层的第一侧。第一纤维层是熔喷纤网，其由至少20％重量的聚酯组成，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯。第二纤维层优选由至少95％重量的熔纺纤维组成。在本发明优选的实施方案中，复合片材的基础重量低于120g/m2和静水压头为至少10cm。按照本发明更加优选的实施方案，第一纤维层中的至少10％的熔喷纤维是多组分纤维。更优选，多组分熔喷纤维具有低特性粘度的聚酯组分和聚乙烯组分。按照本发明，第二纤维层的熔纺纤维可以是具有聚酯组分和聚乙烯组分的多组分纤维。本发明还涉及由本发明复合片材制成的衣服。
本发明还涉及熔喷纤维，其包含至少20％重量的聚酯，该聚酯的重均分子量低于25,000。优选，所述聚酯的重均分子量在5,000到22,000范围内。更优选，所述聚酯的重均分子量在10,000到19,000范围内。
附图描述
图1是用于产生熔喷纤维的设备局部示意图，该熔喷纤维用于本发明的复合非织造织物。
图2是本发明一个实施方案的复合非织造织物的剖面概要图。
图3是本发明另一实施方案的复合非织造织物的剖面概要图。
图4是用于产生本发明复合非织造织物的设备的示意图。
定义
术语“聚合物”在此一般地包括均聚物、共聚物(例如嵌段、接枝、无规和交替共聚物)、三元共聚物和其共混物和改性产物。此外，除非另外特别地限定，术语“聚合物”将包括所有可能的材料几何构型。这些构型包括等规、间规和无规对称性。
术语“聚乙烯”在此不仅包括乙烯的均聚物，而且包括其中至少85％的重复单元是乙烯单元的共聚物。
术语“聚丙烯”在此不仅包括丙烯的均聚物，而且包括其中至少85％的重复单元是丙烯单元的共聚物。
术语“聚酯”在此包括聚合物，其中至少85％的重复单元是二羧酸和二元醇的缩合产物，通过形成酯单元产生聚合物键。其包括芳香族、脂肪族、饱和和不饱和二元酸和二元醇。术语“聚酯”在此还包括共聚物(例如嵌段、接枝、无规和交替共聚物)、共混物和其改性产物。聚酯的普通的例子是聚对苯二甲酸乙二醇酯，其是乙二醇和对苯二甲酸的缩合产物。
术语“熔纺纤维”在此指通过以长丝形式从大量细的、通常圆形的喷丝头毛细管挤出熔体热塑性聚合物材料，然后迅速地降低挤出长丝的直径形成的纤维。熔纺纤维通常是连续的和平均直径高于约5微米。
术语“熔喷纤维”在此指通过以熔体丝或者长丝形式挤出熔体热塑性聚合物通过大量细的、通常圆形的毛细管到高速气体(例如空气)流中形成的纤维。高速气流拉细熔融热塑性聚合物材料的长丝，将其直径降低到约0.5和10微米之间。熔喷纤维通常是不连续的纤维。由高速气流携带的熔喷纤维通常沉积在收集面上以形成随机分散纤维的纤网。
术语“纺粘纤维”在此指通过以长丝形式从喷丝头的大量细的毛细管挤出熔融热塑性聚合物材料、拉伸、随机沉积在网板上和粘合在一起形成的纤维。
术语“非织造织物、片材或者纤网”在此指单根纤维或者丝的结构，它们以无规方式定位形成平面材料，而没有如针织物中的可识别的图案。
术语“多组分熔喷纤网”在此指熔喷纤维，其以熔融长丝形式纺自细的毛细管，该长丝包含多种不同的聚合物组分，该熔融长丝由高速气流拉细和以随机分散纤维的纤网形式沉积在收集面上。
在此，“纵向”是片材平面内的运动方向，即片材被生产的方向。“横向”是片材平面内垂直于纵向的方向。
试验方法
在上述描述和以下实施例中，使用以下试验方法测定各种报告的特性和性能。ASTM指美国测试和材料学会，和AATCC指美国纺织品化学师和着色师协会。
特性粘度(IV)是测量聚合物溶液流动内阻的尺度，并且用ASTM D-2857测定，其在此引入作为参考，和以dl/g报告。用于在玻璃毛细管粘度计中研究聚对苯二甲酸乙二醇酯特性粘度的溶剂和温度是含有0.01M三氟醋酸钠的六氟丙醇和35℃。用于在玻璃毛细管粘度计中研究聚对苯二甲酸丙二醇酯特性粘度的溶剂和温度是邻氯苯酚和25℃。
重均分子量使用具有三重检测器系统的空间排阻色谱分析进行测量。该系统可以独立于校准标准的类型测量绝对分子量。聚对苯二甲酸乙二醇酯的平均分子量在含有0.01M三氟醋酸钠的六氟异丙醇中使用100微升的注射体积于1.000ml/min流速在35℃下操作进行测定。
纤维直径通过光学显微法测量和以微米为单位报告平均值。
基础重量是测量织物或者片材单位面积上的质量的尺度，并且用ASTM D-3776测定，其在此引入作为参考，和以g/m2报告。
抓样抗张强度是测量片材抗断强度的尺度，并且按照ASTM D 5034进行，其在此引入作为参考，和以牛顿报告。
静水压头是测量片材对于液态水在静压下渗透阻力的尺度。该试验按照AATCC-127进行，其在此引入作为参考，和以厘米报告。
Frazier透气性是测量气流在指定的片材面之间压力差下通过片材的尺度，并且按照ASTM D 737进行，其在此引入作为参考，和以m3/min/m2报告。
水冲击是测量片材对于冲击水渗透的阻力的尺度，并且按照AATCC42-1989进行，其在此引入作为参考，和以克报告。
发明详述
现在详述参考本发明目前优选的实施方案，其中实施例说明如下。本发明涉及熔喷聚酯纤维，其纺自低粘度的聚酯，以制备较细的纤维。如在此具体化的，熔喷纤维由至少20％重量的聚酯组成，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯。过去进行熔喷的聚对苯二甲酸乙二醇酯聚酯的特性粘度通常在0.65到0.80dl/g范围之内。聚合物的特性粘度或者“IV”是聚合物分子量的指示，较高的IV表示较高的分子量。IV低于约0.55dl/g的聚对苯二甲酸乙二醇酯被认为是“低IV”聚酯。IV低于约0.80dl/g的聚对苯二甲酸丙二醇酯(“PTT”)被认为是“低IV”聚酯。可用于本发明的低IV聚酯的重均分子量低于25,000。优选，所述聚酯的重均分子量在5,000到22,000范围内。更优选，所述聚酯的重均分子量在10,000到19,000范围内。
低IV聚酯未曾被用于生产熔喷纤维或者纤网。已经发现，当低IV聚酯被熔喷时，生产的纤维与由常规IV的聚酯熔喷得到的纤维相比具有较小的直径。这些较小直径的纤维，当用于复合SMS织物时，提供改善的阻隔性能。
按照本发明，本发明的细聚酯熔喷纤维按照常规的熔喷方法生产。在熔喷方法中，一个或多个挤出机提供熔融聚合物到模头顶端，其中聚合物在通过细的毛细管孔时被纤维化，形成长丝幕。该长丝被气动地拉伸和通常用围绕模头中细毛细管孔的空气喷射断裂。纤维被沉积在运送带或者网板、纱布或者另一纤维层上。通过熔体喷射生产的纤维通常是不连续的纤维，其有效直径在约0.5到约10微米范围内。在此，具有不规则横断面的纤维的“有效直径”等于具有相同横截面积的假想圆形纤维的直径。
为了生产更加柔韧和耐用的热粘合熔喷聚酯纤网，熔喷纤维可以多组分纤维形式纺丝，其中纤维组分之一由低IV聚酯组成。在本发明多组分熔喷纤网中的纤维通常是不连续的纤维，其平均有效直径在0.5微米和10微米之间，和更优选在约1和6微米之间和最优选在约2和4微米之间。多组分熔喷纤网由至少两种同时从纺丝组合体纺丝的聚合物形成。优选，多组分熔喷纤网是由两种聚合物构成的双组分纤网。纤维在双组分纤网中的构型优选是并列式排列，其中大部分纤维由两种并列式聚合物组分组成，它们延伸各自纤维长度的大的部分。可选择地，双组分纤维可以具有皮/芯式排列，其中一种聚合物由另一种聚合物围绕，“海-岛”排列，其中一种聚合物的许多线包埋在另一聚合物中，或者任何其他常规的双组分纤维结构。不希望被理论束缚，相信熔喷纤维的拉细实际上可以使多组分长丝破裂成甚至更细的长丝，其中一些可以仅仅包含一种聚合物组分。
按照本发明，多组分熔喷纤网的第二聚合物组分包括一种或多种形成纤维的合成聚合物，其比聚酯更加柔韧。优选，第二组分的熔融温度低于第一组分的熔融温度，以便在热粘合时有助于粘结熔喷纤维，这产生更加柔韧的纤网。优选，该其他聚合物是γ辐射稳定的聚合物，例如聚乙烯。可选择地，第二聚合物组分可以是非幅射灭菌的聚合物，例如聚丙烯，如果片材的最终用途不要求该片材是可幅射灭菌的。
本发明优选的多组分熔喷纤网是由低IV PET和聚乙烯组成的双组分熔喷纤网。优选，低IV PET组分构成20％到98％重量的熔喷纤网和聚乙烯组分构成2％到80％重量的熔喷纤网。更优选，低IV PET组分构成55％到98％重量的熔喷纤网和聚乙烯组分构成2％到45％重量的熔喷纤网。甚至更优选，低IV PET组分构成65％到97％重量的熔喷纤网和聚乙烯组分构成3％到35％重量的熔喷纤网。最优选，低IV PET组分构成80％到95％重量的熔喷纤网和聚乙烯组分构成5％到20％重量的熔喷纤网。
本发明的熔喷纤网的纤维可以使用具有类似示于图1的毛细管模孔的熔喷设备进行熔喷，其更充分地描述于美国专利号4,795,668，其在此引入作为参考。在示于图1的熔喷模头20的剖视图中，两种不同的聚合物组分在平行挤出机23和24中被熔融和分别地通过齿轮泵(未显示)和导管25和26计量到模腔22。在该模腔中，聚合物组分形成层状物质，其中该两种组分以分立的层分离。该层状物质通过毛细管喷嘴21的线道挤出。在需要单组分纤维时，相同聚合物通过两个挤出机23和24提供，或者仅仅使用一个挤出机。来自于通道28的热风射流拉细出来的聚合物长丝。不希望被理论束缚，相信空气射流可以使长丝破裂成甚至更细的长丝。得到的长丝被认为包括双组分长丝，其中每一长丝由两种分离的聚合物组分组成，两者以并列式构型延伸熔喷纤维的长度。层14的细纤维可以可选择地通过其他已知的熔喷方法生产，例如通过其中单独的空气喷嘴围绕每一聚合物毛细管的方法生产，如公开于美国专利号4,380,570中的。
引入本发明熔喷纤网的复合非织造片材示于图2。片材10是三层复合材料织物，其中内层14由非常细的熔喷聚合物纤维组成，其夹在外层12和16之间，后者各自由较粗和较强的和粘合的纤维组成。内层14的非常细的纤维，当形成层14时，产生具有极细通道的阻隔层。层14起到流体阻隔的作用，但是不妨碍水蒸气的通过。粘合纤维层12和16由粗的和较强的纤维组成，其为复合片材提供强度，和在有些情况下提供阻隔。复合片材可以可选择地以双层的复合材料18的形式形成，如图3所示。在该双层的复合片材中，细熔喷纤维层14仅仅附着在粗的和较强的粘合层12的单面上。按照本发明选择性的实施方案，复合片材可以用多个类似于层14的细熔喷纤维层制成，或者可以用超过两层的类似于层12和16的粗的和较强的纤维层制成。
层12和16的较粗和较强的粘合纤维优选是常规熔纺纤维或者某些其他类型的强纺粘纤维。优选，熔纺纤维是实质上连续纤维。可选择地，层12和16可以是气流成网或者湿法成网短纤维纤网或者梳理纤网，其中纤维互相粘合形成强纤网结构。层12和16的纤维应该由这样一种聚合物组成，对于该聚合物，芯层14的含聚乙烯的细纤维可以容易地粘合。层12和16的纤维优选是可以γ辐射灭菌的，其中它们具有由非聚丙烯的聚合物组成的外层，该聚合物例如是聚酯、聚乙烯、聚酰胺或者其某些结合。在复合材料织物不会被用于使用辐射灭菌的最终用途时，层12和16的纤维也可以由例如聚丙烯的聚合物组成，该聚合物不是可以γ辐射灭菌的。
对于层12和16，优选的熔纺纤维是由聚酯和聚乙烯组成的双组分纤维。聚酯组分为织物提供强度，而聚乙烯组分使织物更柔软和更悬垂。此外，纤维的聚乙烯组分比聚酯组分具有更低的熔化温度，使得层12和16更易于使用热粘合方法粘合到芯层14的细熔喷纤维。可选择地，层12和16可以由单聚合物组分纤维的共混物组成，例如其中一部分纤维是聚乙烯纤维和一部分纤维是聚酯纤维的纺粘纤网。
优选，层12和16的较粗和较强的纤维实质上是连续的纺粘纤维，其使用高速熔体纺丝方法生产，例如公开于美国专利号3,802,817；5,545,371和5,885,909中的高速纺丝方法，其在此引入作为参考。按照优选的高速熔体纺丝方法，一个或多个挤出机提供熔融聚合物到纺丝组合体，其中聚合物通过开口被纤维化，形成长丝幕。该长丝在空气急冷区中被部分地冷却。然后长丝被气动地拉伸，以降低其尺寸和赋予增加的强度。长丝被沉积在运动筛、皮带、纱布或者其他纤维层上。通过优选的高速熔体纺丝方法生产的纤维实质上是连续的和直径为5到30微米。这些纤维可以作为单组分纤维、多组分纤维或者其某些结合生产。多组分的纤维可以生产成各种已知的横截面构型，包括并列式、皮-芯式、链段饼形或者海-岛式构型。
引入上述低特性粘度聚酯熔喷纤网的复合非织造织物可以使用示意性地显示在图4中的设备在线地生产。可选择地，复合片材的层可以独立地生产和随后结合和粘合形成复合片材。示于图4的设备包括本领域众所周知的纺粘纤网生产部分80和94。图4的设备另外包括熔喷纤网生产部分82，引入了对于上述的图1描述的熔喷设备。为了说明，两个纺粘纤网生产部分80和94和熔喷纤网生产部分82显示为生产双组分纤维。考虑到纺粘纤网生产部分80和94和熔喷纤网生产部分82可以替代为设计成能生产具有仅仅一种聚合物组分或者具有三种或更多聚合物组分的纤网的单元。也考虑到超过一个纺粘纤网生产部分可以串联使用以生产由不同的单或者多组分纤维的共混物构成的纤网。同样地，考虑到超过一个熔喷纤网生产部分可以串联使用以生产具有多个熔喷层的复合片材。另外考虑到用于各种纤网生产部分的聚合物可以互相不同。在希望生产具有仅仅一个纺粘层和一个细纤维层的复合片材时(如图3所示)，第二纺粘纤网生产部分94可以停下或者除去。
按照本发明优选的实施方案，在示于图4设备的纺粘纤网生产部分80和94中，两种热塑性聚合物组分A和B被熔融、过滤和计量(未显示)到纺丝组合体56和96。熔融聚合物长丝60和100从纺丝组合体挤出分别通过喷丝头组58和98。长丝可以作为具有需要横截面例如皮-芯式长丝横截面的双组分长丝挤出。优选，较低熔化温度的聚合物被用于皮部分，而较高熔化温度的聚合物被用于芯部分。得到的长丝60和100用骤冷空气62和102冷却。接下来长丝进入气动拉伸射流64和104并由拉伸空气66和106拉伸。来自纺粘纤网生产部分80的纤维67被沉积在形成网板68上以便在皮带上形成纺粘层12。
按照本发明优选的实施方案，低特性粘度聚酯聚合物和另一聚合物被结合以在熔喷纤网生产部分82中生产熔喷双组分纤网。该两种聚合物C和D被熔融、过滤和然后计量(未显示)到纺丝组合体84。熔融聚合物在纺丝组合体84中被结合和通过毛细管孔86的线道出来，其如关于图1描述的那些。优选，纺丝组合体84产生需要的并列式纤维长丝横截面。选择性的纺丝组合体排列可用于生产选择性的纤维横截面，例如皮-芯式横截面。来自于通道90的热风88的射流冲击在离去长丝91的相对侧，并且在每一长丝离开其毛细管孔之后立即拉细每一长丝91。在拉细工艺期间熔喷长丝91通常断裂。熔喷长丝纤维91沉积在纺粘层12上以产生多组分熔喷纤网层14。
在使用第二纺粘纤网生产部分94时，来自纺粘纤网生产部分80的实质上连续的纺粘纤维107被沉积在熔喷层14上以便形成复合片材的第二纺粘层16。层12和16不必须具有相同厚度或者基础重量。
纺粘-熔喷-纺粘纤网结构在热粘合辊72和74之间通过以生产复合非织造纤网10，其被收集在辊78上。优选，粘合辊72和74是加热辊，维持在复合材料中最低熔化温度聚合物的正或者负20℃的温度。对于本发明的含聚乙烯复合片材，在115-120℃范围内的粘合温度和在350-700N/cm范围内的粘合压力适于获得优良的热粘合。对于粘合复合片材的层，选择性的方法包括压延机粘合、through-air粘合、蒸汽结合和粘合剂结合。
任选地，含氟化合物涂料可以施加到复合非织造纤网，以降低纤维面的表面能并因此提高织物对于液体渗透的阻力。例如，织物可以用后整理(topical finish)处理进行处理，以改善液体阻隔和尤其是改善对低表面张力液体的阻隔。许多后整理处理方法是本领域众所周知的，并且包括喷涂、辊式涂布、泡沫施加、浸-挤施加等等。典型的整理成分包括ZONYL含氟化合物(可得自DuPont，Wilmington，DE)或者REPEARL含氟化合物(可得自Mitsubishi Int.Corp，New York，NY)。后整理工艺既可以在线地随着织物生产进行，也可以在分离工艺步骤中进行。可选择地，这类含氟化合物也可以作为熔体添加剂纺入纤维。
复合非织造片材优选的基础重量在10到120g/m2范围内和更优选在30到90g/m2范围内和最优选在50到70g/m2范围内。复合非织造片材的抓样抗张强度可以在很大程度上变化，取决于使用的热粘合条件。典型的抓样拉伸片材强度(在纵向和横向两者中)为35到400N和更优选40到300N和最优选50到200N。复合片材的内部熔喷纤维层通常的基础重量在2和40g/m2之间和更优选在5和30g/m2之间和最优选在12和25g/m2之间。复合材料的外层为复合非织造织物提供强度，和某些情况下提供阻隔性。每一外层通常的基础重量在3和50g/m2之间和更优选在8和40g/m2之间和最优选在12和35g/m2之间。优选，复合片材的层通过热粘合固定在一起，例如借助于细纤维层14和/或较粗纤维层12和16中的低熔点组分聚合物的熔化。按照本发明优选的实施方案，复合片材具有的静水压头为至少10cm和更优选至少25cm和更加优选至少45cm和最优选至少60cm。进一步优选的是复合片材具有的水冲击低于5g和更优选低于2g和最优选低于0.5g。最后，优选的是复合片材具有的Frazier透气性高于1m3/min/m2和更优选高于5m3/min/m2。
现在将通过以下实施例说明本发明，其是用来说明本发明的，而不是以任何方式限制本发明。
实施例
在实施例1和对比实施例A中，制备了单组分聚对苯二甲酸乙二醇酯熔喷纤维。这些纤维按照上述方法参考示于图1的设备进行熔喷，其中相同的聚合物被用于双组分熔喷纺丝设备的两侧。
在实施例2和对比实施例B中，制备了单组分聚对苯二甲酸丙二醇酯熔喷纤维。这些纤维按照上述方法参考示于图1的设备进行熔喷，其中相同的聚合物被用于双组分熔喷纺丝设备的两侧。
在实施例3和4和对比实施例C和D中，制备了双组分聚对苯二甲酸乙二醇酯熔喷纤维并引入到纺粘-熔喷-纺粘复合片材。按照上述方法参考图1的设备生产熔喷纤维，其中聚对苯二甲酸乙二醇酯在双组分熔喷纺丝设备的一侧使用和聚乙烯/聚对苯二甲酸丁二醇酯共混物在另一侧使用。这些双组分熔喷纤维的层夹在纺粘外层之间，使复合片材类似于图2中所示的。纺粘层分别使用上述关于示于图5方法的纺粘纤网生产部分80描述的高速熔体纺丝方法各自地生产。然而，代替在一种参考图5描述的连续方法中制备所有层，纺粘层各自分别地纺丝、铺设和卷起。两个纺粘层和熔喷层被随后铺开、合并和热粘合以生产纺粘-熔喷-纺粘复合结构。
实施例1
熔喷单组分纤维用聚对苯二甲酸乙二醇酯制成，其可以Crystar聚酯(Merge 3949)得自DuPont。该聚对苯二甲酸乙二醇酯的特性粘度为0.63dl/g和重均分子量为35,600。聚对苯二甲酸乙二醇酯原样使用，不进行任何调节或者干燥并且水分含量为约1300ppm。该聚对苯二甲酸乙二醇酯聚合物在分离挤出机中被加热到575(300℃)。两种聚合物组分被分别地挤出、过滤和计量到双组分纺丝组合体，合并成单组分纤维。纺丝组合体的模头被加热到600(315℃)。模头具有601个毛细管孔，排列在24英寸(61cm)线中。聚合物通过每个毛细管以0.80g/孔/min的聚合物通过速率被纺丝。拉细空气被加热到615(323℃)的温度并以225标准立方英尺/分(6.4m3/min)的速率通过两个0.8mm宽空气通道提供。两个空气通道沿着毛细管孔的24英寸线的长度，在毛细管组的线的每个侧面有一个通道，距离毛细管孔向后1mm。聚对苯二甲酸乙二醇酯的两个物流以12kg/hr的速率提供给纺丝组合体。长丝收集在运动成形网板上。当聚对苯二甲酸乙二醇酯被熔喷时，发生水解和热降解，其降低分子量，因此降低形成熔喷纤维的聚合物的特性粘度。熔喷纤维中的聚对苯二甲酸乙二醇酯的特性粘度为0.34dl/g和重均分子量为16,500。纤维平均直径报告在表1中。
对比实施例A
熔喷单组分纤维按照实施例1的过程形成，除了将聚对苯二甲酸乙二醇酯在熔喷之前于120℃干燥4小时，其产生约50ppm的较低的水分含量。熔喷纤维中的聚对苯二甲酸乙二醇酯的特性粘度为0.59dl/g和重均分子量为31,000。纤维平均直径报告在表1中。
实施例1具有较高湿含量的未干燥聚对苯二甲酸乙二醇酯在纺丝之后导致与对比实施例A具有较低的水分含量的干燥聚对苯二甲酸乙二醇酯相比较低的重均分子量和较低的特性粘度。在较高的水分含量实施例中存在另外的水，与在较低的水分含量实施例中相比，提供较大的聚合物链断裂。表1显示由实施例1较低IV的聚对苯二甲酸乙二醇酯构成的熔喷纤维，与对比实施例A的常规IV的聚对苯二甲酸乙二醇酯相比，具有较小的纤维平均直径。实施例1纤维的聚对苯二甲酸乙二醇酯的较低的特性粘度和重均分子量，使纤维能够被拉伸到较小的纤维平均直径。
实施例2
按照实施例1的过程形成熔喷单组分纤维，除了聚对苯二甲酸丙二醇酯被用于代替聚对苯二甲酸乙二醇酯。聚对苯二甲酸丙二醇酯树脂的特性粘度为0.70dl/g。将聚对苯二甲酸丙二醇酯于110℃干燥8小时。按照实施例1的方法将该聚合物熔喷，除了将挤出机加热到约518(270℃)和将纺丝组合体模头加热到约518(270℃)。纤维平均直径报告在表1中。
对比例B
按照实施例2的过程形成熔喷单组分纤维，除了该聚对苯二甲酸丙二醇酯树脂具有0.84dl/g的较高的特性粘度。纤维平均直径报告在表1中。
表1显示，用实施例2的较低特性粘度的聚对苯二甲酸丙二醇酯制成的熔喷纤维，与由对比实施例B的较高特性粘度的聚对苯二甲酸丙二醇酯生产的纤维相比，具有较小的纤维平均直径。
表1熔喷纤维性能
实施例       PET           PTT          平均纤维直径
              IV            IV            (微米)
            (dl/g)        (dl/g)
  1          0.34                          3.6
  A          0.59                          4.9
  2                        0.70            2.9
  B                        0.84            5.5
PET＝聚对苯二甲酸乙二醇酯
PTT＝聚对苯二甲酸丙二醇酯
实施例3
熔喷双组分纤网用聚对苯二甲酸乙二醇酯组分和包含聚乙烯/聚对苯二甲酸丁二醇酯共混物的第二组分制成。将该熔喷纤网引入纺粘-熔喷-纺粘复合片材。
在熔喷纤网中，聚对苯二甲酸乙二醇酯组分是Crystar聚酯(Merge 3949)，其可得自DuPont。该聚对苯二甲酸乙二醇酯的特性粘度为0.63dl/g和重均分子量为35,600。聚对苯二甲酸乙二醇酯原样使用，不进行任何调节或者干燥并且水分含量为约1300ppm。聚乙烯/聚对苯二甲酸丁二醇酯双组分共混物包含90％重量的线型低密度聚乙烯，其熔体指数为150g/10min(按照ASTM D-1238测量)，可以ASPUN6831 A得自Dow，和10％重量的聚对苯二甲酸丁二醇酯，其可以Merge1300A得自Hoechst。该双组分聚合物共混物通过在挤出机中于265℃混合聚乙烯和聚对苯二甲酸丁二醇酯制备。在分离的挤出机中，将聚对苯二甲酸乙二醇酯聚合物加热到575(300℃)和聚乙烯/聚对苯二甲酸丁二醇酯双组分聚合物共混物加热到510(265℃)。两种聚合物组分被分别地挤出、过滤和计量到双组分纺丝组合体，设置成提供并列式长丝横截面。纺丝组合体的模头被加热到600(315℃)。模头具有601个毛细管孔，排列在24英寸(61cm)线中。聚合物通过每个毛细管以0.80g/孔/min的聚合物通过速率被纺丝。拉细空气被加热到615(323℃)的温度并以300标准立方英尺/分(8.5m3/min)的速率通过两个0.8mm宽空气通道提供。两个空气通道沿着毛细管孔的24英寸线的长度，在毛细管组的线的每个侧面有一个通道，距离毛细管孔向后1mm。聚对苯二甲酸乙二醇酯以12kg/hr的速率提供给纺丝组合体和聚乙烯/聚对苯二甲酸丁二醇酯以12kg/hr的速率提供给纺丝组合体。双组分熔喷纤网生产成含有50重量百分数的聚对苯二甲酸乙二醇酯和50重量百分数的聚乙烯/聚对苯二甲酸丁二醇酯。长丝被收集在运动成型网板上以生产熔喷纤网。将熔喷纤网收集在辊上。该熔喷纤网的基础重量为17g/m2。
当聚对苯二甲酸乙二醇酯被熔喷时，发生水解和热降解，其降低分子量，因此降低形成熔喷纤维的聚合物的特性粘度。熔喷纤维中的聚对苯二甲酸乙二醇酯的特性粘度为0.34dl/g和重均分子量为16,500。
纺粘外层是具有皮-芯式横截面的双组分纤维。纺粘纤维使用上述关于图4描述的设备生产。生产了具有两种基础重量(17g/m2和24g/m2)的纺粘纤网，用于复合片材的外层。纺粘双组分纤维由以下组分制成：线型低密度聚乙烯，其熔体指数为27g/10min(按照ASTM D-1238测量)，可以ASPUN 6811 A得自Dow，和聚对苯二甲酸乙二醇酯聚酯，其特性粘度为0.63dl/g和重均分子量为大约35,600，可以Crystar聚酯(Merge 3949)得自DuPont。该聚酯树脂在使用以前在180℃温度下结晶和在120℃温度下干燥到水分含量低于50ppm。
在分离的挤出机中将用于纺粘层的聚对苯二甲酸乙二醇酯加热到290℃和聚乙烯加热到280℃。将聚合物挤出、过滤和计量到双组分纺丝组合体，其维持在295℃和设计成能提供皮-芯式长丝横截面。将聚合物通过喷丝头纺丝以生产双组分长丝，其具有聚乙烯皮和聚对苯二甲酸乙二醇酯芯。对于17g/m2基础重量纤网，每纺丝组合体毛细管的总聚合物通过量是1.0g/min，和对于24g/m2纤网为1.0g/min。将聚合物计量以提供基于纤维量包含30％聚乙烯(皮)和70％聚酯(芯)的长丝纤维。利用真空抽吸，将得到的较小、较强的实质上连续的长丝沉积在沉积皮带上。在两个纤网(17g/m2和24g/m2基础重量)中的纤维的有效直径在9到12微米范围内。得到的纤网分别地通过两个热粘合辊，以轻轻地将纤网粘合在一起，用于输送，其中使用点粘结图案，在100℃温度和100N/cm轧点压力下进行。粘合期间的线速度，对于17g/m2基础重量纤网是206m/min，对于24g/m2基础重量纤网是146m/min。轻轻粘合的纺粘纤网各自收集在辊上。
通过将17g/m2基础重量纺粘纤网在运送带上铺开制备复合材料非织造片材。将熔喷双组分纤网铺开和铺设在运动的纺粘纤网之上。将第二卷24g/m2基础重量的纺粘纤网铺开和铺设在纺粘-熔喷纤网之上，以生产纺粘-熔喷-纺粘复合非织造纤网。将复合纤网在刻花油加热金属砑光辊和平滑油加热金属砑光辊之间热粘合。两个辊的直径为466mm。刻花辊具有铬涂覆的非硬化钢面，具有菱形图案，点尺寸为0.466mm2，点深度为0.86mm，点间隔为1.2mm和粘结面积为14.6％。平滑辊具有硬化钢表面。复合纤网在110℃温度、350N/cm轧点压力和20m/min线速度下被粘合。将粘合复合片材收集在辊上。该复合非织造片材的最终的基础重量为58g/m2。片材的物理性能报告在表2中。
对比实施例C
复合片材按照实施例3的过程形成，除了将聚对苯二甲酸乙二醇酯在熔喷之前于120℃干燥4小时，其产生约50ppm的较低的水分含量。熔喷纤维中的聚对苯二甲酸乙二醇酯聚合物的特性粘度为0.59dl/g和重均分子量为31,000。复合片材的物理性能报告在表2中。
表2显示，用实施例3的较低粘度的聚对苯二甲酸乙二醇酯构成的熔喷纤维制成的复合片材，与对比实施例C的复合片材相比，具有提高的静水压头。
实施例4
复合片材按照实施例3的过程形成，除了在熔喷工艺期间气流速率为310标准立方英尺/分(8.8m3/min)，代替300标准立方英尺/分(8.5m3/min)的气流速率。片材的物理性能报告在表2中。
对比实施例D
复合片材按照对比实施例C的过程形成，除了在熔喷工艺期间气流速率为500标准立方英尺/分(14.1m3/min)，代替300标准立方英尺/分(8.5m3/min)的气流速率。片材的物理性能报告在表2中。
表2显示，用实施例4的较低粘度的聚对苯二甲酸乙二醇酯构成的熔喷纤维制成的复合片材，与对比实施例D的复合片材相比，具有提高的静水压头。
表2
非织造纤网性能
 实施例      熔喷PET IV(dl/g)      熔喷PET Mw   静水压头(cm)  Frazier+(m3/min/m2)    抓样强度MD(N)  抓样强度XD(N)
    3     0.34     16,500     77     27     143.4     77.5
    C     0.59     31,000     40     65     139.8     86.0
    4     0.34     16,500     83     28     140.2     81.5
    D     0.59     31,000     58     39     147.8     77.5
PET＝聚对苯二甲酸乙二醇酯
IV＝特性粘度
Mw＝重均分子量
MD＝纵向
XD＝横向
+Frazier透气性

Claims (20)

1.一种熔喷纤维，其包含至少20％重量的聚酯，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯。
2.权利要求1的熔喷纤维，其中该纤维的平均有效直径低于10微米，和其中聚对苯二甲酸乙二醇酯的特性粘度在0.20到0.50dl/g范围之内和聚对苯二甲酸丙二醇酯的特性粘度在0.45到0.75dl/g范围之内。
3.权利要求2的熔喷纤维，其中聚对苯二甲酸乙二醇酯的特性粘度在0.25到0.45dl/g范围之内和聚对苯二甲酸丙二醇酯的特性粘度在0.50到0.70dl/g范围之内。
4.权利要求1的熔喷纤维，其中所述纤维是多组分纤维，其由20％和98％重量之间的聚对苯二甲酸乙二醇酯和80％和2％重量之间的第二聚合物组分组成。
5.权利要求4的熔喷纤维，其中所述第二聚合物组分包含至少10％的聚乙烯聚合物。
6.一种熔喷纤维纤网，所述纤网由至少20％重量的聚酯组成，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯。
7.权利要求6的纤网，其中该纤网的纤维的平均有效直径低于10微米，和其中聚对苯二甲酸乙二醇酯的特性粘度在0.20到0.50dl/g范围之内和聚对苯二甲酸丙二醇酯的特性粘度在0.45到0.75dl/g范围之内。
8.权利要求7的纤网，其中聚对苯二甲酸乙二醇酯的特性粘度在0.25到0.45dl/g范围之内和聚对苯二甲酸丙二醇酯的特性粘度在0.50到0.70dl/g范围之内。
9.权利要求6的纤网，其中该纤网由多组分纤维组成和该纤网由20％和98％重量之间的聚对苯二甲酸乙二醇酯和80％和2％重量之间的第二聚合物组分组成。
10.权利要求9的纤网，其中所述第二聚合物组分包含至少10％重量的聚乙烯聚合物。
11.一种复合片材，其包括：
第一纤维层，其具有第一侧和相反的第二侧；
第二纤维层，其粘合到所述第一纤维层的所述第一侧；
所述第一纤维层是熔喷纤网，其由至少20％重量的聚酯组成，该聚酯选自特性粘度低于0.55dl/g的聚对苯二甲酸乙二醇酯和特性粘度低于0.80dl/g的聚对苯二甲酸丙二醇酯；
所述第二纤维层由至少95％重量的熔纺纤维组成；
所述复合片材的基础重量低于120g/m2和静水压头为至少10cm。
12.权利要求11的复合片材，其中
在所述第一纤维层中的熔喷纤维的至少10％是具有长度的多组分纤维，
所述多组分纤维具有第一和第二聚合物组分，其排列方式使得所述第一和第二聚合物组分各自实质上沿着所述双组分纤维的整个长度延伸。
13.权利要求12的复合片材，其中所述双组分熔喷纤维的所述第一和第二聚合物组分以并列方式排列。
14.权利要求12的复合片材，其中
所述第一聚合物组分构成20％和98％重量之间的所述第一纤维层和所述第二聚合物组分构成80％和2％之间的所述第一纤维层，和
所述第一纤维层的所述第二聚合物组分基本上由聚乙烯组成。
15.权利要求14的复合片材，其中所述第二纤维层的熔纺纤维是多组分纤维，其具有聚酯组分和聚乙烯组分，其中该聚酯组分构成至少10％重量的所述第二纤维层和该聚乙烯组分构成至少10％重量的所述第二纤维层。
16.由权利要求11的复合片材组成的衣服。
17.一种熔喷纤维，其包括至少20％重量的聚酯，该聚酯的重均分子量低于25,000。
18.权利要求17的熔喷纤维，其中所述聚酯的重均分子量在5,000到22,000范围内。
19.权利要求18的熔喷纤维，其中所述聚酯的重均分子量在10,000到19,000范围内。
20.权利要求17的熔喷纤维，其中所述聚酯是聚对苯二甲酸乙二醇酯。
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CN1312337C (zh) * 2003-12-21 2007-04-25 浙江恒逸集团有限公司 对苯二甲酸乙二醇酯和对苯二甲酸丙二醇酯共混纺丝及其生产方法
CN100334272C (zh) * 2004-05-13 2007-08-29 株式会社晓星 复合纤维及其制造方法
CN112236551A (zh) * 2018-06-08 2021-01-15 奥升德功能材料运营有限公司 可调纳米纤维非织造布产品
CN112940231A (zh) * 2019-12-10 2021-06-11 长春人造树脂厂股份有限公司 一种聚酯、树脂组合物、熔喷纤维、复合熔喷纤维、复合薄片、滤网和隔音材料
CN112940231B (zh) * 2019-12-10 2023-08-18 长春人造树脂厂股份有限公司 一种聚酯、树脂组合物、熔喷纤维、复合熔喷纤维、复合薄片、滤网和隔音材料
CN114603949A (zh) * 2020-12-09 2022-06-10 财团法人纺织产业综合研究所 透气防水织物

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KR100746466B1 (ko) 2007-08-03
JP2004501287A (ja) 2004-01-15
DE60135213D1 (de) 2008-09-18
EP1280947B1 (en) 2008-08-06
US20020025748A1 (en) 2002-02-28
AU2001259720A1 (en) 2001-11-20
CA2404698A1 (en) 2001-11-15
US6797655B2 (en) 2004-09-28
EP1280947A1 (en) 2003-02-05
CN1190535C (zh) 2005-02-23
KR20030023625A (ko) 2003-03-19

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