CN110114209A - 多层复合材料及制造方法 - Google Patents

多层复合材料及制造方法 Download PDF

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Publication number
CN110114209A
CN110114209A CN201780081033.5A CN201780081033A CN110114209A CN 110114209 A CN110114209 A CN 110114209A CN 201780081033 A CN201780081033 A CN 201780081033A CN 110114209 A CN110114209 A CN 110114209A
Authority
CN
China
Prior art keywords
single layer
fiber
multilayer materials
layer
leather
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201780081033.5A
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English (en)
Inventor
卫斯理·爱德华·哈彻
克里斯托弗·迈克尔·亚当斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dsm Protective Materials Co ltd
Original Assignee
DSM IP Assets BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Priority claimed from PCT/EP2017/084211 external-priority patent/WO2018122120A1/en
Publication of CN110114209A publication Critical patent/CN110114209A/zh
Pending legal-status Critical Current

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Classifications

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    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract

本发明涉及多层复合材料，其包含与至少一个单层接触的皮革层，所述单层包含平行排列的纤维和基质材料。所述复合材料还可包含膜层(一个或多个)，所述膜层可以是可透气和/或防水的。多层复合材料适用于衣服和户外装备和服装。

Description

多层复合材料及制造方法
本发明一般性地涉及可用作防弹毯的多层复合材料，尤其涉及包含与单层人造纤维接触的皮革层的多层复合材料，及其制造方法。
防弹毯是世界各地执法部门和军队中使用的防弹装备的部件。除其他应用外，防弹毯尤其可用作炸弹爆炸保护的覆盖物。例如，Carter等人在美国专利No.7,389,718中已经公开了防弹毯。该文献公开了一种防弹毯，其包括封装在外壳中的内部防弹芯。内部防弹芯覆盖有内部覆盖物。内部防弹芯可以基于高性能纤维，例如芳族聚酰胺或超高分子量聚乙烯(“UHMWPE”)。Carter进一步公开了使用芳族聚酰胺板作为内部防弹芯的用途，并且内部覆盖物可以由尼龙制成。此外，Carter教导外壳可以由织物、乙烯基树脂、皮革或其他柔软材料制成。
尽管该文献公开了具有可接受性能的产品，但仍然存在不断地推动开发进一步改进的多层复合材料产品(例如防弹毯)的动力。
在本公开的各种实施方式中，描述了多层复合材料，其在强度重量比、减小的厚度和额外的美观方面具有进一步的改进。
一般而言，本发明提供了一种多层复合材料，其包含：皮革层；以及与该皮革层接触的单层。单层可以包含与基质材料一起在单纤维方向上排列的平行的纤维。单层也可称为单向层。在一些方面，多层复合材料可包含一个或多个粘合(bonded)在其上的额外单层，形成多个层的层叠物，其中皮革层是其中的一个外层。每个连续的单层可以相对于相邻单层偏移(offset)高达90°，使得一个单层中的平行的纤维相对于相邻层中的平行的纤维处于不同的方向。以这种方式，可以使用许多单层并且纤维方向可以永远不会重复，或者几个单层可以彼此偏移，直到在某点处层中的纤维方向与层叠物中进一步较低的单层重复。
每个连续单层可包含在基质材料中的平行的纤维。每个单层的基质材料可以具有不同的组成或者相同的组成。在各种实施方式中，包含皮革层和一个或多个单层的多层复合材料还可包含至少一个聚合物膜，该聚合物膜与任意一个单层接触，以形成复合材料的外层。以这种方式，单层的层叠物可以包括复合材料的芯，该复合材料具有皮革层和作为两个暴露的外层的膜层。在各种示例中，一个或多个膜层可以是防水/可透气的膜，或者防水和不可透气的膜，或者可湿气通过的和可蒸汽通过的(moisture passive and vaporpassive)任何组合。
在各种实施方式中，在该一个或多个单层中所使用的纤维可以具有至少0.5GPa的强度。在其他示例中，纤维可以具有至少2.5GPa的强度。纤维可包含UHMWPE或一些其他合成纤维。例如，纤维可包含特性粘度为至少4dl/g的UHMWPE纤维。
在多层复合材料内该一个或多个单层的每个单层可包含基质材料，例如其中纤维是被涂布的或嵌入的。基质材料的示例包括聚丙烯酸酯、用丙烯酸酯基团官能化的聚合物、和聚氨酯。基质材料可以具有至少3MPa的刚度。
在任意一个单层中的纤维密度可以是1至50克/平方米(g/m2或“gsm”)。
本公开还提供一种制造多层复合材料的方法，其包括：提供包含皮革层、至少一个单层和可选地至少一个聚合物膜层的组件，所述单层包含基质材料和平行排列的纤维，所述组件具有两个外表面，其中一个外表面是皮革层；并且，在1至5bar的压力和35至120℃的温度下压缩该组件。在压缩期间，覆盖物C可以布置于一个或两个外层上，并且覆盖物可以是在压缩步骤后能够与多层复合材料移除的。这样的覆盖物可以具有纹理，因此覆盖物上的图案或纹理可以压印在复合材料的任意一个外层或两个外层上。
本文中所描述的多层复合材料可用于制造鞋类、运动装备、衣服、行李箱、动物皮革制品、箱包、帽子、夹克、钱包、手提包、袋、家具装饰品和手套。
图1以横截面的方式描绘了根据本公开的多层复合材料(M)的一个实施方式，其包含：(10)皮革层；(20)第一单层；(30)可选的第二单层；(40)可选的第三单层；(90)可选的第n(4<n<8)单层；以及(100)膜层。
根据本发明的多层复合材料包含与第一单层(20)接触的皮革层(10)，该单层包含基质材料和平行排列的纤维。在本领域中，包含基质材料和平行排列的纤维的这种单层也被称为单向层。例如，本文中的单层可包含嵌入在基质材料中的平行的纤维。
在本发明的上下文中，“皮革”是指来自各种动物来源(通常称为天然来源)的天然皮革。在本发明的另一个实施方式中，本发明的多层复合材料包含人造皮革或仿制皮革，而不是天然皮革。用于本文中的多层复合材料中的皮革可以来源于动物生皮，通常来自牛，但也可以来自爬行动物、鸟类或其他动物。常用的皮革类型来自奶牛(cow)、小牛(calf)、绵羊和水牛。更多的奇异皮革可以有鱼类来源，例如鲑鱼或鳗鱼皮，或者可以来自例如蛇、鳄鱼(crocodile)、钝吻鳄(alligator)、袋鼠、鸡或大象。天然皮革包括粒面皮革，包括全粒面革、头层粒面革(top grain)和正绒面革(经过砂磨或抛光的头层粒面牛皮革)，和真皮皮革(corium leather)，包括绒面革(suede)，以及(成品)剖层革。皮革可以进行处理，例如鞣制、着色、调理、打蜡、砂磨、抛光、工装(tooling)或压花。在本发明的一个优选实施方式中，在形成本发明的多层复合材料之后或期间对皮革进行压花。皮革可以经由苯胺、半苯胺或着色技术来着色，并且可以包括面漆，例如蜡涂饰剂或抛光剂。
本文中使用的皮革层可以具有任意厚度。在各种实施方式中，典型的厚度范围在0.5-6mm之间。优选地，皮革的厚度范围为0.7-4mm，更优选0.7-2.8mm。
根据本发明的优选的多层复合材料包含小牛皮作为皮革层，并且优选地小牛皮的厚度为0.7-2.4mm，更优选0.7-1.6mm。已发现这些厚度范围提供最柔软的多层复合材料。
本领域技术人员将理解，本发明还可以应用于包含皮革替代品和人造皮革或仿制皮革的多层复合材料中，例如由海带、树皮或树皮布制成的所谓的海洋皮革，通常来自栓皮栎的软木革，基于天然纤维的替代品，例如来源于竹子和菠萝等多种来源的纤维素纤维，基于蘑菇的材料，例如MuSkin，以及轧光棉。在各种示例中，在这些替代皮革中可以包含再循环物质。
人造皮革包括例如聚氨酯、乙烯基树脂和丙烯酸基人造皮革，以及它们的组合。此外，本文中可使用人造革和聚酯基皮革替代品，例如再生聚酯(PET)、可降解聚氨酯，和
与原始(人造)皮革材料相比，根据本发明的复合材料的优点是一致性增加，因而产品更好地保持其原始形状和尺寸并且不易于下垂。此外，它们更耐用，这意味着如果它们在边缘上施加多次(至少1000次)以诸如5毫米或更小的低弯曲半径，它们不易于裂开或撕裂。当复合片材通过例如缝合组合在一起时，撕裂也是重要的。当缝合部件处于撕裂力下时，大部分力将集中在缝合部件上，尤其是缝合纤维和缝合的孔上。在那种情况下，可能会发生孔撕裂或孔周围撕裂。较好的抗撕裂性能使最终产品更耐用，特别是在负载下更耐用。
本发明的一个特别优选的实施方式涉及一种基于纸材而非皮革的复合材料。这种纸可能是皮革纸(也称为羊皮纸)，也可以是打印纸、书写纸、绘图纸、相纸、手工纸和卡片。纸的厚度通常表示为每单位表面积的重量，在60g/m2至200g/m2之间(在23℃/50％RH的环境条件下调理24小时后，在这些条件下测定)，优选地在70g/m2至160g/m2之间，更优选地在80g/m2至120g/m2之间。
纸的特殊实施方式涉及钞票纸。这些通常包括棉/亚麻基，但也可以由聚合物制成，例如由下文公开内容中提到的聚合物膜。在本公开的各种实施方式中，本文的多层复合材料包括钞票。具有本文的多层复合材料结构的钞票比普通钞票更具抗撕裂性，同时具有可辨识的手感。
本发明的另一个优选实施方式涉及基于棉、羊毛或亚麻层而非皮革的复合材料。棉、羊毛或亚麻层可以是编织结构。在各种实施方式中，用于绘画的画布基于这样的复合材料。即使在50年或更长时间之后，这种画布上的漆料的油漆也不会随着时间的推移而开裂。
多层复合材料中的皮革层可任选地在其暴露侧(即与第一单层相对的一侧)上覆盖有膜层，如下文所进一步说明。膜层的替代品可以是涂层或其替代品，例如通过真空沉积涂覆的材料。在整个外皮革层上的膜层可用于赋予复合材料特殊的视觉外观，并用于保护皮革，例如保护皮革抵抗恶劣的户外条件(例如海盐)或沾污。
根据本发明的多层复合材料包含第一单层，该第一单层包含基质材料和平行排列的纤维。
单层可以通过如下方式获得：在一个平面中以平行方式定向多个纤维，例如通过在梳子上从纤维筒管架中拉出许多纤维或纱线，并且在定向之前、期间或之后以本领域技术人员已知的方式用基质材料浸渍纤维。在该方法中，所提供的纤维可以具有至少一种除塑料基质材料之外的组分或聚合物的涂饰剂，以便例如在处理过程中保护纤维或者以便获得纤维在单层的塑料上的更好的粘附性。优选地，使用不具有涂饰剂的纤维。在涂饰之前或者纤维与基质材料接触之前，纤维可以已经被表面处理过。这种处理可以包括用化学试剂处理，例如氧化剂或蚀刻剂，但优选地包括等离子体处理或电晕处理。
在一个单层中纤维的量通常为1至50克/平方米。纤维的量也可以称为层的纤维密度。优选地，一个单层中的纤维量为2至30克/平方米，更优选地3至20克/平方米。已经发现，在这些范围内的纤维密度有助于保持根据本发明的多层复合材料的柔韧性。
在单层中使用的基质材料优选地包含热塑性材料。特别合适的是那些在涂覆前能够分散在水中的基质材料。合适的聚合物材料的实例包括但不限于聚丙烯酸酯、聚氨酯、改性聚烯烃和乙烯共聚物，包括SEBS和SIS聚合物(例如防弹制品领域中已知的)和乙烯-乙酸乙烯酯。
优选地，基质材料包含一种聚氨酯。例如，聚氨酯可包含基于聚醚二醇的聚醚-氨基甲酸酯，其在宽温度范围内提供良好性能。在另一个实例中，聚氨酯可包含基于聚醚二醇的聚酯-氨基甲酸酯，其在宽温度范围内提供良好性能。
在一个特定的实施方式中，聚氨酯或聚醚-氨基甲酸酯基于脂族二异氰酸酯，因为这进一步改善了产品性能，包括其颜色稳定性。此外，改善了形状相干性，从而最终产品更好地保持其原始形状。用于单层的这些基质材料的100％模量优选地为至少3MPa。更优选地，100％模量为至少5MPa。100％模量通常低于500MPa。
在另一个优选的实施方式中，特别是在复合材料的柔软性最具重要性的情况下，优选地使用100％模量为至多2MPa的的基质材料。更优选100％模量为至多1.5MPa，最优选100％模量为至多1.0MPa。合适的基质材料可以是其可适当地由水分散体施加。
在另外一个优选的实施方式中，基质材料可包含丙烯酸基树脂或者包含丙烯酸酯基团的聚合物。
另外一种类型的基质材料包含乙烯和/或丙烯的均聚物或共聚物，其中聚合物树脂具有根据ISO1183测量的在860至930kg/m3范围内的密度，在40°至140℃范围内的峰值熔融温度，以及至少5J/g的熔化热。
具有单向纤维的单层和基质体系的进一步细节可以在例如美国专利No.5,470,632中找到，该专利全文通过引用并入本文。
在一个单层中基质材料的量通常为10至95wt％；优选地20至90wt％，更优选地30至85wt％，且更优选地35至80wt％。这确保了皮革和/或单层(一个或多个)以及其它组分之间足够的粘合强度，从而减少了在重复弯曲循环后复合材料中过早分层的可能性。
在第二单层和随后的单层中的基质材料可以与第一单层中的基质材料相同，但也可以不同。在各种实施方式中，多层复合材料包含第一单层和第二单层，第一单层包含在第一基质材料中的平行的纤维，第二单层包含在第二基质材料中的平行的纤维。
本文中使用时，术语“纤维”是指不仅包括单丝，而且还包括复丝纱线或带。
带可以通过各种已知技术制造，包括固态聚合物加工、凝胶技术和纤维熔接。带的宽度与厚度之比为至少5，优选至少10，更优选至少100，最优选至少1000。
用于在根据本发明的多层复合材料中的合适的纤维可以是碳纤维。
用于根据本发明的多层复合材料中的尤其合适的纤维包括，例如基于聚酰胺的纤维，包括聚酰胺6和聚酰胺6.6；和聚酯，包括聚对苯二甲酸乙二醇酯；聚丙烯和聚乙烯。此外，优选的纤维包括芳族聚酰胺纤维(通常也称为芳纶纤维)，尤其是聚(对苯二甲酰对苯二胺)；液晶聚合物和梯状聚合物纤维，诸如聚苯并咪唑类或聚苯并恶唑类，例如聚(1,4-苯撑-2,6-苯并二恶唑)(PBO)，或聚(2,6-二咪唑[4,5-b-4',5'-e]亚吡啶基-1,4-(2,5-二羟基)苯撑)(PIPD；也称为M5)；聚芳醚酮，包括聚醚醚酮，和高度取向的例如聚烯烃、聚乙烯醇和聚丙烯腈的纤维，诸如例如通过凝胶纺丝工艺获得的那些。优选地使用高度取向的聚烯烃纤维、芳纶纤维、PBO纤维和PIPD纤维或其中至少两种纤维的组合。高度取向的聚烯烃纤维包括聚丙烯和聚乙烯纤维，并且具有至少1.5GPa的拉伸强度。
尤其优选的是高性能聚乙烯纤维，也被称为高度拉伸或取向的聚乙烯纤维，其由聚乙烯长丝组成，所述聚乙烯长丝通过凝胶纺丝工艺制备，例如在GB 2042414A或WO 01/73173中所述。这些纤维的优点在于它们具有非常高的拉伸强度和轻的重量，因此它们特别适用于极薄的层。优选地，使用具有至少5dl/g的特性粘度的超高摩尔质量聚乙烯的复丝纱线，更优选地，这些聚乙烯纱线具有至少8dl/g的特性粘度。这种特性粘度值的优点涉及根据本发明的复合材料的更高的撕裂强度，特别是在涉及通过缝合制成的复合材料(例如接缝)的缝合和连接时更是如此。
这些纤维或纱线的单根长丝的纤度通常小于10旦尼尔，优选地小于5旦尼尔，更优选地小于3旦尼尔，甚至更优选地这些纤维的单根长丝的纤度小于2旦尼尔。这导致本发明的多层复合材料具有更好的悬垂性。
在本发明的多层复合材料中的纤维通常具有至少0.5GPa、优选地至少0.6GPa、更优选地至少0.8GPa的拉伸强度。在一个优选的实施方式中，纤维、优选地聚乙烯纤维的强度是至少3.0GPa，优选地至少3.5GPa，更优选地至少4.0GPa且最优选地至少4.5GPa。出于经济原因，纤维的强度优选地小于5.5GPa。纤维的拉伸强度优选地为3.1至4.9GPa，更优选地为3.2至4.7GPa，且最优选为3.3至4.5GPa。
在第二单层和随后的单层中的纤维可以与第一单层中的纤维相同，但在每个单层中的纤维也可以不同。
一个替代性的实施方式涉及层内混杂，其中在一个单层和相同单层中使用至少2种上文提到的纤维。
参考图1，根据本发明的多层复合材料还可包含第二单层(30)，其包括平行排列的纤维和与第一单层(20)接触的基质材料。在具有两个这样的具有平行纤维的单层的多层复合材料中，第二单层(30)中的纤维方向可以相对于(相邻的)第一单层(20)中的纤维方向旋转或“偏移”，例如大于0°且至多90°的最小角度。
为了进一步微调多层复合材料的性质，可以决定添加第三单层(40)和随后的单层，直至n个单层，与相邻单层接触并相对于相邻单层旋转以偏移纤维方向。在各种实施方式中，单层的总数n可以为约4至约8，(4<n<8)。根据应用，可以选择n的值以适合特定的应用或最终用途。在根据本发明的多层复合材料中，每个单层可以相对于先前的单层旋转。
除单层之外，多层复合材料还可包含平纹棉麻(scrim)层。平纹棉麻层是非常轻的纺织品，其具有优选地层压到多层复合材料中的纤维的稀松编织物，其可提供额外的稳定性。
本发明的另一个优选实施方式包括多层复合材料，其包含第一皮革层的第一外层；与包含基质材料和平行排列的纤维的第一单层接触，至少一个随后的单层相对于第一单层和第二皮革外层旋转。这样产生了一种外部全皮革的产品，同时仍然保持受益于所存在的复合材料的特性。
本发明的一个优选的实施方式包括多层复合材料，其包含皮革层；与包含基质材料和平行排列的纤维的第一单层接触，以及3个随后的单层，至少一个单层具有小于20克/平方米的纤维。优选地，至少两个单层具有小于20克/平方米的纤维。可选地，这种多层复合材料在与皮革层相对的外侧具有纤维。相邻单层中的纤维方向以大于0°且至多90°的最小角度旋转。
继续参考图1，根据本发明的多层复合材料还可包含聚合物膜(100)。优选地，这种聚合物膜被设置成在与皮革层相对的一侧上与最外面的单层接触。以这种方式，皮革层和膜层形成根据本发明的多层复合材料的外层。
所使用的膜可以包含例如聚烯烃膜，包括可在商标下获得的线性低密度聚乙烯，聚丙烯膜和聚酯膜。
在一个优选的实施方式中，膜是双轴拉伸聚烯烃薄膜。其实例是双轴拉伸的高密度聚乙烯和双轴拉伸的聚丙烯膜。
用于根据本发明的多层复合材料的另一种类型的膜是金属箔或金属涂覆的膜、织物或非织造物。
在另一个优选的实施方式中，聚合物膜是防水/可透气(W/B)膜。W/B膜用作阻挡层，其允许气体(包括水蒸气)穿过材料而不允许液态水的穿过。这种膜包括品牌为和的ECTFE和EPTFE，脂肪族聚氨酯，芳香族聚氨酯，聚酰胺，聚酯，PVF，PEN，特别设计有UHMWPE薄膜(例如薄膜)和微孔聚丙烯薄膜。
本发明中的W/B膜的一个特定实施方式可以是织造织物的形式，这种织物可以涂布或(部分地)浸渍有基质材料，以使其具有W/B性质。
本发明中的W/B膜的另一个特定实施方式可以具有非织造织物的形式，这种织物可以涂布或(部分地)浸渍有基质材料，以使其具有W/B性质。非织造织物的一个典型例子包括毡。
这些膜的厚度通常为1至50微米，并且优选地2至25微米。
这种(W/B)聚合物膜的优点是其可以防止皮革在该表面上被沾污并增加皮革、单丝和基质层本来不具有的阻隔性能。另外，膜可以添加触感更柔软的纹理或增加耐磨性。
根据本发明的多层复合材料可以适宜地通过以下步骤制得：将所要求的皮革层和单层和所提到的可选的层进行层叠，并在1.05至5bar的绝对压力、优选地1.1至4bar的绝对压力、更优选地1.2至3bar的绝对压力下将这些层进行压缩。在这些条件下的压缩是在静态压机(包括高压釜)中完成的。优选地，连续压机以压延机或连续带式压机的形式使用。压缩期间的温度优选地为35℃至120℃。更优选地，压制期间的温度为40至100℃，且最优选压制期间的温度为45至90℃。这使得复合材料具有更好的挠曲性能，并且在反复挠曲后不易发生表面开裂。或者，复合材料在加工过程中不易发生表面劣化。例如，当将根据本发明的复合材料的片缝合在一起时，缝合期间的穿孔很少受到劣化或变形的影响，这意味着它们更窄更清晰，穿孔没有增大或破裂或裂开。这对性能产品非常有益，例如当视觉外观很重要时。
压力和温度处理的时间根据预期的最终用途而变化，并且可以通过简单的试验和错误实验来优化。典型的压缩时间在30秒到30分钟之间变化。
在制造多层复合材料的方法的一个特定形式中，复合材料的两个外表面中的至少一个在压力和温度处理期间与优选地可移除的覆盖物接触。覆盖物可以是玻璃纤维增强的PTFE片材，或者可以是钢带在诸如连续带式压机中，可选地具有离型层，例如以硅化纸的形式的离型层。这种可移除的覆盖物的一种替代形式包括基于橡胶的柔软材料。根据ISO7619的硬度计测试，橡胶的肖氏A值小于95，更优选小于80，优选至少50。在该方法的甚至更优选的版本中，多层复合材料夹在2个这样的覆盖物之间。
制造多层复合材料的方法可包括放置皮革层与可移除的覆盖物接触，可移除的覆盖物具有根据用于在压力和温度处理中在其制造期间对多层复合材料的皮革表面层进行压花或纹理化的预设设计的图案。对于根据本发明的复合材料的两个外层，也可以进行压花。该方法产生了根据本发明的进一步改进的多层复合材料，由于其纹理化表面，其可以用于各种应用领域中。
在压力和温度处理以获得根据本发明的多层复合材料之后，可以对材料进行进一步后处理，以进一步改善其柔韧性，例如通过在多个方向上使复合材料挠曲来实现。这种挠曲可以适当地通过在短半径上弯曲来完成。
根据本发明的多层复合材料以及根据本发明的纹理化的多层复合材料可以适宜地用于制造鞋类、运动装备、衣服、行李箱；动物皮革制品，包括皮带、鞭子、鞍，袋和行李箱。此外，用于制造帽子/夹克、钱包、手提包、袋、家具装饰品、手套，包括工作服手套和运动手套，如棒球手套、航海手套等。
测试方法
下文是本文中提及的测试方法：
UHMWPE的特性粘度(IV)是根据ASTM D1601在135℃下在萘烷中通过将不同浓度下测定的粘度外推至零浓度来测定的，溶解时间为16小时，采用以2g/l溶液的量的DBPC作为抗氧化剂。
拉伸性能(在25℃下测定)：拉伸强度(或强度)、拉伸模量(或模量)和断裂伸长率是按照ASTM D885M中的规定使用名义标定长度为500mm的纤维、50％/min的十字头速度在复丝纱线上确定和定义的。在测量的应力-应变曲线的基础上，由0.3-1％应变之间的斜率来确定模量。为了计算模量和强度，将所测量的拉伸力除以纤度，该纤度通过称重10米长的纤维来确定；假设密度为0.97g/cm3来计算单位为GPa的值。薄膜的拉伸性能根据ISO 1184(H)测量。
基质材料的模量根据ISO 527来测定。100％模量是在100mm长(夹具之间的自由长度)和24mm宽的膜条上测定的。100％模量是0％和100％的应变之间的正割模量。
熔化热和峰值熔融温度分别根据标准DSC方法ASTM E 794和ASTM E 793以对第二加热曲线来说10K/min的加热速率测量，并在氮气下在脱水样品上进行。

Claims (15)

1.多层复合材料(M)，其包含与第一单层(20)接触的皮革层(10)，所述第一单层(20)包含第一基质材料和在第一纤维方向上排列的平行的UHMWPE纤维。
2.如权利要求1所述的多层复合材料，其还包含与所述第一单层(20)接触的第二单层(30)，所述第二单层(30)包含第二基质材料和在第二纤维方向上排列的平行的纤维，其中在所述复合材料中所述第一单层(20)相对于所述第二单层(30)旋转，使得所述第二纤维方向相对于所述第一纤维方向偏移至多90度。
3.如权利要求2所述的多层复合材料，其包含平行的纤维的额外单层，每个单层包含基质和平行的纤维，所述单层层叠并排布在所述多层复合材料中，使得所述额外单层中的一个单层与所述第二单层接触，并且其中每个连续的单层相对于相邻单层旋转，使得纤维方向在每个连续层中偏移。
4.如权利要求1、2或3所述的多层复合材料，其还包含与单层接触的聚合物膜(100)，以形成所述复合材料的外层。
5.如权利要求4所述的多层复合材料，其中所述膜是防水/可透气的。
6.如前面权利要求中任一项所述的多层复合材料，其中所述纤维的强度是至少0.5GPa。
7.如前面权利要求中任一项所述的多层复合材料，其中所述纤维的强度是至少2.5GPa。
8.如前面权利要求中任一项所述的多层复合材料，其中所述纤维是特性粘度为至少5dl/g的UHMWPE纤维。
9.如前面权利要求中任一项所述的多层复合材料，其中至少一个基质材料具有至多2MPa的刚度。
10.如权利要求9所述的多层复合材料，其中至少一个基质材料包含聚丙烯酸酯、用丙烯酸酯基团官能化的聚合物、和聚氨酯中的至少一种。
11.如前面权利要求中任一项所述的多层复合材料，其中任何一个单层中的纤维密度为1至50克/平方米。
12.制造多层复合材料的方法，其包括：提供包含皮革层、至少一个单层和可选地至少一个聚合物膜层的组件，所述单层包含基质材料和平行排列的纤维，所述组件具有两个外表面，其中一个外表面是所述皮革层；并且在1至5bar的压力和35至120℃的温度下压缩所述组件。
13.如权利要求12所述的方法，其中在压缩期间，至少一个所述外表面与覆盖物C接触。
14.如权利要求13所述的方法，其中所述覆盖物C具有预定的表面纹理或波纹，并且所述覆盖物C在压缩过程中至少与所述皮革层接触。
15.如权利要求1-11中任一项所述的多层复合材料在以下应用中的用途：制造鞋类、运动装备、衣服、行李箱、动物皮革制品、箱包、帽子、夹克、钱包、手提包、袋、家具装饰品和手套。
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