CN102802922A - 具有聚合物无纺织物的多轴无屈曲织物 - Google Patents

具有聚合物无纺织物的多轴无屈曲织物 Download PDF

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Publication number
CN102802922A
CN102802922A CN2011800144638A CN201180014463A CN102802922A CN 102802922 A CN102802922 A CN 102802922A CN 2011800144638 A CN2011800144638 A CN 2011800144638A CN 201180014463 A CN201180014463 A CN 201180014463A CN 102802922 A CN102802922 A CN 102802922A
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China
Prior art keywords
fabric
flexing
yarn
layer
polymers compositions
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Granted
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CN2011800144638A
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CN102802922B (zh
Inventor
R·沃卡茨
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Teijin Carbon Europe GmbH
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Toho Tenax Europe GmbH
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    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
    • D04B21/165—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads with yarns stitched through one or more layers or tows, e.g. stitch-bonded fabrics
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    • B29C70/06—Fibrous reinforcements only
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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    • D10B2505/00—Industrial
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]

Abstract

本发明涉及一种由至少两个重叠布置的层组成的无屈曲织物，该层由相对彼此平行并排布置的复丝增强纱组成，其中无屈曲织物在由复丝增强纱组成的层之上和/或之间具有至少一个由热塑性聚合物材料形成的无纺织物的层，其中无纺织物包括第一聚合物组分和第二聚合物组分，所述聚合物组分的熔点低于增强纱的熔点或分解温度，其特征在于，第一聚合物组分具有比第二聚合物组分低的熔点，第一聚合物组分能溶解在环氧基体树脂、氰酸酯基体树脂、或苯并噁嗪基体树脂、或这些基体树脂的混合物中，而第二聚合物组分不能溶解在环氧基体树脂、氰酸酯基体树脂、或苯并噁嗪基体树脂、或这些基体树脂的混合物中。此外，本发明还涉及由这种无屈曲织物形成的预制件。

Description

具有聚合物无纺织物的多轴无屈曲织物
技术领域
本发明涉及一种由至少两个重叠布置的复丝增强纱层组成的无屈曲织物（Gelege），其中所述无屈曲织物在由复丝增强纱组成的层之上和/或之间具有至少一个由热塑性聚合物材料的无纺织物形成的层。
背景技术
长久以来由增强纤维或增强纱组成的无屈曲织物在市场上是已知的。为此经常使用多轴无屈曲织物，其具有由多个彼此重叠布置的纱线层组成的结构，其中纱线层由彼此平行布置的增强纱的经纱组成。纱线层如此重叠地铺设，即所述层的增强纤维平行地或彼此交叉地定向。角度几乎可以任意地调节。然而，多轴无屈曲织物的角度通常设定为0°、90°、正负25°、正负30°、正负45°或正负60°，并如此选择结构，即相对于零度方向得到对称的结构。
像提到的多轴无屈曲织物由于其构造可以专门用于制造复杂的结构。在此，无屈曲织物在没有基体材料的情形下铺设在一模具中并适应该模具的轮廓。由此得到所谓的预制件，接着制造复合材料构件所需的基体材料通过浸渍或注射、同时在使用真空的情况下被引入该预制件中。在此，已知的方法有所谓的液体模塑成型（LM法）或与之类似的方法像树脂传递模塑（RTM）、真空辅助树脂传递模塑（VARTM）、树脂膜熔渗（RFI）、液体树脂灌注成型（LRI）或柔性模具树脂渗透成型（RIFT）。
利用这种由增强纤维形成的无屈曲织物制成的纤维复合材料构件特别适于直接平衡作用于由构件的受力方向/荷载方向引入的力，并因此保证高的强度。在此，多轴无屈曲织物中纤维密度和纤维角度与构件中的负荷方向的匹配实现了低的单位面积重量。
重叠布置的纱线层可以通过多个彼此并排布置且彼此平行延伸形成线圈的缝纫线或针织线彼此连接和相对彼此固定，因此通过这种方式增强多轴无屈曲织物。在此，缝纫线或针织线形成多轴无屈曲织物的零度方向。例如，这种多轴无屈曲织物可以借助于普通的经编机或缝编机制造，例如借助于本领域技术人员已知的LIBA机或Karl Mayer机。例如，在DE 10252671C1、DE 19913647B4、WO 98/10128或EP 0361796A1中描述了通过缝纫线或针织线连接的多轴无屈曲织物及其制造。
EP 1352118A1公开了一种多轴无屈曲织物，其中增强纤维的层借助于可熔的缝纫纱固定，该缝纫纱实现了多轴无屈曲织物在高于缝纫纱熔点温度下的良好的可成型性以及在随后冷却时的形状稳定性。通常使用由例如聚酰胺或聚酯的热塑性聚合物形成的缝纫纱，例如像在EP 1057605中公开的那样。
在US 2005/0164578中描述了一种用于复合材料预制件的半成品，该半成品具有至少一个由增强纤维织物形成的层，且其中为了稳定纤维集成/内置在至少一个所述层中，当预制件承受升高的温度时，该纤维稳定/增强预制件，且所述纤维溶解在随后为了制造复合材料构件而使用的基体树脂中。WO 02/16481也公开一种由增强纤维组成的结构，该结构例如用于预制件，其中所述结构包含柔性的聚合物成分，该聚合物成分例如以纤维的形状被引入增强纤维之间、或者作为缝纫线使增强纤维彼此连接。柔性的聚合物成分由可溶解在所使用的可硬化的基体材料中的材料组成。
根据DE 19809264A1，可以在所公开的纤维无屈曲织物的由增强纤维形成的、彼此缝合的层之间铺放由热塑性聚合物形成的粘合无纺织物。当构成这种无纺织物的聚合物被加热超过熔点时，通过这些熔融粘合的无纺织物，纤维无屈曲织物可以简单地成型为三维结构，所述三维结构在冷却后由于基本上不存在复位力而保持其形状。
无定向/随机铺设的纤维垫或无纺织物、或短（切）纤维织物或垫也部分地放置在由增强纤维形成的纱线层之间，以便例如改进无屈曲织物的可浸润性或者改进冲击强度。例如在DE 3535272C2或US 2007/0202762中描述了具有这种垫状中间层的多轴无屈曲织物，其中对DE 3535272C2中的无纺织物或垫来说，公开的单位面积重量在100到1200g/m2之间，而US 2007/0202762中公开的单位面积重量为40g/m2到161g/m2。
EP 1473132的主题是多轴无屈曲织物及用于制造这种多轴无屈曲织物的方法以及由该多轴无屈曲织物制成的预制件。此处的多轴无屈曲织物在单向铺设的增强纤维所形成的层之间具有由热塑性纤维形成的中间层，其中该中间层可以是由双组分纤维组成的无纺织物或者由彼此混合的不同纤维组成的混合无纺织物。构成中间层的聚合物应该与随后注射在预制件中的基体树脂兼容。尤其地如此设计：中间层在树脂灌注中对于基体树脂来说应该是可渗透的，且在树脂灌注期间以及随后应该固定增强层。在使用环氧树脂的情况下，无纺织物由聚氨酯纤维形成。该无纺织物可以通过针织线圈或通过熔融粘合与增强纤维层连接。
EP 1772258也公开了一种用于制造纤维增强的塑料部件的层压结构。这种层压结构具有单位面积重量在100到500g/m2之间的无纺织物层作为核心层，以及具有至少一个由增强纤维组成的覆盖层。无纺织物层例如是由支架纤维和热塑性粘合纤维组成的纤维混合物，且粘合纤维的熔点低于支架纤维的熔点。根据EP 1772258，当在高于粘合纤维的熔点且低于支架纤维的熔点的温度下进行热处理时，实现了无纺织物层的热增强并进而实现了无纺织物层较高的内部强度和尺寸稳定性。同时，无纺织物层保证了在利用基体树脂进行渗透时的高渗透性。
US 2008/0289743A1公开了一种由交替布置的增强纤维层和无纺织物（其作为中间层由热塑性纤维形成）组成的多轴无屈曲织物，其中中间层布置在增强层之间且通过针织线圈或熔融粘合与增强层连接。在一实施方式中，无纺织物可以由两种或多种材料构成，因此可以是混合无纺织物或双组分、三组分无纺织物等。根据一特殊的实施方式，无纺织物可以由芯-皮纤维组成，其中芯由聚酰胺形成而皮由聚亚安酯形成。无纺织物另外用于固定单向布置的增强纤维、以及在树脂渗透/灌注期间用于保证树脂流。在优选的实施方式中，应该在低于中间层热塑性纤维的熔点温度下进行固化。
之前描述的现有技术中无屈曲织物构造的缺点在于，未由增强纤维组成的材料的份额相对较高，这种材料未对得到的构件的强度作出贡献。基体材料必然与增强纤维和无纺织物的总量有关，因此相对于构件体积，导致构件中增强纤维的份额较少并因此导致强度较小。
EP 1705269公开了一种由聚羟基醚组成的热塑性纤维材料，这种纤维材料例如可用于由增强纤维形成的多轴无屈曲织物中，例如作为无纺织物插入增强纤维的层之间。在施加热量时，聚羟基醚材料变得粘稠和具有粘性，因此可以在增强纤维嵌入基体之前实现增强纤维固定于限定的几何布置/构造中。随后，当温度高于玻璃化温度时，聚羟基醚纤维材料完全溶解在基体材料中。
US 2006/0252334中描述了一种由多个增强纤维层组成的无屈曲织物，为了改进由该无屈曲织物制成的构件的冲击强度，该无屈曲织物在增强纤维层之间包含有例如由聚合物纤维组成的无纺织物。在此，该聚合物纤维应该可溶解在基体树脂中，由此根据US 2006/0252334的实施方案，与可熔融但不可溶解的热塑性塑料相比，实现了形成该纤维的聚合物在树脂基体中更均匀的分布。
因为在US 2006/0252334的和EP 1705269的无屈曲织物中，聚合物纤维可溶解在基体材料中且因此在利用基体树脂渗透无屈曲织物期间被溶解，所以在构件制造的该阶段中没有充分保证增强层的可靠固定。
因此，要求基于增强纤维的无屈曲织物在成型为预制件之后仍具有良好的悬垂性以及形状稳定性、以及在基体树脂渗透期间具有良好的渗透性。同时由该无屈曲织物制成的构件应该尤其在压力加载时具有高的强度特征值和高的冲击强度。
发明内容
因此，本发明的目的在于提供这种无屈曲织物。
该目的通过由至少两个重叠布置的层组成的无屈曲织物实现，所述层由相对彼此平行并排布置的复丝增强纱组成，其中无屈曲织物在由复丝增强纱组成的层之上和/或之间具有至少一个由热塑性聚合物材料无纺织物组成的层，且其中所述无纺织物包括第一聚合物组分和第二聚合物组分，所述聚合物组分的熔点低于增强纱的熔点或分解温度，其特征在于，第一聚合物组分具有比第二聚合物组分更低的熔点，且第一聚合物组分可溶解在环氧树脂基体、氰酸酯树脂基体或苯并噁嗪树脂基体或这些树脂基体的混合物中，而第二聚合物组分不可溶解在环氧树脂基体、氰酸酯树脂基体或苯并噁嗪树脂基体或这些树脂基体的混合物中。
第一聚合物组分优选具有落在80到135℃之间的范围内的熔点，而第二聚合物组分优选具有落在140到250℃之间的范围内的熔点。
由于根据本发明的无屈曲织物的特殊构造，所以该无屈曲织物的特点是：无屈曲织物层在预制件中的良好的悬垂性和固定/强度；在渗透基体树脂时良好的渗透性；以及利用该无屈曲织物可制成具有高机械强度和高冲击强度的构件。当加热至第一聚合物组分的熔点时，通过由根据本发明的聚合物组合形成的至少一个无纺织物层可以实现无屈曲织物层之间相对彼此的可移动性。无纺织物的熔融的第一聚合物组分一定程度上起到润滑剂的作用，因此在向预制件的成型过程中，增强纱的层可以滑动至期望的位置。在冷却预制件时，第一聚合物组分起到热熔粘合剂的作用并把增强层固定在其位置中。
随后在利用基体树脂对无屈曲织物构造进行渗透时（这通常在温度高于第一组分的熔点而低于第二组分的熔点的情况下进行），由于根据本发明的至少一个无纺织物的第二聚合物组分的较高熔点，保证了基体树脂的良好的渗透性。相反地，第一聚合物组分溶解在基体树脂中并通过这种方式失去其相对于基体树脂作为独立的相的识别性/身份。因此，第一聚合物组分的份额包括在基体材料中，基体树脂的待渗透的份额可以减少该第一聚合物组分的份额。因此，可以在得到的构件中设定/调节增强纤维的高的纤维体积份额，并进而把机械强度特征值的水平保持在高水平上。
在根据本发明的无屈曲织物中使用的无纺织物可以由熔点不同的单组分纤维的混合物组成，亦即为混合无纺织物。然而，该无纺织物也可以由双组分纤维组成，例如由芯皮纤维组成，其中芯纤维由较高熔点的聚合物组成，而皮由较低熔点的聚合物组成。与由双组分纤维组成的无纺织物类似，无纺织物例如也可以由通过第二聚合物组分形成的无定向纤维层构成，其中第一聚合物组分例如通过喷射或通过涂层涂覆在第二聚合物组分的纤维上。例如，该涂层可以通过浸渍在第一聚合物组分的悬浮液/分散物或溶液中获得，其中在浸渍后去除溶剂或悬浮液的液体部分。由第二聚合物组分的纤维构成的无纺织物同样还可以包含形式为细小的、位于第二聚合物组分的纤维之间的颗粒的第一聚合物组分。无纺织物优选为混合无纺织物。已证明有利的是，无纺织物具有质量百分比份额在2％至40％的第一聚合物组分和质量百分比份额在60％至98％的第二聚合物组分。尤其优选的是，第一聚合物组分的质量百分比份额在5％至35％的范围内，而第二聚合物组分的质量百分比份额在65％至95％的范围内。在另一个优选的实施方案中，无纺织物具有质量百分比份额在20％至40％的第一聚合物组分和质量百分比份额在60％至80％的第二聚合物组分。
在一个优选的实施方案中，在基体树脂——亦即环氧树脂、氰酸酯树脂或苯并噁嗪树脂——的固化温度时，第一聚合物组分通过交联反应与正在固化的基体树脂起化学反应，并由此形成均质基体的整体的一部分。因此，第一聚合物组分优选是通过化学交联反应与环氧树脂、氰酸酯树脂或苯并噁嗪基体树脂反应的聚合物。第一聚合物组分尤其优选是聚羟基醚。例如在EP 1705269中描述了这种聚羟基醚，在此明确地通过参引的方式将其内容结合到本文中。
根据本发明，第二聚合物组分具有比第一聚合物组分更高的熔点。优选地，第二聚合物组分在所使用的基体树脂的固化温度下、或者在第一聚合物组分的熔点与基体树脂的固化温度之间的温度范围内熔化。通过这种方式，第二聚合物组分同样地结合到基体材料中，然而，与第一聚合物组分不同，第二聚合物组分在固化的基体树脂中形成自身的相。在固化过程期间和在随后的构件中，由第二聚合物组分形成的相有助于限制裂缝的扩展并因此例如特别有利于改善冲击强度。
作为在根据本发明的无屈曲织物中使用的无纺织物的第二聚合物组分，通常可使用可加工成热塑性纱线的聚合物，例如像聚酰胺、聚酰亚胺、聚酰胺-酰亚胺、聚酯、聚丁二烯、聚亚安酯、聚丙烯、聚醚酰亚胺、聚砜、聚醚砜、聚苯砜、聚苯硫醚、聚醚酮、聚醚醚酮、聚芳基酰胺、聚酮、聚邻苯二甲酰胺、聚苯醚酮、聚对苯二甲酸丁二酯、或聚对苯二甲酸乙二酯或这些聚合物的共聚物或混合物，只要该纱线满足符合要求的条件。
关于之前所述的基体树脂，优选的是，第二聚合物组分是聚酰胺均聚物或聚酰胺共聚物，或者是聚酰胺均聚物和/或聚酰胺共聚物的混合物。聚酰胺均聚物或聚酰胺共聚物尤其优选是聚酰胺6、聚酰胺6.6、聚酰胺6.12、聚酰胺4.6、聚酰胺11、聚酰胺12或者基于聚酰胺6/12的共聚物。
在无屈曲织物厚度方向的材料特性的均质化方面，有利的是，在根据本发明的无屈曲织物中，在每个复丝增强纱的层之间布置无纺织物层。在由根据本发明的无屈曲织物制成的构件的特性和机械特性尽可能高的特征值水平方面，同样优选的是，无纺织物具有落在5到25g/m2的范围内的单位面积重量。该单位面积重量尤其优选地落在6到20g/m2的范围内。
在根据本发明的无屈曲织物中，普遍用于制造纤维增强的复合材料的增强纤维或增强纱被用作增强纤维。复丝增强纱优选是碳纤维、玻璃纤维、或芳族聚酰胺纱或者优选是高延展的UHMW聚乙烯纱，尤其优选是碳材料纤维纱。
在所获得的构件中高机械性能的方面，有利的是，增强纱在由复丝增强纱组成的层中相对彼此平行地布置、且并排地紧邻。由此可以得到高的纤维体积份额，并在构件中避免了具有低纤维份额的区域。
在另一个优选的实施方案中，当沿垂直于层平面的方向观察时，重叠布置的层的增强纱彼此形成一角度。因此，可以在随后的构件中相对于受力方向进行增强纱方向的适配并确保沿这些受力方向所需的强度。有利的是，增强纱的层相对于零度方向以限定的角度交替地布置，由此得到对称的或近似各向同性的构造。因此，例如根据本发明的无屈曲织物可以具有这样的结构，该结构例如具有+45°层、-45°层、+45°层和-45°层，也就是说，其中在各个单层内部单向布置的增强纱相对于零度方向具有+45°、-45°、+45°和-45°的角度。在这种多轴无屈曲织物中，角度α通常应该位于±20°至约±80°的范围内。典型的角度α为±25°、±30°、±45°和±60°。
为了例如考虑在随后的构件中其它的受力方向，根据本发明的无屈曲织物优选还包括止这样的复丝增强纱的层：其中增强纱相对于零度方向形成0°角，和/或包括这样的层：其中增强纱相对于零度方向形成90°角。该0°或90°层优选位于以角度α定向的层之间。然而，例如也可以形成具有如下方向的结构：90°、+30°、-30°、0°、-30°、+30°、90°，也就是说一结构，其中由90°的层形成外部层。
在根据本发明的无屈曲织物中，复丝增强纱的层可以由复丝增强纱的预制的单向织物组成。在该单向织物中，构成各个层的、彼此平行布置的增强纱通过由松散的成圈线形成的链彼此连接，该成圈线的链大致横向于增强纱地延伸。例如，在EP 0193479B1或EP 0672776中描述了这种单向织物，明确参考其中与此相关的公开内容。
在根据本发明的无屈曲织物中，为了尤其在树脂注射时保持较高的稳定性，以及例如为了避免增强层不期望的移动/滑动，在根据本发明的优选的设计方案中，由复丝增强纱组成的层和至少一个无纺织物层通过缝纫线或针织结合线——其相对彼此平行延伸且相对彼此隔开一针距/针迹宽度并形成线圈/针脚——彼此连接并相对彼此固定。缝纫线由此限定了无屈曲织物的零度方向。
根据本发明的无屈曲织物的、单个的、由复丝增强纱组成的层可以借助于常规的方法和设备制造，并相对于零度方向以限定的角度重叠地铺放。像已经描述的那样，本领域的已知的机器是LIBA机或Karl Mayer机。因此，增强纱相对于彼此可如此地在层内部定位，即它们彼此紧贴，也就是说基本上无间隙地并排布置。
通常用于制造纱无屈曲织物的纱（线）用作缝纫线。在本发明的框架内，缝纫线理解为下述类型的纱线，其不通过缝制被引入根据本发明的多轴无屈曲织物中，而是通过其它形成线圈的纺织过程、例如尤其通过针织过程被引入。缝纫线通过线圈把多轴无屈曲织物的层彼此连接，该线圈可以具有在多轴无屈曲织物中常见的组织类型，例如像经编针织或编链组织。优选是编链组织。
缝纫线优选是复丝纱。可以使用这种复丝纱，其在随后的树脂注射中例如在树脂注射温度之上但在所使用的树脂的固化温度之下熔化。该纱也可以在固化温度时熔化。缝纫纱也可以是这种类型，其例如在基体树脂的注射期间或在基体树脂的固化期间可溶解在基体树脂中。例如在DE 19925588、EP 1057605或US 6890476中描述了这种缝纫线，在此明确援引与此相关的公开内容。缝纫线优选由聚酰胺、芳族聚酰胺、聚酯、丙烯酸类聚合物、聚羟基醚或这些聚合物的共聚物组成。缝纫线尤其优选是由聚酯、聚酰胺、或聚羟基醚或这些聚合物的共聚物组成的复丝纱。
有利地，在室温时，缝纫线具有≥50%的断裂伸长率。通过高的断裂伸长率可以实现根据本发明的多轴无屈曲织物的改进的悬垂性，由此还可以实现更复杂的结构或构件。
在缝纫或针织的根据本发明的无屈曲织物的优选的实施方案中，缝纫线具有落10至35dtex的范围内的细度。即显示出，当无屈曲织物中缝纫线的细度处于所述的范围内时，特别明显地改进了压力负荷下的稳定性。这是因为，由于使用了这种缝纫线，相比于已知的多轴无屈曲织物，单个纱线层中的纤维结构明显地均匀化。尤其是观察到，增强纱的单丝表现出比在现有技术的无屈曲织物中更笔直的走向。缝纫线的细度特别优选地落在10至30dtex的范围内，并尤其优选地落在15至25dtex的范围内。
如所述的，缝纫线形成线圈/针脚并限定无屈曲织物的零度方向。在层的增强纱相对于无屈曲织物的零度方向对称地布置、且增强纱的延展方向相对于零度方向形成角度α（该角度不是90°也不是0°）的情况下，由根据本发明的多轴无屈曲织物制成的复合材料构件在压力负荷和/或冲击负荷下的强度令人惊异地示出：当由缝纫线形成的线圈的线迹长度s与针迹宽度w以及根据本发明的多轴无屈曲织物中增强纱的角度α之间满足如下关系式（I）和（II）时，得到特别好的强度水平。
2mm≤s≤4mm                    （I）
以及
s = n · B · w · | tan α 1 | 2.3 - - - ( II )
其中乘数B的值可以落在0.9≤B≤1.1的范围内，而n值可以取0.5、1、1.5、2、3或4，由此对w·|tanα1|/2.3取一个小的值的情形而言，线迹长度s也落在根据等式（I）要求的范围内。针迹宽度w，即缝纫线之间的距离在此以mm（毫米）给出。
角度α1理解为相对于零度方向的角度，在多轴无屈曲织物的俯视图中，第一层的增强纱以该角度布置，其增强纱相对于零度方向具有与90°和0°不同的角度。在多轴无屈曲织物的最上一层或最上数层的增强纱相对于零度方向具有90°角或0°角的情况下，考虑布置在该层或这些层下方的第一层，该第一层的增强纱具有与90°或0°不同的角度。
在检查纤维结构时，也就是说在检查复丝增强纱的纤维或单丝在无屈曲织物的层中的走向时，已经发现，当遵守关系式（I）和（II）时，得到纤维的非常均匀的走向，伴随着纱线波纹度的明显减小和明显减少的在纱线束之间产生的间隙。为此，显然重要的是，沿纱线束或纤维条的走向，缝纫线在纤维条的宽度上于尽可能不同的位置处刺穿纤维条。对于落在由条件（I）和（II）限定的区域之外的针对线迹长度和针迹宽度的通常设定的值来说，已经观察到，沿着增强纱的延伸方向，缝纫线的刺入基本上发生在相同的纤维或单丝之间、或发生在纤维条或增强纱的相同区域之间。由此出现纱走向中明显的波纹度或起伏，并形成单丝之间的间隙。
总之已确定，当使用低细度的缝纫线和当遵守上述条件（I）和（II）时，在增强纱的层的俯视图中，由于缝纫线在无屈曲织物中的刺入位置而导致的纤维偏转——也称为起伏角——可以减少多达约25%。同时，所产生的起伏区——也就是说其中单丝或纱线显示出偏转的面积或区域可以缩小约40%，因此明显减小了纤维之间的自由空间，该自由空间导致树脂份额增大的区域以及构件强度的减小。
同时，根据复合层压制品的显微照片（所述复合层压制品基于根据本发明的多轴无屈曲织物）可以确定，通过使用低细度的缝纫线，在沿着垂直于增强纱层延展方向、并平行于增强纱的观察方向上令人惊异地获得了增强纱特别均匀的走向。因此，当使用细度为23dtex的缝纫线时，获得了增强纱单丝的基本上直线/线性的走向。当使用的缝纫线的细度落在根据本发明要求的范围之外时，在细度为48dtex时，当观察复合材料层压制品的所述横截面时，所有单丝表现出极不规律、波纹形的走向，波动幅度的数量级为增强纱线的一个层的厚度。
线迹长度可以落在2mm到4mm的范围内。当线迹长度大于4mm时，不再能够保证根据本发明的多轴无屈曲织物的足够的稳定性。相反，当小于2mm时，导致无屈曲织物中过多的缺陷位置。此外，还导致了多轴无屈曲织物的制造经济性的大幅度降低。
根据本发明的无屈曲织物的特点是良好的悬垂性和良好的树脂渗透性。此外，其还实现了制造相对于压力负荷具有高稳定性以及相对于冲击负荷具有高耐受力的构件。因此，其特别适合用于制造所谓的预制件——通过该预制件制造更复杂的纤维复合材料构件。因此，本发明尤其还涉及用于制造包含根据本发明的多轴无屈曲织物的纤维复合材料构件的预制件。

Claims (15)

1.由重叠布置的至少两个层组成的无屈曲织物，所述层由相对彼此平行并排布置的复丝增强纱组成，其中所述无屈曲织物在由复丝增强纱组成的层之上和/或之间具有至少一个由热塑性聚合物材料形成的无纺织物的层，其中所述无纺织物包括第一聚合物组分和第二聚合物组分，所述聚合物组分的熔点低于所述增强纱的熔点或分解温度，其特征在于，所述第一聚合物组分具有比所述第二聚合物组分更低的熔点，所述第一聚合物组分能够溶解在环氧基体树脂、氰酸酯基体树脂、或苯并噁嗪基体树脂、或这些基体树脂的混合物中，而所述第二聚合物组分不能溶解在环氧基体树脂、氰酸酯基体树脂、或苯并噁嗪基体树脂、或这些基体树脂的混合物中。
2.根据权利要求1所述的无屈曲织物，其特征在于，所述第一聚合物组分具有落在80到135℃之间的范围内的熔点，而所述第二聚合物组分具有落在140到250℃之间的范围内的熔点。
3.根据权利要求1或2所述的无屈曲织物，其特征在于，所述无纺织物是混合无纺织物。
4.根据权利要求1至3中的一项或多项所述的无屈曲织物，其特征在于，所述第二聚合物组分是聚酰胺均聚物或聚酰胺共聚物，或者是聚酰胺均聚物和/或聚酰胺共聚物的混合物。
5.根据权利要求4所述的无屈曲织物，其特征在于，所述聚酰胺均聚物或聚酰胺共聚物是聚酰胺6、聚酰胺6.6、聚酰胺6.12、聚酰胺4.6、聚酰胺11、聚酰胺12或者基于聚酰胺6/12的共聚物。
6.根据权利要求1至5中的一项或多项所述的无屈曲织物，其特征在于，所述第一聚合物组分是在环氧基体树脂、氰酸酯基体树脂或苯并噁嗪基体树脂交联时与这些基体树脂起化学反应的聚合物。
7.根据权利要求6所述的无屈曲织物，其特征在于，所述第一聚合物组分是聚羟基醚。
8.根据权利要求1至7中的一项或多项所述的无屈曲织物，其特征在于，所述无纺织物包含质量百分比份额在2％至40％之间的第一聚合物组分和质量百分比份额在60％至98％的第二聚合物组分。
9.根据权利要求1至8中的一项或多项所述的无屈曲织物，其特征在于，所述至少一个无纺织物层的单位面积重量落在5到25g/m2的范围内。
10.根据权利要求1至9中的一项或多项所述的无屈曲织物，其特征在于，在每个由复丝增强纱组成的层之间布置有无纺织物层。
11.根据权利要求1至10中的一项或多项所述的无屈曲织物，其特征在于，所述复丝增强纱是碳纤维、玻璃纤维、或芳族聚酰胺纱、或者是高延展的UHMW聚乙烯纱。
12.根据权利要求1至11中的一项或多项所述的无屈曲织物，其特征在于，当垂直于层平面观察时，重叠布置的层的增强纱彼此形成角度。
13.根据权利要求1至12中的一项或多项所述的无屈曲织物，其特征在于，由复丝增强纱组成的层和至少一个无纺织物层通过彼此平行延伸并彼此隔开的缝纫线彼此连接。
14.根据权利要求13所述的无屈曲织物，其特征在于，一个层以及相邻层内的增强纱通过相对彼此隔开针迹宽度s的缝纫线彼此连接并相对彼此固定，其中所述缝纫线形成具有线迹长度s的线圈，无屈曲织物的零度方向通过缝纫线限定，所述层的增强纱相对于无屈曲织物的零度方向对称地布置、且增强纱的延展方向与零度方向形成不等于90°和0°的角度α，其中所述缝纫线具有落在10至35dtex范围内的细度，其中所述缝纫线的线迹长度s取决于针迹宽度以及所述增强纱的角度α1，并且满足关系式（I）和（II）：
2mm≤s≤4mm                        （I）
s = n · B · w · | tan α 1 | 2.3 - - - ( II )
其中
w=针迹宽度[mm]，
0.9≤B≤1.1以及
n=0.5、1、1.5、2、3或4，
其中，角度α1理解为在俯视图中多轴无屈曲织物的第一层的增强纱相对于零度方向的角度α，其增强纱相对于零度方向具有不同于90°和0°的角度。
15.用于制造复合材料构件的预制件，其特征在于，所述预制件包括根据权利要求1至14中的一项或多项所述的多轴无屈曲织物。
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