CN1202237A - 抗穿刺复合材料 - Google Patents

抗穿刺复合材料 Download PDF

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CN1202237A
CN1202237A CN96198408A CN96198408A CN1202237A CN 1202237 A CN1202237 A CN 1202237A CN 96198408 A CN96198408 A CN 96198408A CN 96198408 A CN96198408 A CN 96198408A CN 1202237 A CN1202237 A CN 1202237A
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F·V·普菲斯特
A·谢玲
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EIDP Inc
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Abstract

本发明涉及一种抗穿刺复合材料,该复合材料含有至少1层纤维纱片,按照ASTM D－885测定的纤维韧度为至少900MPa(7g/旦),纤维纱片与一种聚合物连续介质粘合,该聚合物连续介质具有按照ASTM D－790测定的挠曲模量为42～1000MPa,按照ASTM D－638测定的断裂拉伸强度为至少10MPa,按照ASTM D－638测定的断裂伸长率为至少100%。本发明进一步涉及含有多片此种复合材料的护甲,以及制造此种复合材料的方法。

Description

抗穿刺复合材料
                        发明背景
发明领域：
本发明涉及一种抗穿刺复合材料，含有至少1层这种复合材料的护甲，以及此种复合材料的制造方法。
先有技术介绍：
已知在多层结构中使用高韧性纤维，例如聚芳酰胺纤维，可以赋予防弹服以防弹性能。并且还已知，在多层结构中嵌入1层或多层上冲击力吸收层，可以进一步减缓穿透该结构的连续层的枪弹的速度，达到提高防弹效率的目的。
此类已知防弹结构的显著缺点是，这种结构提供的抗穿刺性能通常相当低，因为刀和尖锐物体会把高韧性纤维推向一边并刺进冲击力吸收层(如有吸收层的话)。当防弹作为主要目的时，冲击力吸收层通常不设计成可以耐受刀和尖锐物体的穿刺。
采用既可以防枪弹又可以抗穿刺的结构可以克服防护性能差的缺点，即在结构内部嵌入相当厚实的抗穿刺层，例如由陶瓷材料、钢、钛或铝制作的抗穿刺层，抗穿刺层通常置于高韧性纤维层的外侧，面朝外。但是，由于比重(表示为kg/cm2)相当高，以及由于此类多层结构缺乏柔性，穿着由此类结构制作的防弹服时，感到相当不舒适。
护甲制作厂家和使用者都十分希望获得防护性能优良的抗穿刺复合材料，此类复合材料既能够防枪弹，又能够耐受锋利和/或尖锐物体(如刀和尖钉)的穿刺，同时能够使穿着者感到轻便和舒适，不象上述那种笨重的多层结构。
                       发明概述
本发明涉及一种抗穿刺复合材料，该复合材料含有至少1层纤维纱片，按照ASTM D-885测定的纤维韧度为至少900MPa(7g/旦)，纤维纱片与一种聚合物连续介质粘合，该聚合物连续介质具有按照ASTMD-790测定的挠曲模量为42～1000MPa，按照ASTM D-638测定的断裂拉伸强度为至少10MPa，按照ASTM D-638测定的断裂伸长率为至少100％。
                       详细说明
长期以来，人们懂得把纤维粘合到聚合物片材上，或者用聚合物浸渍纤维片，以便利用纤维和聚合物连续介质两者的性能，或者只是为了将纤维粘合一起形成固定结构。更具体讲，把以织造织物或非织造织物形式存在的纤维片粘合到聚合树脂上，制成防枪弹结构的部件。然而在这种结构中使用的聚合物树脂，其本身对防枪弹性能没有显著贡献，只是起固定纤维作用；还需嵌入抗穿刺性能较好的聚合物材料(如聚碳酸酯)或金属片，最后制成比重相当高的防枪弹组件。
如同发明概述中所述，本发明通过把“坚牢”纤维粘合到一种具有相当高的挠曲模量、拉伸强度和拉伸性能的聚合物连续介质上，克服了已知抗穿刺复合材料的缺点。
在按照本发明的复合材料中可以使用各种类型的纤维，例如聚烯烃(如聚乙烯)、聚酰亚胺、聚酯或聚芳酰胺纤维，但要求按照ASTM D-885测定的纤维韧度为至少900MPa，该值约相当于7克/旦。按照本发明，为了使一种复合材料对冲击该复合材料的枪弹、刀和其他锋利和/或尖头物体具有优异的抗穿刺性能，按照ASTM D-885测定的纤维韧度优选为至少2000MPa。
按照本发明，聚芳酰胺纤维最适合用于多种应用场合，因为聚芳酰胺纤维能够具有所需韧度，甚至可超过优选的2000MPa极限，此外，聚芳酰胺纤维还具有耐化学品性能。上述聚芳酰胺性能与一种耐化学品的粘合聚合物相配合，可得到一种耐化学品性能优良的抗穿刺复合材料，这种抗穿刺复合材料适合在最苛刻的环境条件下应用。
复合材料中纤维可以以多种形式存在，优选形式是作为针织织物、织造织物、单向织物组织结构、单向结构或多向薄片(例如纤维交叉角度为20°-90°)、非织造片(例如毡片)，或甚至为单纤维。单向织物组织结构是指一种织造结构，其中该结构中至少80％(重量)的纤维排列方向相同，作为该织物结构的经纱或纬线。单向结构是指这样的一种结构，即其中该结构中全部纤维的排列方向相同。
按照本发明，由于制造效率、可得性及几何强度(确定的稳定结构)等原因，优选用高韧性纤维织造织物来制造多种复合材料。虽然其他织造结构同样可以使用，然而该织造织物以平纹织物为宜，并且取决于具体用途，织物经纬密度典型地为42×42、28×28、14×14或6.7×6.7根/cm。此类织物的比重一般为0.02～0.5Kg/M2，优选为0.05～0.5Kg/M2，更优选为0.08～0.3Kg/M2，目的是在于保持抗穿刺性能与比重之间的均衡，特别是当多层此类织物应用于制造本发明的复合材料时，尤其要考虑保持上述两者之间的均衡。即使织物用聚芳酰胺纤维织造，若织物比重低于0.02Kg/M2，织物的防枪弹性能一般也不能接受，然而，若织物比重超过0.5Kg/M2，由于重量限制，则在实际应用中不能够使用许多层织物片。
本发明的复合材料使用的纱线的各根单丝，其旦数(定义为9000米长的纤维的重量克数)为0.1～1000旦，优选为0.2～200旦；纱线纤度为10～3500旦。
对于某些应用，取决于织物重量/防弹性能比，纤度为1000～3000旦的纱线用于要求不很严格的应用场合；而对于其他应用，例如要求高性能/低比重的应用场合，则要求纱线纤度为10～1000旦，特别优选50～1000旦。在许多应用场合，纱线纤度10～3000旦为最佳。
复合材料中使用的纤维可不经过涂复处理，或者经过涂复处理，或者作其他预处理(例如预拉伸或热处理)。使用聚芳酰胺纤维时，聚芳酰胺纤维一般不必作涂复或其他预处理，只要把聚芳酰胺纤维织造成适当织物片或制作成非织造织物片即可。但是，在某些应用场合，则要求对聚芳酰胺进行涂复处理，以提高纤维与聚合物连续介质之间的粘合强度。
按照本发明，多种聚合物可用作聚合物连续介质。基于稍后述及的关于制造方面的理由，以及由于具有所要求的拉伸强度和伸长率的各种热塑性聚合物能够从市场上买到，因此适宜采用热塑性树脂。适宜的聚合物有特种聚乙烯、聚酰亚胺、聚醚醚酮、离聚物树脂、酚醛改性树脂、聚酯等。
优选的热塑性树脂为离聚物树脂，更优选是含阳离子的离聚物树脂，其中阳离子可选自锂、钠、锌，尤其是这些阳离子用量为0.1～0.3％(重量)。
热塑性树脂也可以是酚醛改性树脂，特别是酚醛-聚乙烯醇缩丁醛树脂。
当制造本发明的抗穿刺复合材料，特别是同时也具有抗尖锐物体穿刺的复合材料时，选用的聚合物连续介质的断裂拉伸强度应为至少20MPa，断裂伸长率应为至少200％，更优选为至少300％，断裂拉伸强度和断裂伸长率均按照ASTM D-638方法进行测定。
复合材料中聚合层的柔软度是一个重要因素，它关系到复合材料的抗穿刺性能，也关系到由1层或多层此种复合材料制作的防弹服的穿着舒适性。按照ASTM D-790进行测定，该聚合物挠曲模量应为42～1000MPa，尤其应为50～800MPa。挠曲模量高于1000MPa，表明聚合物过于硬挺，不能够有效耐受穿刺，作为防弹服穿着缺乏舒适性，而挠曲模量低于42MPa，表明聚合物材料过于柔软，对抗穿刺复合材料不能够提供任何有效劲度。含有这种聚合物的防弹服的另一个优点是当枪弹击中防弹服时，产生反向力形变程度低。
本发明的复合材料中的聚合物层的另一个重要性质是其面密度(表示为Kg/cm2)。当复合材料用于制作防弹服时，低面密度对于易于穿着是重要的。低面密度由于重量减轻，对于含有该复合材料的任何其它物件的处置及有效管理来说也是重要的。
连续介质中聚合物密度优选为低于2.5g/cc，更优选低于1.5g/cc。密度低于1g/cc的离聚物是特别优选的。
聚合物连续介质可用作复合材料中的一个层片，视具体用途及制作方法可得性，在聚合物连续介质的一侧或两侧粘有纤维层。在本发明优选的一个实例中，为了固定纤维，把含纤维的层片嵌入聚合物连续介质中，从而制得一种非常坚牢的复合材料。所得到的聚合物和纤维的层片可采用本技术中已知的任何间歇或连续工艺进行粘合，例如压延、挤出涂复、胶合、浸渍、热粘合，以及把两种不同材料片材结合一起的其他层合方法，或者甚至采用就地聚合方法，最后形成带有纤维的聚合物连续介质。热粘合(例如模塑)是一种优选的粘合方法。
本发明进一步涉及一种制造上述抗穿刺复合材料的方法，即把厚度为10～300微米的聚合物层片与纱线纤度为10～3500旦的纤维片粘合，具体操作是在一定压力和温度下把不同片材压合在一起，操作压力为2～100巴，操作温度高于聚合物熔点，优选操作温度最多比聚合物熔点高150℃，压合时间为0.01～30min。
选择一种适当的聚合物对有效制造抗穿刺复合材料至关重要，要求聚合物熔点相当低，并且在适宜温度范围内熔体粘度足够低，以形成聚合物与纤维层片的良好粘合。基于上述理由，聚合物的平均分子量应不太高，但是另一方面要求平均分子量应足够高，以便为复合材料提供足够的强度，同时保证在高温下形成并维持为一种聚合物连续介质。该材料中聚合物的平均分子量优选为5000～500,000，以保证连续性层合工艺顺利操作。此外，如同正常织物一样，纤维层片和聚合物层片可做成料卷，从而可通过连续性工艺制作护甲。与此相反，现有护甲制作方法为非连续性工艺。在非连续性工艺中，小型板(通常是小型金属板)用铆钉、胶或其他连接方法进行连接。
本发明的复合材料及其制造工艺的另一重要优点是当复合材料用于防弹服或防护服时，可以把复合材料成型加工(例如模塑)成任何连续形状，尤其是三维体形状。而嵌有护板的市售非连续性防弹服则不能够做到这一点。因为本发明的复合材料可以以连续性片材形式使用，所以防弹服的防护性能优于用非连续性材料制作的防弹服。
按照本发明，在复合材料中及在制作工艺中使用的聚合物层片的最佳厚度取决于1片聚合物片上所粘合的含纤维的层片数目。若仅在聚合片一侧粘合纤维片，则聚合物层片的厚度优选为10～200μm。若在聚合物层片两侧粘合纤维片，则聚合物层片厚度优选为20～400μm，更优选为100～300μm。聚合物层片厚度存在差别的主要原因是相对于要粘合在其中的纤维材料而言必须有足够的聚合物，以便形成聚合物充分复盖的纤维互穿网络。
因此，在制得的复合材料中，在制造复合材料中所用的聚合物层片可以不再以明显的一层或多层形式存在，而是以复盖纤维层片的聚合物连续介质形式存在。
按照ASTM F-1342-91进行测定，本发明的复合材料的抗穿刺力优选为至少100N/(Kg/M2)，特别是至少200N(Kg/M2)。
本发明也涉及护甲，例如防弹服(特别是抗穿刺背心)，或固定式或移动式护甲，如护板、护毯或护帘，这些防护品均含有本发明的多层片抗穿刺复合材料。
根据用途，多层片抗穿刺复合材料可以随机叠置，或者相对于单片抗穿刺复合材料中纤维的主要取向成一定角度进行叠置。
按照本发明，所述抗穿刺复合材料也可用于防护服，例如抗砍及抗穿刺手套、套袖、鞋和其他工作服及运动服，以及用作包装材料。
本发明用以下实例加以说明：实例1
使用的纤维片为聚芳酰胺纤维织物，纤维纤度为200旦，织物经纬密度为28×28根/cm，比重为0.13kg/M2。按照ASTM D-885测定的纤维韧度为3400MPa。使用的聚合物层片为以聚乙烯为基料的离聚物，含钠离子1.44％(重量)，按照ASTM D-638测定的断裂拉伸强度为29MPa，按照ASTM D-638测定的断裂伸长率为440％，厚度为150μm。按照ASTM D-790测定的聚合物挠曲模量为220MPa，聚合物密度为940Kg/m3。聚合物层片两侧粘合纤维层片，采用模塑法将各层片压合在一起，层合压力为10巴，层合温度为120℃(高于聚合物熔点)，层合时间15min。
按照ASTM F-1342-91进行测定，加工得到的复合材料的抗穿刺力为400N(Kg/m2)。比较例2
制作一种护甲结构，该结构含有45层聚芳酰胺纤维(365型)织物片，纤维纤度为840旦，织物经纬密度为11.7×11.7根/cm，比重为0.220Kg/m2。按照ASTM D-885测定的纤维韧度为3492MPa。该防弹服结构不含有聚合物连续介质，这种防弹服结构的抗穿刺性能达不到欧州标准(European Norm)CEN/TC 162/WG 5N479，该标准规定：冲击能量为25J时穿刺深度应低于20mm。比较例3
制作一种护甲结构，该结构只含有多个例1所述的离聚物层片，比重与比较例2中所述聚芳酰胺纤维结构相似。这种结构也不符合抗穿刺要求，即使每层片厚度为150μm的聚合物层片的断裂拉伸强度为29MPa，断裂伸长率为440％(两者均按照ASTM D-638方法进行测定)，按照ASTM D-790测定的挠曲模量为220MPa，聚合物密度为940Kg/m3。实例4
制作一种由多个抗穿刺复合材料层片组成的护甲结构，每层片抗穿刺复合材料含有1片比较例3中所述离聚物层片，在该聚合物层片两侧粘合有比较例2中所述的聚芳酰胺纤维片，粘合方法如例1所述的层压法。制得的结构的比重与比较例2和3中所述结构的比重相近。
然而，本发明的这种混杂型防弹服结构却符合比较例2中所述的抗穿刺标准。比较例5
制作一种完全由聚芳酰胺纤维织物层片组成的护甲结构，该结构比重为10.8Kg/m2，并且具有与比较例2中所述结构相同的特征。这种结构刚好达到欧州标准CEN/TC 162/WG 5N 479，即冲击能量为25焦耳时穿刺深度为20mm。但是，因为这种结构不含有聚合物连续介质，所以它不是本发明所述的抗穿刺复合材料。实例6
制作一种护甲结构，该结构含有多层片实例4中所述的抗穿刺复合材料片，比重为7.5Kg/m2。按照欧州标准CEN/TC 162/WG 5N 479对这种结构进行抗穿刺性能测定，冲击能量为25焦耳时穿刺深度仅为13mm，说明抗穿刺性能远远超过抗穿刺性能欧州标准。因此，当这种结构与比较例5中的结构进行比较时，抗穿刺性能提高35％，而比重降低25％。比较例7
制作一个护甲结构，该结构仅含有4层聚芳酰胺纤维织物，比重为0.120Kg/m2，织物经纬密度为28×28根/cm，纤维纤度为200旦，按照ASTM D-885测定的纤维韧度为3492MPa。
按照ASTM F-1342-91对该结构进行抗穿刺性能测试，测试结果是抗穿刺力为16.9Kg。实例8
制作一种护甲结构，该结构含有比较例3所述离聚物层片，在该聚合物层片两侧粘合有比较例7中所述聚芳酰胺纤维织物层片，按照实例1中所述方法进行片材层合。制得的护甲结构的比重与比较例7中所述护甲结构相似，但是前一结构的抗穿刺力为22.4Kg(按照ASTM F-1342-91测试)，表明抗穿刺性能提高32.5％。实例9
制作一种护甲结构，该结构含有38层复合材料，每层复合材料含有1片聚芳酰胺纤维织物片和1片离聚物片；聚芳酰胺纤维片为杜邦公司(E.I.du Pont de Nemours and Company)销售的KEVLAR纤维片，纤度840旦，织物经纬密度为11×11根/cm；纤维织物片和聚合物片按实例1中所述方法层合。但是，离聚物片与KEVLAR聚芳酰胺纤维织物片在靠近该聚合物熔点，即在96℃进行层合。按照CEN/TC 162/WG 5N 479进行测试，冲击能量为25焦耳时，该护甲结构的背衬材料被刺入的深度为19.5mm。实例10
制作一种护甲结构，该结构含有与实例9中所述同样数目(38)的离聚物片和KEVLAR聚芳酰胺纤维织物片。层合温度为146℃，比该离聚物熔点高50℃。按照CEN/TC 162/WG 5N 479进行测试，冲击能量为25焦耳时，该护甲结构的背衬材料被刀刺入的深度为11.2mm；当刺入深度与实例9所述相同(19.5mm)时，该护甲结构将吸收至少32焦耳能量，在比重(Kg/m2)相同的情况下，比实例9的护甲结构多吸收28％能量。

Claims (15)

1.一种抗穿刺复合材料，该复合材料含有至少1层纤维纱片，按照ASTM D-885测定的纤维韧度为至少900MPa(7g/旦)，该纤维纱片与一种聚合物连续介质粘合，该聚合物连续介质具有按照ASTM D-790测完的挠曲模量为42～1000MPa，按照ASTM D-638测定的断裂拉伸强度为至少10MPa，按照ASTM D-638测定的断裂伸长率为至少100％。
2.按照权利要求1的复合材料，其中含有聚芳酰胺纤维。
3.按照权利要求1的复合材料，其中所述纤维以机织织物形式存在。
4.按照权利要求1的复合材料，其中所述纤维以单向结构形式存在。
5.按照权利要求1的复合材料，其中所述纤维以单向织物结构形式存在。
6.按照权利要求1的复合材料，其中所述纤维以多向薄片形式存在。
7.按照权利要求1的复合材料，其中所述纱的纤度为10～3500旦。
8.按照权利要求1的复合材料，其中热塑性树脂为离子交联聚合物树脂。
9.按照权利要求1的复合材料，其中聚合物层片两侧粘合有纤维片。
10.按照权利要求9的复合材料，其中聚合物层片厚度为20～400μm。
11.按照权利要求1的复合材料，其中聚合物片一侧粘合有纤维片。
12.按照权利要求11的复合材料，其中聚合物片厚度为20～400μm。
13.按照权利要求1的复合材料，该复合材料具有按照ASTM F-1342-91测定的抗穿刺力为至少100N。
14.一种护甲，该护甲含有多层权利要求1所述的复合材料。
15.抗穿刺复合材料的制造方法，该方法包括下述步骤：把纤维纱片粘合到聚合物片上，所述纤维纱纤度为10～3500旦，按照ASTM D-885测定的纤维韧度为至少900MPa(7g/旦)，所述聚合物具有按照ASTMD-790测定的挠曲模量为42～1000MPa，按照ASTMD-638测定的断裂拉伸强度为至少10MPa，按照ASTM D-638测定的断裂伸长率为至少100％，厚度为10～300μm，在2～100巴压力和高于该聚合物熔点的温度条件下，将所述片材压合在一起保持0.01～30min。
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CN1784585B (zh) * 2003-05-08 2012-03-28 帝人芳纶有限公司 柔韧的防穿透组件及其应用
CN101568428B (zh) * 2006-12-27 2013-01-02 纳幕尔杜邦公司 柔性防弹织物及其制品
CN105264140A (zh) * 2013-03-20 2016-01-20 可隆工业株式会社 高强度纤维复合材料、其制备方法以及使用该复合材料的头盔
CN105264140B (zh) * 2013-03-20 2017-12-05 可隆工业株式会社 高强度纤维复合材料、其制备方法以及使用该复合材料的头盔

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IN190196B (zh) 2003-06-28
WO1997021334A2 (en) 1997-06-12
EP0862722B1 (en) 2002-01-30
US6022601A (en) 2000-02-08
EP0862722A2 (en) 1998-09-09
TW353715B (en) 1999-03-01
CN1071451C (zh) 2001-09-19

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