CN101370649A - 碎片防护物 - Google Patents

碎片防护物 Download PDF

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Publication number
CN101370649A
CN101370649A CNA2006800516146A CN200680051614A CN101370649A CN 101370649 A CN101370649 A CN 101370649A CN A2006800516146 A CNA2006800516146 A CN A2006800516146A CN 200680051614 A CN200680051614 A CN 200680051614A CN 101370649 A CN101370649 A CN 101370649A
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CN
China
Prior art keywords
fiber
fiber web
reinforcement fiber
weight
chip material
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
CNA2006800516146A
Other languages
English (en)
Inventor
A·巴特纳加尔
L·L·瓦格纳
许作民
B·阿维德森
L·默里
D·赫斯特
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.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
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 Honeywell International Inc filed Critical Honeywell International Inc
Publication of CN101370649A publication Critical patent/CN101370649A/zh
Pending legal-status Critical Current

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Classifications

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    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0478—Fibre- or fabric-reinforced layers in combination with plastics layers
    • 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
    • B32B5/28—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 impregnated with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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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    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
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Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

本发明涉及对诸如榴散弹的碎片具有优异防穿透性的织物层压材料。所述织物由使用约7％至约15％重量的弹性基质组合物加固的高强度纤维以及位于织物的每个表面上的聚合物膜的保护层制备。与现有技术的织物相比，所述织物在防碎片性能方面实现显著提高，同时还保持优异的防弹性能。

Description

碎片防护物
发明背景
发明领域
本发明涉及具有优异防弹性能以及对诸如榴散弹的碎片具有优异防穿透性的织物层压材料。更具体地说，本发明涉及由弹性基质中的高强度聚合物纤维制备而成的轻质的、柔软的、无纺的防碎片和防弹材料。
相关技术说明
含有对可变形抛射物具有优异阻抗性能的高强度纤维的防弹制品是众所周知的。诸如军事装备的防弹背心、头盔和结构部件的制品通常是由含这种高强度纤维的织物制备而成的。常规上使用的纤维包括聚乙烯纤维、聚对芳酰胺纤维，例如聚对苯二甲酰苯二胺、石墨纤维、尼龙纤维、玻璃纤维等。对于诸如背心或背心各部分的许多应用来说，可以在机织或针织织物中使用纤维。对于许多其它应用来说，将纤维封装或嵌入在复合材料中，以形成刚性或柔性织物。
用于形成诸如头盔、面板和背心的制品的各种防弹结构是众所周知的。例如，美国专利4,403,012、4,457,985、4,613,535、4,623,574、4,650,710、4,737,402、4,748,064、5,552,208、5,587,230、6,642,159、6,841,492、6,846,758描述了防弹复合材料，所述防弹复合材料包括由诸如延伸链超高分子量聚乙烯的材料制备的高强度纤维，通过引用将所有这些专利结合到本文中。这些复合材料对于来自诸如子弹、炮弹、榴散弹等射弹的高速撞击显示出不同程度的防穿透性能。
美国专利4,403,012和4,457,985公开了包含高分子量聚乙烯或聚丙烯纤维网的防弹复合材料制品和由烯烃聚合物和共聚物、不饱和聚酯、环氧树脂和在纤维熔点下可模压的其它聚合物组成的基质。美国专利4,623,574和4,748,064公开了包含嵌入在弹性基质中的高强度纤维的简单复合结构。美国专利4,737,402和4,613,535公开了具有良好抗冲击性的复合刚性复合材料制品，所述复合材料制品包含高强度纤维网，例如在通过引用也结合在本文中的美国专利4,413,110中公布的超高分子量聚乙烯和聚丙烯，它们嵌入在弹性基质材料和至少一个附加刚性层中，所述附加刚性层位于基质中的纤维的主表面上。美国专利4,650,710公开了一种柔性制品，其包含多个柔性层，所述柔性层包含高强度、延伸链聚烯烃(ECP)纤维。用低模量弹性材料对网的纤维进行涂布。
美国专利5,552,208和5,587,230公开了包含至少一种高强度纤维网和基质组合物的制品和用于制备制品的方法，所述基质组合物包含乙烯基酯和苯二甲酸二烯丙酯。美国专利6,642,159公开了一种具有多个纤维层的抗冲击刚性复合材料，所述纤维层包含在基质中布置的长丝网，其中弹性层位于它们之间。将复合材料粘结到硬板上，以提高防穿甲弹能力。美国专利6,841,492公开了双向和多轴向织物、织物复合材料、其防弹组合体和它们的制备方法。织物包括多组强的基本上平行的单向的纱，这些纱位于平行平面中，一个在另一个之上。美国专利6,846,758公开了具有优异防弹道射弹穿透性能的机织织物层压材料。本发明的层压材料包括由高强度高模量纱、低模量弹性体表面涂层和粘结到其弹性体涂敷表面的塑料膜织造的织物。
当前的防弹织物和制品存在的一个问题是它们对诸如榴散弹的碎片的防穿透性能有限。本发明提供了这一问题的解决方案。已经意外发现，与现有技术的织物相比，由使用约7％至约15％重量的弹性基质组合物加固的高强度纤维的加固网以及位于织物的每个表面上的聚合物膜的保护层制备的无纺织物在防碎片方面实现了显著提高，同时还保持了对可变形抛射物的优异阻抗性能。
发明概述
本发明提供了一种防碎片材料，所述防碎片材料包括：
a)至少一种加固纤维网，所述加固纤维网包括多个交叉层叠的无纺纤维层，每个纤维层包括以基本上平行的阵列排列的多个纤维；所述纤维具有7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维在其上具有弹性基质组合物，所述弹性基质组合物占所述加固纤维网的约7％至约15％重量；用所述基质组合物对所述多个交叉层叠的无纺纤维层进行加固，从而制备所述加固纤维网；所述加固纤维网具有前表面和后表面；其中如果所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，所述基质组合物占所述加固纤维网的至少约11％重量；和
b)至少一层聚合物膜，所述聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
本发明还提供了包含防碎片材料的防碎片制品，所述防碎片材料包括：
a)至少一种加固纤维网，所述加固纤维网包括多个交叉层叠的无纺纤维层，每个纤维层包括以基本上平行的阵列排列的多个纤维；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维在其上具有弹性基质组合物，所述弹性基质组合物占所述加固纤维网的约7％至约15％重量；用所述基质组合物对所述多个交叉层叠的无纺纤维层进行加固，从而制备所述加固纤维网；所述加固纤维网具有前表面和后表面；其中如果所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，所述基质组合物占所述加固纤维网的至少约11％重量；和
b)至少一层聚合物膜，所述聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
本发明还提供了一种制备防碎片材料的方法，所述方法包括：
a)形成至少两个纤维层，每个纤维层通过将多个纤维排列成基本上平行的单向阵列而形成；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维具有施加在其上的弹性基质组合物；
b)将所述纤维层进行排列，其中将每个单向阵列的纤维层以相对于每个相邻层的纵向纤维方向呈非平行角度进行交叉层叠；
c)在足以形成加固纤维网的条件下粘结所述交叉层叠的层，所述加固纤维网具有前表面和后表面；其中所述基质组合物占所述加固纤维网的约7％至约15％重量，并且其中如果所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，所述基质组合物占所述加固纤维网的至少约11％重量；和
d)将至少一层聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
本发明还提供了一种防碎片材料，所述防碎片材料包括：
a)至少一种加固纤维网，所述加固纤维网包括多个交叉层叠的纤维层，每个纤维层包括以阵列排列的多个纤维；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维在其上具有弹性基质组合物，所述弹性基质组合物占所述加固纤维网的约7％至约15％重量；用所述基质组合物对所述多个交叉层叠的纤维层进行加固，从而制备所述加固纤维网；所述加固纤维网具有前表面和后表面；和
b)至少一层聚合物膜，所述聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
发明详述
本发明介绍除具有优异防弹穿透性能之外还具有优异防碎片穿透性能的无纺织物复合材料。为了本发明目的，本发明的具有优异防弹穿透性能的防碎片材料描述了显示出优异防可变形抛射物性能的材料。
本发明的纤维优选用低模量弹性材料进行涂布，其中基质占织物的约7％至约15％重量。所述织物还包括至少一个外聚合物层，该外聚合物层与加固网的每个外表面相连接。贯穿本文所用的术语抗张模量是指由ASTM 2256测试程序对纤维和由ASTM D638测试程序对弹性基质材料所测的弹性模量。
为了本发明目的，纤维是伸长体，它的长度尺寸远大于宽度和厚度的横向尺寸。用于本发明的纤维的横截面可以显著变化。它们的横截面可以是圆形的、扁平的或椭圆形的。因此，术语纤维包括具有规则或不规则横截面的长丝、带、条等。它们也可以是不规则或规则的多叶横截面，其具有从纤维的直线轴或纵向轴伸出的一个或多个规则或不规则的叶。优选的是，纤维是单叶的，并具有基本上圆形的横截面。
本发明的防碎片材料包含至少一种高强度、高抗张模量加固纤维网，其上面具有弹性基质，其中一种加固网是包含多于一个纤维层的“单层”织物结构。本文使用的纤维“网”表示多个排列或互联的纤维层或纱层。“加固网”描述了纤维层与基质组合物的加固组合。本文使用的“单层”结构是指由已经加固成单个整体结构的一个或多个独立纤维层组成的结构。通常，“织物”可以涉及机织或无纺材料。在本发明的优选实施方案中，防碎片织物为无纺材料。“阵列”描述了纤维或纱的有序平行排列。纤维“层”描述了机织或无纺纤维或纱的平面排列。纤维网可以具有各种各样的结构。例如，可以将纤维制成毡或其它机织、无纺或针织物，或通过任何其他常规技术制成网。根据一个特别优选的加固网结构，将多个纤维层组合起来，这样，每个纤维层包括以阵列单向排列的纤维，因此，它们沿着共同的纵向纤维方向基本上彼此平行。
本文使用的“高强度、高抗张模量纤维”是这样的纤维，即具有至少约7克/旦尼尔或更高的优选韧度，具有至少约150克/旦尼尔或更高的优选抗张模量和至少约8J/g或更高的优选断裂能，它们均是由ASTM D2256测试程序所测定。本文使用的术语“旦尼尔”是指线密度的单位，等于每9000米纤维或纱的质量克数。本文使用的术语“韧度”是指拉伸应力，表示为无应变样品的每单位线密度(旦尼尔)的力(克)。纤维的“初始模量”是表示材料抗变形的特性。术语“抗张模量”是指韧度变化(用克力每旦尼尔(g/d)表示)与应变变化(表示为初始纤维长度的分数(in/in))之比。
特别适合的高强度、高抗张模量纤维材料包括延伸链聚烯烃纤维，例如高取向、高分子量聚乙烯纤维，特别是超高分子量聚乙烯纤维和超高分子量聚丙烯纤维。还适合的是延伸链聚乙烯醇纤维、延伸链聚丙烯腈纤维、聚对芳酰胺纤维、聚苯并唑纤维，例如聚苯并噁唑(PBO)和聚苯并噻唑(PBT)纤维，以及液晶共聚酯纤维。
在聚乙烯的情况下，优选的纤维是分子量为至少500,000，优选至少一百万，更优选两百万至五百万的延伸链聚乙烯。这种延伸链聚乙烯(ECPE)纤维可以采用溶液纺丝工艺而生长，例如在美国专利4，137,394或4,356,138中所述，通过引用将这两件专利结合到本文中，或者，可以由溶液进行纺丝，从而形成凝胶结构，例如在美国专利4,551,296和5,006,390中所述，通过引用也将这两件专利结合到本文中。
用于本发明的最优选的聚乙烯纤维是霍尼韦尔国际公司(Honeywell International Inc.)的以商标
Figure A200680051614D00121
出售的聚乙烯纤维。纤维在本领域中是众所周知的。就盎司而言，
Figure A200680051614D00123
高性能纤维比钢强十倍，同时也足够轻，从而浮在水上。此纤维也具有其它重要性能，包括抗冲击、抗潮湿、耐磨损化学品和防刺破。这些纤维是优选使用已知作为凝胶纺丝的方法来制备的。在此方法中，将延伸链聚乙烯分子溶解于加热的溶剂中，并使其通过称为喷丝嘴的小喷嘴。所产生的喷射溶液冷却并硬化成聚合物纤维，然后将聚合物纤维进行拉伸、干燥并缠绕到线轴上，以便于进一步制备。这些技术在本领域中是众所周知的。此方法调整延伸链聚乙烯分子，从而每个分子的氢原子与其邻体的原子相连接。这种纤维内的高度碳碳分子键合使
Figure A200680051614D00131
纤维显示出极大的抗张强度。
Figure A200680051614D00132
纤维已经为人熟知了相当长一段时间，并且例如在Harpell等人共同共有的美国专利4,623,547和4,748,064中做了描述。
适合的聚丙烯纤维包括高度取向延伸链聚丙烯(ECPP)纤维，如在美国专利4,413,110中所述，通过引用将此专利结合到本文中。例如，在美国专利4,440,711和4,599,267中描述了适合的聚乙烯醇(PV-OH)纤维，通过引用将这两件专利结合到本文中。例如，在美国专利4,535,027中公开了适合的聚丙烯腈(PAN)纤维，通过引用将此专利结合到本文中。这些纤维类型中的每种都是常规众所周知的，并可广泛地通过商业渠道获得。
适合的芳族聚酰胺(芳族聚酰胺)纤维可通过商业渠道获得，并且例如在美国专利3,671,542中做了描述。例如，有用的聚对苯二甲酰对苯二胺长丝是由杜邦公司商业制备的，商标名为
Figure A200680051614D0013125347QIETU
。在本发明的实施中还有用的是由杜邦商业制备的聚间苯二甲酰间苯二胺纤维，商标名为
Figure A200680051614D00133
用于实施本发明的适合的聚苯并唑纤维可通过商业渠道获得，并且例如在美国专利5,286,833、5,296,185、5,356,584、5,534,205和6,040,050中公开，通过引用将这些专利都结合到本文中。优选的聚苯并唑纤维是出自Toyobo Co的
Figure A200680051614D00134
商标的纤维。用于实施本发明的适合的液晶共聚酯纤维可通过商业渠道获得，并且例如在美国专利3,975,487、4,118,372和4,161,470中公开，通过引用将这些专利都结合到本文中。
用于本发明的其它适合的纤维类型包括玻璃纤维、由碳制备的纤维、由玄武岩或其它矿物制备的纤维、
Figure A200680051614D00135
纤维和所有以上材料的组合，它们都可通过商业渠道获得。
Figure A200680051614D00136
纤维是由Magellan SystemsInternational of Richmond，Virginia制备的，并且例如在美国专利5,674,969、5,939,553、5,945,537和6,040,478中做了描述，通过引用将这些专利都结合到本文中。特别优选的纤维包括
Figure A200680051614D00137
纤维、聚乙烯
Figure A200680051614D00141
纤维、聚对苯二甲酰对苯二胺和聚对亚苯基-2，6-苯并二噁唑纤维。最优选地，纤维包括高强度、高模量聚乙烯
Figure A200680051614D00142
纤维。
用于本发明目的的最优选的纤维为高强度、高抗张模量延伸链聚乙烯纤维。如上所述，高强度、高抗张模量纤维为这样的纤维，即具有由ASTM D2256所测的约7克/旦尼尔或更高的优选韧度、约150克/旦尼尔或更高的优选抗张模量和约8J/g或更高的优选断裂能。在本发明的优选实施方案中，纤维的韧度应当为约15克/旦尼尔或更高，优选约20克/旦尼尔或更高，更优选约25克/旦尼尔或更高，最优选约30克/旦尼尔或更高。本发明的纤维的优选抗张模量为约300克/旦尼尔或更高，更优选约400克/旦尼尔或更高，更优选约500克/旦尼尔或更高，更优选约1,000克/旦尼尔或更高，最优选约1,500克/旦尼尔或更高。本发明的纤维的优选断裂能为约15J/g或更高，更优选约25J/g或更高，更优选约30J/g或更高，最优选具有约40J/g或更高的断裂能。这些组合的高强度性能可通过采用溶液生长或凝胶纤维方法获得。美国专利4,413,110、4,440,711、4,535,027、4,457,985、4,623,547、4,650,710和4,748,064一般讨论了在本发明中采用的优选的高强度、延伸链聚乙烯纤维，通过引用将这些专利的公开内容结合到本文中。
制备本发明的织物的优选技术是用弹性组合物对纤维的至少一个表面进行涂布，优选基本上对每个独立纤维进行涂布或包封，然后压在一起，并将多个这种涂层纤维熔融。因此，本文将此弹性体组合物称为基质组合物。本文使用的术语“基质”在本领域中是众所周知的，并用于表示在加固之后与纤维粘结在一起的聚合材料。术语“复合”是指纤维与基质材料的加固组合。在本发明的优选实施方案中，首先用弹性基质组合物对本发明的纤维进行涂布，然后将多个纤维排列成无纺纤维层。或者，可以将纤维排列在一起，然后用弹性基质组合物进行涂布。
弹性基质组合物可以包括各种各样的聚合物和非聚合物材料。优选的弹性基质组合物包括低模量弹性材料。为了本发明目的，低模量弹性材料具有根据ASTM D638测试程序所测的约6,000psi(41.4MPa)或更小的抗张模量。优选地，弹性体的抗张模量为约4,000psi(27.6MPa)或更小，更优选约2400psi(16.5MPa)或更小，更优选1200psi(8.23MPa)或更小，最优选为约500psi(3.45MPa)或更小。弹性体的玻璃化转变温度(Tg)优选小于约0℃，更优选小于约-40℃，最优选小于约-50℃。弹性体还具有至少约50％的优选断裂伸长率，更优选至少约100％，最优选具有至少约300％的断裂伸长率。
各种各样的弹性材料和制剂可以用在本发明中。适合的弹性体的典型实例的结构、性能、制剂以及交联过程在Encyclopedia of PolymerScience，Volume 5 in the section Elastomers-Synthetic(John Wiley &Sons Inc.，1964)中做了概述。基本要求是本发明的基质材料具有适当低模量，并在纤维熔点之下可模压。适合的低模量弹性材料包括聚丁二烯、聚异戊二烯、天然橡胶、聚乙烯、交联聚乙烯、氯磺化聚乙烯、聚丙烯、乙烯共聚物、丙烯共聚物、乙烯-丙烯共聚物、乙烯-丙烯-二烯烃三元共聚物、聚硫化物聚合物、聚氨酯弹性体、环氧树脂、聚氯丁二烯、塑化聚氯乙烯、丁二烯丙烯腈弹性体、异丁烯-异戊二烯共聚物、聚丙烯酸酯、酚醛树脂、聚缩丁醛、聚酯、聚醚、含氟弹性体、聚硅氧烷弹性体、热塑性弹性体和苯乙烯类嵌段共聚物，例如苯乙烯-异戊二烯-苯乙烯或苯乙烯-丁二烯-苯乙烯类型等。
共轭二烯烃和乙烯基芳族单体的嵌段共聚物是特别有用的。丁二烯和异戊二烯是优选的共轭二烯烃弹性体。苯乙烯、乙烯基甲苯和叔丁基苯乙烯是优选的共轭芳族单体。可以将结合聚异戊二烯的嵌段共聚物氢化，从而制备具有饱和烃弹性体链段的热塑性弹性体。聚合物可以是简单的类型A-B-A的三嵌段共聚物、类型(AB)n(n＝2-10)的多嵌段共聚物或类型R-(BA)x(x＝3-150)的径向结构共聚物；其中A为来自聚乙烯基芳族单体的嵌段，B为来自共轭二烯烃弹性体的嵌段。这些聚合物中许多都是由Kraton Polymers of Houston，TX商业制备，并在公报“
Figure A200680051614D00161
 Thermoplastic Rubber”，SC-68-81中做了描述。最优选的基质聚合物包括由Kraton Polymers商业制备的以商标
Figure A200680051614D00162
出售的苯乙烯类嵌段共聚物。
最优选地，低模量弹性材料基本上由至少一种上述弹性体组成。低模量弹性材料还可以包括诸如炭黑、二氧化硅等填充物，并可以使用对于橡胶技术人员来说众所周知的方法，用油进行延伸，并由硫、过氧化物、金属氧化物或辐射固化系统进行硫化。不同弹性材料的共混物可以一起使用，或者一种或多种弹性体材料可以与一种或多种热塑性材料混合。可以将高密度、低密度和线性低密度聚乙烯交联，以获得单独的或作为共混物的适当性能的涂层基质材料。在每种情况下，涂层的模量不应当超过由ASTM D638测试程序所测的6,000psi(41.4MPa)。
可以采用各种方法将涂层施加于纤维，例如将弹性体的溶液喷涂或辊涂到纤维表面上，然后进行干燥。一种方法是将纯涂层材料作为液体、粘性固体或悬浮液中的颗粒或者作为流化床施加于纤维。或者，可以将涂层应用为适当溶剂中的溶液或乳剂，所述溶剂在应用温度下不会负面影响纤维的性能。虽然可以使用能够溶解或分散涂层聚合物的任何液体，优选的溶剂包括水、石蜡油和芳族溶剂或烃溶剂，其中示例性的具体溶剂包括石蜡油、二甲苯、甲苯、辛烷、环己烷、甲基乙基酮(MEK)和丙酮。用于将涂层聚合物溶解或分散在溶剂中的技术将是那些常规用于将类似的弹性材料涂布在各种基材上的技术。
可以使用用于将涂层施加于纤维的其它技术，包括：在从纤维除去溶剂之前或之后(如果使用凝胶纺丝纤维制备技术)，在纤维经过高温拉伸操作之前涂布高模量前体(凝胶纤维)。然后，可以在升高温度下将纤维进行拉伸，从而制备涂层纤维。可以在实现所需涂层的条件下，使凝胶纤维通过适当涂层聚合物的溶液。在纤维通过溶液之前，凝胶纤维中的高分子量聚合物的结晶可能已经发生或可能还未发生。或者，可以将纤维挤出到适当聚合物粉末的流化床中。此外，如果实施拉伸操作或其它操作方法，例如溶剂交换、干燥等，则可以将涂层施加于最终纤维的前体材料。
在另一涂层技术中，首先形成纤维层，然后将层浸渍到含有低模量弹性涂层材料的溶液的浴中。蒸发溶剂，从而制备出弹性材料涂层纤维网。可以根据需要将浸渍步骤重复多次，从而将所需量的弹性材料涂层置于纤维上。
干燥基质组合物与总织物的比例相对较低，基于织物的总重量，优选为约7％至约15％重量。更优选地，干燥基质组合物占织物的约11％至约15％重量。更优选地，干燥基质组合物占织物的约7％至约14％重量，更优选约7％至约13％，更优选约7％至约12％，更优选约7％至约11％重量。已经意外发现，织物以及织物上的外聚合物膜层中的总基质含量的减少使得织物除了具有优异防弹性能之外还具有优异防碎片性能。如果所述纤维包含芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，则基质组合物优选占所述加固纤维网的至少约11％重量。
在本发明的优选实施方案中，首先使用以上技术中的一种对本发明的纤维进行涂布，然后将多个纤维排列成无纺纤维层。优选地，将各个纤维设置为彼此相邻并彼此接触，并将其排列成片状纤维阵列，其中将纤维排列为沿着共同的纵向纤维方向彼此基本上平行。在用于将纤维排列成这种结构的特别有效的技术中，使纤维通过含有弹性材料的溶液的浴，然后围绕并沿着诸如圆柱体的适当形式的长度将其螺旋缠绕成单片状的层。然后蒸发溶剂，从而留下平行排列的纤维的预浸渍片，可以将其从圆柱形上去掉，并切成所需尺寸。或者，可以使多个纤维同时通过弹性体溶液的浴，并以紧密设置的基本上彼此平行将其铺放在适当的表面上。蒸发溶剂，从而留下包括弹性体涂层纤维的预浸渍片，所述弹性体涂层纤维基本上平行，并沿着共同的纤维方向排列。
优选遵循以上方法，以形成至少两个单向纤维层，由此使用低模量弹性基质组合物在所有纤维表面上对纤维充分进行涂布。然后，将纤维层优选加固成单层加固纤维网。这可以通过以下方法实现，即，将各个纤维层进行层叠，一个在另一个之上，然后，在将总体结构热定形的热和压力下，将它们粘结在一起，从而使基质材料流动并占据任何剩余空隙空间。在本领域中常规众所周知，当独立的纤维层交叉层叠时，使得一层的纤维排列方向相对于另一层的纤维排列方向以一定角度进行旋转，因而它们是不平行的，从而实现了优异的防弹性能。例如，优选的结构具有本发明的两个纤维层，将它们设置在一起，使得一层的纵向纤维方向垂直于另一层的纵向纤维方向。在另一例子中，形成5层结构，其中相对于第一层，将第二层、第三层、第四层和第五层旋转+45°、-45°、90°和0°，但不一定以这种次序。为了本发明目的，可以将相邻层相对于另一层的纵向纤维方向以约0°和约90°之间的几乎任何角度进行排列，但约0°和约90°的纤维取向是优选的。虽然以上例子描述了包括两个或五个独立纤维层的织物，但这不旨在具有限制性。应当理解的是，本发明的单层加固网通常可包括任意数量的交叉层叠的层，例如约20至约40或更多层，如各种应用所要求。
用于加固纤维层并连接聚合物膜层的适当粘结条件包括常规众所周知的层压技术。一种典型的层压方法包括在约200psi(1379kPa)压力下，在约110℃下，将聚合物膜压在交叉层叠的材料上约30分钟。本发明的独立纤维层的加固优选在约200℉(～93℃)至约350℉(～177℃)的温度下，更优选在约200℉至约300℉(～149℃)的温度下，最优选在约200℉至约250℉(～121℃)的温度下，并在约25psi(～172kPa)至约500psi(3447kPa)或更高的压力下实施。加固可以在高压釜中实施，这在本领域中是常规众所周知的。
当加热时，可以在不完全熔化的情况下使基质粘附或流动。但通常，如果使基质材料熔化，则需要相对小的压力，以形成复合材料，但如果仅将基质材料加热到粘附温度，则通常需要更大的压力。加固步骤通常可占用约10秒至约24小时。但是，层压温度、压力和时间通常取决于基质聚合物的类型、基质聚合物含量和纤维的类型。
在纤维层加固之后，通过常规方法，优选将聚合物层连接到单层加固网的前表面和后表面。用于所述聚合物层的适当聚合物非限制性地包括热塑性和热固性聚合物。适当的热塑性聚合物非限制性地可选自聚烯烃、聚酰胺、聚酯、聚氨酯、乙烯基聚合物、含氟聚合物和共聚物以及它们的混合物。其中，聚烯烃层是优选的。优选的聚烯烃为聚乙烯。聚乙烯膜的非限制性实例为低密度聚乙烯(LDPE)、线形低密度聚乙烯(LLDPE)、线形中密度聚乙烯(LMDPE)、线形极低密度聚乙烯(VLDPE)、线形超低密度聚乙烯(ULDPE)、高密度聚乙烯(HDPE)。其中，最优选的聚乙烯为LLDPE。适当的热固性聚合物非限制性地包括热固性烯丙基类树脂、氨基类树脂、氰酸酯、环氧树脂、酚醛树脂、不饱和聚酯、双马来酰亚胺树脂、刚性聚氨酯、硅树脂、乙烯基酯和它们的共聚物及共混物，例如在美国专利6,846,758、6,841,492和6,642,159中所述。如本文所述，聚合物膜包括聚合物涂层。
使用众所周知的层压技术，优选将聚合物膜层连接到单层加固网。通常，通过以下方法进行层压，即在使层组合成单一膜的足够热和压力的条件下，将各层相互叠置。将各层相互叠置，然后通常通过本领域中众所周知的技术，将此组合通过一对加热层压辊的辊隙。可以在以下条件下进行层压加热，即，温度为约95℃至约175℃，优选约105℃至约175℃，压力为约5psig(0.034MPa)至约100psig(0.69MPa)，持续时间为约5秒至约36小时，优选约30秒至约24小时。在本发明的优选实施方案中，聚合物膜层优选占总织物的约2％至约25％重量，更优选总织物的约2％至约17％重量，最优选2％至12％。通常，聚合物膜层的重量百分数将根据形成多层膜的织物层的数量而改变。虽然本文将加固和外聚合物层层压步骤描述成两个独立的步骤，但也可以通过本领域的常规技术将它们组合成单个加固/层压步骤。
聚合物膜层优选是非常薄的，优选层厚度为约1μm至约250μm，更优选约5μm至约25μm，最优选约5μm至约9μm。各个织物层的厚度将对应于各个纤维的厚度。因此，本发明的优选单层加固网的优选厚度为约25μm至约500μm，更优选约75μm至约385μm，最优选约125μm至约255μm。虽然这些厚度是优选的，但应当理解的是，可以制备其它膜厚度，以满足特定需要，并且还落在本发明的范围内。
本发明的织物还显示出良好的剥离强度。剥离强度是纤维层间的粘结强度的指标。通常，基质聚合物含量越低，粘结强度越低，但防碎片性能越高。但是，在临界粘结强度以下，防弹材料在诸如背心的制品的材料切割和组装过程中损失耐用性，并且还导致制品的长期耐用性降低。在优选的实施方案中，
Figure A200680051614D0020125544QIETU
 Shield(0°，90°)结构中的
Figure A200680051614D0020125544QIETU
纤维材料的剥离强度对于良好的防碎片性能而言为优选至少约0.17 1b/ft2，更优选至少约0.188 1b/ft2，更优选至少约0.2061b/ft2。已经发现，对于具有至少约11％至约15％基质含量的本发明的织物来说，特别对于芳族聚酰胺纤维和聚对亚苯基苯并二噁唑纤维来说，实现了最佳的剥离强度。
在织物形成之后，它们可以用于各种应用。例如，可以通过使它们经受热和压力而将它们模制成制品。用于模制的温度可以为约20℃至约175℃，优选约100℃至约150℃，更优选约110℃至约130℃。还适合的是在以下专利中描述的适于制备制品的技术，例如美国专利4,623,574、4,650,710、4,748,064、5,552,208、5,587,230、6,642,159、6,841,492和6,846,758。
在本发明的优选实施方案中，将多个单层加固纤维网排列在一起，以形成柔性制品，包括诸如背心、裤子、帽子的服装或其它衣服制品，这在本领域中是众所周知的。还可以根据需要将本发明的织物制备成诸如头盔的其它个人防护制品，或可以将其制备成防护屏、防护罩或防护层。纤维网可以单独保持织物的高柔度特性，并优选保持彼此分开，即不粘结在一起。或者，可以将多层织物缝合在一起或用粘合材料或其它热塑性或非热塑性纤维或材料粘结在一起。因此，本发明的制品可包括组装成粘结或非粘结阵列的多个无纺的防碎片织物。
可以通过在本领域中常规已知的方法来制备本发明的服装。优选地，通过将本发明的防碎片织物与衣服制品结合来制备服装。例如，防碎片背心可以包括与本发明的防碎片织物结合的普通织物背心，由此将本发明的织物插入到战略设置的袋中。这使得防碎片和防弹性能实现最大化，同时使得背心的重量实现最小化。本文使用的术语“邻接”或“邻接的”旨在包括连接，例如通过缝合或粘附等，以及与另一织物不连接的偶合或并列，使得可以任选从背心或其它衣服制品容易地去掉防碎片织物。
包括根据本发明构造的多层织物的背心或其它衣服制品具有良好的柔性和舒适度，以及优异的防弹和防碎片性能。小的尖角射弹可以通过使纤维横向移位且未将它们破裂而穿过盔甲。在这种情况下，防穿透性能取决于如何容易地将纤维推开，因此取决于纤维网的性质。无纺织物的防弹或防碎片性能的一个重要因素是交叉层叠的单向复合材料中的交叉周期性和纤维旦尼尔、纤维与纤维摩擦力、基质特性、层间粘结强度等。
锐利的碎片可以通过剪切纤维而穿透。射弹也可以破坏处于拉伸状态的纤维。射弹对织物的冲击导致应变波传播通过织物。如果应变波可以快速并且无妨碍地传播通过织物并涉及越大体积的纤维，则防弹性能越好。实施方案的层间的界面结合越低，能量吸收越高。实验和分析工作已显示出，在所有实际情况下，存在所有穿透模式，并且它们的相对重要性受到复合材料设计的极大影响。
使用本领域中众所周知的标准测试程序测定防弹和防碎片性能。例如，防弹复合材料的遮护研究通常采用具体重量、硬度和尺寸的22口径的非变形钢碎片(Mil-Spec.MIL-P-46593A(ORD))。
通常，结构的防护能力或防穿透性能通过引用冲击速度来表示，其中50％的射弹穿透复合材料，同时50％被防护物阻挡，还称之为V50值。本文使用的制品的“防穿透性能”是防指定威胁穿透的能力，例如包括子弹、碎片、榴散弹等的物理对象和诸如爆炸冲击波的非物理对象。对于相等面密度的复合材料而言，面密度即复合材料板的重量除以表面积，V50越高，复合材料的阻挡性能越好。对指定威胁的防穿透性能还可以用防弹材料的总比能量吸收(“SEAT”)来表示。总SEAT是威胁的动能除以复合材料面密度。SEAT值越高，复合材料对威胁的阻挡性能越好。
本发明的织物的防弹和防碎片性能将根据许多因素特别是用于制备织物的纤维类型而变化。但是，已经意外发现，与具有更大量的基质聚合物的类似织物相比，本发明的织物具有提高的V50值和提高的目标的比能量吸收，这可以参见以下实施例和数据表。
以下非限制性的实施例用于描述本发明。
实施例
实施例1(对比)
弹道射击组件(ballistic shoot pack)是通过将18个织物层层叠在一起而制备的，每个织物层包括加固网，所述加固网具有用
Figure A200680051614D0022125639QIETU
热塑性聚合物浸渍的两片(层)单向高模量聚乙烯(HMPE)纤维，每一层都以彼此呈直角的方式(0度/90度)交叉层叠，并层压在两片线形低密度聚乙烯(LLDPE)膜之间。
HMPE纤维是由霍尼韦尔国际公司生产的
Figure A200680051614D0022125657QIETU
 1000，1100旦尼尔，并具有36克/旦尼尔的韧度和1250克/旦尼尔的抗张模量。所用的
Figure A200680051614D0022125715QIETU
聚合物为聚苯乙烯-聚异戊二烯-聚苯乙烯-嵌段共聚物。在添加聚乙烯膜之前，基于织物的总重量，每个织物层包含79％重量的纤维和21％重量的
Figure A200680051614D0022125715QIETU
聚合物。
LLDPE膜各自具有9μm的厚度。每个LLDPE膜的面密度为8gsm(gram/m2)。在110℃、约200psi(1379kPa)压力下，将LLDPE膜层压到交叉层叠的材料，持续时间为至少30分钟。一个织物层的总面密度为116gsm。制备连续的材料层压片，并将其卷绕到滚筒上。层压片具有0.006”(0.1524mm)的厚度。然后，将片进行剪切，从而形成18个独立层，每层具有18”X 18”(45.7mm X 45.7mm)的长度和宽度。然后，将这18层松散地层叠在一起，以形成射击组件。这些层不相互粘结。射击组件的面密度为0.43 1b/ft2(2.09kg/m2)。
为了测试防碎片性能，将射击组件安装在测试框架上，并牢固地夹在框架的上部。将框架安装在与从牢固安装的通用接收机射出的碎片的线路呈90度的方向。17格令碎片模拟弹(FSP)用于进行测试，并符合依照MIL-P-46593A的形状、尺寸和重量。V50防弹测试是根据MIL-STD-662F程序进行的。V50防弹极限测试是在实验上确定速度的统计测试，子弹在此速度下具有50％的机会穿透测试目标。
发射数个17格令FSP碎片，改变每个碎片的速度。根据之前碎片射击是否完全穿透或部分穿透射击组件的一些层，将每个碎片的速度调低以及调高。通过在约125英尺每秒(fps)的速度范围内优选包括约四个部分穿透和约四个完全碎片穿透来取得平均速度。将部分穿透和完全穿透的平均速度称为V50。测得该射击组件的V50为1201 fps。计算目标的比能量吸收(SEAT)为34.88J-m2/kg。
实施例1A(对比)
重复实施例1，但采用的射击组件具有面密度为0.44 1b/ft2(2.15kg/m2)的19个层叠的织物层。测得该射击组件的V50为1217 fps。计算目标的比能量吸收(SEAT)为35.01 J-m2/kg。
实施例2
弹道射击组件是通过将如实施例1所述
Figure A200680051614D0023125802QIETU
 1000，1100旦尼尔的20个织物层层叠在一起而制备的。每个织物层包含基于织物层重量的88.7％重量的纤维，并包含基于织物层重量的11.3％重量的基质聚合物。LLDPE膜具有9μm的厚度。LLDPE膜的面密度为8gsm。一个织物层的总面密度为103.9gsm。材料的层压片具有0.1524mm的厚度。
射击组件的尺寸为18”X 18”(45.7mm X 45.7mm)。片的层叠不彼此连接。射击组件的面密度为0.43 1b/ft2(2.09kg/m2)。如实施例1一样，测试组件的防碎片性能。测得该射击组件的V50为1412fps。计算目标的比能量吸收(SEAT)为48.2J-m2/kg。此实施例显示出用具有11％基质聚合物(与实施例1的21％相比)的
Figure A200680051614D0023125802QIETU
1000，1100旦尼尔织物实现优异的防碎片性能。
实施例3(对比)
重复实施例1，但射击组件包括32个织物层，并针对9mm全金属外壳(FMJ)子弹进行测试。射击组件的尺寸为18”X 18”(45.7mm X45.7mm)。射击组件的面密度为0.74 1b/ft2(3.61kg/m2)。为了测试对9mm FMJ子弹的阻挡性，将射击组件安装在用Plastilina #1粘土填充的测试框架上，并缚在框架上。将Plastilina填充的框架安装在与从牢固安装的通用接收机射出的碎片的线路呈90度的方向。用于进行测试的9mm FMJ子弹符合依照国家司法学会(National Institute ofJustice)(NIJ)0101.04试验标准的形状、尺寸和重量。
根据MIL-STD-662F的程序进行防弹测试。发射数个9mm FMJ子弹，改变每一个的速度。根据之前碎片射击是否完全穿透或部分穿透射击组件的一些层，将每个9mm FMJ子弹的速度调低以及调高。通过在125fps的速度范围内包括约四个部分穿透和约四个完全子弹穿透来取得平均速度。计算部分和完全穿透速度的平均值，并称之为V50。测得该射击组件的V50为1525fps。计算目标的比能量吸收(SEAT)为236.81 J-m2/kg。
实施例4
重复实施例2，但针对9mm FMJ子弹进行测试。射击组件的尺寸为18”X 18”(45.7mm X 45.7mm)。射击组件的面密度为0.43 1b/ft2(2.09kg/m2)。如实施例3一样，进行防弹测试。测得该射击组件的V50为1272fps。计算目标的比能量吸收(SEAT)为284.46 J-m2/kg。此实施例显示出用具有11％基质聚合物(与实施例3的21％相比)的
Figure A200680051614D00251
 1000，1100旦尼尔织物实现优异的防弹性能。
实施例5(对比)
弹道射击组件是通过将27个织物层层叠在一起而制备的，每个织物层包括加固网，所述加固网具有用
Figure A200680051614D00252
聚合物浸渍的两片单向HMPE纤维，每片都以彼此呈直角的方式交叉层叠，并层压在两片LLDPE膜之间。
HMPE纤维是由霍尼韦尔国际公司生产的
Figure A200680051614D00253
1000，1300，并具有36克/旦尼尔的韧度和1150克/旦尼尔的抗张模量。每个织物层包含基于织物重量的79％重量的纤维，并包含基于织物重量的21％重量的基质聚合物。LLDPE膜各自具有9μm的厚度。LLDPE膜的面密度为8gsm。一个织物层的总面密度为150.0gsm。材料的层压片具有0.1651mm的厚度。
射击组件的尺寸为18”X18”(45.7mm X 45.7mm)。27片的层叠不彼此连接。射击组件的面密度为0.84 1b/ft2(4.1kg/m2)。如同实施例1，进行防碎片测试。测得该射击组件的V50为1501fps。计算目标的比能量吸收(SEAT)为27.86 J-m2/kg。
实施例6
弹道射击组件是通过将如实施例5所述
Figure A200680051614D00254
 1000，1300的29个织物层层叠在一起而制备的。每个织物层包含基于织物层重量的92.9％重量的纤维，并包含基于织物重量的7.1％重量的基质聚合物。一个织物层的总面密度为129.0gsm。射击组件的尺寸为18”X 18”(45.7mm X 45.7mm)。片的层叠不彼此连接。射击组件的面密度为0.771b/ft2(3.75kg/m2)。
如同实施例1，进行碎片测试。计算八个部分和完全穿透速度的平均值，并称之为V50。测得该射击组件的V50为1660fps。计算目标的比能量吸收(SEAT)为37.12J-m2/kg。此实施例显示出用具有7％基质聚合物(与实施例5的21％相比)的
Figure A200680051614D00261
 1000，1300织物实现优异的防碎片性能。
实施例7
弹道射击组件是通过将如实施例5所述
Figure A200680051614D00262
 1000，1300纤维的28个织物层层叠在一起而制备的。每个织物层包含基于织物层重量的89.9％重量的纤维，并包含基于织物层重量的10.1％重量的基质聚合物。一个织物层的总面密度为132.8gsm。射击组件的尺寸为18”X 18”(45.7mm X 45.7mm)。片的层叠不彼此连接。射击组件的面密度为0.77 1b/ft2(3.75kg/m2)。
如同实施例1，进行碎片测试。测得该射击组件的V50为1616fps。计算目标的比能量吸收(SEAT)为35.73 J-m2/kg。此实施例显示出用具有10％基质聚合物(与实施例5的21％相比)的
Figure A200680051614D00263
 1000，1300织物实现优异的防碎片性能。
实施例7A
弹道射击组件是通过将如实施例7所述
Figure A200680051614D00264
 1000，1300纤维的29个织物层层叠在一起而制备的。每个织物层包含基于织物层重量的85.0％重量的纤维，并包含基于织物层重量的15.0％重量的基质聚合物。射击组件的面密度为0.83 1b/ft2(4.05kg/m2)。
如同实施例1，进行碎片测试。测得该射击组件的V50为1648fps。计算目标的比能量吸收(SEAT)为34.03 J-m2/kg。此实施例显示出用具有15％基质聚合物(与实施例5的21％相比)的
Figure A200680051614D00265
 1000，1300织物实现优异的防碎片性能。
实施例8(对比)
重复实施例5，但针对如实施例3所述的9mm FMJ子弹进行测试。测得该射击组件的V50为1450fps。计算目标的比能量吸收(SEAT)为189.22 J-m2/kg。
实施例9
重复实施例7，但针对如实施例3所述的9mm FMJ子弹进行测试。如同实施例3，进行测试。测得该射击组件的V50为1519fps。计算目标的比能量吸收(SEAT)为226.54J-m2/kg。此实施例显示出用具有10％基质聚合物(与实施例8的21％相比)的
Figure A200680051614D00271
 1000，1300织物实现优异的防弹性能。
在下表中总结从实施例1-9收集的数据：
Figure A200680051614D00281
(*)用环已烷作为溶剂的
Figure A200680051614D00282
聚合物。
(**)乳液聚合物聚苯乙烯-聚异戊二烯-聚苯乙烯-嵌段共聚物。
射击组件(目标)尺寸18”X 18”：面密度是弹道射击组件的重量，用1bs/ft2(psf)表示。
SEAT为目标的比能量吸收。
实施例10-12
测试
Figure A200680051614D00283
 Shield LCR的三个不同样品的剥离强度性能，每个样品具有不同的基质聚合物含量。
 Shield LCR样品分别包含以下分层构造的四层结构：LLDPE膜/0°纤维层/90°纤维层/LLDPE膜。标准剥离强度试验是通过在纤维层之间剥离而进行的。在下表中总结结果：
Figure A200680051614D00292
实施例10-12显示出，基质聚合物含量越低，粘结强度越小。但是，在临界粘结强度以下，防弹材料在诸如背心等制品的材料切割和组装过程中损失耐用性，并且还导致制品的长期耐用性降低。具有6.04％基质聚合物含量的实施例10的样品显示出0.089lbs/ft2的不可接受的剥离强度。具有11.43％基质聚合物含量的实施例11的样品显示出0.188lbs/ft2的良好剥离强度。此样品还显示出优异的防碎片和防弹性能。具有20.0％基质聚合物含量的实施例12的样品显示出1.766lbs/ft2的强剥离强度，但此样品仅显示出勉强够格的防碎片性能。
虽然已经参照优选实施方案具体显示并描述了本发明，但本领域普通技术人员将容易地认识到，在不脱离本发明的精神和范围的基础上，可以做出各种改变和修改。应当将权利要求书解释为涵盖所公开的实施方案、以上已讨论的那些供选方案及其所有等同物。

Claims (33)

1.一种防碎片材料，所述防碎片材料包括：
a)至少一种加固纤维网，所述加固纤维网包括多个交叉层叠的无纺纤维层，每个纤维层包括以基本上平行的阵列排列的多个纤维；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维在其上具有弹性基质组合物，所述弹性基质组合物占所述加固纤维网的约7％至约15％重量；用所述基质组合物对所述多个交叉层叠的无纺纤维层进行加固，从而制备所述加固纤维网；所述加固纤维网具有前表面和后表面；其中如果所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，所述基质组合物占所述加固纤维网的至少约11％重量；和
b)至少一层聚合物膜，所述聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
2.权利要求1的防碎片材料，其中所述纤维包括韧度为约15克/旦尼尔或更高并且抗张模量为约400克/旦尼尔或更高的纤维。
3.权利要求1的防碎片材料，其中所述纤维包括韧度为约30克/旦尼尔或更高并且抗张模量为约1000克/旦尼尔或更高的纤维。
4.权利要求1的防碎片材料，其中所述纤维包括选自延伸链聚烯烃纤维、芳族聚酰胺纤维、聚苯并唑纤维、聚乙烯醇纤维、聚酰胺纤维、聚对苯二甲酸乙二醇酯纤维、聚萘二甲酸乙二醇酯纤维、聚丙烯腈纤维、液晶共聚酯纤维、玻璃纤维和碳纤维的材料。
5.权利要求1的防碎片材料，其中所述纤维包括聚乙烯纤维。
6.权利要求1的防碎片材料，其中所述基质组合物包括选自聚丁二烯、聚异戊二烯、天然橡胶、乙烯-丙烯共聚物、乙烯-丙烯-二烯烃三元共聚物、聚硫化物聚合物、聚氨酯弹性体、氯磺化聚乙烯、聚氯丁二烯、塑化聚氯乙烯、丁二烯丙烯腈弹性体、异丁烯-异戊二烯共聚物、聚丙烯酸酯、聚酯、聚醚、含氟弹性体、聚硅氧烷弹性体、乙烯共聚物以及它们的组合的材料。
7.权利要求1的防碎片材料，其中所述基质组合物包括聚苯乙烯-聚异戊二烯-聚苯乙烯嵌段共聚物。
8.权利要求1的防碎片材料，其中所述基质组合物占所述加固纤维网的约7％至约14％重量。
9.权利要求1的防碎片材料，其中所述基质组合物占所述加固纤维网的约7％至约13％重量。
10.权利要求1的防碎片材料，其中所述基质组合物占所述加固纤维网的约7％至约12％重量。
11.权利要求1的防碎片材料，其中所述基质组合物占所述加固纤维网的约7％至约11％重量。
12.权利要求1的防碎片材料，其中所述基质组合物占所述加固纤维网的约11％至约15％重量。
13.权利要求1的防碎片材料，其中所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，并且所述基质组合物占所述加固纤维网的约11％至约15％重量。
14.权利要求1的防碎片材料，其中所述聚合物膜层占总材料的约2％至约25％重量。
15.权利要求1的防碎片材料，其中所述聚合物膜层包括选自聚烯烃、聚酰胺、聚酯、聚氨酯、乙烯基聚合物、含氟聚合物和共聚物以及它们的组合的材料。
16.权利要求1的防碎片材料，其中所述聚合物膜层包含线形低密度聚乙烯。
17.权利要求1的防碎片材料，其中所述每个纤维层以相对于每个相邻纤维层的纵向纤维方向呈90°角度交叉层叠。
18.一种包含防碎片材料的防碎片制品，所述防碎片材料包括：
a)至少一种加固纤维网，所述加固纤维网包括多个交叉层叠的无纺纤维层，每个纤维层包括以基本上平行的阵列排列的多个纤维；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维在其上具有弹性基质组合物，所述弹性基质组合物占所述加固纤维网的约7％至约15％重量；用所述基质组合物对所述多个交叉层叠的无纺纤维层进行加固，从而制备所述加固纤维网；所述加固纤维网具有前表面和后表面；其中如果所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，所述基质组合物占所述加固纤维网的至少约11％重量；和
b)至少一层聚合物膜，所述聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
19.权利要求18的防碎片制品，所述防碎片制品包括以粘结阵列组装的多个加固纤维网。
20.权利要求18的防碎片制品，所述防碎片制品包括以非粘结阵列组装的多个加固纤维网。
21.权利要求18的防碎片制品，所述防碎片制品包括服装，所述服装具有与其邻接的多个加固纤维网。
22.权利要求21的防碎片制品，其中所述服装包括背心，所述背心具有与其邻接的所述多个加固纤维网。
23.权利要求18的防碎片制品，其中所述基质组合物占所述加固纤维网的约7％至约11％重量。
24.权利要求18的防碎片制品，其中所述基质组合物占所述加固纤维网的约11％至约15％重量。
25.权利要求18的防碎片制品，其中所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，并且所述基质组合物占所述加固纤维网的约11％至约15％重量。
26.权利要求18的防碎片制品，其中所述每个纤维层以相对于每个相邻纤维层的纵向纤维方向呈90°角度交叉层叠。
27.一种制备防碎片材料的方法，所述方法包括：
a)形成至少两个纤维层，每个纤维层通过将多个纤维排列成基本上平行的单向阵列而形成；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维具有施加到其上的弹性基质组合物；
b)将所述纤维层进行排列，其中将每个单向阵列的纤维层以相对于每个相邻层的纵向纤维方向呈非平行角度交叉层叠；
c)在足以形成加固纤维网的条件下粘结所述交叉层叠的层，所述加固纤维网具有前表面和后表面；其中所述基质组合物占所述加固纤维网的约7％至约15％重量，并且其中如果所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，所述基质组合物占所述加固纤维网的至少约11％重量；和
d)将至少一层聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
28.权利要求27的方法，其中所述基质组合物占所述加固纤维网的约7％至约11％重量。
29.权利要求27的方法，其中所述基质组合物占所述加固纤维网的约11％至约15％重量。
30.权利要求27的方法，其中所述纤维包括芳族聚酰胺纤维或聚对亚苯基苯并二噁唑纤维，并且所述基质组合物占所述加固纤维网的约11％至约15％重量。
31.权利要求27的方法，其中所述每个纤维层以相对于每个相邻纤维层的纵向纤维方向呈90°角度交叉层叠。
32.一种防碎片材料，所述防碎片材料包括：
a)至少一种加固纤维网，所述加固纤维网包括多个交叉层叠的纤维层，每个纤维层包括以阵列排列的多个纤维；所述纤维具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的抗张模量；所述纤维在其上具有弹性基质组合物，所述弹性基质组合物占所述加固纤维网的约7％至约15％重量；用所述基质组合物对所述多个交叉层叠的纤维层进行加固，从而制备所述加固纤维网；所述加固纤维网具有前表面和后表面；和
b)至少一层聚合物膜，所述聚合物膜与所述加固纤维网的所述前表面和后表面相连接。
33.一种制品，所述制品包括权利要求32的防碎片材料。
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US7629277B2 (en) 2009-12-08
ES2420956T3 (es) 2013-08-28
WO2007089317A8 (en) 2008-07-10
KR101360856B1 (ko) 2014-02-21
TWI359935B (en) 2012-03-11
BRPI0619072A2 (pt) 2011-09-20
EP1951510A2 (en) 2008-08-06
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IL191662A0 (en) 2008-12-29
WO2007089317A3 (en) 2007-09-27

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