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CN1320071A - 混合的保护复合材料 - Google Patents

混合的保护复合材料 Download PDF

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CN1320071A
CN1320071A CN99811378A CN99811378A CN1320071A CN 1320071 A CN1320071 A CN 1320071A CN 99811378 A CN99811378 A CN 99811378A CN 99811378 A CN99811378 A CN 99811378A CN 1320071 A CN1320071 A CN 1320071A
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composite
polybenzoxazole
woven fabric
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CN1123442C (zh
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M·J·奇欧
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
    • A41D31/245—Resistant to mechanical stress, e.g. pierce-proof using layered materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced 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
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2571/00—Protective equipment
    • B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/911—Penetration resistant layer
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    • 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.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
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    • Y10T442/2623—Ballistic resistant
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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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.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3472—Woven fabric including an additional woven fabric layer
    • Y10T442/348—Mechanically needled or hydroentangled
    • Y10T442/3488—Four or more layers
    • 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.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3472—Woven fabric including an additional woven fabric layer
    • Y10T442/3504—Woven fabric layers comprise chemically different strand material

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  • Textile Engineering (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Woven Fabrics (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Multicomponent Fibers (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

公开了抵抗刀刺穿的复合材料(10),该复合材料由至少一层编织的聚苯并噁唑或聚苯并噻唑织物层(12)和至少一层另一种聚合物的纤维网层(14)制成。

Description

混合的保护复合材料
                    本发明背景
本发明领域
本发明涉及在刀刺抵抗领域的保护复合材料，与当前可得的其它保护复合材料比较，该复合材料一方面在给定重量下提供了更大的保护，另一方面在更轻的重量中提供相等的保护。本发明的复合材料是柔韧性的，也提供好的保护抵抗射击的威胁。
先有技术的说明
1993年10月14日公布的国际公开WO93/20400公开了聚苯并噁唑和聚苯并噻唑纤维在射击抵抗制品中的使用。
                     本发明概述
本发明提供一种保护的复合结构，该复合结构具有至少一层包含聚苯并噁唑(PBO)或聚苯并噻唑(PBT)纤维的编织织物和至少一层其它聚合物材料纤维网。除了其它材料外，所述其它聚合物材料可以是聚酰胺和聚烯烃。
                      附图概述
附图表示本发明复合材料的放大透视图。
                      详细说明
尽管刀刺保护经常作为在射击保护之后的次要性能，复合材料的刀刺保护的改进仍是我们不断寻找的。通常，在警卫、警察等穿戴的衣装中需要刀刺保护；射击保护在这类衣装中也是一种需要的性能。这类衣装必须尽可能柔软，以保证充分舒适，使得衣装容易穿戴。
为了获得一定水平的刺保护，由于本发明的材料的混合复合结合与获得同样保护程度的仅是单一材料比较，需要较少量的材料，因此表现为柔韧性增大。或者，本发明材料的混合复合可以组合成具有提高的刺保护，所用材料的总数与在所述复合材料中当仅使用单一材料时所需的量相等。
该混合复合材料在一部分至少一层是聚苯并噁唑或聚苯并噻唑，在另一部分至少一层是另一种聚合物。
聚苯并噁唑和聚苯并噻唑通常如在前述WO93/20400的描述(通过引用结合到本文中来)。优选聚苯并噁唑和聚苯并噻唑由以下结构的链节组成：
Figure A9981137800051
虽然显示连接氮原子的芳香基团可以是杂环的，但优选它们是碳环；虽然它们可能是稠合或非稠合多环体系，但优选它们是单一的六员环。虽然在二唑系主链中显示的基团优选为对-亚苯基团，但该基团可能被不阻碍聚合物合成的任何二价的有机基团取代，或完全没有基团取代。例如，该基团可能是至多为12个碳原子的脂肪族的、甲代亚苯基、亚联苯基、二亚苯基醚等。
用来制备本发明的纤维的聚苯并噁唑和聚苯并噻唑应具有至少25个，优选至少100个链节单元。在前述的国际公开WO93/20400中公开了这些聚合物的制备和这些聚合物的纺丝。
其它聚合物材料通常可以是生产具有至少每分特(dtex)10克的韧性和至少每分特160克的初始模量的纤维的任何材料。其它聚合物材料的优选材料是聚酰胺、聚烯烃、聚乙烯醇、聚丙烯腈等。优选的聚酰胺是芳族聚酰胺，特别是对芳族聚酰胺。其它聚酰胺包括脂肪族的聚酰胺，例如尼龙66、脂族-芳族的聚酰胺、芳族-杂环的聚酰胺等。优选聚烯烃是聚乙烯或聚丙烯，特别是线性的所谓的伸长链聚乙烯或聚丙烯。其它聚烯烃包括聚丁烯、聚甲基-1-戊烯等。
本发明提供保护复合结构，所述复合结构具有其中一部分是至少一层包含聚苯并噁唑或聚苯并噻唑纤维的编织织物和一部分是至少一层其它聚合物材料纤维网。
聚苯并噁唑和聚苯并噻唑纤维以任何通常使用的织物构型编织，例如平纹、四经破缎纹、席纹和缎纹等编织。优选平织。
我们相信本发明中的任何线密度的纤维和纱线将有效提高刺抵抗力。单丝的优选线密度为0.3-17分特，最优选0.5-3.5分特。优选在100-3300分特，最优选220-1700分特范围的纱线。线密度大于3300分特的纱线一般更难生产和有效使用，线密度小于100分特的纱线对其没有损害下较难编织。
当所述其它聚合物是聚酰胺时，优选是芳族聚酰胺。术语“芳族聚酰胺”的意思是聚酰胺，其中至少85％酰胺键(-CO-NH-)直接地连在两个芳环上。适合芳族聚酰胺纤维在W.Black等著，国际科学出版社于1968年出版的人造纤维-科学与技术，第二卷，节标题为芳香聚酰胺纤维的形成，第297页中描述。美国专利4,172,938、3,869,429、3,819,587、3,673,143、3,354,127和3,094,511也公开了芳族聚酰胺纤维。
添加剂可用在所述芳族聚酰胺中，已经发现至多10％(重量)的其它聚合物材料可与所述芳族聚酰胺混合，或可以使用的该共聚物具有差不多10％取代所述芳族聚酰胺的二胺的其它二胺，或差不多10％取代二酰氯或芳族聚酰胺的其它二酰氯。
优选芳族聚酰胺是对-芳族聚酰胺和聚(对-亚苯基对苯二酰胺)(PPD-T)是优选的对-芳族聚酰胺。PPD-T的意思是由对-亚苯基二胺和对-苯二酰氯摩尔对摩尔聚合产生的均聚物，也是由少量的具有对-亚苯基二胺的其它二胺和少量的具有对-苯二酰氯的其它二酰氯产生的均聚物。作为一般的规则，其它二胺和其它二酰氯可以至多是所述对-亚苯基二胺或所述对-苯二酰氯的10％(摩尔)的量使用，或也许稍微高一些，条件是其它二胺和二酰氯没有防碍聚合反应的反应基团。PPD-T的意思也是由其它芳族二胺和其它芳族二酰氯例如2,6-萘二甲酰氯(naphthaloyl)或氯代或二氯对-苯二酰氯或3,4’-二氨基二苯醚结合产生的共聚物。
当所述其它聚合物是聚烯烃时，优选聚乙烯或聚丙烯。聚乙烯的意思主要优选分子量超过一百万的线形聚乙烯材料，其中包含较少数量的支链或每100个主链碳原子不超过5个改性单元的共聚单体，此外也可能包含混合的不超过大约50％(重量)的一种或多种聚合物添加剂，例如烯烃-1-聚合物，特别是低密度聚乙烯、丙烯等或低分子量添加剂例如抗氧化剂、润滑剂、紫外屏蔽剂、着色剂等通常掺合的添加剂。这种通常称为伸长链聚乙烯(ECPE)。同样地，聚丙烯主要优选分子量超过一百万的线性聚丙烯材料。高分子量线性聚烯烃纤维是商业可得到的。聚烯烃纤维的制备在US4,457,985中论述。
在本发明的复合材料中，另一种聚合物以纤维的网存在。所述网可能是编织、针织或非编织结构；非编织的意思是单向的(如果包含在一个基体树脂之内)、粘结起来的等。编织的意思是任何通常使用的织纹，例如平纹、四经破缎纹、席纹、缎纹等。
本发明的复合材料是一部分聚苯并噁唑或聚苯并噻唑层和一部分其它聚合物纤维网状层的结合。通常，需要那些材料的每一种多于一层以提供所需的刺保护。聚苯并噁唑和聚苯并噻唑的每一层通常具有每平方米75-450克的面密度，并且通常使用1-15层。纤维网层的面密度非常依赖纤维网的形式、纤维的种类和线密度。然而，通常聚苯并噁唑和聚苯并噻唑纤维构成所述复合材料重量的10-90％，优选15-50％。形成所述复合材料部分的层可通过例如缝合在一起或它们可以堆积在一起进行连接，并例如保留在织物包裹中。组成每一部分的层经常放在一起，因此可看见所述复合材料具有两个不同部分的层的结构。然而，通过以任何方式混合不同层可以构成所述复合材料，以致各部分不会不同。所述聚苯并噁唑或聚苯并噻唑织物部分可与所述纤维网部分结合产生任何顺序的不同材料层。例如，可以通过所述聚苯并噁唑或聚苯并噻唑层与所述纤维网层交替制造复合材料。
我们已经发现获得最好刀刺抵抗力的复合材料的优选排列部分具有所述聚苯并噁唑或聚苯并噻唑部分层并一起暴露于刀刺，而所述纤维网部分层位于所述复合材料的内部，远离刀刺。
图表示本发明的保护复合材料10具有聚苯并噁唑或聚苯并噻唑编织层12的部分11和其它聚合物材料纤维网层14的部分13。层12和14可以以任何顺序混和，以致于部分11和13不会不同，优选所述层和部分基本上如显示的安排，使部分11暴露于刀刺和部分13远离刀刺。
                     试验方法
线密度。纱线的线密度通过称量已知长度的纱线测定。“分特”定义为10,000米纱线的重量(克)。
在实际操作中，在试验开始之前，将所测的纱线样品的分特、测试条件和样品标记输进计算机；当纱线断掉时，计算机记录它的荷重伸长曲线，然后计算其性能。
拉伸性能。首先将用于测试拉伸性能的沙线调湿(conditioned)，然后扭转至扭转倍数为1.1倍。纱线的扭转倍数(TM)定义为：
      TM=(圈数/厘米)(分特)1/2/30.3
待试验的纱线在25℃、相对湿度55％下调湿至少为14小时，在这种条件下进行拉伸试验。通过在英斯特朗试验仪(InstronEngineering Corp.,Canton,Mass.)上的纱线断裂试验测定强度(断裂强度)、断裂伸长和模量。
强度、伸长和初始模量与ASTM D2101-1985中规定的一样，用计量长度为25.4厘米和伸长率为50％应变/分钟的纱线测定。模量从应力-应变曲线中在1％应变的斜率计算，等于在1％应变(绝对的)应力(克)乘100，再除以试验纱线的线密度。
穿透抵抗力。在试验样品上，用具有15厘米(6英寸)长的单边刀片和大约2厘米(0.8英寸)宽、向着末端逐渐变细并具有C-55洛氏硬度的拆骨刀(由Russell Harrington Cutlery,Inc.(Southbridge,Massachusetts,U.S.A)制造))测定刀穿透抵抗力。测试按照H.P.White实验室公司制定的HPW试验TP-0400.03(1994年11月28日)进行。测试样品放在10％明胶衬垫上，用重量4.55千克(10磅)的刀从各种高度落下冲击，直到在试验条件下样品的穿透大于6毫米算完成。通过在穿透高度的能量(单位kg·m)乘以9.81得到的报告结果为穿透能(焦耳)。
                      实施例
层的制备。
把几种不同的纱线编织或制成织物或纤维的层，然后制成复合结构在其上面进行刺抵抗试验。
1. 1560旦(1733分特)聚苯并噁唑纱线的平编织织物制成具有面密度为每平方英尺0.47磅(每平方米2.3千克)的每英寸21×21根纱线(每平方厘米8.3×8.3根纱线)。该纱线可从Toyobo有限公司的商品名为Zylon中获得。
2. 400旦(444分特)聚(对-亚苯基对苯二酰胺)纱线的平编织织物制成具有面密度为每平方英尺0.92磅(每平方米4.49千克)的每英寸31×31根纱线(每平方厘米12.2×12.2根纱线)。该纱线可从E.I.du Pont deNemours公司的商品名为Kevlar中获得。
3. 650旦(722分特)聚乙烯纱线的平编织织物制成具有面密度为每平方英尺0.50磅(每平方米2.44千克)的每英寸35×35根纱线(每平方厘米13.8×13.8根纱线)。该纱线可从AlliedSignal公司的商品名为Spectra900中获得。
4. 单向伸长链聚乙烯纤维(UDECPE)层以0/90度方向交叉(crossplied)，中间夹心聚乙烯薄膜，以面密度为每平方英尺0.51磅(每平方米2.49千克)使用。这些层全部可从AlliedSignal公司生产的商品名为Spectra Shield Plus的商品获得。
实施例1
将聚苯并噁唑(PBO)层和其它聚合物层的结合进行装配并测试刺抵抗力，将结果与单独的聚苯并噁唑或单独的其它聚合物制造的相等面密度的结构相比。结果在以下展示：
  结构               穿透能              面密度
                     (焦耳)      (psf)           (kgsm)
8层(PBO)              22.6        0.47            2.30
平8.3×8.3
40(PPDT)              18.1        0.92            4.49
平12.2×12.2
12层(ECPE)            11.3        0.50            2.44
平13.8×13.8
22(UDECPE)            20.3        0.51            2.49
8层(PBO)   (T)        67.8        1.39            6.79
40(PPDT)   (B)
40层(PPDT) (T)        61.0        1.39            6.79
8层(PBO)   (B)
8层(PBO)   (T)        76.8        0.97            4.74
12层(ECPE)  (B)
12层(ECPE)  (T)        50.8        0.97         4.74
8层(PBO)    (B)
8层(PBO)    (T)        74.6        0.98         4.78
22层(UDEDPE)(B)
22层(UDECPE)(T)        45.0        0.98         4.78
8层(PBO)    (B)
(T)表示顶部或刀刺面
(B)表示底部或内表面
可见复合结构提供的穿透能结果比预期的从结合的独立成分的简单总和的结果高得多。同样可见当聚苯并噁唑部分位于顶部(暴露于刀刺)时，穿透抵抗力非常高。

Claims (10)

1．保护的复合结构，包括：
a)至少一层包含聚苯并噁唑或聚苯并噻唑纤维的编织织物
b)至少一层包含其它聚合物材料纤维网。
2．根据权利要求1的复合材料，其中所述纤维网包括聚酰胺纤维。
3．根据权利要求2的复合材料，其中所述聚酰胺纤维是对-芳族聚酰胺。
4．根据权利要求1的复合材料，其中所述纤维网包括聚烯烃纤维。
5．根据权利要求4的复合材料，其中所述聚烯烃纤维是聚乙烯。
6．权利要求3的复合材料，其中所述编织织物为所述复合材料重量的10-90％。
7．权利要求5的复合材料，其中所述编织织物为所述复合材料重量的10-90％。
8．用于防护刀刺穿透的复合结构，包含：
a)一部分暴露于刀刺的包含至少一层含有聚苯并噁唑或聚苯并噻唑纤维的编织织物
b)一部分远离刀刺的包含至少一层含有其它聚合物材料的纤维网。
9．根据权利要求1的复合材料，所述复合材料具有小于每平方英尺1.4磅(每平方米6.83千克)的面密度和大于45焦耳的穿透抵抗力。
10．根据权利要求8的复合材料，所述复合材料具有小于每平方英尺1.4磅(每平方米6.83千克)的面密度和大于45焦耳的穿透抵抗力。
CN99811378A 1998-09-29 1999-08-10 混合的保护复合材料 Expired - Fee Related CN1123442C (zh)

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