CN101203377A - 层压防弹防外伤组合物 - Google Patents

层压防弹防外伤组合物 Download PDF

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CN101203377A
CN101203377A CNA2006800226815A CN200680022681A CN101203377A CN 101203377 A CN101203377 A CN 101203377A CN A2006800226815 A CNA2006800226815 A CN A2006800226815A CN 200680022681 A CN200680022681 A CN 200680022681A CN 101203377 A CN101203377 A CN 101203377A
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thermoplastic
trauma prevention
prevention combination
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CN101203377B (zh
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C·伯特格
A·费尔斯
E·万舍尔
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Teijin Aramid GmbH
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    • B32—LAYERED PRODUCTS
    • 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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    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • 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
    • B32B2307/514—Oriented
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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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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2571/02—Protective equipment defensive, e.g. armour plates, anti-ballistic clothing
    • 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
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    • Y10T428/00—Stock material or miscellaneous articles
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T442/2615—Coating or impregnation is resistant to penetration by solid implements
    • Y10T442/2623—Ballistic resistant
    • 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
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    • Y10T442/3016—Including a preformed layer other than the elastic woven fabric [e.g., fabric or film or foil or sheet layer, etc.]
    • 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
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    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3854—Woven fabric with a preformed polymeric film or sheet

Abstract

本发明涉及一种防外伤组合物，其包括至少一个塑性材料板和附着在所述板上的至少一个织物层，该织物层由纤维拉伸强度为至少900MPa的纱线制成，其中，所述板的塑性材料是由聚烯烃聚合物的单丝、纤维、条材或带材制成的自加强热塑性材料，并且，至少一个织物层在其整个表面粘合到自加强热塑性材料上。

Description

层压防弹防外伤组合物
技术领域
本发明涉及一种防外伤组合物，包括至少一个塑性材料板和附着在所述板上的至少一个织物层，该织物层由纤维拉伸强度为至少900MPa的纱线制成。
背景技术
GB-A-2 234 156公开了一种用于柔性人体护甲的减轻外伤组合物，该组合物使用一塑性材料板。在塑料板的至少一面附着有一防弹织物层。该织物可通过点粘合附着在塑料板上，或优选按螺旋花型缝制于塑料板上。塑料板优选由聚丙烯构成。缝制有防弹织物的聚丙烯板与多个防弹织物层一起用于柔性防护服，所述板定位在织物层之后、即面向穿着者的身体。如果聚丙烯板仅在一面设有防弹织物层，则该织物层应面向穿着者的身体。聚丙烯板的厚度优选为1.5mm，织物优选使用芳族聚酰胺纱线，其单位面积的质量为300g/m2。
子弹在冲击含有多个防弹织物层组合物的防护服时无法穿透织物组合物，但却使其严重形变，从而导致防护服穿着者受到外伤。据说GB-A-2 234156公开的附着有防弹织物层的塑性材料板能够减小外伤作用。
发明内容
因此，本发明的目的是提供一种开头所述的防外伤组合物，该防外伤组合物能够进一步减小外伤作用。
该目的通过一种防外伤组合物实现，该防外伤组合物包括至少一个塑性材料板和附着在所述板上的至少一个织物层，该织物层由纤维拉伸强度为至少900MPa的纱线制成；其中，所述板的塑性材料是由多个织物层构成的自加强热塑性材料，这些织物层由聚烯烃聚合物的单丝、纤维、带材或条材制成，它们彼此紧密接触，并在高温下通过聚合物的部分熔融及随后的压制而彼此粘合，其中至少一个织物层在其整个表面粘合到自加强热塑性材料上。
这种自加强热塑性材料也叫做热压合自加强热塑性材料。如果所述聚烯烃聚合物是例如单丝、纤维、带材或条材以拉伸形式存在于其中的取向聚烯烃聚合物则是特别有利的。
聚烯烃聚合物选自聚丙烯均聚物、主要含有聚丙烯的共聚物；或聚乙烯均聚物、主要含有聚乙烯的共聚物；或其混合物。
织物优选通过层压而整面粘合在自加强热塑性材料上，织物也可借助于热塑性薄膜层压到自加强热塑性材料上。如果将把织物层压到自加强热塑性材料的工序整合到生产自加强热塑性材料的生产过程中，从而在单个过程步骤中实现防外伤组合物的高效的生产，则是特别有利的。此外，整面粘合到自加强热塑性材料的织物可提供有另外的自加强热塑性材料板。例如，可在层压之前将一织物层定位在热塑性材料层之间，并在单次操作中将两面都整面粘合到塑性材料上。
拉伸强度为至少900MPa(根据标准ASTM D-885测定)的纤维优选由芳族聚酰胺、超大分子量聚乙烯、超大分子量聚丙烯、聚乙烯醇、聚丙烯腈、聚苯并恶唑、聚苯并噻唑或玻璃纤维制成的纤维，最好是芳族聚酰胺纤维、特别是由聚对苯二甲酰对苯二胺制成的纤维，例如Teijin TwaronGmbH公司出售的商标名为TWARON的纤维。将这些纤维的纱线加工成织物，本发明优选采用机织布形式的织物。
所述自加强热塑性材料的斜向伸长率优选为5-15％、更优选为8-11％。
另外，可将该防外伤组合物插入一包括多层的组合物中或置于其后，该包括多层的组合物由纤维拉伸强度为至少900MPa的纱线制成。
本发明的防外伤组合物可用于生产人体护甲部件如护胫，特别适用于防弹背心。
由取向热塑性纤维制成的自加强热塑性材料可从Propex FabricsGmbH公司得到，其商标名为Curv。然而，该市售产品仍不足以满足本发明的目标。
具体实施方式
现在将结合示例详细说明本发明。
通过以下示例研究外伤作用，其中，将现有技术的防外伤组合物和本发明的防外伤组合物置于24层TWARONCT 709(930dtex f1000，平纹，经密度和纬密度为10.5根/厘米，单位面积质量为200g/m2)组合物之后。在下述示例中、在塑性材料粘合有由纤维拉伸强度为至少900MPa的纱线制成的织物的情况下，将防外伤组合物放置在24层TWARONCT 709组合物之后，使得织物朝向穿着者的身体、即远离冲击方向。在示例2中，使用一TWARONT 751层(3360dtex f2000，平纹，经密度和纬密度为4.5根/厘米，单位面积质量为300g/m2)作为粘合到塑性材料上的织物。在示例3、5、6、7和9中，所用织物是前文所述的TWARONCT 707(930dtexf1000，平纹，经密度和纬密度为8.5根/厘米，单位面积质量为160g/m2)。
示例1(比较例)
在该示例中，对不带有另外的防外伤组合物的24层TWARONCT709进行如下所述的弹道学试验。
示例2(比较例)
根据GB-A-2 234 156的优选实施方式，将由1.5mm厚聚丙烯板和按螺旋花型缝制在该聚丙烯板一面的TWARONT 751织物构成的防外伤组合物置于24层TWARONCT 709组合物之后。将该防外伤组合物定位成缝制织物层远离冲击方向。
示例3(比较例)
与示例2相比，防外伤组合物包括两个聚丙烯板、单个TWARONCT707织物层，每个聚丙烯板厚0.75mm，织物层按螺旋花型缝制在每个板上。
示例4(比较例)
防外伤组合物包括两个市售商标名为Curv的自加强热塑性材料的塑料板，该自加强热塑性材料由压合在一起的聚丙烯带材的织物层构成。每个塑料板的厚度为0.6mm。
示例5
该示例使用两个由取向聚丙烯带材的压合织物层制成的塑料板，在每个板上层压有一TWARONCT 707层。带有层压织物的自加强塑性材料板的厚度为0.85mm。但是，为了实现本发明的目的，对拉伸聚丙烯带材压合织物层自加强材料的生产过程进行改变，以代替在示例4中使用的商标名为Curv的市售材料。将把TWARONCT 707织物层层压到每个板的过程整合到生产过程中。使用四层拉伸聚丙烯带材织物层(Propex织物97 9 393 100)生产本发明的防外伤组合物。通过撕裂聚丙烯膜制得用于所述织物的带材。然后拉伸所述条材并织造成斜纹织物。随后，在已预热到180℃的静压机(Schwabenthan公司，POLYSTAT 400S)中同时压合所述织物层、一厚度为50μm的聚丙烯膜和一TWARONCT 707织物层。压合压力为18.8巴。将该叠置的层在该压力和温度下保持25分钟。随后，保持该压力，冷却15分钟以上以达到约40℃的温度。然后将压合材料从压机中移出，并在不施压的情况下在空气中冷却到室温。
将该防外伤组合物定位在24层防弹层之后，使得层压织物层远离冲击方向。
示例6
对本发明的另一种防外伤组合物进行试验，该防外伤组合物由两个自加强塑料板制成，每个板厚0.85mm并由取向聚丙烯条材的压合织物层制成，在每个板上层压有一TWARONCT 707层。可按照示例5所述生产该防外伤组合物。
示例7
将示例6的防外伤组合物置于19层TWARONCT 709防弹层之后，从而使层压在两个自加强塑性材料板中每一个的一面上的织物层朝向冲击方向。将另外5层防弹织物层置于防外伤组合物之后。
示例8(比较例)
从示例6的防外伤组合物(包括两个自加强聚丙烯板，每个板上层压有一TWARONCT 707层)中去除之前层压的织物层。
示例9(比较例)
已在示例8中将层压织物层从两板中去除；在该示例中，再将一TWARONCT 707织物层按螺旋花型缝制到所述两板中的每一个上。将防外伤组合物置于24层防弹层之后，使得缝制织物层远离冲击方向。
表1对比了市售产品Curv(示例4)和在根据本发明的示例5和示例6中所用的自加强热塑性材料在去除了之前层压的TWARON织物层后的机械性能——根据DIN EN ISO 527-3测定纵向和横向抗撕裂性、纵向和横向伸长率、纵向和横向拉伸模量和斜向伸长率。为了测定斜向伸长率，将试件裁剪成使得试件中的聚丙烯条材与试验所加载荷的方向成45°角。表1中所示的斜向伸长率代表6次单独测量的平均值。其余各机械性能表示5次单独测量的平均值。同时给出了各种情况下的标准偏差。
表1
  示例4   示例5   示例6
  斜向伸长率[％]   24.1±6.0   9.2±2.4   10.2±2.3
  抗撕裂性(纵向)[MPa]   119.1±8.4   128.9±6.3   126.6±6.2
  抗撕裂性(横向)[MPa]   113.8±7.1   127.8±3.5   119.2±5.1
  伸长率(纵向)[％]   17.1±1.2   20.0±1.7   19.1±0.8
  伸长率(横向)[％]   16.6±1.1   19.3±1.0   17.3±0.8
  拉伸模量(纵向)[GPa]   3.2±0.1   2.5±0.1   2.4±0.1
  拉伸模量(横向)[GPa]   2.4±0.1   2.4±0.1
这些数据表明，市售产品Curv比本发明所用的自加强热塑性材料具有明显较高的斜向伸长率。同时，本发明所用的材料由于较高的抗撕裂性和伸长率、以及反而较低的拉伸模量而区别于市售产品。
在另外的试验中，通过测量试样所吸收的能量和因而发生的形变来研究材料的冲击强度。根据ASTM D 5628进行试验。为了进行该试验，从试样的不同部位取下5个面积为1dm2的圆形试件。使用Instrom公司的经校准的Dynatyp 9250 G仪器化冲击试验用试验装置进行该试验。使用直径为19.5mm的半球体作为冲击元件。所用总重为24.3kg。落重从0.23m的高度释放，并通过引导管到达夹持在气动夹具上的试件。所述夹具具有一40mm的开口，所述半球体可通过该开口击打试样。在启动触发机构之后、在冲击元件最初接触试样时，上述设置将造成55焦耳的最大冲击能量和2.13m/s的速度。在试验中测定穿透试样所需的力和能量、在试样失效前经过的时间和失效时的形变量。
在每个示例中使用单层自加强热塑性材料。对于示例5和6中的试样使用最大冲击能量104焦耳；在该两个示例中，层压织物层不像在示例8中那样被去除。用半球击打自加强热塑性材料来对带有层压织物层的单层自加强热塑性材料进行试验。表2所示数值代表5次单独测量的平均值。
表2
  示例4   示例8   示例5   示例6
  冲击强度[J]   6.7±1.9   16.4±0.7   58.5±18.9   77.3±23.7
  形变量[mm]   7.3±0.8   9.3±0.2   9.3±0.8   10.9±0.5
该表表明，所用的根据本发明的自加强热塑性材料的冲击强度明显高于市售产品的冲击强度——即使不具有层压织物层。
已知由子弹造成的在与冲击方向相反的一侧的形变量可作为外伤的量度。将防弹织物层组合物置于一层Weible可塑粘土(Weible plasticine)上并经受弹道学试验，其中，在所述防弹织物层之后或之间按照适当地方式放置有防外伤组合物。在以下示例中，使用0.357 Magnum JSP子弹，子弹速度约440m/s，每个组合物接受8次射击。4次射击对准组合物的外侧区域，余下的4次射击对准内侧区域。测量每次射击标记在可塑粘土中的穿透深度，并从中确定出在外侧区域的4个穿透深度的平均值和在内侧区域的4个穿透深度的平均值。
表3表示在对上述示例的防外伤组合物进行弹道学试验后在外侧区域和在内侧区域的穿透深度的平均值、以及组合物单位面积质量的近似值。比较例在表中用星号标注。
表3
  示例   组合物重量[kg/m2]   外伤，外侧区域[mm]   外伤，内侧区域[mm]
  1*   4.8   35.5   37.5
  2*   6.5   34.3   31.8
  3*   6.5   31.5   25.0
  4*   5.9   36.8   26.5
  5   6.3   26.5   17.5
  6   6.3   26.7   14.3
  7   6.3   25.8   21.0
  8*   5.9   28.8   22.8
  9*   6.2   28.0   22.0
表3的数据表明，现有技术的防外伤组合物(示例2和3)与仅由防弹织物层组成的组合物(示例1)相比，仅能减小在内侧区域的外伤，而对于外侧区域的轰击几乎没有改善。即使是两层市售自加强热塑性材料(示例4)也仅能减小在内侧区域的外伤。相比之下，所用的根据本发明的热塑性材料在最初的层压织物层已被去除的情况下(示例8)也表明能使外伤明显减小。这通过如现有技术那样按螺旋花型缝制织物层而略微得以改善(示例9)。但是，无论如何，本发明的示例5、6和7的防外伤组合物在内侧区域和外侧区域都具有最小的外伤数值。

Claims (13)

1.一种防外伤组合物，包括至少一个塑性材料板和附着在所述板上的至少一个织物层，该织物层由纤维拉伸强度为至少900MPa的纱线制成，其特征在于，所述板的塑性材料是由多个织物层构成的自加强热塑性材料，这些织物层由聚烯烃聚合物的单丝、纤维、条材或带材制成，它们彼此紧密接触，并在高温下通过聚合物的部分熔融和随后的压制而彼此粘合；特征还在于，至少一个织物层在其整个表面粘合到所述自加强热塑性材料上。
2.根据权利要求1所述的防外伤组合物，其特征在于，所述聚烯烃聚合物是取向聚烯烃聚合物。
3.根据权利要求1或2所述的防外伤组合物，其特征在于，所述聚烯烃聚合物选自聚丙烯均聚物、主要含有聚丙烯的共聚物；聚乙烯均聚物、主要含有聚乙烯的共聚物；或其混合物。
4.根据权利要求1-3中一项或多项所述的防外伤组合物，其特征在于，所述织物通过层压而整面粘合到所述自加强热塑性材料上。
5.根据权利要求4所述的防外伤组合物，其特征在于，所述织物借助于热塑性薄膜层压到所述自加强热塑性材料上。
6.根据权利要求4或5所述的防外伤组合物，其特征在于，把织物层压到自加强热塑性材料上的工序整合在自加强热塑性材料的生产过程中。
7.根据权利要求1-6中一项或多项所述的防外伤组合物，其特征在于，所述整面粘合到自加强热塑性材料上的织物可提供有另外的自加强热塑性材料板。
8.根据权利要求1-7中一项或多项所述的防外伤组合物，其特征在于，所述拉伸强度为至少900MPa的纤维包括芳族聚酰胺、超大分子量聚乙烯、超大分子量聚丙烯、聚乙烯醇、聚丙烯腈、聚苯并恶唑、聚苯并噻唑或玻璃纤维。
9.根据权利要求1-8中一项或多项所述的防外伤组合物，其特征在于，所述自加强热塑性材料的斜向伸长率为5-15％，优选为8-11％。
10.根据权利要求1-9中一项或多项所述的防外伤组合物，其特征在于，该防外伤组合物插入一包括多层的组合物中，该包括多层的组合物由纤维拉伸强度为至少900MPa的纱线制成。
11.根据权利要求1-9中一项或多项所述的防外伤组合物，其特征在于，该防外伤组合物放置在一包括多层的组合物之后，该包括多层的组合物由纤维拉伸强度为至少900MPa的纱线制成。
12.根据权利要求1-11中一项或多项所述的防外伤组合物用于生产人体护甲部件的用途。
13.根据权利要求1-11中一项或多项所述的防外伤组合物用于生产防弹背心的用途。
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