CN1223698A - 抗穿透性芳族聚酰胺制品 - Google Patents

抗穿透性芳族聚酰胺制品 Download PDF

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CN1223698A
CN1223698A CN97195804A CN97195804A CN1223698A CN 1223698 A CN1223698 A CN 1223698A CN 97195804 A CN97195804 A CN 97195804A CN 97195804 A CN97195804 A CN 97195804A CN 1223698 A CN1223698 A CN 1223698A
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penetration
yarn
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CN1063240C (zh
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M·J·基奥
B·E·福瓦
L·H·迈纳
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Abstract

一种防止锐器穿透的性能更好的芳族聚酰胺制品。该制品具有用低纤度长丝的高韧性、低分特芳族聚酰胺纱线机织成的紧密平纹组织结构;当以多层形式使用时,不将各层缝合在一起。

Description

抗穿透性芳族聚酰胺制品
目前，存在着对改进防护服的防止尖头器物穿透性能的需要。然而，迄今的注意力一直主要集中于旨在对付枪弹威胁的弹道学和防弹衣上面。本发明涉及防止诸如锥子或破冰铁凿之类锐利器具刺伤或穿透的防护制品。
1996年(USSN 08/421,350,1995年4月12日提交)授予Foy和Miner的申请的美国专利公开了一种抗穿透性制品，由紧密织造的低线密度、高韧性芳族聚酰胺纱线制成。
1993年2月9日授予Harpell等人的美国专利5,185,195公开了一种抗穿透性构造，其中相邻的芳族聚酰胺或线型聚乙烯机织布层沿规则紧密排列的路径被彼此固定在一起。这种固定优选地通过缝合实现。
1989年7月25日授予Droste等人的美国专利4,850,050公开了一种人体盔甲，由多层芳族聚酰胺织物经层合制成，其中织物的纱线由线密度小于1.5分特的长丝构成。
发明概述
本发明涉及一种抗穿透性制品，它基本上由芳族聚酰胺纱线织成织物紧密系数至少是0.75的织物构成，其中纱线的线密度小于500分特、韧性至少是30焦耳/克，纱线中长丝的线密度小于1.67分特。本发明还涉及此类抗穿透性制品，其中制品包含至少2层织物，它们在制品的边缘以允许相邻层彼此自由地相对移动的方式结合在一起。
附图简述
图1是本发明织物中纱线的长丝线密度与相应织物的抗穿透性性能之间关系的图示。
图2是纱线线密度与抗穿透性织物的织物紧密系数之间关系的图示。
发明详述
本发明的防护制品是，区别于防弹保护，专门提供防止锐利器具穿透而开发的。过去，为改进防弹衣已做了相当大的努力；长期以来，人们一直以为，改进后的防弹衣也同样具有改进的防刺伤或抗穿透性性能。本发明人现已发现，这种想法是不正确的，还发现一种集几种必要品质于一身的织物制品，它的确表现出改进的抗穿透性性能。
本发明人现已发现，当用以制造该制品织物的纱线采用线密度小于约1.67分特的长丝制成时，织物制品的抗穿透性将显著改善。据信，低线密度长丝所制成的织物制品中，丝与丝之间的间隙缩小，从而使制成的制品更难以被锐器穿透。
虽然防弹衣由几层防护织物制成，但这几层差不多总是以一种使相邻层的表面保持彼此相对固定的方式装配在一起的，而现已发现，如果防护服中相邻层不是彼此固定在一起，而是可彼此自由地相对移动的，则抗穿透性将会得到改善。当相邻层紧密缝合在一起时，抗穿透性将会变差。
本发明制品完全由机织织物构成，没有刚性板或片且织物材料中没有浸渍基质树脂。与提供类似保护作用的先有技术抗穿透性构造相比，本发明的制品弹性更好、重量更轻、手感更好、更柔韧。
本发明的织物由芳族聚酰胺纤维的纱线构成。所谓“芳族聚酰胺”是指一种聚酰胺，其中至少85％酰胺(-CO-NH-)键直接与2个芳环相连。合适的芳族聚酰胺纤维可参见《人造纤维一科学与技术》，第2卷，题为“成纤芳族聚酰胺”一节，297页，W.Black等人，国际科学出版公司，1968。芳族聚酰胺纤维还公开在美国专利4,172,938、3,869,429、3,819,587、3,673,143、3,354,127以及3,094,511中。
芳族聚酰胺中可加入添加剂，而且已发现，可在芳族聚酰胺中掺入至多10％(重量)的其他聚合材料，或者使用共聚物，其中可包含至多10％其他二胺以代替该芳族聚酰胺的二胺，或者包含至多10％其他二酰氯以代替该二酰氯或芳族聚酰胺。
对位芳族聚酰胺是本发明纱线纤维中的主要聚合物，而聚(对亚苯基对苯二甲酰胺)(PPD-T)则是优选的对位芳族聚酰胺。所谓PPD-T是指对苯二胺与对苯二甲酰氯按1∶1的摩尔比聚合生成的均聚物，或者是含有少量其他二胺的对苯二胺与含有少量其他二酰氯的对苯二甲酰氯的共聚物。通常，其他二胺和其他二酰氯的用量可至多为对苯二胺或对苯二甲酰氯的约10％(摩尔)，或许再稍高一些，条件仅是所述其他二胺和二酰氯不包含干扰聚合反应的活性基团。PPD-T也涵盖含有其他芳族二胺和诸如2,6萘二甲酰氯，或氯代或二氯代对苯二甲酰氯或3,4’-二氨基二苯醚之类的芳族二酰氯的共聚物。PPD-T的制备可见诸于美国专利3,869,429、4,308,374及4,698,414。
所给出的“织物紧密系数”及“覆盖系数”是指织物的组织密度。覆盖系数是涉及组织几何学的计算值，表示织物的纱线覆盖织物毛表面积的百分率。覆盖系数的计算公式如下(引自《织造：由纱线转化为织物》，Lord and Mohamed,Merrow公司出版(1982),141～143页)：
dw=织物经纱的直径
df=织物纬纱的直径
pw=经密(单位长度根数)
pf=纬密 c w = d w pw c f = d f pf 织物覆盖系数=Cfab=被遮蔽的总面积/织物包络面积 c fab = ( p w - d w ) d f + d w pf p w pf =(Cf+Cw-CfCw)
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根据织物组织的类型之不同，最大覆盖系数可能会相当低，尽管织物纱线靠得很近。鉴于这样的原因，一种更有用的织物紧密度指标被称作为“织物紧密系数”。织物紧密系数是一种织物组织紧密度的度量，它不同于作为覆盖系数的函数的最大组织紧密度。
织物紧密系数=实际覆盖系数/最大覆盖系数
例如，平纹组织织物的最大覆盖系数可达0.75；而一种实际覆盖系数为0.68的平纹组织织物的织物紧密系数就将为0.91。优选用于实施本发明的组织是平纹组织。
虽然芳族聚酰胺纱线有各种各样线密度规格的产品可供使用，但是已确证，可接受的抗穿透性特性，只有当芳族聚酰胺纱线的线密度小于500分特时方可达到。大于500分特的芳族聚酰胺纱线，即便织成织物紧密系数接近1.0，据信也会在相连纱线之间发生移让，致使锐器容易穿透。降低纱线线密度导致抗穿透性改善的效应预计将延续至非常低的线密度；然而，到了约100分特时，纱线就开始变得极其难以织造而不损伤。考虑到这一点，本发明芳族聚酰胺纱线的线密度选定为100～500分特。
本发明人发现，用线密度小于1.67分特的长丝的纱线所织成的织物，在抗穿透性方面有明显改善。请参见图1，这是从本文实例1试验所获数据点的图解。图中的每一点代表对一种织物的测试结果，并根据规格化的织物抗穿透性对纱线长丝的线密度进行标绘。
现在来看图2，这是从本文的验证实例所获试验数据点的图示。图中的每一点代表对一种织物的测试结果，并根据织物紧密系数对纱线线密度进行标绘，在该试验中称之为所谓测得的比抗穿透性(specific penetration resistance)。
正如本文将在下面要解释的，比抗穿透性随着抗穿透性的降低而降低，而当按照本文所做试验得出的比抗穿透性数值等于约30时，则认为就一般用途来说已具有足够抗穿透性能力了。对用芳族聚酰胺纱线制成的图2中的织物来说，直线Y=X6.25×10-4+0.69代表抗穿透性足够与抗穿透性不足之间的分界线。
在该直线的抗穿透性足够一侧有一点，表现出的抗穿透性不足；而这一点则代表的是一种由非芳族聚酰胺纱线制成的织物。
优良的抗穿透性要求若干纱线和织物品质的综合，其中包括特别是纱线线密度和织物紧密系数。从图1和2中可以可以看出，就芳族聚酰胺纤维而言，抗穿透性改善的织物是具有以下特征组合的织物：其长丝线密度小于1.67分特，如图1所示，紧密系数及纱线线密度位于图2曲线的下方，其数值分别在0.75～1.0和500～100分特范围内。
本发明使用的芳族聚酰胺纱线必须具备高断裂强度和高断裂伸长的结合，方可获得高韧性。强度应至少是19克/分特(21.1克/旦)，而且目前尚不存在已知的强度上限。低于约11.1克/分特，则纱线不具有有意义的保护作用所需足够强度。断裂伸长应至少是3.0％，而且目前尚不存在已知的伸长上限。断裂伸长小于3.0％，将导致纱线过脆，造成纱线的韧性不能满足本发明所要达到的保护要求。
“韧性”是纱线在拉伸应力/应变试验中直至其破坏点所能吸收的能量的度量。韧性，有时也称之为“断裂能”。韧性或断裂能是强度和断裂伸长的综合指标，用应力/应变曲线下方，从应变为0应变到断裂这段区间所覆盖的面积来表示。已发现，强度或断裂伸长的少许提高可导致抗穿透性惊人的改善。据信，纱线韧性至少要35焦耳/克，方可满足达到足够实现本发明抗穿透性的需要；优选该韧性至少是38焦耳/克。
单层的本发明机织制品不能提供抗穿透性的功能，因而也不能提供一定程度的保护；相反，本发明通常在最终产品中采用多层结构。而正是在采用多层结构时，本发明方显示出最显著，甚至是惊人的改善效果。已发现，本发明制品，当把多层放在一起，层与层彼此不固定因而允许相邻层之间相对移动时，可提供惊人的有效抗穿透性。相邻层或物品可在边缘处固定，或者隔着相对于物品厚度而言的大间距上具有一定松散的层间连结。例如，层与层之间每隔约15厘米以上的间隔点予以固定，则可满足此种用途的需要，因为它们基本上不受将各层维系在一起的方法的限制。沿各层整个表面缝合在一起的多层结构可提供更有效的防弹保护；然而此种缝线导致层间无法移动，而且由于某种尚不完全理解的原因，实际上会降低多层结构的抗穿透性效果，即达不到根据单层试验结果所作出的预期效果。
试验方法
线密度。纱线或长丝的线密度是通过称取已知长度纱线或长丝的重量予以确定的。分特的定义是10,000米材料重量的克数。“旦”是9000米材料重量的克数。
在实际测定时，将纱线或长丝样品的分特测量值、测试条件及样品名称在测试开始之前预先输入电脑；电脑记录下样品直至断裂的荷载-伸长曲线，然后计算出各项性质指标。
拉伸性能。首先让准备测定拉伸性能的纱线进行调节，然后加捻至1.1的捻度系数。纱线捻度系数(TM)的定义是：TM=(捻数(twists)/厘米)/(分特数)-1/2/30.3=(捻数/英
    寸)(旦数)-1/2/73
待测纱线放在25℃,55％相对湿度的条件下调节至少14小时，然后在同样的条件下进行拉伸试验。强度(断裂强度)、断裂伸长及模量是通过在Instron试验机(Instron工程公司，Canton，麻省)上将样品纱线拉断的过程来测定的。
按照ASTM D2101-1985的规定，强度、伸长和初始模量的测定应采用纱线隔距长度25.4厘米及拉伸速率50％应变/分钟的条件进行测定。模量是根据应力-应变曲线上应变为1％的一点处的斜率计算出来的，它等于1％应变处应力的克数(绝对值)乘上100，除以样品纱线的线密度。
单根丝的强度、伸长及初始模量的测定方法与纱线相同，只是单丝不进行加捻处理，仍使用2.54厘米的隔距长度。
韧性。利用拉伸试验所获得的应力-应变曲线，求出纱线应力-应变曲线下方直至拉断一点的面积(A)，即为韧性。通常是采用求积仪，算出以平方厘米为单位的面积予以确定的；而对于芳族聚酰胺，由于通常表现出近似直线的应力-应变曲线，故韧性可按照强度乘上伸长的乘积的一半来估计。分特数(D)可参见上文“线密度”的一段描述。韧性(To)按下列公式计算：
To=A×(FSL/CFS)(CHS/CS)(1/D)(1/GL)
其中
FSL=全量程荷载，克
CFS=仪表纸(长图)全量程，厘米
CHS=十字头(滑动横梁)速度，厘米/分钟
CS=仪表纸速度(厘米/分钟)
GL=样品的隔距长度，厘米
自然，可向电脑输入数字化应力/应变数据以直接计算出韧性。结果是以dN/tex(特)为单位的To，乘上1.111可换算为克/旦(g/d)。当整个过程中长度单位均相同时，上面的公式算出的To的单位就仅由力(FSL)和D所选单位决定了。
抗穿透性。抗穿透性，在单层或少数几层的制品情况下，是按照如ASTM F1342所规定的“用于抗穿透性防护服材料的标准方法”测定的。在该试验中，测定锐利尖端穿刺探头穿透样品所需要的力。样品被夹牢在扁平金属板中间，2板上开有彼此吻合的0.6厘米孔，并置于穿刺探头下方2.5厘米处，后者装在测试机上，机器以50.8厘米/分钟的速度驱动探头，使之在金属板开孔处穿透样品。记录穿透前的最大力，即作为抗穿透性值。
抗穿透性，在测定多层制品的情况下，是采用调质钢锥，18厘米(7英寸)长、0.64厘米(0.25英寸)锥杆直径，洛克威尔硬度(RH)为C-45，或者采用破冰铁凿，同样长度、锥杆直径0.42厘米、RH为C-42，进行测定的。测试是按照H.P.White Lab.公司发布的HPW试验TP-0400.02(1988年7月22日)的程序进行的。样品经受配重至7.35千克(16.2磅)的锥子从各种不同高度下落所造成的冲击。
实例
实例1
在该实例中，用220分特(200旦)的由各种不同线密度长丝组成的芳族聚酰胺纱线(机)织成几种织物。这些织物是纱线密度为70×70根、织物紧密系数1.0的平纹织物。
纱线规格如下：
       长丝线      长丝        韧性
       密度    强度    伸长  (g/dtex)
纱线  (dtex)  (g/dtex) (％)    (2)
1-1    1.67    25.4    3.8    0.483
1-2    2.50    24.6    4.0    0.492
1-3    5.00    22.1    3.8    0.420
1-4    1.22    24.2    3.9    0.472
1-5    0.83    24.5    3.7    0.453
1-6    0.83    23.6    3.6    0.425
1-7    1.67    23.2    4.0    0.464
1-8    0.83    23.1    4.0    0.462
测定了用这些纱线织成织物的抗穿透性，样品按10层的组合结构，程序按照上面的落锥法。抗穿透性试验结果载于表1，表中数据分别是以焦耳为单位的最小穿透能量和规格化到表中标为1-1的织物纱线韧性的最小穿透能量(仍为焦耳)。
之所以要将抗穿透性规格化到恒定的纱线韧性，是为了消除因韧性差异所带来的差异。
                            表1织物纱线    抗穿透性，焦耳    规格化抗穿透性，焦耳1-1            98.9                  98.91-2            75.0                  73.61-3            58.5                  67.31-4           106.2                 108.71-5           102.5                 109.31-6            95.1                 108.81-7            80.6                  83.91-8           104.3                 109.0
将每一种织物的规格化抗穿透性作为织物中纱线长丝线密度的函数进行标绘，得到的曲线示于图1。可清楚地看出，用所含长丝线密度大于2.0分特的纱线织成的织物表现出非常低的抗穿透性，而采用所含长丝线密度小于1.2分特的纱线织成的织物，则显示出非常高的抗穿透性。这些织物的抗穿透性，随着织物纱线中长丝线密度从2.0分特降低到1.2分特，而急剧增强，似乎在图中曲线的约1.67分特处存在一个转折点。
上面的所有试验都是在恒定高度、织物紧密系数及采用相同线密度纱线的条件下进行的。如同前面指出的，要获得高抗穿透性织物，应采用线密度在100～500分特的纱线以及织物紧密系数大于0.75的织物组织。本发明代表如下的改进发现：抗穿透性，当采用线密度小于1.67分特的长丝时将提高得更为明显。本发明优选的织物要求采用如下要素的组合：即用低于1.67分特的长丝制成100～500分特的纱线，然后机织成紧密系数大于0.75的织物。
验证实例
在该实例中，采用各种不同的纱线织成各种不同织物紧密系数的几种平纹组织织物。
外线规格如下：
     强度     伸长       断裂能      线密度纱线  (gm/dtex)    (％)    (Joules/gm)   (dtex)A       30.1       3.4        41.2         220B       25.4       3.0        31.2         220C       26.6       3.2        33.9         440D       25.5       3.4        34.2        1110E       30.0       3.4        40.5         440F       31.1       3.4        41.4         670G       30.0       3.4        40.5         440H       38.8       3.1        47.8         415
纱线A-G是聚(对亚苯基对苯二甲酰胺)(PPD-T)纱线，杜邦公司出品。
纱线A的商品名为KEVLAR159。
纱线B-D的商品名为KEVLAR29。
纱线E及F的商品名为KEVLAR129。
纱线G的商品名为KEVLARLT。
纱线H是高分子量线型聚乙烯纱线，由联合信号(AlliedSignal)公司出品，商品名SPECTRA1000。
织物规格如下：
            纱线根数    单位重量    紧密系数织物# 所用纱线  (cm×cm)    (g/m2)S-1      A     27.6×27.6    128         1.0S-2      A     24.8×24.8    115         0.93S-3      A     19.7×19.7    89          0.78S-4      B     27.6×27.6    126         1.0S-5      B     24.8×24.8    115         0.93S-6      B     19.7×19.7    89          0.78S-7      C     19.7×19.7    182         1.0S-8      D     12.2×12.2    282         0.99S-9      E     17.3×17.3    159         0.93S-10     E     13.4×13.4    120         0.75S-11     F     14.6×14.6    206         0.94S-12     F     11.8×11.8    164         0.80S-13     G     13×13        125         0.75S-14     G     16×16        139         0.90S-15     H     20.1×19.7    173         1.0
所有织物均作为一层和二层的结构，按照如上所述的ASTMF1342进行了测试。试验结果载于表2中，对一层和二层结构均按照绝对抗穿透性(克力)和比抗穿透性(绝对值/单位重量)给出。
                     表2
                                 抗穿透性
                   单位重量   绝对    比抗穿  测定次数织物# 紧密系数    层数  (g/m2)  (grams)   透性S-1     1.0        1     128      6,800    53.1       3
               2     256     15,400    60.2       3S-2    0.93        1     115      4,900    42.6       3
               2     230     11,300    49.1       5S-3    0.78        1      89      2,300    25.8       6
               2     178      4,400    24.7       3S-4     1.0        1     126      5,100    40.5       6
               2     252     11,400    45.2       3S-5    0.93        1     114      4,100    36.0       9
               2     229      8,100    35.4       7S-6    0.78        1      89      1,600    18.0       9
               2     178      3,600    20.2       7S-7     1.0        1     182      6,000    33.0       9S-8    0.99        1     282      2,400     8.5       5
               1(重复)        2,200     7.8       3S-9    0.93        1     159      3,200    20.1       5
               2     318      8,700    27.4       3S-10   0.75        1     120      1,200    10.0       5
               2     240      3,900    16.2       3S-11   0.94        1     206      2,000     9.7       6
               2     412      4,100    10.0       6S-12   0.80        1     164        800     4.9       6
               2     328      2,600     7.9       6S-13   0.75        1     139      1,900    13.7       6S-14   0.90        1     125      1,000     8.0       6S-15    1.0        1     173      2,300    13.3       6
               2     346      4,600    13.3       6
将这些试验中单层结构的比抗穿透性值标绘成纱线分特数对织物紧密系数的坐标系中，如图2所示。这些数值落在2个易于鉴别的区域内。在公式Y=X6.25×10-4+0.69直线(其中Y代表紧密系数，X是以分特表示的纱线线密度)的一侧，织物具有足够的抗穿透性；而在直线的另一侧，则抗穿透性不足。
从以上测试结果看出，抗穿透性织物应按如下条件制成：采用线密度在100～500分特的芳族聚酰胺纱线，织成织物紧密系数，按下式计算，至少是0.75的织物：
Y=或＞X6.25×10-4+0.69
其中Y=织物紧密系数
X=纱线线密度

Claims (5)

1．一种柔性的抗穿透性制品，基本上由以线密度低于500分特、韧性至少是30焦耳/克，且由线密度低于1.67分特的长丝制成的芳族聚酰胺纱线，织成织物紧密系数至少是0.75的织物组成，其中织物紧密系数与纱线线密度的关系是：
Y=或＞X6.25×10-4+0.69
其中Y=织物紧密系数和
X=纱线线密度。
2．权利要求1的抗穿透性制品，其中制品中包含至少2层织物，这些层在织物的边缘处结合，除此之外基本上不受将各层维系在一起的方法的限制。
3．权利要求1的制品，其中织物紧密系数基本上是1.0。
4．权利要求1的制品，其中韧性至少是40焦耳/克。
5．权利要求1的制品，其中芳族聚酰胺纱线是聚(对亚苯基对苯二甲酰胺)。
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DE69702262T2 (de) 2001-01-04
JP2000513413A (ja) 2000-10-10
WO1997049849A3 (en) 1998-02-05
DE69702262D1 (de) 2000-07-13
CA2257193A1 (en) 1997-12-31
BR9711598A (pt) 1999-08-24
CN1063240C (zh) 2001-03-14
WO1997049849A2 (en) 1997-12-31
EP0918895A2 (en) 1999-06-02
RU2174567C2 (ru) 2001-10-10
US5622771A (en) 1997-04-22
AU3576197A (en) 1998-01-14
EP0918895B1 (en) 2000-06-07
AU720067B2 (en) 2000-05-25
JP4551501B2 (ja) 2010-09-29
CA2257193C (en) 2004-04-06

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