CN107428114A - 复合防弹层压件 - Google Patents

复合防弹层压件 Download PDF

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Publication number
CN107428114A
CN107428114A CN201680010726.0A CN201680010726A CN107428114A CN 107428114 A CN107428114 A CN 107428114A CN 201680010726 A CN201680010726 A CN 201680010726A CN 107428114 A CN107428114 A CN 107428114A
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Prior art keywords
laminate
individual layer
adhesive
orientation
sheet material
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CN201680010726.0A
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CN107428114B (zh
Inventor
J.N.辛格勒塔里
L.A.卡巴贾
W.G.坎佩特
T.A.里伯特
B.B.索尔
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DuPont Safety and Construction Inc
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EI Du Pont de Nemours and Co
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Priority claimed from US14/625,193 external-priority patent/US20160236450A1/en
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Abstract

一种抗冲击穿透的层压件，包括(i)非纤维超高分子量聚乙烯单层和(ii)热塑性粘合剂的多个交替层，该粘合剂具有不大于5gsm的基重和至少1500Pa‑s的零剪切速率粘度，该零剪切速率粘度是在125℃下根据ASTM D 4440进行的以在0.1rad/s与100rad/s之间的频率扫描由振荡盘式流变仪确定的并且由拟合到Carrea‑Yasuda四参数模型计算的，其中(a)将至少90％的单层布置成使得一个单层的取向相对于相邻单层的取向偏移，并且(b)通过该层压件的厚度的弹性模量为至少3GPa。

Description

复合防弹层压件
发明背景
1.技术领域
本发明涉及适合用于硬装甲的抗冲击穿透的层压件。
2.背景技术
Holmes的美国专利4,309,487描述了由一层或多层单向取向的聚乙烯膜或纤维组成的层压装甲结构，这些聚乙烯膜或纤维被定位成使得相邻单元的取向线彼此成角度。这些层的粘合仅通过向定位层的复合物施加热和压力来实现。
Lyons等人的美国专利7,972,679披露了具有夹层型结构的防弹模制物品，其包括围绕第二高模量材料的内部部分的第一高模量材料的两个外部部分。这些外部部分由粘合剂涂覆的交叉合叠非纤维超高分子量聚乙烯带的多个交错层组成。内部部分由嵌入在树脂中的高模量交叉合叠纤维的多个交错层组成。交错层的叠层在高的温度和压力下被压缩以形成包括高模量材料的混合物的混合夹层防弹模制物品。已经发现混合结构的防弹性比具有可比较的面密度的整体式结构的防弹性更高。
Lyons等人的美国专利7,976,932传授了一种防弹面板，该防弹面板包括冲击面部分和背衬部分。该冲击面部分包括非纤维超高分子量聚乙烯带的多个交错层。该背衬部分包括超高分子量聚乙烯的交叉合叠纤维的多个交错层。交错层的整个叠层在高的温度和压力下被压缩以形成在一侧具有冲击面的防弹面板。已经发现，随着冲击面部分相对于背衬部分的重量比减小，防弹性增加。与交叉合叠的高模量纤维的严格交错层的整体式结构相比，具有面板总重量的至多40％的冲击面的复合面板表现出改善的防弹特性。
Bovenschen等人的美国专利8,197,935披露了一种具有包括增强细长体的片材的压缩叠层的防弹模制物品，其中这些细长体中的至少一些是具有至少100,000克/摩尔的重均分子量和至多6的Mw/Mn比的聚乙烯细长体。
Geva等人的美国专利7,993,715涉及具有彼此以一定角度交叉合叠并且压缩的多个单向取向的聚乙烯单层的聚乙烯材料，每个聚乙烯单层由超高分子量聚乙烯构成并且基本上不含树脂。本发明进一步涉及包括或结合本发明的聚乙烯材料的防弹制品以及结合其的材料和制品的制备方法。
发明内容
本发明涉及一种加固的抗冲击穿透的层压件，该层压件包括(i)非纤维超高分子量聚乙烯单层和(ii)热塑性粘合剂的多个交替层，该粘合剂具有不大于5gsm的基重和至少1500Pa-s的零剪切速率粘度，该零剪切速率粘度是在125℃下根据ASTM D4440进行的以在0.1rad/s与100rad/s之间的频率扫描由振荡盘式流变仪确定的并且由拟合到Carrea-Yasuda四参数模型计算的，其中
(a)将至少90％的单层布置成使得一个单层的取向相对于相邻单层的取向偏移，并且
(b)如通过测试方法A测量的通过该层压件的厚度的弹性模量为至少3GPa。
本发明进一步涉及一种制造抗冲击穿透的层压件的方法，该方法包括以下步骤：
(i)提供多个交叉合叠的非纤维超高分子量聚乙烯片材，其中该聚乙烯片材包含由粘合剂分开的两个聚乙烯取向膜单层，将其布置成使得该片材中的一个单层的取向相对于该片材中的另一个单层的取向偏移，其中该粘合剂具有不大于5gsm的基重和至少1500Pa-s的零剪切速率粘度，该零剪切速率粘度是在125℃下根据ASTM D 4440进行的以在0.1rad/s与100rad/s之间的频率扫描由振荡盘式流变仪确定的并且由拟合到Carrea-Yasuda四参数模型计算的，
(ii)按以下布置对包括步骤(i)的多个UHMWPE片材的叠层进行组装：其中将至少90％的片材定位成使得一个片材的单层的取向相对于相邻片材的最接近单层的取向偏移并且该叠层中的聚乙烯片材和粘合剂的组合重量是0.6-600kg/m2，
(iii)使步骤(ii)的该叠层经受从10至400巴的压力和从70℃至150℃的温度持续在5与60分钟之间，并且
(iv)将该层压件冷却至50℃或以下的温度。
由于实际的原因，该层压件由多个交叉合叠的片材组装。
附图说明
图1示出了通过交叉合叠的非纤维超高分子量(UHMWPE)聚乙烯片材的横截面。
图2示出了通过包括多个交叉合叠片材的层压件的横截面。
具体实施方式
本章节提及的规范的日期和/或发布如下：
ASTM D 7744-11，“Standard Test Method for Tensile Testing of HighPerformance Polyethylene Tapes[高性能聚乙烯带的拉伸测试的标准侧试方法]”。2011年9月发布。
ASTM D 4440-07.“Standard Test Method for Plastics：Dynamic MechanicalProperties：Melt Rheology[塑料的标准测试方法：动态机械性能：熔体流变学]”。2007年3月发布。
交叉合叠片材
交叉合叠片材在图1中以10示出并且包括两个超高分子量聚乙烯(UHMWPE)取向膜单层11和12以及两层粘合剂13。UHMWPE是指由具有至少2百万的粘均分子量的聚乙烯聚合物制成的膜。在一些实施例中，分子量在2-6百万或甚至3-5百万之间。更优选地粘均分子量为至少4百万。合适的聚乙烯材料的实例是来自密歇根州奥本山泰科纳工程聚合物公司(Ticona Engineering Polymers，Auburn Hills，MI)的Ticona GUR和来自纽约州莱伊布鲁克三井化学美国公司(Mitsui Chemicals America，Inc.，Rye Brook，NY)的Hi-ZEXMILLIONTM。
每个膜单层是非丝状的并且是高度取向的。高度取向的是指在一个方向(通常是产生取向膜单层的方向)上的模量比在任何其他方向上大至少10倍。优选地，在一个方向上的模量比在任何其他方向上大至少20倍并且更优选地大至少30倍。图1中的两个取向膜单层11和12用粘合剂13组合以形成交叉合叠片材10，其中一个取向膜单层11的取向相对于另一个取向膜单层12的取向偏移。优选地，两个取向膜单层11和12具有彼此基本上正交的取向。通过“基本上正交的”是指两个片材以90+/-15度的角度相对于彼此定位。这有时被称为0/90布置。
两个热塑性粘合剂层13如图1所示定位。上述交叉合叠片材10包括两个单层和两个粘合剂层。这是优选的构造，然而片材可以包含多于两个单层或多于两个粘合剂层，例如以0/90/0/90布置。
如在此使用的术语“膜”是指具有约至少10mm或更大、优选大于约20mm、更优选大于约30mm并且甚至更优选大于约40mm的宽度的通常矩形横截面并且具有光滑边缘的UHMWPE产品，并且特别用于区别约3mm宽或更窄的“纤维状”UHMWPE产品。本发明的UHMWPE膜包括至少约25mm的宽度，在0.038mm与0.102mm之间的厚度和在ASTM D7744中定义为“M1”的至少约100N/Tex、优选至少约120N/Tex、更优选至少约140N/Tex、并且最优选至少约160N/Tex的第一模量。在一些实施例中，与具有与厚度基本上相似的宽度的纤维状UHMWPE不同，该膜具有非常高的宽度与厚度比率。根据本发明的UHMWPE膜例如可以包括25.4mm的宽度和0.0635mm的厚度，这表示400：1的宽度与厚度比率。该膜可以在从约660Tex至约1100Tex及更高的线密度下生产。高模量聚乙烯膜的宽度没有理论上的限制，并且它仅受加工设备的尺寸限制。如在此使用的交叉合叠片材意思是指宽度大于约0.2m且高达或超过1.6m宽度(如可以在专门设计用于以这种宽度生产的大型商业设备中生产)并且具有矩形横截面和光滑边缘的材料的薄部分。
粘合剂
将图1中的热塑性粘合剂13邻近每个单层的表面放置以将相邻的单层结合在一起。每个粘合剂层具有不大于5gsm的基重以及至少1500Pa-s的当通过振荡盘式流变仪在125℃下测量时的零剪切速率粘度。在一些实施例中，该粘合剂具有至少10,000Pa-s的零剪切速率粘度。在又其他实施例中，该粘合剂具有至少100,000Pa-s的零剪切速率粘度。在其他实施例中，该粘合剂具有至少1,000,000Pa-s的零剪切速率粘度。
零剪切速率粘度可以根据ASTM D 4440通过测量粘合剂样品的复数粘度来确定。该粘合剂在振荡盘式流变仪中保持在125℃，并经受跨过从0.1rad/s至100rad/s的频率扫描的振荡。然后将作为频率的函数的粘度拟合到所谓的四参数Carreau-Yasuda方程：
η＝(ηo，cy)/[1+(τcyγ’)a]p/a
其中ηo，cy是Carreau-Yasuda零剪切速率粘度，τcy是Carreau-Yasuda时间常数，p是描述幂律区的斜率的Carreau-Yasuda速率常数，并且a是描述在牛顿区与幂律区之间的过渡区的参数。在将数据拟合到方程之前应进行多次频率扫描并进行平均以确定零剪切速率粘度。这种测量是聚合物表征领域的技术人员已知的。已经发现合适的流变仪是来自特拉华州纽卡斯尔TA仪器公司(TA Instruments，New Castle，DE)的ARES LS2。已经发现强制对流烘箱足以控制粘合剂样品的温度。使用该设备，板温度可以使用中间具有热电偶的全氟烷氧基聚合物圆盘校准。具有光滑表面的25mm直径的板用于安装粘合剂样品。粘合剂样品可以被不同地铸造或机械加工以形成接触振荡板所需的圆柱形样品，这取决于粘合剂的性质。应注意在样品制备过程中避免降解粘合剂。将Carreau-Yasuda模型应用于聚合物流动的示例性描述在Stephen L.Rosen，Fundamental Principles of Polymeric Materials[聚合物材料基本原理]，纽约州约翰威利父子公司(John Wiley&Sons，New York)，1982，第207页中给出。
在一些实施例中，该粘合剂层的重量小于4.5gsm或甚至小于4gsm。
粘合剂的合适实例是氨基甲酸乙酯、聚乙烯、乙烯共聚物(包括乙烯-辛烯共聚物)、离聚物、金属茂和热塑性橡胶(例如苯乙烯和异戊二烯或苯乙烯和丁二烯的嵌段共聚物)。该粘合剂可以进一步包含触变胶以降低在压缩过程期间相邻片材相对于彼此滑动的倾向。合适的触变胶包括其形状可以表征为树枝状(其代表为DuPontTM 芳族聚酰胺纤维纸浆)、球形、板状或棒状的有机颗粒或无机颗粒如二氧化硅或三水合铝。该粘合剂可以进一步包括其他功能添加剂，例如纳米材料和阻燃剂。
该粘合剂可以是呈膜、糊剂、液体或非织造稀松布的形式。
抗冲击穿透的层压件
图2示出了包括多个交叉合叠的非纤维超高分子量聚乙烯片材10的示例性层压件。在一些实施例中，至少90％、更优选至少95％或最优选100％的片材位于层压件内，使得一个聚乙烯片材的单层的取向相对于相邻片材的最接近单层的取向偏移。
层压件中的聚乙烯片材的数量将基于最终制品的设计要求而变化，但典型地在从20至1000的范围内，给出在从0.1至600kg/m2或从1至60kg/m2或甚至从1至40kg/m2的层压件重量范围。该层压件在粘合剂将流动的温度下但是低于片材的单层失去取向、以及因此机械强度的温度下通过压缩片材叠层形成。典型地，该粘合剂包含层压件中聚乙烯片材加上粘合剂的组合重量的不超过15重量百分比。
如通过测试方法A测量的，通过压缩层压件的厚度的弹性模量为至少3GPa。在一些实施例中，弹性模量为至少3.2GPa或甚至至少3.5GPa。在另一个实施例中，弹性模量为至少4GPa。优选地，通过压缩层压件的厚度的弹性模量应不高于通过层压件的聚乙烯片材组分的厚度的弹性模量的十倍。
一种制造抗冲击穿透的层压件的方法，该方法包括以下步骤：
(i)提供多个交叉合叠的非纤维超高分子量聚乙烯片材10，其中该聚乙烯片材包含由粘合剂13分开的两个聚乙烯取向膜单层11和12，将其布置成使得一个单层11的取向相对于另一个单层12的取向偏移，其中该粘合剂具有不大于5gsm的基重和至少1500Pa-s的当通过振荡盘式流变仪以在0.1rad/s与100rad/s之间的频率扫描在125℃下根据ASTM D4440测量并且拟合到四参数Carrea-Yasuda模型时的零剪切速率粘度，
(ii)按以下布置对包括步骤(i)的多个UHMWPE片材10的叠层20进行组装：其中将至少90％的片材定位成使得一个片材的单层的取向相对于相邻片材的最接近单层的取向偏移并且该叠层中的聚乙烯片材和粘合剂的组合重量是0.6至600kg/m2，
(iii)使步骤(ii)的该叠层经受从10至400巴的压力和从70℃至150℃的温度持续在5与60分钟之间，并且
(iv)将该层压件冷却至25℃或以下的温度。
优选地，叠层以这样的方式组装，使得叠层包括单层11或12和粘合剂13的交替层。
在一些实施例中，步骤(ii)的叠层中的聚乙烯片材和粘合剂的组合重量为从1至40kg/m2，
在上述加工条件下，已经出人意料地发现，压缩层压件的抗冲击穿透性在高于先前传授的模制温度下增加。
测试方法
测试方法A
通过压缩层压件的厚度的弹性模量(E3)使用通过该部件的厚度的声速C33来确定。C33可以通过声波测距的低压接触超声波速度来确定。在默认设置下，合适的测量装置是来自佐治亚州亚特兰大SoniSys公司的Opus 3-D厚度透射仪器。它需要输入样品面密度，AD，然后自动确定厚度，t，和在1-MHz的频率下以全厚度透射的C33。本领域技术人员可以使用其他装置。
从测量的C33和该部件的密度ρ，E3计算为：E3＝[C33t/AD]1/2
测试方法B
该方法提供了一种评估交叉合叠的非纤维超高分子量聚乙烯片材的加固叠层当经受在255巴的压力和132℃的温度下的压实时是否会经受在前两分钟内大于35巴的压力损失和/或在前5分钟内大于70巴的压力损失的手段。
将如前所述的聚乙烯片材切割成50mm×50mm的正方形，使得包含该片材的单层之一在高取向方向上被切割。包含该片材的第二单层与第一层正交。片材叠层(图2中的20)被组装成使得片材被定位在叠层内，使得一个聚乙烯片材的单层的取向相对于相邻聚乙烯片材的最接近单层的取向以90度的角度偏移。叠层应具有660+/-50gsm的面密度。
测试方法B需要具有高度平行的加热压板的压机，这些加热压板可以被手动加压并指示随时间推移的压力。合适的压机的实例是来自印第安纳州沃巴什卡弗公司(Carver，Inc.，Wabash，IN)的两柱压机型号C。将压机压板预热至132℃。将预先制备的叠层样品放置在薄的耐热离型材料层之间，该离型材料层不会粘附到样品上或允许来自样品的粘合剂流动并污染压板。示例性的离型材料是从特拉华州威明顿杜邦公司(以下“DuPont”)以商品名Kapton可获得的聚酰亚胺膜。将样品放置在压板的中心，并且基于其初始的50mm×50mm尺寸将约255巴的压力施加到该样品上。每分钟监测压力，持续五分钟。释放压力并移出样品。重复该程序，除了不存在叠层，并且监测压力持续五分钟。只有离型材料在压板之间。该测量给出压机的顺应性的指示。两个压力对时间曲线之间的差的绝对值曲线图显示了测试材料的顺应性。已经发现，在两分钟之后显示小于约35巴压力损失和/或在五分钟之后显示小于约70巴压力损失的材料顺应性的样品在层压件的大规模制造期间不太可能相对于彼此具有片材滑动，并且因此提供具有如通过测试方法A测量的至少3GPa的通过层压件的厚度的弹性模量的层压件。
所有的弹道目标都是按照1997年12月18日发布的MIL-STD-662F中描述的“V50”试验方案，在大约13cm厚的塑性(plastilina)建模粘土块的配合下射击的。V50是确定在50％的射击中子弹或碎片穿透装甲设备，而另外50％不穿透的平均速度的统计度量。所测量的参数是在零度下的V50，其中度数角度是指弹丸对目标的倾斜度。
实例
在所有实例中，片材材料包含以0/90度取向交叉合叠的两个UHMWPE单层和两层粘合剂，使得每个单层和每个粘合剂层交替地布置。该单层材料是从特拉华州威明顿杜邦公司可获得的TensylonTM HS等级取向膜。片材材料具有50gsm的标称面积重量。将片材切割成500mm×500mm的正方形，使得包含该片材的单层之一在最高取向方向上被切割。
对比实例系列A
在该实例系列中，组装多个叠层，其中每个叠层包含40个 HS片材，使得一个片材的单层的取向相对于相邻片材的最近单层的取向偏移。在片材中使用的粘合剂是低线性密度聚乙烯的纺粘的6gsm非织造稀松布。该稀松布是来自俄亥俄州凯霍加福尔斯的Spunfab公司(Spunfab Ltd.，Cuyahoga Falls，OH)的在125℃下具有1310Pa-s的零剪切速率粘度的型号PO4605。将叠层放置在型号C卡弗压机中的扁平平行硬质钢压板之间在DuPontTM 聚酰亚胺的薄离型膜之间，并压缩至10巴的压力。然后将温度升至所希望的压板温度，在该温度下存在五分钟的压缩停留。在该停留之后，压力增加，意图是在约20秒内获得204巴的压力。如果达到目标204巴的压力，则将叠层保持在压力下持续五分钟，然后仍然在压力下的同时冷却至低于40℃的压板温度，之后从压力中释放。
在100℃的压板温度下模制的层压件没有改变尺寸。在110℃的压板温度下模制的层压件横向扩展到略大的尺寸，但是通常仍然是正方形。在116℃的压板温度下模制的层压件在达到最大压力之前在模具中滑动，导致失去其预期增强位置和取向的部件，从而导致毁坏的部件。在达到最大压力之前，在121℃的压板温度下模制的层压件在模具中滑动如此远，以致片材层中的一些的最终位置与其初始位置不相交，导致毁坏的部件具有损害模制设备或伤害操作人员的进一步可能性，这取决于其周围的压机和安全防范。
这些对比实验表明，使用通常用于制造聚乙烯层压件的设备在高的温度和压力的组合下不能一致地、正确地或安全地制造在美国专利号7,972,679中传授的UHMWPE片材层压件制品。这解释了为什么以前的教导像美国专利7,972,679使用低于约121℃的模制温度或低于约100巴的模制压力，因为高的温度和压力的组合倾向于使取向的聚乙烯取向膜增强复合物在高的横向温度和压力下不稳定，从而阻止了本领域技术人员试图制造它们。
推导回归曲线的实例
层压件以与对比实例系列A的那些相同的方式制造，除了每个叠层仅包含20个片材。该较低数量的片材足以提供信息以产生回归曲线。层压件在10、102和204巴的最大压力下和在99℃、110℃、121℃、132℃和143℃的温度下模制。然后表征层压件的为全厚度弹性模量(E3)。另外，单个单层的模量也在多个位置处测量。
结果示于表1中。虽然存在一些实验变异性，但E3通常随着模制温度的增加和模制压力的增加而增加。
表1
当单独测试时，单层的E3仅为0.235GPa，其中五次重复的标准偏差为0.007GPa。鉴于在上表中总结的对于复合层压件的发现，这是出人意料的，其中模制的复合层压件的E3远高于组分单层的横向模量。取决于制品制造的条件，增强单层的E3可以比它增强的复合层压件低超过10倍或甚至超过20倍。
从表1的数据，产生了最大模制压力和温度对通过厚度的模量的影响的线性回归模型(“方程1”)：
E3(GPa)＝-7.6731+0.00621283压力(巴)+0.0781059温度(℃)
美国专利7,972,679和US 7,976,932传授，在产生抗冲击穿透制品时，压力高达约204巴并且温度高达约127℃是必需的。那么方程1预测，至多这种复合层压件的E3将小于3.5GPa。与上述发现相反，专利7,972,679传授，这种隐含的高E3是不希望的，表明“随着模制温度降低，面板的防弹性通常增加”。方程1预测在US 8,197,935的实例中制造的制品(指出仅在40-50巴和130℃下模制)将具有2.7-2.8GPa的E3。
实例系列1
聚乙烯片材与对比实例系列A中相同。每个叠层包含40个片材。不同的粘合剂用于不同的实例。所使用的粘合剂是如先前使用的来自Spunfab公司的LLDPE非织造物PO4605，来自俄亥俄州辛辛那提麦可门公司(Michelman)的离聚物树脂分散体2960，以及来自杜邦公司(DuPont)的离聚物树脂膜8920。膜在125℃下具有2,025,860Pa-s的零剪切速率粘度。2960具有无法实际测量的零剪切速率粘度，并且基于其流动的观察，估计在125℃下超过3,000,000Pa-s。粘合剂的基重如表2所示。由于粘合剂作为分散体供应，可以通过涂覆不同量的粘合剂并使粘合剂干燥来提供不同的基重。
每个叠层被模制以根据对比实例但在变化的最大压力和压板温度下形成复合层压件。发现LLDPE非织造物粘合剂允许预成型件在压力增加期间变得不稳定，并且由于在模制期间的滑动而必须丢弃几个部件。由这两种离聚物粘合剂制成的制品没有观察到这个问题，这表明它们可以更好地实现制造具有高E3的制品。
然后，按照1997年12月18日发布的MIL-DTL-662F，使层压件经受针对大约单位长径比的0.26克直圆形钢圆柱体弹丸的弹道试验以确定平均穿孔速度(V50)。
表2总结了层压件压实条件，所得到的弹道结果和从回归曲线预测的E3值。
表2
在每种情况下，增加压缩温度和压力导致较高的估算的E3和增强的弹道性能。表2中数据的回归给出方程2为：
(在V50下吸收的动能)(J)＝49.863E3(GPa)0.394，R2＝0.90。
这个出人意料的发现与美国专利7,972,679的先前传授内容相矛盾，即在较低温度、压力和相应较低的E3下的模制对于层压件中较高的抗冲击穿透性是令人希望的。确实，超过以前在US 7,972,679中传授的压力和温度给出了最高性能。还已经发现粘合剂的选择指示了可以实现的E3上限。
已知在熔融相中具有高抗流动性的离聚物基质的使用被认为是使能够制造取向的聚乙烯抗冲击穿透复合层压件的一个实际解决方案。这些层压件在模制过程中不会滑动，尽管将面板模制为较高的E3。
实例系列2
在另一实例系列中，制备根据实例系列1组装的叠层。所使用的粘合剂是2960或8920。粘合剂的基重如表3所示。
每个叠层被模制以根据对比实例但在变化的最大压力和压板温度下形成复合层压件。发现LLDPE非织造物粘合剂允许预成型件在压力增加期间变得不稳定，并且由于在模制期间的滑动而必须丢弃几个部件。对于由这两种离聚物粘合剂制成的制品我们没有观察到这个问题，这表明它们可以更好地实现制造具有高E3的制品。
然后使层压件经受针对7.62×39mm，8.0g，具有软钢芯的PS球圆形物的弹道试验。所报告的值是每个实例发射的射击数量的平均值。结果示于表4中。E3值是从方程1推断的值。
表3
表4
从表3和表4中可以进行若干观察。E3的以前未被识别的特性对于给定的粘合剂正确地排列了层压件的每重量的保护能力，并且比所使用的特定粘合剂具有更大的影响。增加E3导致每重量更高的抗冲击穿透性，使制造商能够以较低的重量提供同等保护性制品，或者以较高的重量提供更多保护性制品，只要保持E3值。如对比实例所示，有可能增加在由美国专利号7,976,932的现有技术制成的材料上的E3。然而，通过这种方式制造的许多制品在制造过程中移位，导致不期望的产量损失。有可能通过减少基质基量和/或通过在制造温度附近增加粘合剂零剪切速率粘度来消除这个问题。低粘合剂基重、高粘合剂复粘度和制造为高E3的组合似乎提供每重量最高的保护；大约为当使用这种弹丸进行试验时所吸收的比动能的两倍。

Claims (11)

1.一种加固的抗冲击穿透的层压件，包括(i)非纤维超高分子量聚乙烯单层和(ii)热塑性粘合剂的多个交替层，该粘合剂具有不大于5gsm的基重和至少1500Pa-s的零剪切速率粘度，该零剪切速率粘度是在125℃下根据ASTM D 4440进行的以在0.1rad/s与100rad/s之间的频率扫描由振荡盘式流变仪确定的并且由拟合到Carrea-Yasuda四参数模型计算的，其中
(a)将至少90％的单层布置成使得一个单层的取向相对于相邻单层的取向偏移，并且
(b)如通过测试方法A测量的通过该层压件的厚度的弹性模量为至少3GPa。
2.如权利要求1所述的层压件，其中通过该层压件的厚度的弹性模量为至少3.2GPa或至少3.5GPA或至少4GPa。
3.如权利要求1所述的层压件，其中该粘合剂具有至少10,000Pa-s或至少100,000Pa-s或至少1,000,000Pa-s的零剪切速率粘度。
4.如权利要求1所述的层压件，其中该粘合剂进一步包含触变胶。
5.如权利要求1所述的层压件，其中相邻单层具有彼此基本上正交的取向。
6.如权利要求4所述的层压件，其中该触变胶是有机树枝状颗粒或无机颗粒。
7.一种制造抗冲击穿透的层压件的方法，该方法包括以下步骤：
(i)提供多个交叉合叠的非纤维超高分子量聚乙烯片材，其中该聚乙烯片材包含由粘合剂分开的两个聚乙烯取向膜单层，将其布置成使得该片材中的一个单层的取向相对于该片材中的另一个单层的取向偏移，其中该粘合剂具有不大于5gsm的基重和至少1500Pa-s的零剪切速率粘度，该零剪切速率粘度是在125℃下根据ASTM D 4440进行的以在0.1rad/s与100rad/s之间的频率扫描由振荡盘式流变仪确定的并且由拟合到Carrea-Yasuda四参数模型计算的，
(ii)按以下布置对包括步骤(i)的多个UHMWPE片材的叠层进行组装：其中将至少90％的片材定位成使得一个片材的单层的取向相对于相邻片材的最接近单层的取向偏移并且该叠层中的聚乙烯片材和粘合剂的组合重量是0.6-600kg/m2，
(iii)使步骤(ii)的该叠层经受从10至400巴的压力和从70℃至150℃的温度持续在5与60分钟之间，并且
(iv)将该层压件冷却至50℃或以下的温度。
8.如权利要求7所述的方法，其中该粘合剂具有至少10,000Pa-s或至少100,000Pa-s或至少1,000,000Pa-s的零剪切速率粘度。
9.如权利要求7所述的方法，其中该粘合剂进一步包含触变胶。
10.如权利要求9所述的方法，其中该触变胶是有机树枝状颗粒或无机颗粒。
11.一种用于评估交叉合叠的非纤维超高分子量聚乙烯片材的加固叠层当经受在255巴的压力和132℃的温度下的压实时是否会经受在前两分钟内大于35巴的压力损失以及在前5分钟内大于70巴的压力损失的测试方法，该方法包括以下步骤：
(i)提供多个交叉合叠的非纤维超高分子量聚乙烯片材，其中该聚乙烯片材包含由粘合剂分开的两个聚乙烯取向膜单层，将其布置成使得该片材中的一个单层的取向相对于该片材中的另一个单层的取向偏移，其中该粘合剂具有不大于5gsm的基重和至少1500Pa-s的零剪切速率粘度，该零剪切速率粘度是在125℃下根据ASTM D 4440进行的以在0.1rad/s与100rad/s之间的频率扫描由振荡盘式流变仪确定的并且由拟合到Carrea-Yasuda四参数模型计算的，并且
(ii)按以下布置对包括步骤(i)的多个UHMWPE片材的叠层进行组装：其中将至少90％的片材定位成使得一个片材的单层的取向相对于相邻片材的最接近单层的取向偏移并且该叠层中的聚乙烯片材和粘合剂的组合重量是660+/-50gsm，
(iii)使步骤(ii)的该叠层经受255巴的压力和132℃的温度，并且
(iv)测量在2和/或5分钟后的压力损失。
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US20160243790A1 (en) 2016-08-25
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