CN112793249B - 一种防弹插板及其制备方法 - Google Patents

一种防弹插板及其制备方法 Download PDF

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CN112793249B
CN112793249B CN202011529656.4A CN202011529656A CN112793249B CN 112793249 B CN112793249 B CN 112793249B CN 202011529656 A CN202011529656 A CN 202011529656A CN 112793249 B CN112793249 B CN 112793249B
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resin
adhesive film
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core
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解廷秀
张宇
纽瑞祎
宋启海
王亚南
张加加
高小林
王莉娜
王龙生
宋维广
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Shang Hai Yinai New Material Technology Ltd
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Abstract

本发明涉及一种防弹插板，包括陶瓷板、粘结膜和芳纶防弹板，粘结膜设置于陶瓷板和芳纶防弹板之间；芳纶防弹板是由芳纶织物与改性尼龙6树脂构成的的固结板；陶瓷板为碳化硅或碳化硼板材；所述的粘结膜为热熔粘结膜。本发明的改性尼龙6树脂中用于改性尼龙6树脂为“核‑壳结构”纳米粒子，该“核‑壳结构”纳米粒子的重要特征为纳米粒子的外层‑壳是交联结构。该纳米粒子具有硬的在加热时不熔融得壳，可以很容易在挤出机中进行熔融共混时均匀分散，可以在较少添加量的情况下得到更加的效果。同时，由于在“核‑壳结构”纳米粒子中核为橡胶相，进一步提高了防弹材料的防弹性能。

Description

一种防弹插板及其制备方法
技术领域
本发明涉及防护领域，具体涉及一种防弹插板及其制备方法。
背景技术
防弹衣，又叫避弹衣，避弹背心，防弹背心，避弹服等，是单兵护体装具，用于防护弹头或弹片对人体的伤害。
防弹插板是防弹衣的重要组成部分，用于提高防弹衣的防护等级。现有的防弹插板由于防弹弹性能一般，当防弹插板受到子弹冲击后，易造成子弹的贯穿。因此，提供一种防弹性好的防弹插板及其制备方法是十分重要的。
发明内容
本发明的目的之一在于：提供一种防弹性好的防弹插板。
为了实现上述目的，本发明提供如下技术方案：
一种防弹插板，包括陶瓷板、粘结膜和芳纶防弹板，所述的粘结膜设置于陶瓷板和芳纶防弹板之间；所述的芳纶防弹板是由芳纶织物与改性尼龙6树脂构成的的固结板；所述的陶瓷板为碳化硅或碳化硼板材；所述的粘结膜为热熔粘结膜。
进一步地，所述的粘结膜为共聚尼龙膜、共聚酯膜、热塑性聚氨酯膜、EVA膜中的一种；所述的陶瓷板厚度为2～20mm；所述的芳纶防弹板中改性尼龙6树脂的含量为5～30％。
优选地，所述的陶瓷板厚度为5～10mm；所述的芳纶防弹板中改性尼龙6树脂的含量为8～20％。
进一步地，所述的改性尼龙6树脂是用“核-壳结构”纳米粒子来改性尼龙6树脂，所述的“核-壳结构”纳米粒子的核为交联的橡胶相，橡胶相为聚(甲基)丙烯酸丁酯或其共聚物、丁腈橡胶、有机硅橡胶、丁苯橡胶中的一种；壳为交联的甲基丙烯酸甲酯或其共聚物。
进一步地，所述的改性尼龙6树脂的制备方法如下：
(1)纳米核的制备：
将150份乳化剂均匀溶解在去离子水中，将100份甲基丙烯酸丁酯单体在搅拌下滴加到上述溶液中乳化成乳液I；
将30份乳化剂均匀溶解在去离子水中，将200份甲基丙烯酸丁酯单体在搅拌下滴加到上述溶液中乳化成乳液II；
将乳液I加入到反应釜中，在乳液I中加入3份引发剂，搅拌溶解；加热反应釜至60～90℃引发聚合，在搅拌的情况下将乳液II和5份引发剂滴加到反应釜中，反应结束即可得到种子乳液，即纳米核；
(2)“核-壳结构”纳米粒子的制备：
将100份组成壳的单体甲基丙烯酸甲酯及5份交联剂连同15份乳化剂在搅拌下分散在去离子水中成为乳液III；
将2份引发剂溶解在去离子水中得到引发剂溶液备用；
在反应釜中加入步骤(1)得到种子乳液，搅拌，并加热到70～80℃，将引发剂溶液和乳液III滴加到反应釜中发生聚合反应；然后补加0.5份引发剂，升温至80～90℃，使单体反应完全，即可得到具有交联壳的核壳结构乳液，将交联壳的核壳结构乳液破乳，过滤，清洗，干燥即可得到含有交联壳的纳米“核-壳结构”纳米粒子；
(3)尼龙6树脂的改性：
将具有“核-壳结构”纳米粒子与尼龙6树脂混合均匀，通过双螺杆挤出机挤出造粒，得到纳米粒子分散均匀的纳米粒子改性的尼龙6树脂。
进一步地，所述的“核-壳结构”纳米粒子在尼龙6树脂中的添加量为0.1～10％，所述的尼龙6树脂的相对粘度为2.0～3.0。
优选地，所述的“核-壳结构”纳米粒子在尼龙6树脂中的添加量为0.5～2％，所述的尼龙6树脂的相对粘度为2.2～2.6。
本发明的目的之二在于：提供一种防弹性好的防弹插板的制备方法。
为了实现上述目的，本发明提供如下技术方案：
一种防弹插板的制备方法，具体步骤如下：
S1将改性尼龙6树脂在磨粉机上磨成粉末，然后均匀撒在芳纶织物上，交叉叠加多层在热压机上加热、加压，冷却后得到芳纶防弹板；
S2将粘结膜与芳纶防弹板在热压机中复合，将粘结膜附在芳纶防弹板的一侧或两侧，得到至少有一侧附有粘结膜的热塑性芳纶防弹板；
S3将陶瓷板放置在模具中，将附有粘结膜的热塑性芳纶防弹板加热熔融，迅速将附有粘结膜的热塑性芳纶防弹板放入模具中的陶瓷板上，将附有粘结膜的一侧与陶瓷板接触，快速合模，加压，保压一段时间，开模，即可得到，防弹插板。
进一步地，步骤S1中所述的热压机的加热温度为200～280℃，压力为0.1MPa～5MPa，热压时间为0.5～10分钟；改性尼龙6树脂通过磨粉机磨成20～500目的粉末；所述的芳纶织物为平纹编织布，编织布的可重为100～600g/m2；
步骤S2中芳纶防弹板与粘结膜复合时的温度为80～180℃，压力为0.1～3MPa；
步骤S3中附有粘结膜的热塑性芳纶防弹板熔融温度为200～280℃；加压时的压制压力为0.1MPa～3MPa，保压时间为60～600s。
优选地，步骤S1中所述的热压机的加热温度为220～260℃，压力为0.5～3MPa，热压时间为2～6分钟；改性的尼龙6树脂通过磨粉机磨成50～200目的粉末；所述的芳纶织物为平纹编织布，编织布的可重为200～500g/m2；
步骤S2中芳纶防弹板与粘结膜复合时的温度为100～150℃，压力为0.1～3MPa；
步骤S3中附有粘结膜的热塑性芳纶防弹板熔融温度为220～260℃；加压时的压制压力为0.2～1MPa，保压时间为200～400s。
本发明的有益效果在于：
1、本发明的方法采用改性的尼龙6树脂为芳纶防弹板的基体树脂，可以快速熔融、成型，相对比与传统的热固性树脂而言具有更快的制造速度，大大提高效益。
2、本发明采用的尼龙6树脂为热塑性树脂，另一优点是热塑性树脂相对于热固性树脂例如酚醛树脂或环氧树脂具有更好的韧性，可以大大提高在相同厚度是的防弹性能。
3、本发明的改性尼龙6树脂中用于改性尼龙6树脂为“核-壳结构”纳米粒子，该“核-壳结构”纳米粒子的重要特征为纳米粒子的外层-壳是交联结构，完全不同于传统的“核-壳结构”的粒子例如市场上的MBS、ACR等粒子。该纳米粒子具有硬的在加热时不熔融得壳，可以很容易在挤出机中进行熔融共混时均匀分散，可以在较少添加量的情况下得到更加的效果。同时，由于在“核-壳结构”纳米粒子中核为橡胶相，进一步提高了防弹材料的防弹性能。
4、采用热塑性的热熔胶膜粘结陶瓷与有机防弹板，可以大大提高产品的稳定性。
5、采用热塑性的芳纶防弹复合材料和热熔胶膜与陶瓷板通过热压的方式制造，由于模具是冷模，可以大大提高生产效率。
具体实施例
实施例1
一、改性尼龙6树脂的制备方法如下：
(1)纳米核的制备：
在3L玻璃反应釜将100乳化剂聚氧化乙烯烷芳基醚(OP-10)和50克十二烷基磺酸钠溶解在1L的去离子水中，将100克甲基丙烯酸丁酯在搅拌下滴加到反应釜中，形成乳液I。
在玻璃杯中将20克聚氧化乙烯烷芳基醚和10克十二烷基磺酸钠溶解在500ml去离子水中，将200克甲基丙烯酸丁酯在搅拌下加入到该溶液中，得到乳液II。
在乳液I中加入3克引发剂过硫酸铵，搅拌溶解。开启水浴锅加热至75℃，并启动反应釜中的搅拌装置搅拌，引发聚合，用液体计量泵分别将乳液II和5克引发剂过硫酸铵在3小时内滴加完全，升高温度至85℃，搅拌下，继续反应2小时，使反应单体反应完全。得到核的种子乳液，即为纳米核，种子乳液的固含量为23％。
(2)“核-壳结构”纳米粒子的制备：
在烧杯中，将10克聚氧化乙烯烷芳基醚和5克十二烷基磺酸钠溶解在200克去离子水中，在搅拌下将100克甲基丙烯酸甲酯和5克对二乙烯苯加入到乳化剂溶液中，搅拌成乳液III。在3L反应釜中加入上述制造的种子乳液1200克，水浴升温至75℃，搅拌下，用液体计量泵分别将乳液III和引发剂溶液(2克过硫酸铵溶解在20克去离子水中得到引发剂溶液)在3小时内滴加完全后，再补加0.5克引发剂过硫酸铵，升温至85℃，反应1小时，使单体反应完全，即可得到纳米“核-壳结构”乳液。将上述乳液加入硫酸钠溶液，搅拌，破乳。过滤，用去离子水洗涤三遍，去除残留的乳化剂，干燥，即可得到具有“核-壳结构”的纳米粒子。该粒子中的壳是一种交联结构，更有利于分散在热塑性塑料基体中。
(3)尼龙6树脂的改性：
将上述制造的纳米核壳结构粒子100克与2000克尼龙6粒子混合均匀，在双杆挤出机上造粒，得到改性的尼龙6树脂。
二、芳纶防弹板的制备：
改性好的尼龙6树脂在磨粉机上磨成50目的粉末。
在模具中将340g/m2的芳纶布(Kevlar K-49)上均匀撒上改性的尼龙6粉末，撒分量是芳纶布质量15％，共计20层(改性的尼龙6粉末与芳纶布交替铺放)，将模具合模后放置于预热到240℃的平板压机中，加压1MPa,保温保压3分钟后，转移到冷却压机中，在保持1MPa的压力下冷却。得到芳纶防弹板。
三、防弹插板的制备
将粘结膜与芳纶防弹板在热压机中复合(其中温度为120℃，压力为1MPa)，将粘结膜附在芳纶防弹板的一侧或两侧，得到至少有一侧附有粘结膜的热塑性芳纶防弹板；
将陶瓷板放置在模具中，将附有粘结膜的热塑性芳纶防弹板加热熔融(温度为240℃)，迅速将附有粘结膜的热塑性芳纶防弹板放入模具中的陶瓷板上，将附有粘结膜的一侧与陶瓷板接触，快速合模，加压，保压一段时间(压力为1MPa，保压时间为300s)，开模，即可得到，防弹插板。
对比例1
一、芳纶防弹板的制备：
将尼龙6树脂在磨粉机上磨成50目的粉末。
在模具中将340g/m2的芳纶布(Kevlar K-49)上均匀撒上尼龙6粉末，撒分量是芳纶布质量15％，共计20层(改性的尼龙6粉末与芳纶布交替铺放)，将模具合模后放置于预热到240℃的平板压机中，加压1MPa,保温3分钟后，转移到冷却压机中，在保持1MPa的压力下冷却。得到芳纶防弹板。
二、防弹插板的制备
S2将粘结膜与芳纶防弹板在热压机中复合(其中温度为120℃，压力为1MPa)，将粘结膜附在芳纶防弹板的一侧或两侧，得到至少有一侧附有粘结膜的热塑性芳纶防弹板；
S3将陶瓷板放置在模具中，将附有粘结膜的热塑性芳纶防弹板加热熔融(温度为240℃)，迅速将附有粘结膜的热塑性芳纶防弹板放入模具中的陶瓷板上，将附有粘结膜的一侧与陶瓷板接触，快速合模，加压，保压一段时间(压力为1MPa，保压时间为300s)，开模，即可得到，防弹插板。
防弹性能对比
将实施例1和对比例1得到的芳纶防弹板的防弹性能进行比较，得到表1：
表1实施例1和对比例1中芳纶防弹板的防弹性能对比表
项目 测试标准 实施例1 对比例1
防弹性(V50值) GJB 3196-1998 635 578
将实施例1和对比例1得到的防弹插板的防弹性能进行比较，得到表2：
表2实施例1和对比例1中防弹插板的防弹性能对比表
结果分析：
从表1、2中可以看出，采用本发明的方法得到的芳纶防弹板和防弹插板的防弹性能明显优于对比例1，说明对尼龙6树脂采用本发明的方法进行改性有利于提高产品的防弹性。

Claims (6)

1.一种防弹插板，其特征在于：包括陶瓷板、粘结膜和芳纶防弹板，所述的粘结膜设置于陶瓷板和芳纶防弹板之间；所述的芳纶防弹板是由芳纶织物与改性尼龙6树脂构成的固结板；所述的陶瓷板为碳化硅或碳化硼板材；所述的粘结膜为热熔粘结膜；所述的粘结膜为共聚尼龙膜、共聚酯膜、热塑性聚氨酯膜、EVA膜中的一种；所述的陶瓷板厚度为2~20mm；所述的芳纶防弹板中改性尼龙6树脂的含量为5~30%；所述的改性尼龙6树脂是用“核-壳结构”纳米粒子来改性尼龙6树脂，所述的“核-壳结构”纳米粒子的核为交联的橡胶相，橡胶相为聚甲基丙烯酸丁酯；壳为交联的甲基丙烯酸甲酯；所述的改性尼龙6树脂的制备方法如下：（1）纳米核的制备：将150份乳化剂均匀溶解在去离子水中形成溶液I，将100份甲基丙烯酸丁酯单体在搅拌下滴加到上述溶液I中乳化成乳液I；将30份乳化剂均匀溶解在去离子水中形成溶液II，将200份甲基丙烯酸丁酯单体在搅拌下滴加到上述溶液II中乳化成乳液II；将乳液I加入到反应釜中，在乳液I中加入3份引发剂，搅拌溶解；加热反应釜至60~90℃引发聚合，在搅拌的情况下将乳液II和5份引发剂滴加到反应釜中，反应结束即得到种子乳液，即纳米核；（2）“核-壳结构”纳米粒子的制备： 将100份组成壳的单体甲基丙烯酸甲酯及5份交联剂连同15份乳化剂在搅拌下分散在去离子水中成为乳液III；将2份引发剂溶解在去离子水中得到引发剂溶液备用；在反应釜中加入步骤（1）得到种子乳液，搅拌，并加热到70~80℃，将引发剂溶液和乳液III滴加到反应釜中发生聚合反应；然后补加0.5份引发剂，升温至80～90℃，使单体反应完全，即得到具有交联壳的核壳结构乳液，将交联壳的核壳结构乳液破乳，过滤，清洗，干燥即得到含有交联壳的纳米“核-壳结构”纳米粒子；（3）尼龙6树脂的改性：将具有“核-壳结构”纳米粒子与尼龙6树脂混合均匀，通过双螺杆挤出机挤出造粒，得到纳米粒子分散均匀的纳米粒子改性的尼龙6树脂；所述的“核-壳结构”纳米粒子在尼龙6树脂中的添加量为0.1~10%，所述的尼龙6树脂的相对粘度为2.0~3.0。
2.根据权利要求1所述的一种防弹插板，其特征在于：所述的陶瓷板厚度为5~10mm；所述的芳纶防弹板中改性尼龙6树脂的含量为8~20%。
3.根据权利要求1所述的一种防弹插板，其特征在于：所述的“核-壳结构”纳米粒子在尼龙6树脂中的添加量为0.5~2%，所述的尼龙6树脂的相对粘度为2.2~2.6。
4.一种如权利要求1-3任意一项所述的防弹插板的制备方法，其特征在于：具体步骤如下：S1将改性尼龙6树脂在磨粉机上磨成粉末，然后均匀撒在芳纶织物上，交叉叠加多层在热压机上加热、加压，冷却后得到芳纶防弹板；S2将粘结膜与芳纶防弹板在热压机中复合，将粘结膜附在芳纶防弹板的一侧或两侧，得到至少有一侧附有粘结膜的热塑性芳纶防弹板；S3将陶瓷板放置在模具中，将附有粘结膜的热塑性芳纶防弹板加热熔融，迅速将附有粘结膜的热塑性芳纶防弹板放入模具中的陶瓷板上，将附有粘结膜的一侧与陶瓷板接触，快速合模，加压，保压一段时间，开模，即得到防弹插板。
5.根据权利要求4所述的防弹插板的制备方法，其特征在于：步骤S1中所述的热压机的加热温度为200~280℃，压力为0.1MPa~5MPa，热压时间为0.5~10分钟；改性尼龙6树脂通过磨粉机磨成20~500目的粉末；所述的芳纶织物为平纹编织布，编织布的克重为100~600g/m2；步骤S2中芳纶防弹板与粘结膜复合时的温度为80~180℃，压力为0.1~3MPa；步骤S3中附有粘结膜的热塑性芳纶防弹板熔融温度为200~280℃；加压时的压制压力为0.1MPa~3MPa，保压时间为60~600s。
6.根据权利要求4所述的防弹插板的制备方法，其特征在于：步骤S1中所述的热压机的加热温度为220~260℃，压力为0.5~3MPa，热压时间为2~6分钟；改性的尼龙6树脂通过磨粉机磨成50~200目的粉末；所述的芳纶织物为平纹编织布，编织布的克重为200~500g/m2；步骤S2中芳纶防弹板与粘结膜复合时的温度为100~150℃，压力为0.1~3MPa；步骤S3中附有粘结膜的热塑性芳纶防弹板熔融温度为220~260℃；加压时的压制压力为0.2~1MPa，保压时间为200~400s。
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