CN116529930A - 有机硅层叠体 - Google Patents

有机硅层叠体 Download PDF

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Publication number
CN116529930A
CN116529930A CN202180080615.8A CN202180080615A CN116529930A CN 116529930 A CN116529930 A CN 116529930A CN 202180080615 A CN202180080615 A CN 202180080615A CN 116529930 A CN116529930 A CN 116529930A
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silicone
layer
laminate
rubber layer
silicone rubber
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服部真和
木村裕子
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Fuji Polymer Industries Co Ltd
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Fuji Polymer Industries Co Ltd
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Priority claimed from PCT/JP2021/038789 external-priority patent/WO2022224468A1/ja
Publication of CN116529930A publication Critical patent/CN116529930A/zh
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Abstract

本发明提供一种通过包含硅橡胶层(A)(2)和硬度比硅橡胶层(2)低的有机硅层(B)(3)的层层叠而成的有机硅层叠体(1)，有机硅层(B)(3)是选自有机硅海绵层(B1)及有机硅凝胶层(B2)中的至少一个层，硅橡胶层(A)(2)及有机硅层(B)(3)都由通过在燃烧时陶瓷化、成为烧结体从而保持形状的材料形成，有机硅层叠体(1)具有耐火性。硅橡胶层(A)(2)及所述有机硅层(B)(3)交替地层叠，优选将各层层叠2层以上，合计层叠4层以上。由此，提供电池的缓冲材料的耐火性及耐压缩性高的有机硅层叠体。

Description

有机硅层叠体
技术领域
本发明涉及可用于电池单元间的缓冲材料等中的有机硅层叠体。
背景技术
近年来，需求量和生产量逐渐增加的电动车(electric vehicle：EV)、插电式混合动力汽车(PHEV)、混合动力汽车(HEV)等以来自电池的电作为能源，采用电动机(马达)进行行驶。电池通常排列有多个电池单元，收纳在电池壳内使用。电池是通过设想各种异常事态而制作的，其中之一有热失控反应等的异常发热。如果发生异常发热，则存在因单元膨胀而使单元材料变形或破损的顾虑。
专利文献1中提出了一种阻燃性的热膨胀性部件，其在80℃以下时导热率为1W/m·K以上，如果超过80℃则导热率为0.5W/m·K以下。专利文献2中提出了用包含硅橡胶粘合剂和中空玻璃珠的发泡体来充满电池模块容器的开放空间。专利文献3中提出了一种散热体，其用于散发电池的热，包含筒状、截面U字状或螺旋状的散热片、缓冲材料和粘结层。
现有技术文献
专利文献
专利文献1：日本特开2019-172762号公报
专利文献2：日本特表2020-507194号公报
专利文献3：日本特开2021-015696号公报
发明内容
发明要解决的问题
可是，上述以往技术在电池的缓冲材料的耐火性及耐压缩性方面还存在问题，一直在谋求改善。
本发明为了解决上述以往的问题，提供一种电池的缓冲材料的耐火性及耐压缩性高的有机硅层叠体。
用于解决课题的手段
本发明的有机硅层叠体是由包含硅橡胶层(A)和硬度比上述硅橡胶层低的有机硅层(B)的层层叠而成的有机硅层叠体，其中，上述有机硅层(B)是选自有机硅海绵层(B1)及有机硅凝胶层(B2)中的至少一个层，上述硅橡胶层(A)及上述有机硅层(B)都由通过在燃烧时陶瓷化、成为烧结体从而保持形状的材料形成，上述有机硅层叠体具有耐火性。
发明效果
本发明是由包含硅橡胶层(A)和硬度比上述硅橡胶层低的有机硅层(B)的层层叠而成的有机硅层叠体，其中，上述有机硅层(B)是选自有机硅海绵层(B1)及有机硅凝胶层(B2)中的至少一个层，上述硅橡胶层(A)及上述有机硅层(B)都由通过在燃烧时陶瓷化、成为烧结体从而保持形状的材料形成，上述有机硅层叠体具有耐火性，由此，能够提供电池的缓冲材料的耐火性及耐压缩性高的有机硅层叠体。上述特性在电池异常发热时还能够防止材料变形。
附图说明
[图1]图1A是在本发明的一个实施方式的电池单元间配置了有机硅层叠体的示意性剖视图，图1B是图1A发生异常发热时的示意性剖视图。
[图2]图2A是在比较例的电池单元间配置了有机硅材料的示意性剖视图，图2B是图2A发生异常发热时的示意性剖视图。
[图3]图3是在本发明的一个实施方式的多个电池单元间配置了有机硅层叠体的电池的示意性剖视图。
具体实施方式
本发明是由包含硅橡胶层(A)和硬度比上述硅橡胶层低的有机硅层(B)的层层叠而成的有机硅层叠体。优选硅橡胶层(A)的ASKER A硬度为40～80，优选有机硅层(B)的ASKER C硬度为30～70，硬度的关系为A＞B。由此，硬度高的硅橡胶层(A)成为芯材，成为一边维持耐火性及绝热性、一边减少由单元膨胀带来的变形的材料。
有机硅层(B)是选自有机硅海绵层(B1)及有机硅凝胶层(B2)中的至少一个层。由此，成为与硅橡胶层(A)相比硬度低的有机硅层。上述硅橡胶层(A)及上述有机硅层(B)都由通过燃烧时陶瓷化、成为烧结体来保持形状的材料形成。作为这样的有机硅原料，例如有市场上出售的由信越化学公司制造的有机硅底料KE-1734-U。通过使用这样的有机硅原料，上述有机硅层叠体具有耐火性。如果具有耐火性，则即使电池单元异常发热，燃烧的可能性也低。
硅橡胶层(A)及有机硅层(B)交替地层叠，优选将各层层叠2层以上，合计层叠4层以上。硅橡胶层(A)及有机硅层(B)能够设定为规定的厚度，例如各为1～100mm的厚度，可与电池单元的尺寸相符地选择层叠数。
上述硅橡胶层(A)的层叠方向的厚度为1～100mm，上述有机硅层(B)的层叠方向的厚度为1～100mm，优选相对于上述硅橡胶层(A)的厚度上述有机硅层(B)的厚度为0.1～10倍的范围。只要是上述的范围就容易制造。
上述有机硅层叠体的耐火性优选为用气体燃烧器燃烧5分钟时可维持形状的耐火性。气体燃烧器可使用UL94标准中规定的气体燃烧器。只要具有此程度的耐火性，即使电池单元异常发热，燃烧的可能性也低。
优选上述有机硅层叠体不仅具有耐火性，还具有在UL94标准、垂直燃烧试验中满足5VB的阻燃性。为了显示出阻燃性而使用上述耐火性有机硅原料。UL94标准的垂直燃烧试验从上往下分类为5VA、5VB、V-0、V-1、V-2，5VB与V-0、V-1、V-2同样通过垂直燃烧试验进行判定，但试验中采用10倍的燃烧能量的气体燃烧器，如果满足以下3个条件则为合格。
(1)哪个试验片在5次接触火焰后的燃烧都不超过60秒。
(2)无脱落(从试验片落下的粒子)。
(3)哪个试验片都在接触火焰的部分上无明显的损伤。
优选有机硅海绵层(B1)是发泡倍率为1.2～3倍的独立发泡体。如果是该发泡倍率，则在电池单元异常发热时，有机硅海绵层消失或发泡，由于具有耐火性的橡胶层残存，所以还能够发挥绝热性。
有机硅层叠体的50％压缩时的压缩强度优选为1～30N/mm2。由此，在电池单元异常发热时，能够防止电池变形及损伤。从此功能来看，有机硅层叠体作为夹在电池单元间的缓冲材料是有用的。
优选上述硅橡胶层(A)和上述有机硅层(B)都为过氧化物硫化型。过氧化物硫化型与加成硫化的情况相比，加工性良好。
有机过氧化物例如可列举苯甲酰过氧化物、2,4-二氯苯甲酰过氧化物、(双(2,4-二氯苯甲酰)过氧化物)、对甲基苯甲酰过氧化物、邻甲基苯甲酰过氧化物、2,4-二枯基过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化物)己烷、二叔丁基过氧化物、叔丁基过氧苯甲酸酯、1,6-己烷二醇-双-叔丁基过氧碳酸酯等。优选有机过氧化物的添加量相对于硅橡胶成分100质量份为0.1～15质量份，更优选为0.2～10质量份。如果添加量过少则不能充分进行交联反应，有时产生硬度降低或橡胶强度不足、压缩永久应变增大等物性恶化，如果过多则大量产生固化剂的分解物，有时使压缩永久应变增大等物性恶化或所得到的薄板的变色增大。
以下，采用附图进行说明。在以下的附图中，同一符号意味同一物。图1A是在本发明的一个实施方式的电池单元4a、4b间配置了有机硅层叠体1的示意性剖视图。有机硅层叠体1是硅橡胶层(A)2和硬度比上述硅橡胶层低的有机硅层(B)3的有机硅层叠体。有机硅层(B)3是有机硅海绵层(B1)或有机硅凝胶层(B2)。图1B是发生异常发热时的示意性剖视图。硅橡胶层(A)2是具有耐火性的硬度高的硅橡胶层，所以成为芯材，一边维持耐火性及绝热性，一边防止由单元膨胀带来的电池4a、4b间的变形。
图2A是在比较例的电池单元4a、4b间配置了有机硅材料5的示意性剖视图，图2B是图2A的发生异常发热时的示意性剖视图。如果产生异常发热，则例如电池单元4b发生变形，形成膨胀部6，使相邻的电池单元4a损伤。
图3是在本发明的一个实施方式的多个电池单元4a、4b……间配置了有机硅层叠体1的电池的示意性剖视图。该电池单元在冷却装置7上载置有导热性薄板(TIM)8，在其上配置电池单元4a、4b……，在各电池单元4a、4b……间配置有有机硅层叠体1。上部被缓冲材料薄板9和电池壳10覆盖，布线11从电池单元4a中引出来。
实施例
以下，采用实施例进行说明。本发明并不限定于实施例。对于各种参数，用下述的方法进行测定。
<耐火性>
判断采用UL94标准、垂直燃烧试验的V-0、V-1、V-2中所使用的热能的气体燃烧器燃烧5分钟时是否维持形状。
<阻燃性>
测定是否具有在UL94标准、垂直燃烧试验中满足5VB的阻燃性。
<硬度>
使用JIS K 7312中规定的橡胶硬度计，测定ASKER A硬度及ASKER C硬度。
<压缩强度测定方法>
·测定方法：按照ASTM D575-91。
·试样尺寸：纵10mm、横10mm(厚度记载于实施例的表中)
·上下加压板尺寸：纵30mm、横30mm、厚4mm
·压缩速度：5mm/min
·压缩率：10-50％
·试验方法
(1)用上下加压板夹持所层叠的试样。
(2)将感觉到载荷的位置作为测定开始位置，压缩到10-50％。
(3)记录每个压缩量的载荷值。
(实施例1～4、比较例1～5)
1原料成分
(1)硅橡胶层A
(a)相对于信越化学公司制造的有机硅底料KE-1734-U：100重量份，添加2.5重量份的硫化剂(双(2,4-二氯苯甲酰)过氧化物)，用二个辊进行混合。
(b)用加压机在120℃将混合物加压成型5分钟。
(c)在200℃对所得到的薄板进行4小时的二次硫化。
(2)有机硅海绵层B1
(a)相对于信越化学公司制造的有机硅底料KE-1734-U：100重量份，添加2.9重量份的硫化剂(双(2,4-二氯苯甲酰)过氧化物)，将发泡剂添加4重量份，用二个辊进行混合。
(b)用加压机在150℃将混合物加压成型10分钟。在该加压成型时。混合物产生发泡(独立发泡)，发泡倍率为两倍。
(c)在200℃对所得到的薄板进行4小时的二次硫化。
(3)无耐火性的硅橡胶层
(a)相对于DOW·TORAY公司制造的有机硅底料SH502UA/B：100重量份，添加2.5重量份的硫化剂(双(2,4-二氯苯甲酰)过氧化物)，用二个辊进行混合。
(b)用加压机在120℃将混合物加压成型5分钟。
(c)在200℃对所得到的薄板进行4小时的二次硫化。
(d)所得到的薄板的ASKER A的硬度为50。
(4)层叠方法
对固化后的薄板表面实施电晕处理，在80℃加热1小时，进行粘接。
表1及表2中汇总地示出所得到的层叠体的各种物性。
表1
(备注：层叠数为A-B1-A-B1-A-B1-A的7层)
表2
(备注：比较例3-5的层叠数为C-D-C-D-C-D-C的7层)
如表1及表2所示，各实施例与各比较例1相比，确认为耐火性及耐压缩性高的有机硅层叠体。这些特性在电池异常发热时还能够防止材料的变形。
(实施例5～8)
相对于市售的加成反应型有机硅凝胶原料即有机聚硅氧烷(A剂和B剂中一方配合有交联剂，另一方配合有铂系催化剂)100重量份，混合2重量份的交联剂，混合1重量份的铂催化剂，用加压机在100℃将混合物加压成型10分钟。表3中汇总地示出条件及结果。
表3
(备注：层叠数为A-B2-A-B2-A-B2-A的7层)
如表3所示，确认实施例5～8也为耐火性、阻燃性及耐压缩性高的有机硅层叠体。这些特性在电池异常发热时还能够防止材料的变形。
工业上的可利用性
本发明的有机硅层叠体除了可作为电池单元的缓冲材料使用外，还可作为各种缓冲材料使用。
符号说明
1－有机硅层叠体
2－高硬度硅橡胶层(A)
3－低硬度有机硅层(B)
4a、4b－电池单元
5－有机硅材料
6－膨胀部
7－冷却装置
8－导热性薄板(TIM)
9－缓冲材料薄板
10－电池壳
11－布线

Claims (10)

1.一种有机硅层叠体，其特征在于：是包含硅橡胶层(A)和硬度比所述硅橡胶层低的有机硅层(B)的层层叠而成的有机硅层叠体，
所述有机硅层(B)是选自有机硅海绵层(B1)及有机硅凝胶层(B2)中的至少一个层；
所述硅橡胶层(A)及所述有机硅层(B)都由通过在燃烧时陶瓷化、成为烧结体从而保持形状的材料形成；
所述有机硅层叠体具有耐火性。
2.根据权利要求1所述的有机硅层叠体，其中，所述硅橡胶层(A)及所述有机硅层(B)交替地层叠，将各层层叠2层以上，合计层叠4层以上。
3.根据权利要求1或2所述的有机硅层叠体，其中，所述硅橡胶层(A)的ASKER A硬度为40～80，所述有机硅层(B)的ASKER C硬度为30～70。
4.根据权利要求1～3中任一项所述的有机硅层叠体，其中，所述硅橡胶层(A)的层叠方向的厚度为1～100mm，所述有机硅层(B)的层叠方向的厚度为1～100mm，相对于所述硅橡胶层(A)的厚度，所述有机硅层(B)的厚度为0.1～10倍的范围。
5.根据权利要求1～4中任一项所述的有机硅层叠体，其中，所述有机硅层叠体的耐火性为用气体燃烧器燃烧5分钟时维持形状的耐火性。
6.根据权利要求1～5中任一项所述的有机硅层叠体，其中，所述有机硅层叠体不仅具有耐火性，还具有在UL94标准、垂直燃烧试验中满足5VB的阻燃性。
7.根据权利要求1～6中任一项所述的有机硅层叠体，其中，所述有机硅海绵层(B1)是发泡倍率为1.2～3倍的独立发泡体。
8.根据权利要求1～7中任一项所述的有机硅层叠体，其中，所述有机硅层叠体的50％压缩时的压缩强度为1～30N/mm2。
9.根据权利要求1～8中任一项所述的有机硅层叠体，其中，所述硅橡胶层(A)和所述有机硅层(B)都是过氧化物硫化型。
10.根据权利要求1～9中任一项所述的有机硅层叠体，其中，所述有机硅层叠体是夹在电池单元间的缓冲材料。
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