CN115404043B - 一种高韧性高热稳定性阻燃电子封装胶及其制备方法 - Google Patents
一种高韧性高热稳定性阻燃电子封装胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种高韧性高热稳定性阻燃电子封装胶及其制备方法,该封装胶包括环氧官能化笼型聚倍半硅氧烷、双酚A环氧树脂、双酚F环氧树脂、固化剂、固化促进剂和填料的原料制备。本发明制备获得的电子封装胶,固化后具有高韧性、高热稳定性和阻燃性,且粘结性好、安全环保的优点,本发明提供的产品配方简单,生产工艺简单,适合于高压直流工况下的各种大功率电子器件的封装保护。
Description
技术领域
本发明涉及一种高韧性高热稳定性阻燃电子封装胶及其制备方法,具体属于封装胶技术领域。
背景技术
陶瓷基复合材料具有较高的导热率、较强的抗弯强度以及适宜的热膨胀系数,因而被广泛运用于大功率的电子器件的封装上,应用场景为动车组、新能源汽车和充电桩等。目前,陶瓷基复合材料已经成为国际市场中应用率较高的高科技陶瓷材料之一。比如氧化铝、氮化铝、氧化铍、碳化硅等,都是比较常用的陶瓷基复合材料。大功率电子器件工作时,往往需要经受高电压大电流的工况,发热量大,温度高,而且高低温切换频繁。此外,在动车组和新能源汽车的应用场景上,大功率电子器件还要经受频繁的机械震动。因此,就要求电子封装胶具有优异的韧性,能够抗机械震动,抗高低温冲击不开裂;具有优异的热稳定性能(Tg >170℃),并且阻燃和环保安全。
目前,现有技术中,有不少的增韧、提高热稳定性和阻燃的解决方案,这些方案中,有些是方法繁琐,需要进行各种的改性,生产成本高。有些需要用到各种有机溶剂,对环保和人体健康存在风险;而且,效果并不是很理想。
发明内容
(一)要解决的技术问题
为了解决现有技术的上述问题,本发明提供一种高韧性高热稳定性阻燃电子封装胶及其制备方法,采用该方法的配方,无需进行改性、不使用有机溶剂,工艺简单,效果好,环保安全。
(二)技术方案
为了达到上述目的,本发明采用的主要技术方案包括:
一种高韧性高热稳定性阻燃电子封装胶,其包括按如下重量份计的组分环氧官能化笼型聚倍半硅氧烷13-15份、双酚A环氧树脂3-6份、双酚F环氧树脂10-13份、固化剂3-5份和填料63-67份。
进一步,优选环氧官能化笼型聚倍半硅氧烷为15份、双酚A环氧树脂为5份、双酚F环氧树脂为10份、固化剂为5份和填料为63份。
如上所述阻燃电子封装胶,优选地,所述环氧官能化笼型聚倍半硅氧烷为缩水甘油醚氧丙基笼型聚倍半硅氧烷或环氧环己烷基乙基笼型聚聚倍半硅氧烷中的任意一种或它们任意比例的混合物,其中,缩水甘油醚氧丙基笼型聚倍半硅氧烷(1)和环氧环己烷基乙基笼型聚倍半硅氧烷 (2)的分子结构分别如下:
进一步地,环氧官能化笼型聚倍半硅氧烷优选为缩水甘油醚氧丙基笼型聚倍半硅氧烷。
如上所述阻燃电子封装胶,优选地,所述固化剂为4,4'-二氨基二苯砜(DDS)、3,3'-二乙基-4,4'-二氨基二苯甲烷(DEDDM)或3,3'-二甲基 -4,4'-二氨基二环己基甲烷(DMDC)中的任一种或任意几种的混合物,环保安全。
如上所述阻燃电子封装胶,优选地,所述填料为粒径10-30μm的三氧化二铝粉、氧化铍、氮化硅或氮化铝(AlN)中的任一种或任意几种的混合物。
如上所述阻燃电子封装胶的制备方法,优选地,其包括如下步骤:
S1、将环氧官能化笼型聚倍半硅氧烷、双酚A环氧树脂、双酚F环氧树脂和填料,投入反应釜中,搅拌;
S2、在反应釜中,继续投入固化剂,满真空,搅拌,即制得具有高韧性高热稳定性阻燃电子封装胶。
如上所述阻燃电子封装胶的制备方法,优选地,在步骤S1中,搅拌的时间为1-2小时。
如上所述阻燃电子封装胶,优选地,在步骤S2中,搅拌的时间为3-5 小时。
本发明经大量实验研究发现,在上述阻燃电子封装胶优选固化剂为 4,4'-二氨基二苯砜、3,3'-二乙基-4,4'-二氨基二苯甲烷或3,3'-二甲基-4,4'- 二氨基二环己基甲烷使得性能较佳,而选用其他固化剂如二乙烯基三胺 (DETA),性能较差;在上述阻燃电子封装胶中不添加固化促进剂(微胶嚷双肼)和稳定剂(如双(2,4-二叔丁基苯基)季戊四醇双二亚磷酸酯) 与添加固化促进剂和稳定剂的效果、性能没有显著性差异,所以从节约成本考虑,不添加固化促进剂和稳定剂。
(三)有益效果
本发明的有益效果是:
本发明提供的高韧性高热稳定性阻燃电子封装胶,直接采用环氧官能化笼型聚倍半硅氧烷,不需要进行改性,生产工艺简单,不需要添加溶剂,即可制得具有高韧性、高热稳定性和阻燃性,且粘结性好、安全环保的电子封装胶,且其生产成本低。该电子封装胶适合于高压直流工况下的各种大功率电子器件的封装保护。
本发明提供的电子封装胶,使用的环氧官能化笼型聚倍半硅氧烷,其分子结构中的内核笼型聚倍半硅氧烷,英文名称polyhedral oligomeric silsesquioxane,简称POSS,分子结构如(3)所示。POSS是由Si-O 交替连接的硅氧骨架组成的无机内核,其形状如同一个“笼子”,故得名为笼型聚倍半硅氧烷,其三维尺寸在1~3nm之间,其中Si原子之间的距离为0.5nm,R基团之间距离为1.5nm,属于纳米化合物。在增韧方面, POSS纳米粒子能终止因外界应力而产生的银纹(微裂纹)尖端的发展与传播,迫使银纹发展的方向发生偏转,引发银纹及分子链重新排列,规避了银纹进一步发展成裂纹的风险,使得电子封装胶胶体的韧性进一步提高。
此外,环氧官能化笼型聚倍半硅氧烷分子的内核POSS笼子具有比较大的自由体积,遇到外力袭击时易发生弹性形变。当外力撤消后,又能回复到原来的形状,胶体本身并不会产生裂纹。因此,它能吸收瞬间的应力冲击,或者是能够抵抗温度的骤变(高低温冲击),而自身不会开裂。
环氧官能化笼型聚倍半硅氧烷中,缩水甘油醚氧丙基笼型聚聚倍半硅氧烷(1),其分子结构的八个顶角上的缩水甘油醚氧丙基,环氧基与 POSS无机内核连接着的:醚键基团和四个亚甲基基团,如结构式(4),均具有很好的柔性。
以上使得本发明的产品具有较高的韧性,更使本发明的产品可以通过高低温冲击的可靠性测试,并且适应动车组和新能源汽车剧烈震动的工况。
2.高热稳定性
无机内核POSS中的Si-O化学键交替连接的硅氧骨架组成的无机内核,Si-O键的键能很高,为445.2KJ/mol,而相比之下的C-C键能为 350.7KJ/mol,C-O键能为359.1KJ/mol。因此,要想破坏POSS内核中的 Si-O键,就需要很大的能量。
另一方,本发明采用的固化剂优选4,4'-二氨基二苯砜(DDS)(5)、 3,3'-二乙基-4,4'-二氨基二苯甲烷(DEDDM)(6)、3,3'-二甲基-4,4'-二氨基二环己基甲烷(DMDC)(7),其各自的结构式如下:
固化剂分子结构中含有苯环或环己环,均是稳定的结构基团,要打破这些环状结构的基团,同样需要提供很大的能量。
POSS无机内核与固化剂的苯环或环己环的协同作用的结果,使胶体具有很高的热稳定性。换句话说,形成的胶体具有高耐热性,表现出具有很高玻璃化温度(Tg>170℃)。
3.阻燃性
POSS聚倍半硅氧烷内核受热时容易产生含有Si—O和Si—C的无机隔热绝缘保护层,既阻止了燃烧的分解产物外逸,又抑制了高分子材料的热分解,可减少聚合物因热分解而产生的可燃性气体的释放,以凝聚相阻燃的作用机理提高了阻燃效果,使产品达到V0级的阻燃要求。因而,本发明的产品生产时不需另加阻燃剂,例如:卤系、磷系和氢氧化铝等材料,使产品成分不会偏离ROHS的要求,确保产品的环保与安全。
附图说明
图1为剪切力测试试件示意图;
图2为测试试件搭接面积示意图。
具体实施方式
为了更好的解释本发明,以便于理解,下面通过具体实施方式,对本发明作详细描述。实施例中所指的份数若无特别说明,均指重量份数,所用材料若无特别说明均可采用市购产品。
实施例1
称取环氧官能化笼型聚倍半硅氧烷为缩水甘油醚氧丙基笼型聚倍半硅氧烷(1)15份、双酚A环氧树脂5份、双酚F环氧树脂10份、填料 (粒径为10-30μm的三氧化二铝)63份,投入反应釜中,行星搅拌1小时。在反应釜中,继续投入固化剂(DMDC)5份、满真空(-0.095MPa),行星搅拌3小时,即制得具有高韧性高热稳定性阻燃电子封装胶。
实施例2
称取环氧官能化笼型聚倍半硅氧烷为缩水甘油醚氧丙基笼型聚倍半硅氧烷(1)10份、双酚A环氧树脂6份、双酚F环氧树脂13份、填料 (粒径为10-30μm的三氧化二铝)66份,投入反应釜中,行星搅拌2小时。在反应釜中,继续投入固化剂(DEDDM)4份、满真空(-0.095MPa),行星搅拌5小时,即制得具有高韧性高热稳定性阻燃电子封装胶组合物。
实施例3
称取环氧官能化笼型聚倍半硅氧烷为缩水甘油醚氧丙基笼型聚倍半硅氧烷(1)13份、双酚A环氧树脂3份、双酚F环氧树脂12份、填料 (粒径为10-30μm的氮化铝)67份,投入反应釜中,行星搅拌2小时。在反应釜中,继续投入固化剂(DDS)3份,满真空(-0.095MPa),行星搅拌4小时,即制得具有高韧性高热稳定性阻燃单组分电子封装胶。
对比例1
称取双酚A环氧树脂8份、双酚F环氧树脂21份、填料(粒径为 10-30μm的三氧化二铝)63份,投入反应釜中,行星搅拌2小时。在反应釜中,继续投入固化剂(DMDC)5份,满真空(-0.095MPa),行星搅拌5小时,即制得单组分电子封装胶组合物。
对比例2
在实施例1的基础上,固化剂采用二乙烯基三胺,其他条件不变。
对比例3
在对比例1的基础上,固化剂采用二乙烯基三胺,其他条件不变。
将上面各实施例和对比例中获得的单组分电子封装胶组合物进行如此测试:
实验一:高低温冲击测试
-40℃保温(30min)-+125℃保温(30min),温区转换时间20S以内,共1000次循环。胶体不开裂视为OK,开裂视为NG。
实验二:玻璃转化温度(Tg)的测试
采用DSC型仪器测试,在氮气环境下测试,测试固化放热时的升温速率为10℃/min,测试Tg时的升温速率为20℃/min。
实验三:阻燃性测试
参考标准GB/T8333-2008硬质泡沫塑料燃烧性能试验方法垂直燃烧法(ASTMD3014-4a),达到阻燃V-0级的视为OK,未达到阻燃V-0 视为NG。具体操作如下:
1.垂直燃烧级别(V-0,V-1,V-2,V=垂直燃烧)
2.样品要求
所有的样品都应是通过从片材裁剪、或压铸或注塑成型、或传压成型成必要的形状。任何裁剪操作后,应注意要小心的出去表面的灰尘和颗粒,裁剪边应打磨平滑。
3.尺寸
长125±5mm,宽13.0±0.5mm,需要提供测试的最小厚度样品和最大厚度样品;样品最大厚度限制为13.00mm,如最小厚度样品和最大厚度样品测试得出的结果不一致,则还需提供中间尺寸的样品,中间尺寸厚度跨度不超过3.2mm;角半径不超过1.3mm。
4.样品数量20根
5.调节状态
一组5根条状试样应在23℃±2℃和50%±5%(50%±10%)的相对湿度下至少状态调节48小时。
然后,该组5根试样应在70℃±2℃(或75℃±2℃)的空气循环烘箱内老化168h±2h,然后,在干燥试验箱中至少冷却4h。一旦从干燥试验箱中移出,试样应在30min之内试验。
6.试验步骤
夹住试样上端6mm的长度,纵轴垂直,使试样下端高出水平棉层 300mm±10mm,棉层未经压实,其近似尺寸为50mmx50mmx6mm,最大质量为0.08克。
使喷灯管的中心轴保持垂直,将火焰中心加到试样底边的中点,同时使喷灯顶端比该点低10mm±1mm,保持10s±0.5s,必要时,根据试样长度和位置的变化,在垂直平面移动喷灯。随后立即将喷灯撤到足够的距离,以免影响式样,同时记录余焰时间t1,单位为秒。
当试样余焰熄灭后,立即重新把试验火焰放在试样下面,第二次施焰,保持10s±0.5s,之后迅速移开火焰,并记录余焰时间t2和余辉时间t3,注意和记录是否有任何颗粒从试样上滴落下来并且观察是否将棉垫引燃。
若将一组5个试样都测试完成之后,发现其中仅有一个不符合V-0级的所有判据,那么,需要对另外5个试样进行再次的测试(经历程序:5.调节状态,6.实验步骤)。
实验四:剪切强度的测试
参考标准:ASTM D1002,具体操作如下:-
使用的设备及仪器:拉力试验机、干燥箱
采用45碳钢,钢板的尺寸为:100*25*2mm,钢板表面应平整,不应有弯曲、跷曲、歪斜等变形,金属片应无毛刺,边缘保持直角。使用前用丙酮将钢板表面的油污擦净。
用游标卡尺测量搭接面的长度并划线,标准试样的搭接长度是12.0 ±0.5mm,如图1所示试样形状和尺寸。
在搭接面(如图2)涂上被测陶瓷环氧封装胶,将钢板涂有胶水的部位重叠,并用弹簧夹子将钢板对夹。将恒温干燥箱的温度设置在120℃,将涂封装胶的钢板在恒温干燥箱,温度为120℃时放入,固化2小时后将钢板样品取出。试样制备好后在常温下放置5H。试验在温度为20-25℃的环境中进行,用量具测量试样搭接面长度和宽度,精确到0.5mm。把试样对称地夹在上、下夹具中,夹持处至搭接端的距离为50±1mm。开动试验验机,在2mm/min内以稳定速度加载.每次检测试样不得少于5 根。
上述实验测试的数据汇总如下表1。
表1
上表数据结果表明,本发明实施例制备获得的产品,采用缩水甘油醚氧丙基笼型聚倍半硅氧烷与固化剂发挥协同增效的作用,使获得的产品具有高韧性、高热稳定性、阻燃性和良好的粘结强度,适合于高电压大电流工况下的各种大功率电子器件的封装,而且环保安全。而对比例1,不采用缩水甘油醚氧丙基笼型聚倍半硅氧烷,使得其制备的产品性能大大不如本发明制备的产品,对于对比例2采用的固化剂为二乙烯基三胺,不含有环已环,使得玻璃转化温度大大降低,对比例3中不添加缩水甘油醚氧丙基笼型聚倍半硅氧烷,使得阻燃性大大降低。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明做其它形式的限制,任何本领域技术人员可以利用上述公开的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (4)
1.一种高韧性高热稳定性阻燃电子封装胶,其特征在于,其包括按重量份计的组分:环氧官能化笼型聚倍半硅氧烷15份、双酚A环氧树脂5份、双酚F环氧树脂10份、固化剂5份和填料63份;
所述环氧官能化笼型聚倍半硅氧烷为缩水甘油醚氧丙基笼型聚倍半硅氧烷;
所述固化剂为3,3'-二甲基-4,4'-二氨基二环己基甲烷;
所述填料为粒径10-30μm的三氧化二铝粉。
2.如权利要求1所述阻燃电子封装胶的制备方法,其特征在于,
其包括如下步骤:
S1、将环氧官能化笼型聚倍半硅氧烷、双酚A环氧树脂、双酚F环氧树脂和填料,投入反应釜中,搅拌;
S2、在反应釜中,继续投入固化剂、满真空,搅拌,即制得具有高韧性高热稳定性阻燃电子封装胶。
3.如权利要求2所述的制备方法,其特征在于,在步骤S1中,搅拌的时间为1-2小时。
4.如权利要求2所述的制备方法,其特征在于,在步骤S2中,搅拌的时间为3-5小时。
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