CN102136327B - 导热绝缘垫片 - Google Patents
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Abstract
本发明提供了一种导热绝缘垫片,其包含:第一硅橡胶层;第二硅橡胶层;和位于所述第一和第二硅橡胶层之间的中间层,其由涂敷有导热涂层的玻璃纤维布或含有导热填料的聚合物薄膜制成。
Description
技术领域
本发明涉及一种导热绝缘垫片,尤其涉及一种具有改善的导热性能的绝缘垫片。
背景技术
导热绝缘垫片是一种通常由硅橡胶制成的比较薄的电绝缘片,厚度通常在0.1mm~0.3mm范围。例如,美国专利US4574879,US4602678,US4685987中就描述了这样的导热绝缘垫片,其基础结构包括两个导热硅橡胶层和位于两个导热硅橡胶层之间的绝缘层。为了增强其机械性能和耐电压击穿性能,通常使用聚酰亚胺薄膜和玻璃纤维布作为中间的机械加强层。例如,美国专利US4602678,US4685987中采用玻璃纤维作为中间的绝缘层,美国专利US4574879,US4685987中采用聚酰亚胺薄膜层作为中间的绝缘层。但是,由于聚酰亚胺薄膜和玻璃纤维都是导热不良的材料(导热率一般低于:0.3W/m.K),因此制得的导热绝缘垫片的导热效果差,难以满足需要良好的导热效果的场合。
因此,仍然需要开发一种具有良好的导热性能的绝缘垫片。
发明内容
本申请的发明人发现,利用涂敷有导热涂层的玻璃纤维布或含有导热填料的聚酰亚胺薄膜作为绝缘垫片的中间层,可以显著地提高绝缘垫片的导热性能,同时保持了绝缘垫片的机械性能和抗电压击穿强度。
根据本发明的一个方面,提供了一种导热绝缘垫片,其包含:
第一硅橡胶层;
第二硅橡胶层;和
位于所述第一和第二硅橡胶层之间的中间层,其由涂敷有导热涂层的玻璃纤维布或含有导热填料的聚合物薄膜制成。
本发明的导热绝缘垫片具有良好的导热能力、绝缘属性以及与其它基材表面的接触润湿性能,能够应用于对散热性能要求较高的各类电子/通信产品。
附图说明
图1是根据本发明一个实施方案的高性能导热绝缘垫片的结构示意图。
图2是根据本发明另一个实施方案的高性能导热绝缘垫片的结构示意图。
图3是根据本发明上述一个实施方案的高性能导热绝缘垫片的中间层的结构示意图。
图4是根据本发明上述另一个实施方案的高性能导热绝缘垫片的中间层的结构示意图。
具体实施方式
除非特别指明,本发明中术语“玻璃纤维布”是指由玻璃纤维制成的织物或无纺布。
除非特别指明,本发明中术语“滚压”是指采用双辊技术,控制一定的辊间距离对样片实施压力加工,以提供内部填料的密实度。
除非特别指明,本发明中术语“D50”是指中值粒径,即一个样品的累计粒度分布百分数达到50%时所对应的粒径。它的物理意义是粒径大于它的颗粒占50%,小于它的颗粒也占50%。
本发明提供了一种导热绝缘垫片,其包含:
第一硅橡胶层;
第二硅橡胶层;和
位于所述第一和第二硅橡胶层之间的至少一层中间层,所述中间层由涂敷有导热涂层的玻璃纤维布和/或含有导热填料的聚合物薄膜制成。
硅橡胶是本领域熟知的顺从性绝缘材料,其具有突出的介电性能。适用于本发明的硅橡胶包括但不限于甲基硅橡胶、二甲基硅橡胶、甲基乙烯基硅橡胶、氰硅橡胶、氟硅橡胶等。例如,可以商购自迈图高新材料集团,南京东爵有机硅公司等厂商制造的标准牌号为甲基硅橡胶101、甲基乙烯基硅橡胶110-1、甲基乙烯基硅橡胶110-2、甲基乙烯基硅橡胶110-3、甲基苯基乙烯基硅橡胶120-1、甲基苯基乙烯基硅橡胶120-2、氰硅橡胶130-2、氟硅橡胶SF-1、氟硅橡胶SF-2、氟硅橡胶SF-3、二甲基硅橡胶MQ1010、甲基乙烯基硅橡胶MVQ1101、甲基乙烯基硅橡胶MVQ1102、甲基乙烯基硅橡胶MVQ1103等等。优选地,第一和第二硅橡胶层的厚度可以相同或不同,其分别不大于10毫米,更优选不大于1毫米,还优选不大于0.5毫米,最优先不大于0.2毫米。
本发明中,位于所述第一和第二硅橡胶层之间的至少一层中间层是由涂敷有导热涂层的玻璃纤维布和/或含有导热填料的聚酰亚胺薄膜制成的。所述的中间层的厚度优选不大于5毫米,更优选不大于1毫米,最优选不大于0.1毫米。图1给出了本发明一种优选实施方案的结构示意图。在该方案中,涂敷有导热涂层的玻璃纤维布2位于两个硅橡胶层1之间。图2给出了本发明另一种优选实施方案的结构示意图。在该方案中,含有导热填料的聚酰亚胺薄膜2’位于两个硅橡胶层1之间。虽然没有给出图示,但是可以理解,本发明的导热绝缘垫片可以含有多于一层的中间层,这些中间层可以相同或不同,例如,可以都采用涂敷有导热涂层的玻璃纤维布或者都采用含有导热填料的聚酰亚胺薄膜,也可以其中一些层采用涂敷有导热涂层的玻璃纤维布而另一些层采用含有导热填料的聚酰亚胺薄膜。本发明的导热绝缘垫片中,还可以任选地含有常规的玻璃纤维布或聚酰亚胺薄膜。
通过将导热涂料直接涂敷在玻璃纤维布上可以得到涂敷有导热涂层的玻璃纤维布。也可以先将导热涂料涂敷在玻璃纤维上,然后由涂敷有导热涂层的玻璃纤维制成涂敷有导热涂层的玻璃纤维布。可以采用各种涂布方式进行涂敷,包括但不限于浸涂、喷涂、刮涂、刷涂、淋涂、真空镀层,化学沉积镀层等方法。通过涂敷,可以在玻璃纤维表层形成一层均匀的具有一定厚度的电绝缘性的导热涂层。适用于本发明的导热涂料没有特别限制,其可以含有聚合物基质,导热物质和任选的溶剂和各种添加剂。所述聚合物基质例如可以为聚酯树脂,硅橡胶,柔性改性聚乙烯,弹性热塑体橡胶等。导热物质没有特别的限制,但优选使用具有高导热率的氧化铝(Al2O3),氮化硼(BN),氮化硅(SiN)等陶瓷粉末材料。
当中间层为玻璃纤维时,可以先按要求配置一定的含有一定比例导热粒子的母液,在判定分散均匀后,对玻璃纤维进行浸涂,然后在要求温度范围内进行烘干,使得在玻璃纤维表面形成一层被导热粉末包裹层,其结构如图3所示。图3给出了本发明一种优选实施方案的中间层(玻璃纤维布)的结构示意图,其中在玻璃纤维4的外面涂布有一层导热涂层3。根据特别优选的一种连续实施方案,首先使玻璃纤维布通过导热涂料浴从而对其进行浸渍,然后使带有导热涂料的玻璃纤维布通过烘箱烘干,即可得到带有导热涂层的玻璃纤维布。
对于导热涂层的厚度没有特别限制,但是导热涂层厚度优选在50微米以内,更优选1~10微米内厚度范围的厚度。导热涂层中导热物质的重量百分含量优选为5%~90%。
适用于本发明的玻璃纤维布没有特别限制,本领域中常用的玻璃纤维布均可用于本发明。例如,可商购自上海博舍工业有限公司的玻璃布1080、1060。
针对由含有导热填料制成的聚合物薄膜制成的中间层,可以通过将含有导热填料的聚合物拉伸成薄膜而制得。例如,可以采用纳米级别的导热颗粒(尺寸优选以小于100nm为主),按比例加入到高分子薄膜母液中,实施有效分散,然后采用相应的成膜工艺进行成膜,从而形成具有优异柔软性,绝缘性和导热性的薄膜产品。适用于本发明的聚合物优选耐热聚合物,包括但不限于,聚酰亚胺,聚四氟乙烯,超高分子量聚乙烯等耐温等级大于100摄氏度的聚合物。其中最优选聚酰亚胺。适用于本发明的导热填料包括但不限于氧化铝(Al2O3),氮化硼(BN),氮化硅(SiN),碳化硅(SiC)等。对于导热填料的大小和形状没有特别限制,但是优选晶体结构为六角立方晶型,其晶格排布为各向异性的分子型材料。例如,图4给出了本发明一种优选实施方案的中间层(聚酰亚胺薄膜)的结构示意图,其中在聚酰亚胺薄膜2’中均匀地含有导热填料5。采用纳米级别的SiC(例如40纳米)作为导热填料,在聚酰亚胺薄膜成型前称重并添加,混合均匀后,同聚酰亚胺薄膜一起拉伸,即可制得图4所示的含有导热填料的导热聚酰亚胺薄膜。导热填料在中间层中的含量没有特别限制,但是优选占中间层总重量的5-60重量%。
本发明的导热绝缘垫片可以应用于各类电子/通信产品的散热解决方案,其具有优异的导热能力、绝缘属性以及与其它基材表面的接触润湿性能。
下面,结合实施例对本发明进行更详尽的说明。但是,需要指出的是,本发明并不限于这些实施例。在以下实施例和比较例中,除非另外规定,所有的份、比例、百分比都以重量计,温度均是指摄氏度。
实施例
本发明中所使用的原料和来源概括于下表1。
表1 原料一览表
原料名 | 作用 | 来源(厂家) | 备注 |
聚酯树脂R-961 | 涂层溶液母体 | DSM(帝斯曼中国) | |
对十二甲基苯磺酸钠 | 聚酯树脂表面活化剂,提高粒子在聚酯中的分散性 | ||
六方氮化硼(3微米) | 导热添料 | 德国ESK氮化硼公司 | 粒子尺寸:D50 |
纳米碳化硅(40纳米) | 纳米级别的导热粉填料 | 合肥开尔纳米技术发展有限责任公司 | 使用前烘干 |
液态硅橡胶XE15-C4112 | 用于配导热硅橡胶的液体硅橡胶原料 | 迈图高新材料集团 | 分子量20~70万 |
铂金硫化剂XC86-250 | 橡胶催化剂 | 迈图高新材料集团 | |
硅胶表面活化剂BD-3071 | 用于提高纳米级导热粒子在溶液中的分散性能 | 杭州包尔得有机硅有限公司 | |
二甲苯 | 用于硅橡胶的粘度调节 | 江苏金城试剂有限公司 | |
玻璃纤维布1080/1060# | 玻璃纤维基材 | 上海博舍工业有限公司 | |
聚酰亚胺膜 | 高分子膜基材 | 江阴天华科技有限公司 |
比较实施例1-3的准备(用于做为测试参比样品):
分别根据表4、表5所示比例进行材料的称量,混合后加入容器中,高速(800~2000转/分)搅拌3分钟后,加到三辊研磨机上研磨2遍以上,保证分散均匀;最后加入助剂,再到搅拌机上(800转/分)搅拌即制成可以浸涂的导热硅橡胶原料,然后再用浸涂工艺在未经过任何处理的108玻璃纤维上涂层,厚度为2毫米,以此作为参比1~3样品。在参比样品1-3中,仅在普通非导热的玻璃纤维布(1080/1060)两侧的涂覆导热硅胶,其玻璃纤维实质不具备本发明所示的外层导热涂层结构。
导热涂料制备实施例1:适用于玻璃纤维布
根据下表2中给出的配方的三种不同比例分别配制导热涂料。首先,将聚酯树脂R-961熔融,然后加入纳米碳化硅(40纳米)粉末,适当搅拌后,按表2比例加入相应的对十二甲基苯磺酸钠,再800~1200转/分适度搅拌制成可用于对玻璃纤维布(108/106)进行导热改善散的导热涂料1-3。
表2 对玻璃纤维布的纳米碳化硅试验溶液(份数)
氮化硅溶液成分 | 导热涂料1 | 导热涂料2 | 导热涂料3 |
聚酯树脂R-961 | 48~49 | 38 | 22 |
纳米碳化硅(40纳米) | 50 | 60 | 76 |
对十二甲基苯磺酸钠 | 1~2 | 2 | 2 |
导热涂料制备实施例2:适用于玻璃纤维布
根据下表3中给出的配方的三种不同比例分别配制导热涂料。首先,将聚酯树脂R-961熔融,然后加入六方氮化硼(3微米)粉末,800~1500转/分搅拌均匀,制得适用于玻璃纤维布的导热涂料4-6
表3 对玻璃纤维布的六方氮化硼溶液(份数)
六方氮化硼溶液成分 | 导热涂料4 | 导热涂料5 | 导热涂料6 |
聚酯树脂R-961 | 50 | 40 | 24 |
六方氮化硼(3微米) | 50 | 60 | 76 |
导热涂料制备实施例3:适用于玻璃纤维布
根据下表4中给出的三个不同比例的配方分别配制导热涂料。首先,按比例进行材料的称量,混合后加入容器中,高速(800~2000转/分)搅拌3分钟后,加到三辊研磨机上研磨2遍以上,保证分散均匀;最后加入助剂,再到搅拌机上(800转/分)搅拌即制成是用于玻璃纤维浸涂的导热硅橡胶涂料7-9。
表4 纳米氮化硅硅橡胶溶液成分配比
纳米氮化硅硅橡胶溶液成分 | 导热涂料7 | 导热涂料8 | 导热涂料9 |
XE15-C4112 | 100 | 100 | 100 |
二甲苯 | >100 | >100 | >100 |
铂金硫化剂 | 1.5 | 1.5 | 1.5 |
硅胶表面活化剂 | 3 | 3 | 3 |
纳米碳化硅颗粒(40纳米) | 50 | 60 | 76 |
导热涂料制备实施例4:适用于玻璃纤维布
根据下表5中给出的三个不同比例的配方分别配制导热涂料。首先,按比例进行材料的称量,混合后加入容器中,高速(800~2000转/分)搅拌3分钟后,加到三辊研磨机上研磨2遍以上,保证分散均匀;最后加入助剂,再到搅拌机上(800转/分)搅拌即制成是用于玻璃纤维浸涂的导热硅橡胶涂料10-12。
表5 六方氮化硼硅橡胶溶液成分配比
六方氮化硼硅橡胶溶液成分 | 导热涂料10 | 导热涂料11 | 导热涂料12 |
液态硅橡胶XE15-C4112 | 100 | 100 | 100 |
二甲苯 | >100 | >100 | >100 |
铂金硫化剂:XC86-250 | 1~1.5 | 1~1.5 | 1~1.5 |
六方氮化硼(3微米) | 50 | 60 | 76 |
涂布实施例1-4:玻璃纤维布
按照如下方法分别将上述导热涂料1-12涂布到玻璃纤维布上形成厚度0.055mm(采用上海博舍工业有限公司的1080玻璃纤维布)的带有导热涂层的玻璃纤维布1-12:导热液体按要求配好,将玻璃纤维布按顺序串到浸涂装置中,调节平行和张力,速度控制在小于2米/分,涂层厚度由夹辊保障;烘干温度为60~180度,时间为1分钟~5分钟。
采用ASTM D 5470测量玻璃纤维布1-6的热阻及温度差,测试结果概括于下表6-8。
表6:针对50%重量百分含量配比的溶液:
参数 | 电压(V) | 电流(A) | 测试样品两侧的温度差ΔT(℃) | 计算热阻(℃·in2/W) |
参比样品1-3 | 9.78 | 0.168 | 2.0 | 1.22 |
导热涂料4 | 9.79 | 0.168 | 1.80 | 1.09 |
导热涂料1 | 9.77 | 0.168 | 1.90 | 1.16 |
表7:针对60%重量百分含量溶液配比的溶液:
参数 | 电压(V) | 电流(A) | 测试样品两侧的温度差ΔT(℃) | 计算热阻(℃·in2/W) |
参比样品1-3 | 9.78 | 0.168 | 2.00 | 1.22 |
导热涂料5 | 9.78 | 0.168 | 1.65 | 1.00 |
导热涂料2 | 9.78 | 0.168 | 1.75 | 1.07 |
表8:针对76%重量百分含量溶液配比的溶液:
参数 | 电压(V) | 电流(A) | 测试样品两侧的温度差ΔT(℃) | 计算热阻(℃·in2/W) |
参比样品1-3 | 1.22 | 9.78 | 0.168 | 2.0 |
导热涂料6 | 0.88 | 9.78 | 0.168 | 1.45 |
导热涂料3 | 0.91 | 9.78 | 0.168 | 1.50 |
对玻璃纤维布1-6用ASTM D 2240和750-2/D149-30B耐电压测试仪进行耐电压性能的测试。测试结果见表9。
表9 耐电压测试结果
比较实施例4-6的准备,(用于做为测试参比样品):
分别根据表4、表5所示硅橡胶/导热粉等比例进行材料的称量,混合后加入容器中,高速(800~2000转/分)搅拌3分钟后,加到三辊研磨机上研磨2遍以上,保证分散均匀;最后加入助剂,再到搅拌机上(800转/分)搅拌即制成可以浸涂的导热硅橡胶原料,然后再用浸涂工艺在普通的经过双向拉伸制成的聚酰亚胺膜(可以从江阴天华直接购买此种聚酰亚胺膜,厚度25微米)进行导热硅橡胶涂层,连侧厚度分别为1毫米,总厚度为2毫米,以此作为参比4~6样品。在参比样品4-6中,仅在普通的非导热型(未添加导热颗粒)聚酰亚胺膜两侧的涂覆导热硅胶。
导热聚合物薄膜制备实施例1-3:
分别将占导热聚合物薄膜总重量20%,30%,50%的40纳米氮化硅添加到熔融的聚酰亚胺液体中,常温下混合均匀,然后双向拉伸形成厚度0.24μm厚的薄膜的导热聚合物薄膜1-3。
采用ASTM D 5470测量导热聚合物薄膜1-3的热阻及温度差,测试结果概括于下表10。
表10 导热聚合物薄膜1-3的热阻测试结果
参数 | 电压(V) | 电流(A) | 材料两侧的温度差ΔT(℃) | 计算热阻(℃·in2/W) |
参比样品4-6 | 9.72 | 0.167 | 2.0 | 1.23 |
导热聚合物薄膜1 | 10.01 | 0.165 | 1.7 | 1.03 |
导热聚合物薄膜2 | 9.66 | 0.168 | 1.6 | 0.99 |
导热聚合物薄膜3 | 9.67 | 0.168 | 1.65 | 1.02 |
平均值 | 1.01 |
同参比样品2相比,导热聚合物薄膜1-3的热阻平均降低了约20%。
对导热聚合物薄膜1-3用ASTM D 2240和750-2/D149-30B耐电压测试仪进行耐电压性能的测试。测试结果见表11。
表11 耐电压测试
Claims (9)
1.一种导热绝缘垫片,其包含:
第一硅橡胶层;
第二硅橡胶层;和
位于所述第一和第二硅橡胶层之间的至少一层中间层,所述中间层由涂敷有导热涂层的玻璃纤维布制成,其中所述的导热涂层包括聚合物基质和导热物质,其中所述的导热涂层中导热物质的重量百分含量为50%~76%,并且其中所述的聚合物基质选自聚酯树脂、柔性改性聚乙烯和弹性热塑体橡胶中的一种。
2.根据权利要求1的导热绝缘垫片,其中所述的导热物质为选自氧化铝,氮化硼,碳化硅,氮化硅中的至少一种。
3.根据权利要求2的导热绝缘垫片,其中所述的导热物质为碳化硅。
4.根据权利要求1的导热绝缘垫片,其中所述的导热物质的D50尺寸不大于1μm。
5.根据权利要求4的导热绝缘垫片,其中所述的导热物质的D50尺寸不大于0.1μm。
6.根据权利要求4的导热绝缘垫片,其中所述的导热物质的D50尺寸不大于0.01μm。
7.根据权利要求1的导热绝缘垫片,其中所述的玻璃纤维布为选自编织布、非编织布或薄膜中的形式。
8.根据权利要求1的导热绝缘垫片,其中所述的第一和第二硅橡胶层的厚度分别不大于10毫米。
9.根据权利要求1的导热绝缘垫片,其中所述的中间层的厚度不大于5毫米。
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