CN110050021A - 热导性丙烯酸型粘合带及其制备方法 - Google Patents

热导性丙烯酸型粘合带及其制备方法 Download PDF

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CN110050021A
CN110050021A CN201780067263.6A CN201780067263A CN110050021A CN 110050021 A CN110050021 A CN 110050021A CN 201780067263 A CN201780067263 A CN 201780067263A CN 110050021 A CN110050021 A CN 110050021A
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adhesive tape
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thermal conductance
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K·赫尔曼斯
B·克兰兹
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Abstract

本发明涉及热导性丙烯酸型粘合带,其包含600‑800重量份的金属氢氧化物和100重量份的丙烯酸型共聚物,所述丙烯酸型共聚物是基于至少一种(甲基)丙烯酸烷基酯和1‑30重量份的含极性基团的单体,其中热导性丙烯酸型粘合带还包含10‑50重量份的磷酸酯和10‑50重量份的增塑剂。另外,公开了制备所述热导性丙烯酸型粘合带的方法。

Description

热导性丙烯酸型粘合带及其制备方法
描述
热管理对于电子器件例如发光二极管(LED)、集成电路(IC)板和车用电池而言是重要的。为了避免过热,由这些器件产生的热量需要经由受热器去除。为了建立在这些器件之间的热传导路径,通常使用热界面材料。这种材料位于热源和受热器之间,并提供用于传导热量的有效路径。热界面材料有各种形式,例如油脂、胶水、垫和带。本发明涉及热导性丙烯酸型粘合带及其制备方法。
用于热导性丙烯酸型粘合带的各种组分是现有技术中已知的。
例如,JP 11-269438教导了电绝缘热导性阻燃性压敏粘合剂,其包含100重量份的压敏粘合剂组合物,此组合物含有100重量份的丙烯酸型共聚物或部分聚合物,这些聚合物是从基本上由50重量份或更多的具有4-14C烷基的(甲基)丙烯酸烷基酯和0.5-10重量份的可共聚的极性乙烯基单体组成的单体混合物制备的,和含有10-100重量份的增粘剂和50-250重量份的金属水合物化合物。
另一个例子是KR 100482928,其中教导了热导性压敏粘合带,其包含1-20重量份的丙烯酰基单体;80-99重量份的丙烯酰基低聚物;0.005-2重量份的反应引发剂;50-200重量份的热导性填料;和5-50重量份的增塑剂。其中热导性填料是选自二氧化硅、氮化硼、氮化硅、二氧化钛、氧化镁、氧化锌、氧化镍、氧化铜、氧化铝、氧化铁、氢氧化镁和氢氧化铝的至少一种。
现有技术的热导性丙烯酸型粘合带通常通过用热导性填料和其它组分填充基于(甲基)丙烯酸烷基酯单体和含极性基团的单体的部分聚合混合物的浆料以形成可涂布的浆料来制备。所述可涂布的浆料被涂布在基材上,并且单体在暴露于UV光时聚合形成丙烯酸型共聚物,这将可涂布的浆料转化成热导性丙烯酸型粘合带。作为热导性填料,通常选择金属水合物(也称为金属氢氧化物),例如氢氧化铝。氢氧化铝是对UV光透明的,所以由于其与UV固化过程的相容性而通常是优选的。为了达到高的热导率,必要的是将尽可能多的热导性填料引入丙烯酸型粘合带中,且不会损害粘合带所需的粘合/力学性能。另一个挑战是保持可涂布的浆料(其包括热导性填料)的粘度足够低以使其可以被加工成热导性丙烯酸型粘合带。尤其是,难以从具有高粘度的可涂布的浆料去除空气/气袋。所以,从高粘度的可涂布的浆料制备的热导性带可能含有显著量的空气/气体空隙。所述空气/气袋会显著降低热导性粘合带的整体热导率。再一个挑战是制备可涂布的浆料,其是足够稳定的(例如不会胶凝或分相),从而可以加工形成热导性丙烯酸型粘合带。
US 2014/0037924描述了解决具有高热导率的热导性粘合带缺少粘合/力学性能问题的一个方案,其中教导了阻燃性热导性压敏粘合片,其包含:基材以及在基材的至少一个表面上提供的阻燃性热导性压敏粘合剂层,其中基材包括具有10-40微米厚度的聚酯膜。阻燃性热导性压敏粘合剂层含有100重量份的(a)丙烯酸型聚合物和100-500重量份的(b)水合金属化合物。US 2014/0037924教导了具有给定厚度的聚酯膜改进了阻燃性-热导性压敏粘合剂的阻燃性且不会损害热传导性能和不会损害所述聚酯膜。阻燃性-热导性压敏粘合片在处理时容易撕裂或起皱。换句话说,聚酯层向此片材提供力学性能以使其易于处理。
US 2014/0037924的热导性压敏粘合片的缺点是热导率经常不够高,尤其对于严格的应用例如车用电池组和其它高端电子应用而言。
本发明通过提供热导性丙烯酸型粘合带解决上述问题,所述热导性丙烯酸型粘合带包含600-800重量份的金属氢氧化物和100重量份的丙烯酸型共聚物,所述丙烯酸型共聚物是基于至少一种(甲基)丙烯酸烷基酯单体和1-30重量份的含极性基团的单体,其中热导性丙烯酸型粘合带还包含10-50重量份的磷酸酯和10-50重量份的增塑剂。
磷酸酯和增塑剂按照各自10-50重量份的特定量添加,这确保了显著更多的金属氢氧化物能分散在粘合带中,且不会损害其它性能,例如其柔性。
在本发明的一个优选实施方案中,增塑剂也是磷酸酯。
本发明的一个目的是热导性粘合带,其包含高含量的热导性金属氢氧化物填料(因此具有高热导率)以及优良的力学性能和粘合性能,并且不需要额外的基材。
US 2014/003792也教导了丙烯酸型聚合物(a)应当包含(甲基)丙烯酸烷基酯单体和含极性基团的单体,而所述极性基团应当优先不是羧基。含羧基的单体,例如(甲基)丙烯酸或衣康酸,会降低粘合剂的流动性和压敏粘合片的整体粘合性能。但是,包含基于非羧基的极性基团的丙烯酸型共聚物的热导性粘合带是非常弱的且难以处理。此具体问题通过向热导性粘合带组合物引入10-40微米厚的基材来解决。尽管这提高了粘合带的整体力学性能,但没有改进粘合性能,而且由于在其组成中引入了非热导性的元素而降低了粘合带的整体热导率。
US 2014/0037924还教导了尤其当从金属氢氧化物填料和包含含羧基的单体的丙烯酸型共聚物制备热导性丙烯酸型粘合带时会出现上述问题。虽然对于发明人而言,虽尚未完全理解实际的机理,但是热导性填料的氢氧根基团似乎与在丙烯酸型共聚物中的羧基发生反应。这种相互作用导致:
1)当填料含量增加时,可涂布的浆料的粘度快速增加。这限制了可获得的最大填料含量,进而显著限制了带的整体热导率。
2)热导性粘合带的流动性受到这些相互作用的限制。尤其在高的填料含量下,粘合带变硬且不发粘。这也限制了可加入的最大填料量,进而限制了粘合带的热导率。
3)可涂布的浆料倾向于在混合后的数小时/天内胶凝。
为了避免这些问题,在丙烯酸型共聚物的组成中通常不使用羧基。或者,使用含其它极性基团的单体(例如N-乙烯基吡咯烷酮、N-乙烯基己内酰胺和丙烯酰胺)。发现基于这些单体的热导性粘合带具有较低的粘结力和差的粘合性能。
与US2014/0037824的教导相反,在本发明中,含极性基团的单体最优选是含羧基的单体。这种单体的例子是丙烯酸和衣康酸。
与现有技术相反,本发明人发现增塑剂和磷酸酯的特定浓度可以用于获得具有高浓度金属氢氧化物的热导性粘合带,因此具有非常高的热导率。令人惊奇的是,本发明的组合物允许用基于100重量份的丙烯酸型聚合物计600-800重量份、更优选甚至600-900重量份的金属氢氧化物含量制备热导性粘合带,并且可以达到2W/mK和更高的热导率。甚至更令人惊奇的且与现有技术相反,当热导性丙烯酸型粘合带含有含羧基的共聚物时,本发明能获得具有优良粘合性和柔性的热导性粘合带,并且其具有优良的力学性能(且不需要额外的载体层)。这使得本发明的热导性丙烯酸型粘合带能理想地用作热界面材料,尤其是需要粘附的大型非平面器件(例如车用电池组)。
本发明的热导性丙烯酸型粘合带通过以下方法制备:首先使一种或多种丙烯酸烷基酯单体和一种或多种含极性基团的单体的混合物进行部分聚合。一种或多种丙烯酸烷基酯单体和一种或多种含极性基团的单体的部分聚合的混合物称为浆料。接着,向所述浆料加入其它组分(例如热导性填料、交联单体、引发剂等)以形成可涂布的浆料。将可涂布的浆料涂布到基材上并在惰性条件下暴露于UV光。惰性条件是排除(环境)氧气与可涂布的浆料之间接触的条件。这些条件可以例如通过使已涂布的浆料(在被涂布到基材上之后)在UV暴露期间置于氮气或氩气气氛中来实现。或者,可以在UV暴露期间用另一种UV透明基材覆盖所述可涂布的浆料。在暴露于UV光期间,单体聚合形成丙烯酸型共聚物,这将可涂布的浆料转化成热导性丙烯酸型粘合带。在本发明的一个优选实施方案中,通过在涂布之前和/或涂布期间加热可涂布的浆料来改进可涂布的浆料的可涂布性。浆料通常被加热到40-90℃,这取决于可涂布的浆料的实际组成以及所需的涂层厚度。可以使用高温,但是为了实现优良效果通常不需要高温。
在一个优选实施方案中,基材是暂时载体膜,其不会形成实际热导性压敏粘合片的整体部分。实际上,基材仅仅用于涂布可涂布的浆料。在可涂布的浆料进行UV固化期间,此基材将从热导性压敏粘合片被去除,因此不会形成在实际最终应用中所述粘合片的整体部分。合适的暂时载体膜是厚度为50微米的硅化BOPET的膜。在制备期间,可涂布的浆料被涂布到BOPET膜的硅化侧上,使得促进暂时载体膜的容易去除。
在本发明的一个优选实施方案中,浆料具有<1Pas(250rpm,布鲁克菲尔德)的粘度,更优选<0.5Pas(250rpm,布鲁克菲尔德)。具有低粘度的浆料是优选通过将链控制剂加入一种或多种(甲基)丙烯酸烷基酯和一种或多种含极性基团的单体的混合物制备的。链控制剂是能通过终止正在增长的自由基和/或将正在增长的自由基转移至另一个反应性物质(例如单体)来干扰自由基聚合的组分。最优选,所述链控制剂是链转移剂,例如正十二烷基硫醇。链控制剂的存在能显著降低在一种或多种(甲基)丙烯酸烷基酯和一种或多种含羧基的单体的混合物进行部分聚合期间形成的聚合物的分子量。结果,得到具有低粘度的浆料。可加入具有低粘度(<1Pas,250rpm,布鲁克菲尔德)的浆料中的金属氢氧化物的量显著高于可加入具有高粘度(>1Pas,250rpm,布鲁克菲尔德)的浆料中的金属氢氧化物的量。
热导性丙烯酸型粘合带理解为表示片状材料,其可以卷绕成卷,但是不是必须如此。未卷绕成卷的小片状热导性丙烯酸型粘合带有时称为垫,而不是带。在本发明中,这两种物理形式(即,垫和带)被视为是相同的。
本发明的热导性丙烯酸型粘合带具有10-5000微米的厚度,优选厚度是250-3000微米,最优选500-2000微米。
在一个优选实施方案中,本发明的热导性丙烯酸型粘合带在其至少一侧上包含防粘衬里。防粘衬里是暂时性覆盖层,其保护粘合带并促进处理。防粘衬里的例子是PE或PP膜或纸&塑性膜,其已经用防粘层处理,例如硅氧烷化合物的层。防粘衬里的厚度通常是50-200微米。
本发明的热导性丙烯酸型粘合带优选具有至少2W/mK的热导率,优选大于2.5W/mK,最优选大于2.8W/mK。热导率是使用改进的瞬态平面源技术测定的。
本发明的热导性丙烯酸型粘合带包含金属氢氧化物。所述金属氢氧化物优选是氢氧化铝,其也称为三水合铝(ATH)。ATH的平均粒径优选低于150微米,但是大于0.5微米。最优选,ATH具有多模态粒径分布。这可以例如是双模态或三模态粒径分布。多模态粒径分布可以通过合并具有不同粒径的粒子来实现。例如,双模态粒径分布可以通过合并平均直径为5微米的粒子和平均直径为80微米的粒子实现。较小的粒子将填充在较大粒子之间的间隙,这允许这些粒子的紧密堆积。合适的氢氧化铝例如是Apyral 20x(Nabaltec)和OnyxElite(Huber)。
本发明的热导性丙烯酸型粘合带包含10-50重量份的磷酸酯,基于100重量份的丙烯酸型共聚物计。优选,本发明的热导性带包含15-45重量份的磷酸酯,基于100重量份的丙烯酸型共聚物计。所述磷酸酯可以是合适聚合物的磷酸单酯,合适聚合物的磷酸二酯,或它们的衍生物。磷酸酯可以单独使用,或两种或更多种组合使用。
本发明的热导性丙烯酸型粘合带包含10-50重量份的增塑剂,基于100重量份的丙烯酸型共聚物计。优选,本发明的热导性带包含15-45重量份的增塑剂,基于100重量份的丙烯酸型共聚物计。所述增塑剂优选是对苯二甲酸酯,例如对苯二甲酸二丁基酯或对苯二甲酸二辛基酯。
本发明的热导性丙烯酸型粘合带包含丙烯酸型共聚物,丙烯酸型共聚物是基于至少一种(甲基)丙烯酸烷基酯和1-30重量份的含极性基团的单体。可以使用各种(甲基)丙烯酸烷基酯,例如丙烯酸十二烷基酯,丙烯酸癸基酯,丙烯酸异壬基酯,丙烯酸异辛基酯,丙烯酸2-乙基己基酯,丙烯酸己基酯,丙烯酸丁酯,丙烯酸乙酯,以及它们的相应甲基丙烯酸酯。优选,用于本发明的丙烯酸烷基酯是丙烯酸异辛基酯和丙烯酸2-乙基己基酯。含极性基团的单体可以例如是N-乙烯基吡咯烷酮(nVP),丙烯酸(AA),甲基丙烯酸和衣康酸,N-乙烯基己内酰胺(nVC)和丙烯酰基吗啉(ACMO)。最优选,极性基团单体是含羧基的单体,例如(甲基)丙烯酸或衣康酸。
本发明的热导性丙烯酸型粘合带可以还包含光引发剂,例如2,2-二甲氧基-2-苯基苯乙酮。光引发剂用于将可涂布的浆料经由暴露于UV以聚合形成热导性丙烯酸型粘合带。通常,将浓度为0.1-2重量%的光引发剂加入可涂布的浆料。所述光引发剂在此过程中可能没有被完全消耗,所以残余的光引发剂可以存在于热导性丙烯酸型粘合带中。
本发明的热导性丙烯酸型粘合带也可以还包含交联单体。所述单体可以是多官能的丙烯酸酯,例如1,6-己二醇二丙烯酸酯或1,4-丁二醇二丙烯酸酯,其通常按照热导性丙烯酸型粘合带组合物的0.01-1重量%浓度使用。
可以向热导性丙烯酸型粘合带的组合物加入其它添加剂,例如增粘剂、分散剂、流平剂、着色剂、抗氧化剂、UV稳定剂。
实施例
对比例1
通过混合9000份的丙烯酸2-乙基己基酯、1000份N-乙烯基己内酰胺和4份%的2,2-二甲氧基-2-苯基苯乙酮形成混合物。将总共600克的所述混合物置于玻璃容器中,并通过在3升/分钟的速率下吹扫氮气将所述混合物脱气5分钟。在5分钟后,使所述混合物暴露于UV光。UV光包括>80%的UVA光(300-400nm)并具有10mJ/cm2的强度。当所得的浆料具有约1的粘度时停止暴露于UV光。
通过将50份的浆料与50份的氢氧化铝(Onyx Elite-Huber)混合,形成可涂布的混合物。
实施例1:
按照对比例1所述制备浆料。
通过混合443份的浆料与500份的氢氧化铝(Onyx Elite-Huber)、23份的磷酸酯和34份的增塑剂,制得可涂布的浆料。
用布鲁克菲尔德流变仪检测对比例1和实施例1的粘度,结果如下表所示。这些结果清楚地表明,实施例1具有比对比例1显著更低的粘度(具有相同含量的氢氧化铝)。或者,当不以更低的粘度为目的时,可以在达到与对比例1相同的粘度之前,在实施例1中增加金属氢氧化物的量。这些结果显示可以通过在可涂布的浆料中使用特定量的磷酸酯和增塑剂,实现较低的粘度和/或较高的金属氢氧化物含量。
对比例1 实施例1
25rpm 11096mPas 2540mPas
实施例2:
通过混合9000份的丙烯酸2-乙基己基酯、1000份丙烯酸、4份2,2-二甲氧基-2-苯基苯乙酮和2.5份的正十二烷基硫醇形成混合物。将总共600克的所述混合物置于玻璃容器中,并通过在3升/分钟的速率下吹扫氮气将所述混合物脱气5分钟。在5分钟后,使所述混合物暴露于UV光。UV光包括>80%的UVA光(300-400nm)并具有10mJ/cm2的强度。当单体转化率达到约10%并且所形成的浆料具有约500mPas的粘度时停止暴露于UV光。接着,通过将10.94份的浆料与0.012份的1,6-己二醇二丙烯酸酯、0.048份的2,2-二甲氧基-2-苯基苯乙酮、2.3份的磷酸多酯、3.4份的对苯二甲酸二丁基酯和83.3份的氢氧化铝(Apyral 20x-Nabaltec)混合,形成可涂布的浆料。可涂布的浆料在25℃下具有20Pas的粘度(250rpm;布鲁克菲尔德)。通过使可涂布的浆料在真空(<10毫巴)下脱气10分钟,从可涂布的浆料去除气泡。
将厚度为1.5mm的可涂布浆料层涂布到硅氧烷化BOPET膜上,用第二个硅化BOPET膜覆盖,并暴露于UV光达到2.5分钟。UV光包括>80%的UVA光并具有10mJ/cm2的强度。在暴露于UV光期间,通过在硅化BOPET膜的外表面上吹扫空气,除去由可涂布浆料进行UV引发的聚合反应所产生的热量。在除去硅化BOPET膜后得到热导性丙烯酸型粘合带。
通过使用改进的瞬态平面源技术检测所述热导性丙烯酸型粘合带的热导率,测得热导率是3.0W/m K。实施例2显示可通过使用本发明的组合物制备高度热导性丙烯酸型带。
实施例3:
按照实施例2的工序制备热导性丙烯酸型粘合带,不同之处是使用1000份的N-乙烯基己内酰胺代替1000份丙烯酸。
通过检测应力-应变曲线,检测实施例2和实施例3的热导性丙烯酸型粘合带的力学性能,如附图所示。结果如附图所示。这些结果清楚地表明,包含基于1000份丙烯酸的丙烯酸型共聚物的热导性丙烯酸型粘合带具有更好的力学性能。拉伸强度和最大伸长率是显著更高的。
实施例2和实施例3的热导性丙烯酸型粘合带的的粘合性能是通过检测在不锈钢基材、铝背衬箔上的90度剥离强度测定的,其中在室温下的停留时间是8小时。结果如下表所示。这些结果清楚地表明,实施例2的热导性粘合带具有显著更好的剥离强度(粘合性能)。
1000份丙烯酸 1000份N-乙烯基己内酰胺
90度剥离强度 13.5 N/英寸 3.9 N/英寸

Claims (12)

1.热导性丙烯酸型粘合带,其包含600-800重量份的金属氢氧化物和100重量份的丙烯酸型共聚物,所述丙烯酸型共聚物是基于至少一种(甲基)丙烯酸烷基酯和1-30重量份的含极性基团的单体,其特征在于热导性丙烯酸型粘合带还包含10-50重量份的磷酸酯和10-50重量份的增塑剂。
2.根据权利要求1所述的热导性丙烯酸型粘合带,其特征在于所述极性基团包含羧基。
3.根据权利要求1或2所述的热导性丙烯酸型粘合带,其特征在于其具有通过改进的瞬态平面方法检测的热导率为至少2W/mK。
4.根据前述权利要求中任一项所述的热导性丙烯酸型粘合带,其特征在于其具有10-5000微米的厚度,优选250-3000微米,最优选500-2000微米。
5.根据前述权利要求中任一项所述的热导性丙烯酸型粘合带,其特征在于所述金属氢氧化物是氢氧化铝。
6.根据前述权利要求中任一项所述的热导性丙烯酸型粘合带,其特征在于其包含10-50重量份的磷酸酯,基于100重量份的丙烯酸型共聚物计。
7.根据前述权利要求中任一项所述的热导性丙烯酸型粘合带,其特征在于其包含10-50重量份的增塑剂,基于100重量份的丙烯酸型共聚物计。
8.根据前述权利要求中任一项所述的热导性丙烯酸型粘合带,其特征在于其包含丙烯酸型共聚物,此丙烯酸型共聚物是基于至少一种(甲基)丙烯酸烷基酯和1-30重量份的含极性基团的单体。
9.根据前述权利要求中任一项所述的热导性丙烯酸型粘合带,其特征在于其包含交联单体,例如1,6-己二醇二丙烯酸酯和/或1,4-丁二醇二丙烯酸酯。
10.一种制备热导性丙烯酸型粘合带的方法,包括以下步骤:一种或多种(甲基)丙烯酸烷基酯和含极性基团的单体的混合物部分地聚合以得到浆料,然后向所述浆料加入作为热导性填料、交联单体、引发剂等的其它组分以形成可涂布的浆料,并将所述可涂布的浆料涂布到载体膜上,然后通过UV光和在惰性条件下聚合所述可涂布的浆料。
11.根据权利要求10所述的方法,其特征在于向一种或多种(甲基)丙烯酸烷基酯和一种或多种含极性基团的单体的混合物加入链控制剂。
12.根据权利要求11所述的方法,其特征在于链控制剂是正十二烷基硫醇。
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