CN100491489C - 各向异性的导电性粘接剂以及应用该粘接剂的薄膜 - Google Patents

各向异性的导电性粘接剂以及应用该粘接剂的薄膜 Download PDF

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CN100491489C
CN100491489C CNB2004100808293A CN200410080829A CN100491489C CN 100491489 C CN100491489 C CN 100491489C CN B2004100808293 A CNB2004100808293 A CN B2004100808293A CN 200410080829 A CN200410080829 A CN 200410080829A CN 100491489 C CN100491489 C CN 100491489C
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田暎美
郑润载
张钟允
安佑永
韩用锡
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Abstract

本发明提供一种各向异性的导电性粘接剂，其含有绝缘性粘接成分以及分散在上述绝缘性粘接成分中的大量导电性颗粒，其中，在上述绝缘性粘接成分中含有交联性橡胶树脂。连接电路时，通过使各向异性的导电性粘接剂在聚合反应或固化反应中的热收缩最小化，防止粘接剂的剥离或电路粘接强度的降低，从而在连接微细电路时，可以预防相邻电极间的短路，在长期可靠性方面优异。

Description

各向异性的导电性粘接剂以及应用该粘接剂的薄膜
技术领域
本发明涉及各向异性的导电性粘接剂以及应用该粘接剂的薄膜(ACF)。更详细地说，涉及各向异性的导电性粘接剂以及应用该粘接剂的薄膜(ACF)，其特征为，在绝缘性粘接成分中含有交联性橡胶树脂。
背景技术
各向异性的导电性粘接剂是电路连接材料，其在绝缘性粘接成分中分散有导电性颗粒，将对置的电路进行机械连接的同时，由于导电性颗粒的存在，电路电极之间形成电连接。作为绝缘性粘接成分可以使用热塑性树脂和热固性树脂等，但从连接可靠性的方面考虑，主要还是用热固性树脂。
使用热固性树脂作为粘接成分时，使各向异性的导电性粘接剂存在于待粘接构件之间，通过进行热压接合形成连接，为达到充分的连接可靠性和连接强度，需要高温下相当长的固化反应时间。以环氧树脂为代表，在140℃～180℃需要20秒左右的连接时间，或在180℃～210℃需要10秒左右的连接时间。
但是，在这样的连接条件下会发生配线的脱落、邻接电极间的短路及位置的偏移等问题。而且，最近在精密电子仪器领域中电路向高密度化发展，随着电极宽度、电极间隔变得非常狭窄，以上问题愈发严重。另外，连接时间过长则导致生产效率下降，于是为了提高效率需要将连接时间控制在10秒或10秒以下。
为了克服上述问题，过去考虑过使用自由基聚合性树脂为粘接材料，自由基聚合性树脂的特征为，通过低温加热或光固化发生自由基聚合，并通过交联得以固化。但是，即使这种情况下，由于聚合反应导致过度收缩，固化后，连接部分中蓄积内部应力，易发生剥离；当电极间隔很窄时，由于连接材料的收缩，导致电极间隔缩小，因此仍然存在发生短路的问题。
发明内容
本发明基于上述问题点考虑，所要解决的技术性课题为：使用各向异性的导电性粘接剂进行电路连接时，使聚合或固化反应中发生的各向异性的导电性粘接剂的收缩最小，从而防止粘接剂的剥离或由于电极移动而产生短路现象，提供一种长期可靠性优异的各向异性的导电性粘接剂。
本发明还要解决的其他技术性课题在于，提供应用上述各向异性的导电性粘接剂的粘接薄膜。
为了解决上述技术性课题，本发明的各向异性的导电性粘接剂的特征为：其含有绝缘性粘接成分以及分散在所述绝缘性粘接成分中的大量导电性颗粒，所述绝缘性粘接成分中含有交联性橡胶树脂。
所述的各向异性的导电性粘接剂的使用形态可以是薄膜状、糊状、粉末状。
如前所述，通过连接电路时使聚合或固化反应中发生的各向异性的导电性粘接剂的收缩最小，本发明的各向异性的导电性粘接剂防止了由于粘接剂剥离或者电极移动导致的短路现象，长期可靠性优异。
附图说明
图1是本发明实施例所制的各向异性的导电性粘接薄膜的示意简图。
图2是将柔软性电路基板和印刷电路基板分别附着于本发明所制的各向异性的导电性粘接薄膜两面时的示意简图。
具体实施方式
图1是本发明一个实施例所制的各向异性的导电性粘接薄膜的示意简图。如图1所示，由所述各向异性的导电性粘接剂得到的粘接薄膜30是由含有交联性橡胶树脂的绝缘性粘接成分40和导电性颗粒50构成的。
本发明的各向异性的导电性粘接剂中，作为所述交联性橡胶树脂，可以使用选自以下成分中的一种或一种以上的成分：烯烃树脂、丁二烯树脂、丙烯腈-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、异丁烯-异戊二烯共聚物(IIR)、腈基丁二烯橡胶树脂、氯丁二烯橡胶树脂、聚乙烯醇缩丁醛树脂、或硅橡胶树脂。
上述中，作为烯烃树脂，优选乙烯树脂、丁基橡胶树脂、三元乙丙橡胶(EPDM)。
本发明的各向异性的导电性粘接剂中，相对于100重量份的绝缘性粘接成分，优选所述交联性橡胶树脂为1～20重量份。
如果所述交联性橡胶树脂成分的含量大于等于20重量份，此时存在恢复弹性力和固化密度太高而导致粘接力下降的问题；如果其含量小于等于1重量份，则存在连接电路时不能充分进行固化反应的问题。
本发明中的交联性橡胶树脂通过在连接电路时使聚合或固化反应中发生的各向异性的导电性粘接剂的收缩最小，从而防止粘接剂的剥离或电路粘接强度的降低，提供一种长期可靠性优异的各向异性的导电性粘接剂。
作为本发明的各向异性的导电性粘接剂的绝缘性粘接成分，可以使用一种或混合使用两种或两种以上的热塑性树脂、热固性树脂或自由基聚合性树脂。
作为所述的热塑性树脂，可以使用苯乙烯-丁二烯树脂、乙烯-乙烯基树脂、酯类树脂、硅树脂、苯氧基树脂、丙烯酸树脂、酰胺类树脂、丙烯酸酯树脂、聚乙烯醇缩丁醛树脂。
作为所述的热固性树脂，可以使用环氧树脂、酚醛树脂、三聚氰胺树脂。其中，作为环氧树脂，可以使用双酚型环氧树脂、甲酚-线型酚醛环氧树脂、脂肪族聚环氧树脂、二聚酸改性环氧树脂等。
本发明中，粘接成分中含有热固性树脂时，使用固化剂，所述固化剂在常温无活性，加热熔融后被活化，使热固性树脂固化。作为这种固化剂，可以使用咪唑衍生物(含氮杂环衍生物)、二元酸二酰肼、二氰基二酰胺等。相对于100重量份热固性树脂，使用1～200份所述固化剂。
所述自由基聚合性树脂是具有在自由基作用下聚合的官能团的物质，可以使用单体或低聚物等，也可以合并使用单体和低聚物。作为自由基聚合性树脂，可以使用丙烯酸酯类，如丙烯酸甲酯、丙烯酸乙酯、双酚A乙二醇改性的二丙烯酸酯、异氰脲酸乙二醇改性的二丙烯酸酯、三丙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、季戊四醇三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷丙二醇三丙烯酸酯、三羟甲基丙烷乙二醇三丙烯酸酯、异氰脲酸乙二醇改性的三丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、二环戊烯丙烯酸酯、三环癸基丙烯酸酯等；甲基丙烯酸酯类；顺丁烯二酰亚胺化合物；不饱和聚酯；丙烯酸；乙酸乙烯酯；丙烯腈；甲基丙烯腈化合物等。
本发明中，粘接成分中含有自由基聚合性树脂时，使用聚合引发剂，活化自由基聚合性树脂，从而实现形成高分子网状结构或高分子IPN(互穿聚合物网络)结构的功能，并且通过形成这种交联结构来使绝缘性粘接成分固化。作为聚合引发剂，可以使用过氧化物那样的热聚合引发剂和/或羰基化合物、硫化物以及偶氮化合物等光聚合引发剂。聚合引发剂的含量可根据聚合性树脂的种类、目的电路连接工序的可靠性和可操作性等来调节，相对于100重量份自由基聚合性树脂，优选聚合引发剂为0.1～10重量份。
另外，必要时可以在本发明的各向异性的导电性粘接剂的粘接成分中进一步添加填充剂、软化剂、促进剂、着色剂、抗软化剂、光稳定剂、偶联剂、阻聚剂等。例如，添加填充剂时，可以提高连接的可靠性等；添加偶联剂时，可以改善各向异性的导电性粘接剂的粘接界面的粘接性，增加粘接强度以及耐热性、耐湿性，从而提高连接的可靠性。作为这种偶联剂，优选硅烷偶联剂，例如，β-(3，4环氧环己基)乙基三甲氧基硅烷、γ-巯醇基丙基三甲氧基硅烷、γ-甲基丙烯氧基托品基三甲氧基硅烷等。
本发明中，分散在所述绝缘性粘接成分中的大量导电性颗粒可以使用具有导电性的颗粒自身，如镍、铁、铜、铝、锡、锌、铬、钴、银、金等金属或金属氧化物、焊料、碳等，作为导电性颗粒也可以使用通过非电解镀覆法等薄层形成方法在玻璃、陶瓷、高分子等的核材表面形成金属薄层后的颗粒；或者在所述导电性颗粒自身或在核材表面形成有金属薄层的颗粒表面上被覆绝缘性树脂后的颗粒。
所述导电性颗粒的粒径对应所要连接的电路的间距等而不同，优选使用粒径为1～20μm的颗粒，更优选使用粒径为2～10μm的颗粒。
所述导电性颗粒的含量优选为所述内含交联性橡胶树脂的粘接成分的0.1体积％～5体积％。如果所述含量小于等于0.1体积％，则连接电路间的导电性颗粒量少，因而导致连接可靠性下降；如果所述含量大于5体积％，则连接微细电路时在相邻电极间易发生短路。
以下，对本发明的各向异性的导电性粘接剂连接电路时的作用进行说明。
参照图1，本发明的各向异性的导电性粘接剂中的大量导电性颗粒分散在绝缘性粘接成分中。
首先，将所述的各向异性的导电性粘接剂置于上基板10和下基板20之间，上基板10和下基板20分别配有对置的电路电极11和电路电极21(图1)。
接着，按规定的温度和压力进行加热加压，于是在绝缘性粘接成分被固化之前，电路电极11和电路电极21通过导电性颗粒电连接。
之后，绝缘性粘接成分被完全固化，上下基板被牢固地粘接、固定，由此，通过本发明的各向异性的导电性粘接剂使对置的电路电极11和电路电极21间电连接，形成可靠性高的电路连接结构体(图2)。
为了更具体地对本发明进行说明，以下举实施例详细说明。但本发明的实施例等可以变化成多种不同的形式，不能说本发明的范围只限于下述的实施例。提供本发明的实施例等是为了向本专业中具备平均知识水平的人员更完全地说明本发明。
[实施例1]
将50克苯氧基树脂(Inchem Inc.、商品名PKHC、平均分子量45000)溶解于重量比为50/50的甲苯(沸点110.6℃、SP值8.90)/丙酮(沸点56.1℃、SP值10.0)混合溶剂中，得到固体成分占40％的溶液。接着，添加自由基聚合性树脂，25克乙二醇改性的双酚A二丙烯酸酯(Donga SynthesisCo.、商品名M-210)；聚合引发剂，5克叔己基过氧-2-乙基己酸酯(Nipponushi Inc.、商品名パ—キユアHO)；交联性橡胶树脂，7克门尼粘度为ML1+4@100℃：34的EPDM(Kumhopolychem Co.、商品名Vistalon 503K)。此时，按所述粘接性成分的3体积％的量，向其中添加由金属被覆的树脂颗粒(Jeoksoo Chemical Co.、商品名Micropearl AU205，5.0μm)组成的导电性颗粒，然后，分散均匀，制备各向异性的导电性粘接剂。之后，使用涂装装置，将各向异性的导电性粘接剂涂布在单面经过异形处理的厚度为50μm的PET薄膜上，在70℃的温度，热风干燥10分钟后得到粘接剂层厚为35μm的各向异性的导电性粘接薄膜。
[实施例2]
除了添加的交联性橡胶树脂为7克EPDM(Kumhopolychem Co.、商品名KEP-330、门尼粘度为ML1+4@125℃：28)之外，采用和实施例1相同的方法，制造出各向异性的导电性粘接薄膜。
[实施例3]
除了添加的交联性橡胶树脂为7克丁基橡胶树脂(InterService社、商品名为BK-1675N、门尼粘度为ML1+8@125℃：47-54)之外，采用和实施例1相同的方法，制造出各向异性的导电性粘接薄膜。
[比较例1]
除了没有添加交联性橡胶树脂外，采用和实施例1相同的方法，制造出各向异性的导电性粘接薄膜。
[比较例2]
除了添加作为非交联性橡胶树脂的SBR橡胶树脂(SEETEC社，商品名为SB 1500H、门尼粘度为ML1+4@100℃：52)，代替交联性橡胶树脂EPDM橡胶树脂外，采用和实施例1相同的方法，制造出各向异性的导电性粘接薄膜。
[比较例3]
除了添加作为非交联性橡胶树脂的NBR橡胶树脂(Zeon社，商品名为N21L、门尼粘度为ML1+4@100℃：62.5)，代替交联性橡胶树脂EPDM橡胶树脂之外，采用和实施例1相同的方法，制造出各向异性的导电性粘接薄膜。
将所述实施例1至3及比较例1至3所制造的各向异性的导电性粘接薄膜分别置于具有500个其线宽为50μm、间距为100μm、厚度为18μm铜电路的柔软的电路板(FPC)间，在一侧的FPC上附着各向异性的导电性粘接薄膜的粘接面后，在70℃、5kg/cm2的条件下加热加压5秒钟，在宽2mm的范围临时连接，剥离PET薄膜，通过与另一侧的FPC连接而接通电路。之后，在160℃、30kg/cm2的条件下加热加压10秒钟，完成了电路连接结构体。
将通过以上方法制造的电路连接结构体在65℃、相对湿度95％的条件下放置1000小时后，测定粘接强度及连接电阻，另外，各试样中将每100片进行压接，测定短路发生率。测定结果如下表1所示。
表1
Figure C200410080829D00101
参照表1可以看出，使用本发明实施例1至3的各向异性的导电性粘接剂的电路连接结构体在粘接强度、通电电阻以及短路发生率方面均良好。
相反，比较例1至3全部发生了短路，在粘接强度及通电电阻方面也比使用了本发明的各向异性的导电性粘接剂的情况差。

Claims (9)

1、各向异性的导电性粘接剂，其特征为：其含有绝缘性粘接成分以及分散在所述绝缘性粘接成分中的导电性颗粒，且在所述绝缘性粘接成分中含有交联性橡胶树脂、自由基聚合性树脂和聚合引发剂；
其中，所述自由基聚合性树脂是具有在自由基作用下聚合的官能团的物质，使用单体或低聚物，或者合并使用单体和低聚物；
其中，所述聚合引发剂是过氧化物类热聚合引发剂和/或羰基化合物、硫化物以及偶氮化合物光聚合引发剂；
其中，所述导电性颗粒是通过薄层形成方法在核材表面形成金属薄层后的颗粒，或者是在所述导电性颗粒自身或在核材表面形成有金属薄层的颗粒表面上被覆绝缘性树脂后的颗粒；
其中，所述导电性颗粒的含量为含有所述交联性橡胶树脂的粘接成分的0.1体积％～5体积％；
其中，相对于100重量份的所述绝缘性粘接成分，所述交联性橡胶树脂的含量为1～20重量份。
2、如权利要求1所述的各向异性的导电性粘接剂，其特征为：所述导电性颗粒的粒径为2～10μm。
3、如权利要求1所述的各向异性的导电性粘接剂，其特征为：所述交联性橡胶树脂含有选自由丁二烯树脂、丙烯腈-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、异丁烯-异戊二烯共聚物IIR、腈基丁二烯橡胶树脂、氯丁二烯橡胶树脂、聚乙烯醇缩丁醛树脂以及硅橡胶树脂组成的组中的一种或一种以上的成分。
4、如权利要求1所述的各向异性的导电性粘接剂，其特征为：所述交联性橡胶树脂含有乙烯树脂、丁基橡胶树脂和/或三元乙丙橡胶。
5、如权利要求1所述的各向异性的导电性粘接剂，其特征为：所述自由基聚合性树脂是从丙烯酸酯、甲基丙烯酸酯、顺丁烯二酰亚胺化合物、不饱和聚酯、丙烯酸、乙酸乙烯酯、丙烯腈、甲基丙烯腈化合物组成的组中选择的，所述丙烯酸酯包括丙烯酸甲酯、丙烯酸乙酯、双酚A乙二醇改性的二丙烯酸酯、异氰脲酸乙二醇改性的二丙烯酸酯、三丙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、季戊四醇三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷丙二醇三丙烯酸酯、三羟甲基丙烷乙二醇三丙烯酸酯、异氰脲酸乙二醇改性的三丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、二环戊烯丙烯酸酯和三环癸基丙烯酸酯。
6、如权利要求1所述的各向异性的导电性粘接剂，其特征为：相对于100重量份所述自由基聚合性树脂，所述聚合引发剂的含量为0.1～10重量份。
7、如权利要求1所述的各向异性的导电性粘接剂，其特征为：所述各向异性的导电性粘接剂的粘接成分中还含有填充剂、软化剂、促进剂、着色剂、抗软化剂、光稳定剂、偶联剂、阻聚剂中的至少一种物质。
8、如权利要求7所述的各向异性的导电性粘接剂，其特征为：所述偶联剂使用的是β-(3，4环氧环己基)乙基三甲氧基硅烷、γ-巯醇基丙基三甲氧基硅烷或γ-甲基丙烯氧基托品基三甲氧基硅烷那样的硅烷偶联剂。
9、如权利要求1所述的各向异性的导电性粘接剂，其特征为：所述各向异性的导电性粘接剂是薄膜的形式。
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