CN111512502B - 连接结构体及其制造方法 - Google Patents

连接结构体及其制造方法 Download PDF

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CN111512502B
CN111512502B CN201880082955.2A CN201880082955A CN111512502B CN 111512502 B CN111512502 B CN 111512502B CN 201880082955 A CN201880082955 A CN 201880082955A CN 111512502 B CN111512502 B CN 111512502B
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conductive particles
substrate
electrode
adhesive
electronic component
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CN111512502A (zh
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白川哲之
福井崇洋
岩元槙之介
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Lishennoco Co ltd
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Showa Denko KK
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    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
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Abstract

本发明的一个方案为一种制造方法，其为具备如下工序的连接结构体的制造方法，即：在具有第一基板和形成于第一基板上的第一电极的第一电子构件与具有第二基板和形成于第二基板上的第二电极的第二电子构件之间配置粘接剂层，将第一电子构件与第二电子构件借助粘接剂层进行压接，以使第一电极与第二电极彼此电连接，第一电子构件进一步具有形成于第一电极的与第一基板相反一侧的绝缘层，粘接剂层含有：作为枝晶状的导电粒子的第一导电粒子、以及作为第一导电粒子以外的导电粒子的第二导电粒子，所述第二导电粒子为具有非导电性核体和设置于该核体上的导电层的导电粒子。

Description

连接结构体及其制造方法
技术领域
本发明涉及一种连接结构体及其制造方法。
背景技术
近年来，在半导体、液晶显示器等领域中，为了进行电子部件的固定、电路连接等而使用各种粘接剂。在这些用途中，电子部件、电路等的高密度化和高精细化不断进展，对粘接剂也要求更高水准的性能。
例如，在液晶显示器与TCP(Tape Carrier Package，带载封装)的连接、FPC(Flexible Printed Circuit，柔性印刷电路)与TCP的连接、或FPC与印刷配线板的连接中，使用使导电粒子分散于粘接剂中而成的粘接剂。对于这样的粘接剂而言，要求更进一步提高被粘接体间的导电性和可靠性。
例如专利文献1中记载了一种导电性膜，其在基材膜上具备含有预定的枝晶状覆银铜粉粒子的导电膜，并且公开了利用该导电性膜，即使不配合银粉也能够得到充分的导电特性。
现有技术文献
专利文献
专利文献1：国际公开第2014/021037号
发明内容
发明要解决的课题
但是，在电子构件的制造工序中，有时在电极上形成绝缘层。在这种情况下，在将电子构件彼此连接时，为了使电极彼此良好地连接，一般会预先将绝缘层除去。但是，由于除去绝缘层的工序在电子构件的制造工序中会成为负担，因此要求不除去绝缘层也能够将电子构件彼此连接，进一步，其连接时的压力越低越理想(例如1.0MPa左右)。
因此，本发明的目的在于提供一种能够在低压下将形成有绝缘层的电子构件进行连接的连接结构体的制造方法和连接结构体。
用于解决课题的方法
本发明的一个形态为一种制造方法，其为具备如下工序的连接结构体的制造方法，即：在具有第一基板和形成于第一基板上的第一电极的第一电子构件与具有第二基板和形成于第二基板上的第二电极的第二电子构件之间配置粘接剂层，将第一电子构件与第二电子构件借助粘接剂层进行压接，以使第一电极与第二电极彼此电连接，第一电子构件进一步具有形成于第一电极的与第一基板相反一侧的绝缘层，粘接剂层含有作为枝晶状的导电粒子的第一导电粒子、和作为第一导电粒子以外的导电粒子的第二导电粒子，所述第二导电粒子为具有非导电性核体和设置于该核体上的导电层的导电粒子。
本发明的另一形态为一种连接结构体，具备：第一电子构件，其具有第一基板、形成于第一基板上的第一电极、和形成于第一电极的与第一基板相反一侧的绝缘层；第二电子构件，其具有第二基板和形成于第二基板上的第二电极；以及将第一电极与第二电极彼此电连接的连接构件，连接构件含有：作为枝晶状的导电粒子的第一导电粒子、和作为第一导电粒子以外的导电粒子的第二导电粒子，所述第二导电粒子为具有非导电性核体和设置于该核体上的导电层的导电粒子。
在上述各形态中，导电层优选含有选自由金、镍和钯组成的组中的至少一种。
发明效果
根据本发明，能够提供一种能够在低压下将形成有绝缘层的电子构件进行连接的连接结构体的制造方法和连接结构体。
附图说明
图1是表示连接结构体的制造方法的一个实施方式的示意截面图。
图2是表示连接结构体的一个实施方式的示意截面图。
图3是表示实施例中的评价用的连接结构体的制作方法的示意图。
图4是表示实施例中的连接电阻的测定方法的示意图。
具体实施方式
以下，一边适当地参照附图，一边对本发明的实施方式进行详细说明。
图1是表示连接结构体的制造方法的一个实施方式的示意截面图。如图1所示，在该制造方法中，首先，准备第一电子构件1、第二电子构件2、以及粘接剂膜(粘接剂层)3。
第一电子构件1具备第一基板4、形成于第一基板4的主面上的第一电极5、和形成于第一电极5的与第一基板4相反一侧的绝缘层6。第二电子构件2具备第二基板7、和形成于第二基板7的主面上的第二电极8。第二电子构件也可以在第二电极8的与第二基板7相反一侧进一步具备与第一电子构件1同样的绝缘层。在第二电子构件进一步具备绝缘层的情况下，第一电子构件和第二电子构件彼此可以为相同种类也可以为不同种类。
第一基板4和第二基板7分别可以为由玻璃、陶瓷、聚酰亚胺、聚碳酸酯、聚酯、聚醚砜等形成的基板。第一电极5和第二电极8分别可以为由金、银、铜、锡、铝、钌、铑、钯、锇、铱、铂、铟锡氧化物(ITO)等形成的电极。第一电极5和第二电极8的厚度例如可以分别大于或等于5μm、大于或等于10μm、或大于或等于20μm，可以小于或等于200μm、小于或等于100μm、或小于或等于50μm。
绝缘层6例如由聚丙烯等聚烯烃、尼龙等聚酰胺等聚合物形成。绝缘层6的厚度例如可以大于或等于1μm、大于或等于2μm、或大于或等于3μm，可以小于或等于8μm、小于或等于6μm、或小于或等于4μm。这样的绝缘层6例如可通过在形成于第一基板4的主面上的第一电极5上配置上述聚合物的膜那样的绝缘性膜来形成。
在一个实施方式中，粘接剂膜3由含有粘接剂成分9、以及分散于粘接剂成分9中的第一导电粒子10和第二导电粒子11的粘接剂层构成。
粘接剂成分9例如由通过热或光而显示出固化性的材料构成，可以为环氧系粘接剂、自由基固化型的粘接剂、含有聚氨酯、聚乙烯酯等的热塑性粘接剂等。从粘接后的耐热性和耐湿性优异方面出发，粘接剂成分9也可以由交联性材料构成。环氧系粘接剂含有作为热固性树脂的环氧树脂作为主成分。从能够短时间固化且连接作业性良好、粘接性优异等方面出发，优选使用环氧系粘接剂。自由基固化型的粘接剂与环氧系粘接剂相比具有低温短时间内的固化性优异等特征，因此可根据用途适当地使用。
环氧系粘接剂例如含有环氧树脂(热固性材料)和固化剂，且可以根据需要进一步含有热塑性树脂、偶联剂、填充剂等。
作为环氧树脂，例如可列举双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A酚醛清漆型环氧树脂、双酚F酚醛清漆型环氧树脂、脂环式环氧树脂、缩水甘油酯型环氧树脂、缩水甘油胺型环氧树脂、乙内酰脲型环氧树脂、异氰脲酸酯型环氧树脂、脂肪族链状环氧树脂等。这些环氧树脂可以经卤化，也可以经氢化，还可以具有在侧链加成有丙烯酰基或甲基丙烯酰基的结构。这些环氧树脂可以单独使用一种或组合两种以上来使用。
作为固化剂，只要能够使环氧树脂固化就没有特别限制，例如可列举阴离子聚合性的催化剂型固化剂、阳离子聚合性的催化剂型固化剂、加聚型的固化剂等。它们中，从快速固化性优异、且不需要考虑化学当量的方面出发，优选为阴离子或阳离子聚合性的催化剂型固化剂。
作为阴离子或阳离子聚合性的催化剂型固化剂，例如可列举咪唑、酰肼、三氟化硼-胺络合物、
Figure BDA0002549691810000041
盐(芳香族锍盐、芳香族重氮
Figure BDA0002549691810000042
盐、脂肪族锍盐等)、胺酰亚胺、二氨基马来腈、三聚氰胺及其衍生物、多胺的盐、双氰胺等，也可以使用它们的改性物。作为加聚型的固化剂，例如可列举多胺、聚硫醇、多酚、酸酐等。
这些固化剂可以是利用聚氨酯系、聚酯系等高分子物质、镍、铜等金属薄膜、硅酸钙等无机物等被覆并进行微胶囊化而得到的潜伏性固化剂。潜伏性固化剂由于能够延长可使用时间，因此优选。固化剂可以单独使用一种或组合两种以上来使用。
相对于热固性材料和根据需要配合的热塑性树脂的合计量100质量份，固化剂的含量可以为0.05～20质量份。
自由基固化型的粘接剂例如含有自由基聚合性材料和自由基聚合引发剂(也称为固化剂)，且可以根据需要进一步含有热塑性树脂、偶联剂、填充剂等。
作为自由基聚合性材料，例如只要是具有通过自由基进行聚合的官能团的物质就可以没有特别限制地使用。具体地说，例如可列举丙烯酸酯(也包含对应的甲基丙烯酸酯。以下相同。)化合物、丙烯酰氧基(也包含对应的甲基丙烯酰氧基。以下相同。)化合物、马来酰亚胺化合物、柠康酰亚胺树脂、纳迪克酰亚胺树脂等自由基聚合性材料。这些自由基聚合性材料可以为单体或低聚物的状态，也可以为单体与低聚物的混合物的状态。
作为丙烯酸酯化合物，例如可列举丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丙酯、丙烯酸异丁酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、四羟甲基甲烷四丙烯酸酯、2-羟基-1,3-二丙烯酰氧基丙烷、2,2-双[4-(丙烯酰氧基甲氧基)苯基]丙烷、2,2-双[4-(丙烯酰氧基聚乙氧基)苯基]丙烷、丙烯酸二环戊烯酯、丙烯酸三环癸酯、三(丙烯酰氧基乙基)异氰脲酸酯、氨基甲酸酯丙烯酸酯、磷酸酯二丙烯酸酯等。
丙烯酸酯化合物等自由基聚合性材料根据需要也可以与对苯二酚、甲醚对苯二酚等阻聚剂一起使用。从提高耐热性的观点考虑，丙烯酸酯化合物等自由基聚合性材料优选具有至少一种二环戊烯基、三环癸基、三嗪环等取代基。作为丙烯酸酯化合物以外的自由基聚合性材料，例如可以适宜地使用国际公开第2009/063827号中所记载的化合物。自由基聚合性材料可以单独使用一种或组合两种以上来使用。
作为自由基聚合引发剂，只要是例如通过加热或光照射而分解并产生游离自由基的化合物就可以没有特别限制地使用。具体地说，例如可列举过氧化化合物、偶氮系化合物等。这些化合物可以根据目标的连接温度、连接时间、适用期等而适当选择。
作为自由基聚合引发剂，更具体地说，可列举二酰基过氧化物、过氧化二碳酸酯、过氧化酯、过氧化缩酮、二烷基过氧化物、过氧化氢、甲硅烷基过氧化物等。其中，优选为过氧化酯、二烷基过氧化物、过氧化氢、甲硅烷基过氧化物等，更优选为能够得到高反应性的过氧化酯。作为这些自由基聚合引发剂，例如可以适宜地使用国际公开第2009/063827号中所记载的化合物。自由基聚合引发剂可以单独使用一种或组合两种以上来使用。
相对于自由基聚合性材料和根据需要配合的热塑性树脂的合计量100质量份，自由基聚合引发剂的含量可以为0.1～10质量份。
在环氧系粘接剂和自由基固化型的粘接剂中根据需要配合的热塑性树脂例如容易将粘接剂成形为膜状。作为热塑性树脂，例如可列举苯氧树脂、聚乙烯醇缩甲醛树脂、聚苯乙烯树脂、聚乙烯醇缩丁醛树脂、聚酯树脂、聚酰胺树脂、二甲苯树脂、聚氨酯树脂、聚酯氨基甲酸酯树脂、酚醛树脂、萜烯酚醛树脂等。作为热塑性树脂，例如可以适宜地使用国际公开第2009/063827号中所记载的化合物。其中，从粘接性、相溶性、耐热性、机械强度等优异的方面出发，优选为苯氧树脂。热塑性树脂可以单独使用一种或组合两种以上来使用。
关于热塑性树脂的含量，在配合于环氧系粘接剂中的情况下，相对于热塑性树脂和热固性材料的合计量100质量份，可以为5～80质量份。关于热塑性树脂的含量，在配合于自由基固化型的粘接剂中的情况下，相对于热塑性树脂和自由基聚合性材料的合计量100质量份，可以为5～80质量份。
作为粘接剂成分9的其他例子，可列举含有热塑性树脂、30℃的自由基聚合性材料、和自由基聚合引发剂的热自由基固化型粘接剂。热自由基固化型粘接剂与上述粘接剂相比为低粘度。相对于热塑性树脂和自由基聚合性材料的合计量100质量份，热自由基固化型粘接剂中的自由基聚合性材料的含量优选为20～80质量份，更优选为30～80质量份，进一步优选为40～80质量份。
粘接剂成分9还可以为含有热塑性树脂、包含在30℃为液态的环氧树脂的热固性材料、以及固化剂的环氧系粘接剂。在这种情况下，相对于热塑性树脂和热固性材料的合计量100质量份，环氧系粘接剂中的环氧树脂的含量优选为20～80质量份，更优选为40～80质量份，进一步优选为30～80质量份。
在将粘接剂膜3用于IC芯片与玻璃基板、柔性印刷基板(FPC)等的连接的情况下，从抑制因IC芯片与基板的线膨胀系数之差引起的基板翘曲的观点考虑，粘接剂成分9优选进一步含有发挥内部应力缓和作用的成分。作为该成分，具体地说，可列举丙烯酸橡胶、弹性体成分等。或者，粘接剂成分9也可以为国际公开第98/44067号中所记载那样的自由基固化型粘接剂。
以粘接剂膜3的总体积为基准计，粘接剂成分9在粘接剂膜3中所占的体积比例例如可以大于或等于55体积％或大于或等于65体积％，可以小于或等于95体积％或小于或等于85体积％。
第一导电粒子10呈枝晶状(也称为树枝状)，具备一根主轴、以及从该主轴二维地或三维地分支的多个枝。第一导电粒子10可以由铜、银等金属形成，例如可以为用银被覆铜粒子而得到的覆银铜粒子。
第一导电粒子10可以为公知的导电粒子，具体地说，例如可以作为ACBY-2(三井金属矿业株式会社)、CE-1110(福田金属箔粉工业株式会社)、#FSP(JX金属株式会社)、#51-R(JX金属株式会社)等来获得。或者，第一导电粒子10也可以通过公知的方法(例如，上述专利文献1中所记载的方法)来制造。
以粘接剂膜3的总体积为基准计，粘接剂膜3中的第一导电粒子10的含量(第一导电粒子10在粘接剂膜3中所占的体积比例)可以大于或等于2体积％或大于或等于8体积％，可以小于或等于25体积％或小于或等于15体积％。
第二导电粒子11具有非导电性核体、和设置于该核体上的导电层。核体由玻璃、陶瓷、树脂等非导电性材料形成，优选由树脂形成。作为树脂，例如可列举丙烯酸树脂、苯乙烯树脂、有机硅树脂、聚丁二烯树脂或构成这些树脂的单体的共聚物。核体的平均粒径例如可以为2～30μm。
导电层例如由金、银、铜、镍、钯或它们的合金形成。从导电性优异的观点考虑，导电层优选含有选自金、镍和钯中的至少一种，更优选含有金或钯，进一步优选含有金。导电层例如通过将上述金属镀敷于核体上而形成。导电层的厚度例如可以为10～400nm。
从能够适宜地将膜进行薄膜化的观点考虑，第二导电粒子11的平均粒径优选小于或等于30μm，更优选小于或等于25μm，进一步优选小于或等于20μm。第二导电粒子11的平均粒径例如可以大于或等于1μm。第二导电粒子11和构成其的核体的平均粒径通过使用激光衍射-散射法的粒度分布测定装置(Microtrac(产品名，日机装株式会社))来测定。
以粘接剂膜3的总体积为基准计，粘接剂膜3中的第二导电粒子11的含量(第二导电粒子11在粘接剂膜3中所占的体积比例)可以大于或等于2体积％或大于或等于5体积％，可以小于或等于20体积％或小于或等于10体积％。
粘接剂膜3的厚度例如可以大于或等于5μm、大于或等于7μm、或大于或等于10μm，可以小于或等于30μm、小于或等于25μm、或小于或等于20μm。
粘接剂层例如可以通过将糊状的粘接剂组合物涂布于第一电子构件1或第二电子构件2上来准备。糊状的粘接剂组合物例如通过对包含粘接剂成分、第一导电粒子和第二导电粒子的混合物进行加热或使上述混合物溶解于溶剂中而得到。作为溶剂，例如可以使用大气压下的沸点为50～150℃的溶剂。
在连接结构体的制造方法中，接着，在第一电子构件1与第二电子构件2之间配置粘接剂膜(粘接剂层)3，将第一电子构件1与第二电子构件2借助粘接剂膜(粘接剂层)3进行压接。具体地说，为了使第一电极5与第二电极8彼此电连接，沿第一电子构件1、粘接剂膜(粘接剂层)3和第二电子构件2的层叠方向进行加压，并同时进行加热。加热温度例如为50～190℃。压力例如为0.1～30MPa。这些加热和加压例如在0.5秒钟～120秒钟的范围内进行。
通过以上的制造方法可以得到连接结构体。图2是表示连接结构体的一个实施方式的示意截面图。如图2所示，连接结构体20具备：第一电子构件1，其具有第一基板4、形成于第一基板4上的第一电极5、和形成于第一电极5的与第一基板4相反一侧的绝缘层6；第二电子构件2，其具有第二基板7、和形成于第二基板7上的第二电极8；以及将第一电极5与第二电极8彼此电连接的连接构件21。
连接构件21包含粘接剂成分9的固化物22、以及分散于该固化物22中的第一导电粒子10和第二导电粒子11。即，连接构件21为将上述粘接剂膜3固化而成。
在本实施方式涉及的连接结构体的制造方法中，通过并用第一导电粒子10和第二导电粒子11，从而能够适宜地将形成有绝缘层6的第一电子构件1连接。即，由于粘接剂膜3中所含的第一导电粒子10为枝晶状，因此在将电子构件1、2彼此进行压接时，如图2所示，第一导电粒子10也能够穿破绝缘层6而与第一电极5电连接。此外，由于第二导电粒子11成为使第一电极5与第二电极8导通的主要导通路径，因此与使用例如仅含有第一导电粒子10的粘接剂膜的情况相比，即使在低压下也能够实现适宜的连接，并且在可靠性方面也优异。
在上述实施方式中，粘接剂膜3由一层含有粘接剂成分9、第一导电粒子10和第二导电粒子11的粘接剂层构成，但在另一实施方式中，粘接剂膜也可以由两层以上来构成。在这种情况下，第一导电粒子10和第二导电粒子11只要包含在两层以上中的至少一层中即可，彼此可以包含在相同的层中也可以包含在不同的层中。另外，两层以上的层中所含的粘接剂成分9、第一导电粒子10和第二导电粒子11分别可以彼此相同也可以不同。
在另一实施方式中，粘接剂膜可以具备：含有第一导电粒子10的第一粘接剂层和含有第二导电粒子11的第二粘接剂层。在这种情况下，第一粘接剂层可以不含第二导电粒子11，第二粘接剂层可以不含第一导电粒子10。在使用该实施方式涉及的粘接剂膜的情况下，从能够更合适地得到第一导电粒子10穿破绝缘层6那样的上述效果的观点考虑，在电子构件1、2之间配置粘接剂膜时，优选使含有第一导电粒子10的第一粘接剂层朝向具有绝缘层6的第一电子构件1侧来进行配置。
在另一实施方式中，粘接剂膜也可以具备：含有第一导电粒子10和第二导电粒子11的第一粘接剂层、以及不含导电粒子(仅由粘接剂成分构成)的第二粘接剂层。在使用该实施方式涉及的粘接剂膜的情况下，从能够更合适地获得第一导电粒子10穿破绝缘层6那样的上述效果的观点考虑，在电子构件1、2之间配置粘接剂膜时，优选使含有第一导电粒子10的第一粘接剂层朝向具有绝缘层6的第一电子构件1侧来进行配置。
另外，该粘接剂膜例如适合用于第二电子构件2中的第二电极8具有凹凸形状的情况。即，在该粘接剂膜中，不含导电粒子的第二粘接剂层(粘接剂成分)容易流动，因此在将电子构件1、2进行压接时能够沿着第二电极8的凹凸形状流动。因此，粘接剂成分能够良好地填充于电子构件1、2之间，从而能够使电子构件1、2彼此适宜地粘接。
在另一实施方式中，粘接剂膜也可以依次具备：含有第一导电粒子10的第一粘接剂层、含有第二导电粒子11的第二粘接剂层、以及含有第一导电粒子10的第三粘接剂层。在这种情况下，第一粘接剂层和第三粘接剂层可以不含第二导电粒子11，第二粘接剂层可以不含第一导电粒子10。该实施方式涉及的粘接剂膜适合用于在第二电子构件上也设有绝缘层6的情况。即，对于该粘接剂膜而言，第一导电粒子10配置在粘接剂膜的两侧，因此即使在第二电子构件上设有绝缘层6的情况下，第一导电粒子10也能够适宜地穿破该绝缘层6。
实施例
以下，基于实施例进一步具体地说明本发明，但本发明不限于以下的实施例。
(溶液A1的调制)
将50g苯氧树脂(联合碳化物株式会社制，产品名：PKHC，重均分子量：45000)溶解于甲苯(沸点：110.6℃)与乙酸乙酯(沸点：77.1℃)的混合溶剂(以质量比计为甲苯:乙酸乙酯＝1:1)中，得到固体成分40质量％的苯氧树脂溶液。在该苯氧树脂溶液中，将作为自由基聚合性材料的氨基甲酸酯丙烯酸酯(根上工业株式会社制，产品名：UN7700)和磷酸酯二甲基丙烯酸酯(共荣社化学株式会社制，产品名：LIGHT ESTER P-2M)、和作为固化剂的1,1-双(叔己基过氧化)-3,3,5-三甲基环己烷(日油株式会社制，产品名：PERHEXA TMH)以苯氧树脂:氨基甲酸酯丙烯酸酯:磷酸酯二甲基丙烯酸酯:固化剂＝10:10:3:2的固体质量比进行配合，得到溶液A1。
作为导电粒子B1(第一导电粒子)，使用枝晶状的导电粒子(覆银铜粒子，三井金属矿业株式会社制，产品名：ACBY-2)。
(导电粒子C1的制作)
首先，向二乙烯基苯、苯乙烯单体和甲基丙烯酸丁酯的混合溶液中投入作为聚合引发剂的过氧化苯甲酰，一边以高速进行均匀搅拌一边加热以进行聚合反应，从而得到微粒分散液。通过将该微粒分散液过滤并进行减压干燥，从而得到作为微粒的凝聚体的块体。进一步，通过将该块体粉碎，从而分别制作交联密度不同的平均粒径20μm的核体(树脂粒子)。
接着，使钯催化剂(Muromachi Technos株式会社制，产品名：MK-2605)担载于上述核体的表面上，并将用促进剂(Muromachi Technos株式会社制，产品名：MK-370)活化后的核体投入到已加温至60℃的、硫酸镍水溶液、次磷酸钠水溶液和酒石酸钠水溶液的混合液中，进行化学镀敷前工序。将该混合物搅拌20分钟，确认了氢的发泡停止。接着，添加硫酸镍、次磷酸钠、柠檬酸钠和镀敷稳定剂的混合溶液，进行搅拌直至pH变得稳定，并进行化学镀敷后工序直至氢的发泡停止。接着，将镀液过滤，用水将过滤物清洗后，使用80℃的真空干燥机进行干燥，从而制作经镀镍的导电粒子C1(第二导电粒子)。
[实施例1]
＜粘接剂膜的制作＞
使45体积份的导电粒子B1和15体积份的导电粒子C1分散于100体积份的溶液A1中，得到混合溶液。将所得的混合溶液涂布于厚度80μm的氟树脂膜上，通过在70℃进行10分钟热风干燥而除去溶剂，从而得到形成于氟树脂膜上的厚度20μm的粘接剂膜(粘接剂层)。
通过以下所示的步骤来评价将所得的粘接剂膜用于连接构件时的特性。
＜连接结构体的制作和评价＞
(低压连接时的导电性的评价)
如图3(a)、(b)所示，将所得的膜状粘接剂组合物切成6mm×6mm而得到粘接剂膜31，将该粘接剂膜31配置于6mm×50mm的铜箔32的大致中央处，使用株式会社大桥制作所制BD-07进行加热加压(50℃、0.1MPa、2秒钟)来进行粘贴。接着，如图3(c)、(d)所示，准备在50mm×6mm的铝箔表面形成有作为绝缘层的厚度2μm的聚丙烯层的铝层压膜33(藤森工业株式会社制，产品名：铝层压膜ZBP-0513)。按照覆盖粘接剂膜31的方式将铝层压膜33重叠于铜箔32与粘接剂膜31的层叠体上，使用株式会社大桥制作所制BD-07进行加热加压(150℃、1.0MPa、10秒钟)。由此，得到依次层叠有铜箔32、粘接剂膜31、绝缘层(聚丙烯层)和铝箔的评价用连接结构体。如图4所示，对所得的连接结构体连接电流表和电压表，并通过4端子法测定连接电阻(初始)。将结果示于表1中。
(可靠性的评价)
如图3(a)、(b)所示，将所得的膜状粘接剂组合物切成6mm×6mm而得到粘接剂膜31，将该粘接剂膜31配置于6mm×50mm的铜箔32的大致中央处，使用株式会社大桥制作所制BD-07进行加热加压(50℃、0.5MPa、2秒钟)来进行粘贴。接着，如图3(c)、(d)所示，准备在50mm×6mm的铝箔表面形成有作为绝缘层的厚度2μm的聚丙烯层的铝层压膜33(藤森工业株式会社制，产品名：铝层压膜ZBP-0513)。按照覆盖粘接剂膜31的方式将铝层压膜33重叠于铜箔32与粘接剂膜31的层叠体上，使用株式会社大桥制作所制BD-07进行加热加压(150℃、3.0MPa、10秒钟)。由此，得到依次层叠有铜箔32、粘接剂膜31、绝缘层(聚丙烯层)和铝箔的评价用连接结构体。
如图4所示，对所得的连接结构体连接电流表、电压表，并通过4端子法测定连接电阻(初始)。需要说明的是，在将端子与铝层压膜33连接时，将端子强力按压使其充分导通后测定电阻。另外，使用Espec株式会社制TSA-43EL，对连接结构体进行热循环试验，所述热循环试验中，将在-20℃保持30分钟、用10分钟升温至100℃、在100℃保持30分钟、用10分钟降温至-20℃这样热循环重复500次，在进行了上述热循环试验之后，与上述同样地操作，测定连接电阻(热循环试验后)。将结果示于表1中。
[比较例1]
除了在第一粘接剂层和第二粘接剂层中没有使用导电粒子B1(第一导电粒子)以外，与实施例1同样地操作进行粘接剂膜的制作、以及连接结构体的制作和评价。
[比较例2]
除了在第一粘接剂层和第二粘接剂层中没有使用导电粒子C1(第二导电粒子)以外，与实施例1同样地操作进行粘接剂膜的制作、以及连接结构体的制作和评价。
[表1]
Figure BDA0002549691810000121
符号说明
1：第一电子构件、2：第二电子构件、3：粘接剂膜(粘接剂层)、4：第一基板、5：第一电极、6：绝缘层、7：第二基板、8：第二电极、10：第一导电粒子、11：第二导电粒子、20：连接结构体、21：连接构件。

Claims (4)

1.一种制造方法，其为具备如下工序的连接结构体的制造方法：在具有第一基板和形成于所述第一基板上的第一电极的第一电子构件与具有第二基板和形成于所述第二基板上的第二电极的第二电子构件之间配置粘接剂层，将所述第一电子构件与所述第二电子构件借助所述粘接剂层进行压接，使得所述第一电极与所述第二电极彼此电连接，
所述第一电子构件进一步具有形成于所述第一电极的与所述第一基板相反一侧的绝缘层，
所述粘接剂层含有作为枝晶状的导电粒子的第一导电粒子、和作为所述第一导电粒子以外的导电粒子的第二导电粒子，所述第二导电粒子为具有非导电性核体和设置于该核体上的导电层的导电粒子，
所述核体由树脂形成，
所述绝缘层为聚合物的膜，所述聚合物为聚烯烃或聚酰胺。
2.根据权利要求1所述的制造方法，所述导电层含有选自由金、镍和钯组成的组中的至少一种。
3.一种连接结构体，具备：
第一电子构件，其具有第一基板、形成于所述第一基板上的第一电极、和形成于所述第一电极的与所述第一基板相反一侧的绝缘层；
第二电子构件，其具有第二基板、和形成于所述第二基板上的第二电极；以及
将所述第一电极与所述第二电极彼此电连接的连接构件，
所述连接构件含有作为枝晶状的导电粒子的第一导电粒子、和作为所述第一导电粒子以外的导电粒子的第二导电粒子，所述第二导电粒子为具有非导电性核体和设置于该核体上的导电层的导电粒子，
所述核体由树脂形成，
所述绝缘层为聚合物的膜，所述聚合物为聚烯烃或聚酰胺。
4.根据权利要求3所述的连接结构体，所述导电层含有选自由金、镍和钯组成的组中的至少一种。
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