CN101835859A - 电路连接材料、连接结构体及其制造方法 - Google Patents

电路连接材料、连接结构体及其制造方法 Download PDF

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CN101835859A
CN101835859A CN200880112763A CN200880112763A CN101835859A CN 101835859 A CN101835859 A CN 101835859A CN 200880112763 A CN200880112763 A CN 200880112763A CN 200880112763 A CN200880112763 A CN 200880112763A CN 101835859 A CN101835859 A CN 101835859A
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circuit
electrode
connection material
circuit electrode
substrate
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CN101835859B (zh
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中泽孝
有福征宏
小岛和良
望月日臣
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
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    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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Abstract

本发明的电路连接材料用于将在第一基板的主表面上形成有第一电路电极的第一电路部件与在第二基板的主表面上形成有第二电路电极的第二电路部件在使第一电路电极和第二电路电极呈相对配置的状态下进行连接；该电路连接材料含有能产生游离自由基的固化剂、自由基聚合性物质和具有仲硫醇基的化合物。本发明的电路连接材料可在低温短时间进行固化，且保存稳定性优良。

Description

电路连接材料、连接结构体及其制造方法
技术领域
本发明涉及电路连接材料，以及使用该电路连接材料的连接结构体及其制造方法，所述电路连接材料介于相对的电路电极间，并且通过向相对的电路电极加压从而将加压方向的电极间电连接。
背景技术
作为所述半导体元件和液晶显示元件用的电路连接材料，已知有：使用了粘接性高且可靠性高的环氧树脂的热固化性树脂(参考例如专利文献1)。树脂的构成成分一般采用：环氧树脂、具有与环氧树脂的反应性的酚树脂等固化剂、促进环氧树脂与固化剂的反应的潜在性固化剂。潜在性固化剂为决定固化温度和固化速度的重要因素，从室温下的储藏稳定性和加热时的固化速度方面考虑，可使用各种化合物。
另外，近来如下所述的自由基固化型粘接剂引人注目，即，并用了丙烯酸酯衍生物、甲基丙烯酸酯衍生物(以下总称为“(甲基)丙烯酸酯衍生物”。)与作为自由基聚合引发剂的过氧化物的自由基固化型粘接剂。由于作为反应活性种的自由基富有反应性，因此自由基固化可实现短时间固化(参考例如专利文献2、3)。
因此，目前，有利于缩短生产时间的短时间固化型粘接剂逐渐普及起来。为进一步提高自由基固化型粘接剂的反应性，有人正对链转移剂的应用进行研究(例如专利文献4)。通过使用链转移剂，可获得快速固化效果，并可期待低温短时间连接、提高对金属等无机物的密着力。
专利文献1：日本特开平1-113480号公报
专利文献2：日本特开2002-203427号公报
专利文献3：国际公开WO98/044067号公报
专利文献4：日本特开2003-221557号公报
发明内容
本发明的目的在于提供电路连接材料，以及使用了该电路连接材料的连接结构体及其制造方法，所述电路连接材料可有效地获得上述链转移剂的应用优点，即快速固化、低温短时间连接、对金属等无机物的密合力提高等效果。课题的解决手段
本发明人为实现上述目的而进行了锐意研究，结果发现：通过将具有仲硫醇基的化合物用作链转移剂，可获得粘接力提高效果，且可维持保存稳定性，从而完成了本发明。
即本发明提供电路连接材料，所述电路连接材料用于将在第一基板的主表面上形成有第一电路电极的第一电路部件与在第二基板的主表面上形成有第二电路电极的第二电路部件在使第一电路电极和第二电路电极呈相对配置的状态下进行连接；所述电路连接材料含有能产生游离自由基的固化剂、自由基聚合性物质和具有仲硫醇基的化合物。
本发明的电路连接材料中，具有仲硫醇基的化合物的分子量优选为400以上。
另外，本发明提供连接结构体，其具备：在第一基板的主表面上形成有第一电路电极的第一电路部件、在第二基板的主表面上形成有第二电路电极并且按照使第二电路电极与第一电路电极相对的方式来配置的第二电路部件、设计于第一电路部件和第二电路部件之间并将第一电路部件和第二电路部件电连接的粘接层；该粘接层通过使上述本发明的电路连接材料介于第一电路部件和第二电路部件之间并在该状态下进行加压而形成。
另外，本发明提供连接结构体的制造方法，其具备如下所述工序：将在第一基板的主表面上形成有第一电路电极的第一电路部件与在第二基板的主表面上形成有第二电路电极的第二电路部件按照使第一电路电极和第二电路电极相对的方式进行配置、使上述本发明的电路连接材料介于第一电路部件和第二电路部件之间并在该状态下进行加压，从而将第一电路电极和第二电路电极电连接。
利用本发明可提供：可低温短时间固化且保存稳定性优良的电路连接用材料，以及使用了该电路连接材料的连接结构体及其制造方法。
附图说明
[图1]表示连接结构体的一实施方案的示意截面图。
符号说明
[0013]
1...连接结构体，7...导电性粒子，10...粘接层，11...绝缘层，20...第一电路部件，21...第一电路基板，22...第一电路电极(第一连接端子)，30...第二电路部件，31...第二电路基板，32...第二电路电极(第二连接端子)。
具体实施方式
以下详细说明本发明的优选实施方案。
本发明的电路连接材料，用于将在第一基板的主表面上形成有第一电路电极的第一电路部件与在第二基板的主表面上形成有第二电路电极的第二电路部件在使第一电路电极和第二电路电极呈相对配置的状态下进行连接；所述电路连接材料含有：能产生游离自由基的固化剂、自由基聚合性物质和具有仲硫醇基的化合物。
本发明使用的能产生游离自由基的固化剂优选为过氧化合物、偶氮系化合物等通过加热而分解从而产生游离自由基的物质，并根据目的连接温度、连接时间等来适宜选定。配合量为0.05～10％(重量)左右，更优选为0.1～5％(重量)。具体可选自：二酰基过氧化物类、过氧化二碳酸酯类、过氧化酯类、过氧化缩酮类、二烷基过氧化物类、氢过氧化物类等。
二酰基过氧化物类可列举出：2，4-二氯苯甲酰过氧化物、3，5，5-三甲基己酰过氧化物、辛酰过氧化物、月桂酰过氧化物、硬脂酰过氧化物、琥珀酰过氧化物、苯甲酰基过氧化甲苯、苯甲酰过氧化物等。
过氧化二碳酸酯类可列举出，过氧化二碳酸二正丙酯、过氧化二碳酸二异丙酯、过氧化二碳酸双(4-叔丁基环己基)酯、过氧化二碳酸二-2-乙氧基甲氧基酯、二(2-乙基己基过氧)二碳酸酯、过氧化二碳酸二甲氧基丁酯、二(3-甲基-3-甲氧基丁基过氧)二碳酸酯等。
过氧化酯类可列举出：1，1，3，3-四甲基丁基过氧化新癸酸酯、1-环己基-1-甲基乙基过氧化新癸酸酯、过氧化新癸酸叔己酯、过氧化三甲基乙酸叔丁酯、1，1，3，3-四甲基丁基过氧化-2-乙基己酸酯、2，5-二甲基-2，5-二(2-乙基己酰基过氧)己烷、1-环己基-1-甲基乙基过氧化-2-乙基己酸酯、过氧化-2-乙基己酸叔己酯、过氧化-2-乙基己酸叔丁酯、过氧化异丁酸叔丁酯、1，1-双(叔丁基过氧)环己烷、过氧化异丙基单碳酸叔己酯、过氧化-3，5，5-三甲基己酸叔丁酯、过氧化月桂酸叔丁酯、2，5-二甲基-2，5-二(间甲苯酰基过氧)己烷、过氧化异丙基单碳酸叔丁酯、过氧化-2-乙基己基单碳酸叔丁酯、过氧化苯甲酸叔己酯、过氧化醋酸叔丁酯等。
过氧化缩酮类可列举出：1，1-双(叔己基过氧)-3，3，5-三甲基环己烷、1，1-双(叔己基过氧)环己烷、1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷、1，1-(叔丁基过氧)环十二烷、2，2-双(叔丁基过氧)癸烷等。
二烷基过氧化物类可列举出：α，α’-双(叔丁基过氧)二异丙苯、二异丙苯基过氧化物、2，5-二甲基-2，5-二(叔丁基过氧)己烷、叔丁基异丙苯基过氧化物等。
氢过氧化物类可列举出：二异丙基苯过氧化氢、异丙苯过氧化氢等。
这些游离自由基产生剂可单独使用或混合使用，也可与分解促进剂、抑制剂等混合使用。另外，由于可提高保存性，因此优选将这些固化剂用聚氨酯系、聚酯系的高分子物质等进行被覆而形成微胶囊化物。
本发明所使用的自由基聚合性物质可以单体或低聚物的状态来使用，也可将单体和低聚物合用。自由基聚合性物质的具体例可列举出：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、丙烯酸双环戊烯基酯、丙烯酸三环癸基酯、三(丙烯酰氧基乙基)异氰尿酸酯等。这些可单独使用或合用。另外，根据需要，也可适宜地使用对苯二酚、对苯二酚甲基醚类等阻聚剂。另外，具有二环戊烯基和/或三环癸基和/或三嗪环的物质由于可提高耐热性，因而优选。
当上述自由基聚合性物质中含有聚苯乙烯、聚乙烯、聚乙烯醇缩丁醛、聚乙烯醇缩甲醛、聚酰亚胺、聚酰胺、聚酯、聚氯乙烯、聚苯醚、尿素树脂、三聚氰胺树脂、酚树脂、二甲苯树脂、环氧树脂、聚异氰酸酯树脂、苯氧基树脂等聚合物时，由于操作性好且固化时的压力缓和性优良，因而优选；聚合物在具有羟基等的官能团的情况下，由于粘接性提高，因而更优选。更优选通过将各聚合物用自由基聚合性的官能团改性而成的物质。这些聚合物的重均分子量优选为10000以上，从混合性方面考虑，更优选为10000以上1000000以下。本申请所规定的重均分子量是，通过凝胶渗透色谱法(GPC)依照以下条件，使用基于标准聚苯乙烯的标准曲线来进行测定的分子量。
[GPC条件]
使用仪器：日立L-6000型[(株)日立制作所]；柱：凝胶填料(GelPack)GL-R420+凝胶填料GL-R430+凝胶填料GL-R440(合计3根)[日立化成工业(株)制商品名]；洗脱液：四氢呋喃；测定温度：40℃；流量：1.75ml/min；检测器：L-3300RI〔(株)日立制作所]
进而，自由基聚合性物质也可含有：填充剂、软化剂、促进剂、抗老化剂、着色剂、阻燃剂、触变剂、偶联剂以及酚树脂或三聚氰胺树脂、异氰酸酯类等。含有填充剂的情况下，由于可提高连接可靠性等，因而优选。填充剂的最大直径只要低于导电粒子的粒径即可使用，优选为5～60％(体积)的范围。60％(体积)以上时，可靠性提高效果便会饱和。从提高粘接性方面考虑，偶联剂优选为含有乙烯基、丙烯酸基、氨基、环氧基以及异氰酸酯基的物质。
本发明中使用的具有仲硫醇基的化合物，优选为由下述式(1)～(5)表示的化合物。
[化1]
Figure GPA00001109342400051
[化2]
Figure GPA00001109342400052
[化3]
Figure GPA00001109342400061
[化4]
Figure GPA00001109342400062
[化5]
Figure GPA00001109342400063
另外，具有仲硫醇基的化合物的优选实例，可列举出：烯丙基苯硫酚磺酸酯、苯硫酚、邻乙氧基苯硫酚、对乙氧基苯硫酚、2-苯并咪唑硫醇、邻巯基安息香酸、邻巯基安息香酸甲酯、2-苯并噻唑硫醇、仲丁硫醇、2，3-丁二硫醇、己-5-烯-3-硫醇、仲十二烷硫醇、仲庚硫醇、仲己硫醇、萘甲硫醇、巯基苯并噁唑、萘硫醇、仲十八烷硫醇、仲辛硫醇、2-甲基-2-丙硫醇、苯甲硫醇(toluenethiol)、硫代双苯硫醇、对甲氧基-甲苯硫酚等。与醇类相比而言，具有仲硫醇基的化合物由于作为链转移剂的反应性高，因而实用性优良。
具有仲硫醇基的化合物的分子量优选为90以上而低于5000，更优选为150以上而低于2000。分子量低于90的情况下，存在连接时的升温引起到达化合物的沸点因而会蒸发掉，不能赋予充分量的具有仲硫醇基的化合物以反应性的倾向。另一方面，分子量为5000以上的情况下，存在树脂的排除性恶化，连接电阻上升的倾向。
另外，具有仲硫醇基的化合物的硫醇基当量优选为50以上而低于500，更优选为120以上而低于400。硫醇当量低于50的情况下，存在交联密度降低，电路连接材料的电阻的可靠性降低的倾向。另一方面，硫醇当量为500以上的情况下，存在难以获得粘接力提高的效果。
另外，从制造时的作业性和制品的操作性方面考虑，具有仲硫醇基的化合物的分子量更优选为400以上。分子量低于400的情况下，存在在材料配合时或制品操作时的气味强，作业性和操作性降低的倾向。另一方面，分子量为400以上的情况下，气味得到抑制，不妨碍作业性·操作性。
具有仲硫醇基的化合物的添加量，相对于自由基聚合性物质100重量份，优选为1～20重量份，特别优选为2～10重量份。低于1重量份的话，就难以获得粘接力提高效果，20重量份以上的话，存在交联密度会降低，电路连接材料的电阻的可靠性会恶化的倾向。
本发明的电路连接材料可仅包含能产生游离自由基的固化剂、自由基聚合性物质和具有仲硫醇基的化合物，但是根据需要，可进一步含有以下成分。
本发明的电路连接材料可进一步含有分子内具有一个以上的氮氧基(aminoxyl)结构的化合物。本发明的电路连接材料含有具有氮氧基结构的化合物时，可进一步提高电路连接材料的保存稳定性。
另外本发明的电路连接材料可进一步含有热塑性树脂。热塑性树脂可使用：聚乙烯醇缩丁醛树脂、聚乙烯醇缩甲醛树脂、聚酰胺树脂、聚酯树脂、酚树脂、环氧树脂、苯氧基树脂、聚苯乙烯树脂、二甲苯树脂、聚氨酯树脂等。这些热塑性树脂的重均分子量，从制膜性等的观点考虑，优选为10000以上，从混合性的观点考虑，更优选为10000以上而低于1000000。热塑性树脂的重均分子量，可与自由基聚合性物质中所包含的聚合物的聚合平均分子量同样地进行测定。
另外，热塑性树脂可优选使用Tg(玻璃化转变温度)为40℃以上并且重均分子量为10000以上的含羟基的树脂(例如苯氧基树脂)。含羟基的树脂也可通过含环氧基的弹性体、自由基聚合性的官能团来改性。用自由基聚合性的官能团改性的物质由于耐热性提高，因而优选。
苯氧基树脂可通过使二官能酚类与表卤代醇进行反应至高分子量而获得，或者通过使二官能环氧树脂与二官能酚类进行加聚反应而获得。
进一步，本发明的电路连接材料中也可含有填充剂、软化剂、促进剂、抗老化剂、着色剂、阻燃剂、触变剂、偶联剂以及酚树脂、三聚氰胺树脂、异氰酸酯类等。
作为偶联剂，具有乙烯基、丙烯酸基、氨基、环氧基或异氰酸酯基中的至少一种的化合物，从提高粘接性的观点考虑是优选的。
本发明的电路连接材料，即使不含导电性粒子，也可在连接时通过使相对的电路电极直接接触来实现连接，但如果进一步含有导电性粒子，那么就可实现更稳定的连接。
导电性粒子可列举出：Au、Ag、Ni、Cu、焊料等金属粒子和碳等。另外，也可以是用Au等贵金属类将Ni等过渡金属类的表面进行被覆而成的物质。为了获得充分的适用期，表层不是Ni、Cu等过渡金属类，而优选表层为Au、Ag、铂族贵金属类，更优选采用Au。另外，导电性粒子为通过用所述导电性物质将玻璃、陶瓷、塑料等非导电性粒子的表面进行被覆等的方法，在非导电性粒子表面形成导通层，进一步用贵金属类构成最外层而成的物质，或导电性粒子为热溶融金属粒子的情况下，通过加热加压而具有变形性，因而在连接时增加了与电极的接触面积，提高了可靠性。
导电性粒子的配合量可根据用途来适宜地设定，但是相对于粘接剂树脂成分100体积份而言，通常为0.1～30体积份的范围。为防止由过剩导电性粒子引起的邻接电路的短路等，更优选为0.1～10体积份。
另外，将电路连接材料分割为2层以上，在分离成含固化剂层和含导电性粒子层的情况下，可提高适用期。
接着，说明本发明的连接结构体及其制造方法。
图1为表示连接结构体的一实施方案的概略截面图。图1中所示的连接结构体1具备：具有第一电路基板21以及形成于所述第一电路基板21的主表面21a上的第一电路电极(第一连接端子)22的第一电路部件20，具有第二电路基板31以及形成于所述第二电路基板31的主表面31a上的第二电路电极(第二连接端子)32的第二电路部件30，介于第一电路部件20和第二电路部件30之间并将它们粘接的粘接层10。将第二电路部件30与第一电路部件20相对配置，使得第二电路电极32与第一电路电极22相对。
粘接层10通过使上述本发明的电路连接材料介于第一电路部件20和第二电路部件30之间，通过在该状态下加压而形成。而且，本实施方案中表示了，通过使用具有导电性的电路连接材料来形成粘接剂层10情况下的一个实例，粘接层10由绝缘层11和分散于绝缘层11的导电性粒子7构成。绝缘层11来源于粘接剂中的除了导电性粒子以外的成分，是通过自由基聚合性化合物的自由基聚合而形成的固化体。
相对的第一电路电极22和第二电路电极32隔着导电性粒子7而电连接。另一方面，形成于同一电路基板上的第一电路电极22彼此绝缘，以及第二电路电极32彼此绝缘。
第一电路基板31和第二电路基板21可列举出半导体芯片、电阻芯片、电容器芯片等芯片零件、印刷基板等基板等。通常，电路部件上设有多个连接端子，根据情况连接端子也可以是一个。
更具体而言，可使用半导体、玻璃及陶瓷等无机材料的基板，塑料基板，或者玻璃/环氧基板。塑料基板可列举出，聚酰亚胺膜、聚碳酸酯膜及聚酯膜。第一电路电极和第二电路电极由铜等金属形成。为了获得更良好的电连接，优选第一电路电极和第二电路电极中的至少一个的表面优选为选自金、银、锡和铂族的金属。表面层选自金、银、铂族或锡中的任意一种，也可将它们组合使用。另外，也可如铜/镍/金这样将多种金属组合来制成多层构造。
另外，第一电路部件20和第二电路部件30中的一个可以为：具有作为电路基板的玻璃基板或者塑料基板，并具有由ITO等形成的连接端子的液晶显示面板。另外，第一电路部件20和第二电路部件30中的一个也可以为：具有聚酰亚胺膜作为电路基板的挠性印刷线路板(FPC)、带载封装(TCP)或者覆晶薄膜(COF)，或者具有半导体基板作为电路基板的半导体硅芯片。根据需要，可将上述各种电路部件进行适当组合来构成连接结构体。
另外，为了排除由于连接时加热所产生的挥发成分对连接的影响，对于设计有电路电极的基板而言，优选在使用电路连接材料的连接工序之前，进行预加热处理。
连接结构体1，例如，通过将第一电路部件20、膜状粘接剂及第二电路部件30，按照该顺序进行层叠以使第一连接端子22和第二连接端子32相对峙，并通过在该状态下加压或者进一步加热来形成。压力只要在不对被粘体造成损伤的范围就不受特别限制，但是一般优选为0.1～10MPa。加热温度虽然不受特别的限制，但是优选100～250℃。这些加压和加热优选在0.5秒～120秒的范围内进行，也可通过在140～200℃、3MPa、10秒的加热条件下进行粘接。
实施例
以下，基于实施例和比较例进一步具体地说明本发明，但是本发明不受以下的实施例的任何限定。
[1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮的合成]
将1，3，5-三(2-羟乙基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮120mmol(31.35g)、3-巯基丁酸(淀化学(株)制)378mmol(45.42g)、对甲苯磺酸一水合物(纯正化学(株)制)8.1mmol(1.51g)以及甲苯63g装入100ml梨形烧瓶中，安装Dean-Stark装置和冷却管。一边搅拌内容物一边在油浴温度140℃下加热并进行4小时反应。然后放置冷却，用10％碳酸氢钠水溶液100ml中和反应液。进一步用离子交换水将反应液洗净3次后，用无水硫酸镁(纯正化学(株)制)进行脱水·干燥。接着将甲苯蒸馏去除，从而获得1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮(由上述式(1)表示的具有硫醇基的化合物)。所获得的化合物为高粘度的无色透明液体。
[季戊四醇四(3-巯基丁酸酯)的合成]
将2，2-双(羟甲基)1，2-丙二醇(季戊四醇，广荣化学工业(株)制)60mmol(8.17g)，3-巯基丁酸(淀化学(株)制)252mmol(30.28g)，对甲苯磺酸一水合物(纯正化学(株)制)5.2mmol(0.98g)以及甲苯40g装入100ml梨形烧瓶中，安装Dean-Stark装置和冷却管。一边搅拌内容物一边在油浴温度140℃下加热并进行4小时反应。然后放置冷却，用10％碳酸氢钠水溶液100ml中和反应液。进一步用离子交换水将反应液洗净3次后，用无水硫酸镁(纯正化学(株)制)进行脱水·干燥。接着将甲苯蒸馏去除，从而获得季戊四醇四(3-巯基丁酸酯)(由上述式(2)表示的具有硫醇基的化合物)。所获得的化合物为高粘度的无色透明液体。
[实施例1]
配合下述物质：将作为热塑性树脂的双酚A·F共聚合型苯氧基树脂(ZX-1356-2，东都化成制)溶解于甲苯/醋酸乙酯＝50/50的混合溶剂而获得的40％(重量)溶液87.5重量份(按照固体成分换算为35重量份)、将聚氨酯树脂(T-6075N，DIC Bayer Polymer(株)制)溶解于甲乙酮而获得的15％(重量)溶液100重量份(按照固体成分换算为15重量份)、将苯乙烯-马来酸酐共聚物(D-250，Nova Chemicals Japan(株)制)溶解于甲苯而获得的20％(重量)溶液25重量份(按照固体成分换算为5重量份)、作为自由基聚合性物质的、氨酯丙烯酸酯低聚物(UA5500T，新中村化学制)的甲苯溶解品70％(重量)溶液42.86重量份(按照不挥发成分换算为30重量份)、二环戊二烯型二丙烯酸酯(DCP-A，东亚合成制)15重量份、2-甲基丙烯酰氧基乙基酸式磷酸酯(P-2M，共荣社化学制)3重量份、作为具有仲硫醇基的化合物的1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮(分子量567.7)2重量份、以及作为产生游离自由基的固化剂的2，5-二甲基-2，5-二(2-乙基己酰)己烷(PERHEXA 25O，日本油脂(株)制)4重量份(PERHEXA 25O为50％溶液，2，5-二甲基-2，5-二(2-乙基己酰)己烷的实际配合量为8重量份)，进而，配合具有带刺栗壳状(毬栗状，chestnut in itsburr)的表面形状的平均粒径为2～3.3μm的Ni粉体5重量份。通过涂布器将该混合溶液涂布于PET薄膜上，通过70℃的10分钟的热风干燥，从而获得粘接剂层的厚度为35μm的电路连接材料。
[实施例2]
除了使用季戊四醇四(3-巯基丁酸酯)(分子量：544.77)2重量份来替代1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮以外，与实施例1同样地获得电路连接材料。
[实施例3]
除了将1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮(分子量567.7)的使用量设为3重量份以外，与实施例1同样地获得电路连接材料。
[比较例1]
除了不使用具有仲硫醇基的化合物以外，与实施例1同样地获得电路连接材料。
[比较例2]
除了使用作为具有伯硫醇基的化合物的三[(3-巯基丙酰氧基)-乙基]异氰尿酸酯(TEMPIC，分子量：525.62，堺化学工业(株)制)2重量份来代替1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮以外，与实施例1同样地获得电路连接材料。
[比较例3]
除了使用作为具有伯硫醇基的化合物的季戊四醇四(3-巯基丙酸酯)(PEMP，分子量：488.66，堺化学工业(株)制)2重量份来代替1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮以外，与实施例1同样地获得电路连接材料。
[比较例4]
除了使用作为具有叔硫醇基的化合物的乙二醇双(2-巯基异丁酸酯)(EGMIB，依照日本特开2004-149755号公报中记载的合成法来合成，分子量：266.38)2重量份来代替1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮以外，与实施例1同样地获得电路连接材料。
[比较例5]
除了使用作为二硫化物化合物的二苯基二硫化物(住友精化(株)制，分子量：218.34)2重量份来代替1，3，5-三(3-巯基丁酰乙基)-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮以外，与实施例1同样地获得电路连接材料。
[连接结构体的制作(COF与PWB的连接)]
通过使用实施例1～3以及比较例1～5的各电路连接材料，以120℃、2MPa、10秒、宽度2.0mm将挠性电路板(COF-TEG)与玻璃环氧多层印刷线路板(PWB-TEG)进行连接，所述挠性电路板为具有直接形成于厚度为38μm的聚酰亚胺上的线宽为100μm，间距为200μm，厚度为8μm的铜电路的挠性电路板，所述玻璃环氧多层印刷线路板为形成有线宽为100μm、间距为200μm、厚度为35μm的铜电路。此时，将电路连接材料的粘接面贴附于玻璃环氧多层印刷线路板上后，以70℃、1Mpa、3秒进行加热加压而临时连接，其后，将PET膜剥离而与COF-TEG连接。在上述工序中，根据有无气味，对各电路连接材料的作业性和操作性进行了评价。所获得的结果列于表1。
[粘接强度的测定]
对于已制作完的电路部件的连接结构，以剥离速度50mm/min测定了在90°下剥离时的粘接强度。分别对初期的电路连接材料以及40℃下处理5日后的电路连接材料进行了测定。所获得的结果列于表1。
[连接电阻的测定]
连接电路后，对含有上述连接部的FPC-PWB的邻接电路间的电阻值，采用万用表进行测定初期以及在将电路连接材料于40℃下处理5日后的值。电阻值设为邻接电路间的电阻值150点的x+3σ。相比于初期电阻而言，40℃下处理5日后的电阻的上升倍率为1.2倍以内时，为保存稳定性良好的水平。所获得的结果列于表1。
[表1]
如表1所示，在实施例1～3中，初期以及在40℃下处理5日后的结果都可实现粘接力和电阻的兼顾。另一方面，在比较例1、4、5的情况下，初期的粘接力低。而且，可以认为比较例4、5的粘接力低的原因在于：叔硫醇或二苯基二硫化物的立体阻碍大，缺乏作为链转移剂的反应性。另外，比较例2、3中：在40℃下处理5日后的电阻值的上升倍率超过了1.2倍，结果是保存稳定性差。

Claims (4)

1.电路连接材料，用于将在第一基板的主表面上形成有第一电路电极的第一电路部件与在第二基板的主表面上形成有第二电路电极的第二电路部件在使所述第一电路电极和所述第二电路电极呈相对配置的状态下进行连接；所述电路连接材料含有能产生游离自由基的固化剂、自由基聚合性物质和具有仲硫醇基的化合物。
2.权利要求1记载的电路连接材料，所述具有仲硫醇基的化合物的分子量为400以上。
3.连接结构体，其具备：
在第一基板的主表面上形成有第一电路电极的第一电路部件、
在第二基板的主表面上形成有第二电路电极并且按照使所述第二电路电极与所述第一电路电极相对的方式配置的第二电路部件、
设置于所述第一电路部件和所述第二电路部件之间，将所述第一电路部件和所述第二电路部件电连接的粘接层；
所述粘接层通过使权利要求1或2中记载的电路连接材料介于所述第一电路部件和所述第二电路部件之间、在该状态下进行加压而形成。
4.连接结构体的制造方法，其具备如下所述工序：
将在第一基板的主表面上形成有第一电路电极的第一电路部件与在第二基板的主表面上形成有第二电路电极的第二电路部件按照使所述第一电路电极和所述第二电路电极相对的方式配置，使权利要求1或2记载的电路连接材料介于所述第一电路部件和所述第二电路部件之间，在该状态下进行加压，从而将所述第一电路电极和所述第二电路电极电连接。
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