CN101821347A - 粘合薄膜、连接方法及接合体 - Google Patents

粘合薄膜、连接方法及接合体 Download PDF

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Publication number
CN101821347A
CN101821347A CN200880100418A CN200880100418A CN101821347A CN 101821347 A CN101821347 A CN 101821347A CN 200880100418 A CN200880100418 A CN 200880100418A CN 200880100418 A CN200880100418 A CN 200880100418A CN 101821347 A CN101821347 A CN 101821347A
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binder layer
resinous principle
substrate
transition temperature
order transition
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CN200880100418A
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CN101821347B (zh
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石松朋之
大关裕树
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Dexerials Corp
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Sony Chemical and Information Device Corp
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    • 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

本发明的目的为提供一种能够不引起短路地将电子部件连接到基板上的粘合薄膜、连接方法及接合体。本发明的粘合薄膜，包括：分散有导电性粒子的第一粘合剂层和粘附于所述第一粘合剂层的第二粘合剂层，所述第一粘合剂层和所述第二粘合剂层分别含有副树脂成分，其特征在于，所述第一粘合剂层中含有玻璃化转变温度高于所述副树脂成分的第一主树脂成分，所述第二粘合剂层中含有玻璃化转变温度高于所述副树脂成分且玻璃化转变温度低于所述第一主树脂成分的第二主树脂成分，所述第一粘合剂层和所述第二粘合剂层升温过程中，所述第一粘合剂层和所述第二粘合剂层的反应放热峰温度，低于所述第一主树脂成分的玻璃化转变温度且高于所述第二主树脂成分的玻璃化转变温度。

Description

粘合薄膜、连接方法及接合体
技术领域
本发明涉及用于连接电子部件的粘合薄膜、连接方法及接合体。
背景技术
一直以来，将电子部件或线路板连接到基板上时都使用各向异导电性粘合剂。各向异导电性粘合剂含有粘结剂和分散于粘结剂中的导电性粒子。
在基板的配置有端子的面与电子部件的配置有端子的面之间，配置各向异导电性粘合剂，进行热挤压时，被软化的粘结剂从基板端子与电子部件端子之间被挤出，导电性粒子被夹持在基板端子与电子部件端子之间，从而电性连接基板和电子部件。
但是，当粘结剂被挤出时，一部分导电性粒子也会随着粘结剂一起被挤出，被挤出的导电性粒子将会流入基板上的邻接端子之间，或者流入电子部件的邻接端子之间，从而邻接的端子之间由于导电性粒子而发生短路(Short)。
同时，随着导电性粒子从基板端子与电子部件端子之间被挤出，被基板端子和电子部件端子所夹持的导电性粒子数也变少，导通可靠性也随其变低。
专利文献1：日本专利特开2006-32335号公报
专利文献2：日本专利特开平7-230840号公报
发明内容
本发明的课题为，解决上述现有诸问题，实现如下目的：
即，本发明的目的为，提供一种能够不引起短路(Short)地将电子部件连接到基板上的粘合薄膜、连接方法及接合体。
解决上述课题的方案为如下所示：即，
<1>一种粘合薄膜，包括：第一粘合剂层和粘附于所述第一粘合剂层的第二粘合剂层，并且，所述第一粘合剂层中分散有导电性粒子，所述第一粘合剂层和所述第二粘合剂层分别含有副树脂成分，对所述第一粘合剂层和所述第二粘合剂层进行升温，则所述第一粘合剂层和所述第二粘合剂层中的所述副树脂成分发生反应，使所述第一粘合剂层和所述第二粘合剂层固化，其特征在于，所述第一粘合剂层中含有玻璃化转变温度高于所述副树脂成分的第一主树脂成分，所述第二粘合剂层中含有玻璃化转变温度高于所述副树脂成分且玻璃化转变温度低于所述第一主树脂成分的第二主树脂成分；在所述第一粘合剂层和所述第二粘合剂层升温过程中，所述第一粘合剂层和所述第二粘合剂层的放热量最大的反应放热峰温度，低于所述第一主树脂成分的玻璃化转变温度且高于所述第二主树脂成分的玻璃化转变温度。
<2>如<1>所述的粘合薄膜，第一粘合剂层的膜厚为导电性粒子平均粒径的0.5倍以上2.0倍以下。
<3><1>至<2>中任一项所述的粘合薄膜，第二主树脂成分的玻璃化转变温度为50℃以上110℃以下。
<4><1>至<3>中任一项所述的粘合薄膜，第一粘合剂层反应放热峰温度与第二粘合剂层反应放热峰温度之差为10℃以下。
<5>一种连接方法，其特征在于，隔着<1>至<4>中的任意一项所述粘合薄膜使第一基板的电极和第二基板的电极对峙，通过热挤压所述第一基板和所述第二基板，将所述粘合薄膜中的导电性粒子夹持于所述第一基板的电极和所述第二基板的电极之间，从而连接所述第一基板和所述第二基板。
<6>一种接合体，其特征在于，具备使用<5>所述的连接方法进行连接的第一基板和第二基板。
根据本发明，则能解决上述现有的诸问题，实现上述目的，能够提供不引起短路(Short)地将电子部件连接到基板上的粘合薄膜、连接方法及接合体。
本发明具有如上的结构，副树脂成分为加热则发生聚合的树脂(例如热固化性树脂)。
对所述第一粘合剂层和所述第二粘合剂层进行升温，则副树脂成分将在第一粘合剂层和第二粘合剂层中发生反应。副树脂成分的反应具体为，副树脂成分单独进行聚合，或与固化剂等其它成分进行反应后单独聚合或共聚。无论是哪种情况，第一粘合剂层和第二粘合剂层都会发热。该发热量随着温度越高越增大，但超过一定温度之后反而会减少。
本发明中，对分散导电性粒子状态的第一粘合剂层进行升温时，发热量从增加变为减少的温度称为第一粘合剂层的反应放热峰温度，对第二粘合剂层进行升温时，发热量从增加变为减少的温度称为第二粘合剂层的反应放热峰温度。发热量和反应放热峰温度例如可通过DSC(差示扫描量热法)来测定。
第一粘合剂层是通过以玻璃化转变温度高于第一粘合剂层及第二粘合剂层的反应放热峰温度的第一主树脂成分为原料，将该原料与其它原料(副树脂成分和添加剂)一起混合于溶剂中制造原料液，将该原料液涂布在剥离薄膜表面形成涂布层之后，对该原料液进行干燥去除多余的溶剂而形成。
第二粘合剂层，是通过以玻璃化转变温度低于第一主树脂成分玻璃化转变温度且低于第一粘合剂层及第二粘合剂层的反应放热峰温度的第二主树脂成分为原料，将该原料与其它原料(副树脂成分和添加剂)一起混合于溶剂中制造原料液，涂至剥离薄膜表面上形成涂布层之后，对该原料液进行干燥去除多余的溶剂而形成。
第一主树脂成分及第二主树脂成分是玻璃化转变温度(Tg)高于常温(30℃)(30℃以上，优选50℃以上)的高分子物质，化学性稳定。
因此，第一主树脂成分的玻璃化转变温度，无论是在作为原料被混合到溶剂中之前，还是在混合和干燥后存在于第一粘合剂层中的状态下，均高于第一粘合剂层及第二粘合剂层的反应放热峰温度。
同时，第二主树脂成分的玻璃化转变温度，无论是在作为原料混合到溶剂中之前，还是在混合和干燥后存在于第二粘合剂层中的状态下，均低于第一主树脂成分的玻璃化转变温度且低于第一粘合剂层及第二粘合剂层的反应放热峰温度。
第一主树脂成分及第二主树脂成分的玻璃化转变温度相同时，第一粘合剂层及第二粘合剂层几乎同时开始溶融。但是，在本发明中因第一主树脂成分的玻璃化转变温度高于第二主树脂成分的玻璃化转变温度，所以第一粘合剂层及第二粘合剂层开始溶融的温度不同，在第二粘合剂层溶融的温度下，第一粘合剂层将不会溶融。
将粘合薄膜挟持在端子之间加热挤压时，即使第二粘合剂层发生溶融而从端子间被挤出，第一粘合剂层仍因不溶融而存留，所以在第一粘合剂层中分散的导电性粒子不会从端子间流出，而残留于第一粘合剂层中。
由于导电性粒子不从对峙的端子间被挤出，残留于第一粘合剂层之中，所以能增加被捕捉到对峙端子间的导电性粒子数。同时，在邻接的端子间将不会流入导电性粒子，所以在该邻接端子间不发生导电性粒子短路(short)。因此，用本发明的粘合薄膜将电子部件连接到基板上的接合体有很高的导通可靠性。
附图说明
图1A为用于说明本发明粘合薄膜制造工序的剖面图(其1)。
图1B为用于说明本发明粘合薄膜制造工序的剖面图(其2)。
图1c为用于说明本发明粘合薄膜制造工序的剖面图(其3)。
图2A为用于说明将电子部件连接到基板的工序的剖面图(其1)。
图2B为用于说明将电子部件连接到基板的工序的剖面图(其2)。
图2C为用于说明将电子部件连接到基板的工序的剖面图(其3)。
图2D为用于说明将电子部件连接到基板的工序的剖面图。
图3为用于说明电子部件被连接到基板上的状态的剖面图。
图4为表示卷绕粘合薄膜的卷筒。
图5为表示第一主树脂成分和第二主树脂成分，以及第一粘合剂层和第二粘合剂层的DSC曲线的图。
具体实施方式
(粘合薄膜)
本发明的粘合薄膜，至少有相互粘附的第一粘合剂层及第二粘合剂层，并且还包括根据需要适宜选择的其它层。
<第一粘合剂层>
上述第一粘合剂层，至少包括导电性粒子、副树脂成分、以及第一主树脂成分，还包括根据需要适宜选择的其它成分。
-导电性粒子-
对于上述导电性粒子，只要是被分散于上述第一粘合剂层中，则无特别限制，可根据目的适宜选择。
具体有以镍、铜和钴等金属作为主要成分的金属粒子，或在上述金属粒子表面上进一步实施了镀金的粒子，或在有机微粒子表面上实施了镀镍、镀铜，镀金和镀焊料等的导电性镀膜的粒子。
对于上述导电性粒子，可向第一粘合剂层中分散单独的一种，也可向同一个第一粘合剂层分散两种以上。被粘合体(电子部件和基板)的连接端子表面容易氧化的情况时，可以向导电性粒子表面设置镍等突起物后使用。
另外，为了与上述连接端子的精细节距对应，可以使用在上述导电性粒子表面涂层了热溶融树脂的绝缘性镀膜粒子。
上述导电性粒子的粒径(平均粒径)，将根据连接端子的节距及面积选择使用，但是，本发明中优选为平均粒径在1μm以上50μm以下。上述导电性粒子的平均粒径比1μm小的情况下，容易引起凝集，反而会引起短路。
并且，上述导电性粒子的平均粒径大于50μm时，无需使用以精细节距连接为主目的的粘合薄膜，本发明的效果将变得不明显。
-副树脂成分-
对于上述副树脂成分无特别限制，可根据目的适宜选择，例如有液态树脂及结晶性树脂等。
上述副树脂成分是玻璃化转变温度低于后述第一主树脂成分及第二主树脂成分的玻璃化转变温度的，在规定的固化温度以上时发生聚合的树脂，对粘合剂层赋予固化性。
上述液态树脂是玻璃化转变温度低于常温(30℃)的，常温(30℃)下为液体，被加热到高于常温(30℃)的规定固化温度以上时发生聚合的树脂。其聚合物在常温(30℃)下为固体。
上述结晶性树脂，虽然在常温(30℃)下为固体(结晶)，但只要被加热到高于常温(30℃)的规定溶融温度进行溶融之后，在回到常温(30℃)时将是液态的树脂。溶融之后的结晶性树脂被加热到规定的固化开始温度以上时发生聚合。其聚合物在常温(30℃)下为固体。
作为上述结晶性树脂，可例举的具体物质有，环氧树脂、丙烯酸酯、甲基丙烯酸酯、硅烷偶联剂、密胺树脂和酚醛树脂等。
上述第一粘合剂层及后述的第二粘合剂层，可以含有同样种类的副树脂成分，也可以含有不同种类的副树脂成分，但是，为了提高第一粘合剂层及第二粘合剂层的粘附性，优选含有同样种类的副树脂成分。
-第一主树脂成分-
对于第一主树脂成分，只要是其玻璃化转变温度高于上述副树脂成分，则无特别限制，可根据目的适宜选择。例如有，酚氧树脂、聚氨酯树脂、饱和聚酯、丙烯酸橡胶、NBR橡胶、聚丁二烯橡胶、聚苯乙烯、聚乙烯、聚醋酸乙烯树脂及其共聚物等。这些树脂为热塑性树脂。
上述第一主树脂成分，是在常温(30℃)下为固体的固态树脂。即，第一主树脂成分的玻璃化转变温度高于常温(30℃)。
上述第一主树脂成分作为用于制成薄板状的膜成分，起着重要的作用。
上述第一主树脂成分是以玻璃化转变温度为界线在固态和液态之间进行变化的树脂，只要其玻璃化转变温度高于常温(30℃)，则并不局限于热塑性树脂，例如，可使用玻璃化转变温度低于聚合开始温度且高于常温(30℃)的热固化性树脂。作为上述热固化性树脂可以例举主骨骼末端结合了环氧基的高分子环氧树脂，或者对末端环氧基进行丙烯化的环氧丙烯酸酯等。作为上述第一主树脂成分使用的热固化性树脂，其分子量高于作为副树脂成分使用的热固化性树脂。
-其它成分-
对于上述其它成分无特别限制，可根据目的适宜选择，如无机填充物、有机填充物等。
<第二粘合剂层>
上述第二粘合剂层，至少含有副树脂成分及第二主树脂成分，还含有根据目的适宜选择的其它成分。并且，上述第二粘合剂层中的副树脂成分如同上述第一粘合剂层中所记载。
-第二主树脂成分-
对于第二主树脂成分，只要其玻璃化转变温度高于上述副树脂成分且低于上述第一主树脂成分的玻璃化转变温度，则无特别限制，可根据目的适宜选择。例如，酚氧树脂、聚氨酯树脂、饱和聚酯、丙烯酸橡胶、NBR橡胶、聚丁二烯橡胶、聚苯乙烯、聚乙烯、聚醋酸乙烯树脂及其聚合物等。这些的树脂为热塑性树脂。
上述第二主树脂成分是在常温(30℃)下为固体的固态树脂。即，第二主树脂成分的玻璃化转变温度高于常温(30℃)。
上述第二主树脂成分作为用于制成薄板状的膜成分起着重要的作用。
上述第二主树脂成分以玻璃化转变温度为界线在固体和液体之间进行变化的树脂，只要玻璃化转变温度高于常温(30℃)，则并不局限于热塑性树脂，例如，可以使用玻璃化转变温度低于聚合开始温度且高于常温(30℃)的热固化性树脂。作为上述热固化性树脂可以例举主骨骼末端结合了环氧基的高分子环氧树脂，或者对末端环氧基进行丙烯化的环氧丙烯酸酯等。作为上述第一主树脂成分使用的热固化性树脂，其分子量高于作为副树脂成分使用的热固化性树脂。
上述第一粘合剂层及上述第二粘合剂层中可以各自含有上述第一主树脂成分及上述第二主树脂成分的一种，也可以在第一粘合剂层及上述第二粘合剂层中各自含有二种以上。
作为上述第一主树脂成分及上述第二主树脂成分，可以使用相同种类的树脂，也可以用不同种类的树脂。如果作为第一主树脂成分及上述第二主树脂成分，使用同种类的树脂时，只要以比上述第二主树脂成分的分子量高的树脂作为上述第一主树脂成分，则上述第一主树脂成分的玻璃化转变温度将会高于上述第二主树脂成分的玻璃化转变温度。
上述第一主树脂成分，使用玻璃化转变温度高于第一反应放热峰温度(第一粘合剂层的反应放热峰温度)以及第二反应放热峰温度(第二粘合剂层的反应放热峰温度)的物质。
与此相对，作为上述第二主树脂成分使用玻璃化转变温度低于上述第一主树脂成分的玻璃化转变温度且低于第一反应放热峰温度及第二反应放热峰温度的物质。
上述反应放热峰温度是指，在进行差示扫描量热法(DSC)时，所得DSC曲线的发热峰成为最大的温度。
上述第一反应放热峰温度及上述第二反应放热峰温度优选为，各自在60℃以上140℃以下的范围。
上述第一反应放热峰温度及上述第二反应放热峰温度低于60℃时，将粘合薄膜临时固定到基板等被粘接体上时，存在上述第一粘合剂层及上述第二粘合剂层开始发生反应的可能性，所以不优选。
并且，上述第一反应放热峰温度及上述第二反应放热峰温度高于140℃时，在利用两个被粘接体挟持粘合薄膜并进行热挤压的主压接工序中，使上述第一粘合剂层及上述第二粘合剂层固化所需要的时间将超过20秒，无法进行短时间内的连接，从而降低批量生产性。而且，就算在20秒以下的短时间内能够完成连接，但是这种情况下，连接只能在250℃以上的高温下进行，因此会对被粘接体带来巨大的损坏，所以并不优选。
若上述第一反应放热峰温度和上述第二反应放热峰温度的差超过10℃，则上述第一粘合剂层及上述第二粘合剂层中的，反应放热峰温度低的一方先发生固化，从而不仅在主压接工序中对压入速度造成限制，且连接完成时间上也会产生差，所以不易实现短时间内的连接，缺乏实用性。
作为上述第一主树脂成分及上述第二主树脂成分，使用玻璃化转变温度在30℃以下的物质时，把粘合薄膜制成卷状产品，放置在常温(30℃)以上的环境时容易发生粘合剂的泄露，成为堵塞(无法拉出)的原因，所以不优选。
-其它成分-
对于其它成分无特别限制，可根据目的适宜选择，例如，导电性粒子、无机填充物、有机填充物等。
<其它的层>
对于其它的层也无特别限制，可根据目的适宜选择。
在此，参照附图，详细说明本发明的粘合薄膜的制造工序的一个例子。
混合副树脂成分、第一主树脂成分、导电性粒子、偶联剂或固化剂等的添加剂和溶剂，制造第一原料液。
混合副树脂成分、比第一主树脂成分玻璃化转变温度低的第二的主树脂成分、偶联剂或固化剂等的添加剂和溶剂，制造第二原料液。
为了促进在上述第一粘合剂层及第二粘合剂层中的副树脂成分的聚合反应，优选使第一原料液及第二原料液分别含有固化剂。
对于上述固化剂，只要能热固化上述第一粘合剂层及上述第二粘合剂层的副树脂成分，则无特别限制，可根据目的适宜选择。例如，聚胺、聚酰胺、咪唑、对它们进行微胶囊化的胺系固化剂、鎓盐或鋶鎓盐等的阳离子系固化剂，有机化氧化物等的游离基引发剂，酸酐，和硫醇系固化剂等。
上述固化剂可单独向第一原料液及第二原料液添加，也可以向第一原料液及第二原料液添加两种以上。
并且，优选为，以上述第一反应放热峰温度及上述第二反应放热峰温度的差成为10℃以下的方式，对第一主树脂成分、第二主树脂成分、副树脂成分和固化剂进行组合，制造原料液。
图1A和图1B中，在剥离薄膜21和剥离薄膜22表面上分别涂布第一原料液及第二原料液，形成涂布层之后，干燥涂布层去除多余的溶剂，形成薄膜状的第一粘合剂层11及第二粘合剂层12。
如上所述，由于第一原料液含有导电性粒子15，所以在图1A中，第一粘合剂层11中分散有导电性粒子15。同时，第二粘合剂层12中没有分散导电性粒子15，即使分散，其粒子密度也小于第一粘合剂层11。
通过对第一粘合剂层11及第二粘合剂层12的无剥离薄膜的面相互进行粘附，用挤压滚筒等进行挤压，使第一粘合剂层11和第二粘合剂层12粘贴，由此得到本发明的粘合薄膜10(图1C)。
并且，粘合薄膜10的制造方法，并不局限于对第一粘合剂层11和第二粘合剂层12进行粘贴，也可以在薄膜状第一粘合剂层11的表面涂布第二原料液之后，进行干燥，形成第二粘合剂层12。也可以在薄膜状第二粘合剂层12的表面涂布第一原料液之后，进行干燥，形成第一粘合剂层11。
以第一粘合剂层11及第二粘合剂层12的表面中的任意一方，或双方上，粘贴剥离薄膜21及剥离薄膜22的状态，对粘合薄膜10进行卷绕，就可以得到粘合薄膜10的卷筒18(图4)。
当第一粘合剂层11及第二粘合剂层12发生软化时，软化了的部分将露出，粘合薄膜10彼此发生粘合，从而变得无法从卷筒18拉出粘合薄膜10(堵塞)。
若作为第一主树脂成分及第二主树脂成分使用玻璃化转变温度在30℃以上的物质，则在常温(30℃)下第一粘合剂层11及第二粘合剂层12不软化、不溶融，即使在常温(30℃)下长期保存卷筒18也不会发生堵塞，卷筒18的保存时间将变长。
下面，对使用本发明的粘合薄膜10，将电子部件连接到基板上的工序的一个例子进行说明。
对于用本发明的粘合薄膜10进行连接的被粘合体，无特别限制，例如，作为电子部件4(第二基板)，除了半导体芯片以外，还可以是电阻元件、COF(Chip On Film)设备、TAB(Tape Automated Bonding)设备等。
作为基板3(第一基板)，并不只局限于玻璃基板，还可以是刚性线路板，挠性线路板等。
图2A中，作为被粘合体的基板3(LCD面板等)具有，在如玻璃板的基板本体31和基板本体31表面上，相隔规定间隔地被配置的多个第一端子35(电极)。
从第一粘合剂层11剥离剥离薄膜21，露出第一粘合剂层11的表面，将粘合薄膜10的露出第一粘合剂层11的表面，与基板3的露出第一端子35的表面相互粘附，进行临时粘贴(图2B)。
若第二粘合剂层12上粘附有剥离薄膜22时，在临时粘贴之前，或在临时粘贴之后，剥离剥离薄膜22，使第二粘合剂层12的表面露出。
图2C的基板3上连接的电子部件4，是平面形状小于基板3的电子部件，电子部件4具有部件本体41和被配置在部件本体41一面上的多个第二端子45(电极)。
各第一端子35的中心位置之间的距离(节距)和各第二端子45的中心位置之间的距离(凸块间的空间)相等，以第二端子45分别位于各第一端子35的正上方的位置的方式，对电子部件4进行定位，如图2D所示地，将电子部件4的配置有第二端子45的一侧面粘附于第二粘合剂层12的表面上，进行临时固定。
第一粘合剂层11及第二粘合剂层12的反应放热峰温度，均低于第一主树脂成分的玻璃化转变温度且高于第二主树脂成分的玻璃化转变温度。
将加热装置51升温至高于第一主树脂成分的玻璃化转变温度的温度，然后将该加热装置51按压到被临时固定的基板3和电子部件4的任意一方上或双方上(图2D)。
第一粘合剂层11及第二粘合剂层12，因热传导慢慢升温，首先达到第二主树脂成分的玻璃化转变温度，第二粘合剂层12开始溶融，通过挤压，第二端子45的前端将挤退溶融的第二粘合剂层12。
被挤退的第二粘合剂层12虽然流入邻接的第二端子45之间，但因第二粘合剂层12中没有分散导电性粒子，所以邻接的第二端子45之间不会发生短路(short)。
第一主树脂成分的玻璃化转变温度因高于第二主树脂成分的玻璃化转变温度，所以第一粘合剂层11不溶融，第一粘合剂层11不会从第一端子35和第二端子45之间流出。因此，导电性粒子15不会从第一端子35和第二端子45之间流出，而残留在第一粘合剂层11中。
在第一粘合剂层11及第二粘合剂层12达到反应放热峰温度之前，从第二端子45的前端挤退第二粘合剂层12，使其前端与第一粘合剂层11接触并进行进一步的挤压(图3)。
第一粘合剂层11，在第二主树脂成分的玻璃化转变温度以上、反应放热峰温度以下的温度范围内，不溶融，不固化，虽然没有流动性，但可以弹性变形。
第一粘合剂层11的膜厚变成较薄的、导电性粒子15平均粒径的0.5倍以上2.0倍以下的程度，在第二端子45与第一粘合剂层11接触的状态下进行进一步的加热挤压时，第一粘合剂层11将发生弹性变形，第一端子35与第二端子45将夹持导电性粒子15，被电性连接。
导电性粒子15之间至少存在第一粘合剂层11，第一端子35及第二端子45的前端，不仅与导电性粒子15，还与第一粘合剂层11接触。
继续加热挤压，在第一端子35与第二端子45之间挟持导电性粒子15之后，将第一粘合剂层11及第二粘合剂层12升温至反应放热峰温度，进行第一粘合剂层11及第二粘合剂层12的副树脂成分的聚合反应，固化第一粘合剂层11及第二粘合剂层12，第一端子35及第二端子45的前端因固化了的第一粘合剂层11被固定。
并且，因挤压而流入第二端子45之间的第二粘合剂层12，以与第二端子45的周围，和互相邻接的第二端子45间露出的部件本体41粘附的状态进行固化。
第一粘合剂层11，在加热挤压时不会从第一端子35与第二端子45之间流出，而是发生变形，以与互相邻接的第一端子35间的基板本体31粘附的状态进行固化。因此，不仅是第一端子35及第二端子45的前端，其周围的部分也被固化了的第一粘合剂层11及第二粘合剂层12所固定，使电子部件4机械性地被连接到基板3上。
并且，第一粘合剂层11只要发生固化，则达到第一主树脂成分的玻璃化转变温度也不会发生溶融。即，第一粘合剂层11不论在固化之前还是固化之后均不溶融，导电性粒子15不会从第一端子35上流出，所以第一端子35和第二端子45之间的导电性粒子15仍以高密度的状态被维持，而邻接的第一端子35之间的导电性粒子15的密度不会变高。所以，用本发明的粘合薄膜10进行连接的电子部件4和基板3的连接可靠性高。
若以邻接端子间形成的凹部的深度作为端子的高度，则与第一粘合剂层11粘附一侧的被粘合体(如基板3)的第一端子35的高度低于，与第二粘合剂层12粘附一侧的被粘合体(如电子部件4)的第二端子45的高度，若在临时固定后或在主压接后，使邻接的第一端子35间的凹部底面与第一粘合剂层11接触，则第一粘合剂层11和被粘合体的接触面积将变大，增加接合体的机械强度。
下面，根据实施例及对比例，对本发明进行具体的说明，但本发明并不局限于下列实施例。
将主树脂成分溶解于以1∶1混合甲苯及乙酸乙酯的混合溶媒中，获取含有30重量％固形成分(主树脂成分)的溶液。
向各溶液，以下表1中所记载的配比(重量比)混合副树脂成分、导电性粒子和偶联剂，配制了各4种的第一原料液及第二原料液。
将各第一原料液及第二原料液涂布到剥离薄膜21和剥离薄膜22上，在60℃下干燥10分钟，制造了第一粘合剂层A1～A4及第二粘合剂层N1～N4。
在表1中表示第一粘合剂层A1～A4和第二粘合剂层N1～N4的原料液中所用的固形成分的配比。
表1：第一、第二粘合剂层的组成
Figure GPA00001009072100151
其中，在上述表1的玻璃化转变温度(Tg点)栏中的「-」表示室温下呈液态。
固化剂(旭化成化学(株)制，商品名「HX3941HP」)是对胺系固化剂进行了微胶囊化的微胶囊型胺系环氧固化剂。副树脂成分(日本环氧树脂(株)制，商品名「EP828」)是双酚A型液态环氧树脂，常温(30℃)下为液态的热固化性树脂。
主树脂成分中，商品名「YP70」是玻璃化转变温度(Tg点)为84℃、分子量为5.5万的东都化成社制酚氧树脂；商品名「YDF2001」是玻璃化转变温度(Tg点)为54℃的东都化成社制固态双酚F环氧树脂；商品名「FX293」是玻璃化转变温度(Tg点)为163℃、分子量为4.5万的东都化成社制酚氧树脂；商品名「EP4250」是玻璃化转变温度(Tg点)为108℃、分子量为6万的日本环氧树脂(株)公司制酚氧树脂；商品名「SG708-6T」是玻璃化转变温度(Tg点)为-8℃、分子量为50万的固形成分15％(甲苯/乙酸乙酯＝1/1)Nagase ChemteX(株)公司制丙烯酸橡胶。
商品名「KBE403」是信越化学工业(株)公司制环氧硅烷。
商品名「AUL704」是积水化学工业(株)公司制镀Ni/Au树脂粒子(平均粒径4μm)。
用TAInstruments公司制的DSC Q100，第一粘合剂层11及第二粘合剂层12的升温速度为10℃/分钟的条件下，对各第一粘合剂层A1～A4及第二粘合剂层N1～N4进行了DSC测量，测定反应放热峰温度。图5表示所得第一粘合剂层A4的DSC曲线、主树脂成分(商品名「YP70」和商品名「FX293」)的DSC曲线。
图5的横轴表示温度，纵轴表示热流量。图5中，第一粘合剂层A4的DSC曲线为Ld，商品名「FX293」的DSC曲线为La，商品名「YP70」的DSC曲线为Lb。
图5中，第一粘合剂层A4在121℃时热流量最大，即，副树脂成分的聚合反应所引起的发热量变成最大，表示第一粘合剂层A4的反应放热峰温度为121℃。
并且，「FX293」的DSC曲线La和「YP70」的DSC曲线Lb，在163℃和84℃时，由于溶融吸热而热流量变低，表示「FX293」和「YP70」的玻璃化转变温度分别为163℃和84℃。
接着，对第一粘合剂层A1～A4和第二粘合剂层N1～N4进行如下表2所示的组合，用橡胶辊加工粘合，获得膜厚20μm的实施例X4、Y1～Y3及对比例X1～X3的粘合薄膜10。
表2：第一、第二粘合剂层的组合
对实施例X4、Y1～Y3及对比例X1～X3的粘合薄膜10进行光学显微镜观察，测量每1mm2当中的导电性粒子密度的结果，如上述表2所示，各粘合薄膜10的导电性粒子密度相同。
接着，使用实施例X4、Y1～Y3及对比例X1～X3的粘合薄膜10，在下述的组装工序中，进行了电子部件(IC芯片)和基板的连接。
<组装工序>
作为评价基材准备了评价试验用IC芯片(材质：硅，平面积1.8mm×20mm，厚：0.5mm，金凸块，凸块高度：15μm，凸块面积：20μm×85μm，凸块间空间10μm，凸块中心间距离(节距)：30μm)和评价试验用ITO布线玻璃基板(基板本体：Corning公司、产品名称「1737F」，玻璃尺寸：50mm×30mm×0.7mm，ITO接点(端子)尺寸20μm×85μm，接点中心间距离(节距)：30μm)。
将剪切成纵2.0mm×横25mm长方形状的对比例X1～X3及实施例X4、Y1～Y3的粘合薄膜10，通过膜厚70μm的聚四氟乙烯(テフロン：注册商标)缓冲材料，用临时压接机(工具尺寸2.0mm×50mm)进行挤压并临时粘贴于ITO布线玻璃基板上。临时粘贴条件：临时压接机温度为80℃，临时压接机的挤压力为1MPa，时间为2秒。
从各粘合薄膜10剥下剥离薄膜21及剥离薄膜22之后，调准IC芯片后搭载于粘合薄膜10，临时固定到玻璃基板上。
接着，通过膜厚50μm的聚四氟乙烯(テフロン：注册商标)缓冲材料，将主压接装置(工具尺寸30mm×50mm)按压到IC芯片，进行加热挤压，获取7种接合体(主压接)。主压接条件：主压接装置的温度为190℃，主压接装置的挤压力为3Mpa，时间为10秒。
<捕捉效率>
上述组装工序中，对临时固定后的IC芯片的1个凸块下方存在的导电性粒子的数，以及被主压接后的IC芯片的1个凸块及ITO布线玻璃基板的1个ITO接点所挟持的导电性粒子的数(粒子捕捉数)进行了测定。
对100个凸块进行了测定。粒子捕捉数的最大值、最小值、平均值和捕捉效率(单位：％)，如下列表3所示。
表3：捕捉效率
Figure GPA00001009072100181
(连接面积＝1700μm2，测定数N＝100)
其中，捕捉效率，是以百分比表示相对于临时固定IC芯片时在凸块下存在的粒子数，主压接后捕捉到几个粒子的数值。其可根据下式(1)求出。
捕捉效率(％)＝(主压接后的粒子捕捉数)/(临时固定后在凸块下存在的粒子数)×100......式(1)
实施例X4、Y1～Y3获得了较高的捕捉效率(43％～71％)。其中，实施例Y1～Y3中，呈60％以上的捕捉效率，更优选。
<导通电阻>
对主压接后的，1个凸块和1个端子之间的导通电阻进行了测定。对100处进行了测定。导通电阻的最小值，最大值和平均值，如上述表3所示。
从上述表3可看出，实施例Y1～Y3的粒子捕捉数多于对比例X1～X3，导通电阻也有低的倾向，因此可以确定使用本发明的粘合薄膜10连接电子部件，则能提高连接可靠性。
<短路发生率>
将IC芯片的凸块和ITO布线玻璃基板的线路(ITO接点)，向横向偏离7mm的方式进行了错误调准以外，用上述组装工序所记载的条件，将IC芯片连接到ITO布线玻璃基板，制造了接合体。
在接合体邻接的ITO接点间施加30V的电压，测量了绝缘电阻。短路发生的基准为，1.0×10-6Ω以下时判定为短路，对短路发生数进行计数。并且，对接合体通电的状态下，在温度85℃、湿度85％的高温高湿环境下放置500小时之后，在400处测定短路发生数，求得短路发生率。测定结果如下表4所示。
表4：短路发生率
(邻接端子间空隙＝7μm，测定数N＝100)
从上述表4可看出，实施例X4、Y1～Y3与对比例X1～X3相比，无论是初期，还是在高温高湿环境下放置后的短路发生率都低。
<堵塞>
将实施例X4、YI～Y3及对比例X1～X3的粘合薄膜10，分别切成宽度1.5mm、长度100m，并卷绕到卷筒上，然后确认是否发生堵塞。其中，粘合薄膜10是以在一侧面上粘贴了剥离薄膜的状态，被卷绕到卷筒上的。
作为堵塞的确认方法，首先在卷绕的导电性粘合薄膜的末端部挂30g的秤锤，在30℃的环境(模拟压接装置内的环境)下放置2小时。然后，在常温环境中试着拉出导电性粘合薄膜，查看是否发生了粘合薄膜卷不能拉出的现象(堵塞)。
将第一粘合剂层11及第二粘合剂层12发生露出，露出的部分粘接，从而无法拉出时用×，能正常拉出时用○表示。其结果如下表5所示。
表5：堵塞
Figure GPA00001009072100201
从上述表5可看出，作为第一主树脂成分及第二主树脂成分，使用玻璃化转变温度不满30℃的物质的对比例X1中发生了堵塞，而实施例X4、Y1～Y3中没有发生堵塞。
实施例X4、Y1～Y3中，第二主树脂成分的玻璃化转变温度在50℃以上110℃以下的范围，第一主树脂成分的玻璃化转变温度则超过110℃，比第二主树脂成分的玻璃化转变温度还高。
所以，若第二主树脂成分的玻璃化转变温度在50℃以上110℃以下的范围中，第一主树脂成分的玻璃化转变温度高于第二主树脂成分的玻璃化转变温度时，可以确定在粘合薄膜10的实际使用中，很少发生无法向外卷拉的问题。

Claims (6)

1.一种粘合薄膜，包括：第一粘合剂层和粘附于所述第一粘合剂层的第二粘合剂层，并且，所述第一粘合剂层中分散有导电性粒子，所述第一粘合剂层和所述第二粘合剂层分别含有副树脂成分，对所述第一粘合剂层和所述第二粘合剂层进行升温，则所述第一粘合剂层和所述第二粘合剂层中的所述副树脂成分发生反应，使所述第一粘合剂层和所述第二粘合剂层固化，其特征在于，
所述第一粘合剂层中含有玻璃化转变温度高于所述副树脂成分的第一主树脂成分，所述第二粘合剂层中含有玻璃化转变温度高于所述副树脂成分且玻璃化转变温度低于所述第一主树脂成分的第二主树脂成分，
所述第一粘合剂层和所述第二粘合剂层的升温过程中，所述第一粘合剂层和所述第二粘合剂层的放热量最大的反应放热峰温度，低于所述第一主树脂成分的玻璃化转变温度且高于所述第二主树脂成分的玻璃化转变温度。
2.如权利要求1所述的粘合薄膜，第一粘合剂层的膜厚为导电性粒子平均粒径的0.5倍以上2.0倍以下。
3.如权利要求1至2中任一项所述的粘合薄膜，第二主树脂成分的玻璃化转变温度为50℃以上110℃以下。
4.如权利要求1至3中任一项所述的粘合薄膜，第一粘合剂层反应放热峰温度与第二粘合剂层反应放热峰温度之差为10℃以下。
5.一种连接方法，其特征在于，隔着权利要求1至4中的任意一项所述粘合薄膜使第一基板的电极和第二基板的电极对峙，通过热挤压所述第一基板和所述第二基板，将所述粘合薄膜中的导电性粒子夹持于所述第一基板的电极和所述第二基板的电极之间，从而连接所述第一基板和所述第二基板。
6.一种接合体，其特征在于，具备使用权利要求5所述的连接方法进行连接的第一基板和第二基板。
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