CN104870595B - 粘合剂、粘合膜、半导体器件及其制造方法 - Google Patents

粘合剂、粘合膜、半导体器件及其制造方法 Download PDF

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CN104870595B
CN104870595B CN201380068190.4A CN201380068190A CN104870595B CN 104870595 B CN104870595 B CN 104870595B CN 201380068190 A CN201380068190 A CN 201380068190A CN 104870595 B CN104870595 B CN 104870595B
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adhesive
group
different
formula
polyimides
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CN104870595A (zh
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藤丸浩
藤丸浩一
野中敏央
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Toray Industries Inc
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Toray Industries Inc
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
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    • H05K3/305—Affixing by adhesive
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    • C09J2479/00—Presence of polyamine or polyimide
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Abstract

本发明涉及一种将半导体芯片安装于电路基板等时使用的粘合剂，本发明所要解决的课题是提供一种保存稳定性和连接可靠性这两种特性均优异的粘合剂，用于解决上述课题的手段是含有(a)聚酰亚胺、(b)环氧化合物及(c)酸改性松香的粘合剂。

Description

粘合剂、粘合膜、半导体器件及其制造方法
技术领域
本发明涉及一种在将LSI、LED、激光二极管(laser diode)等半导体芯片粘合或直接电接于挠性基板、玻璃环氧树脂基板、玻璃基板、陶瓷基板、硅中介层等电路基板时，或者在将半导体芯片彼此接合或层合时所使用的粘合剂等。
背景技术
近年来，伴随半导体器件的小型化和高密度化，作为在电路基板上安装半导体芯片的方法，倒装芯片(flip chip)安装受到关注，正迅速推广。在倒装芯片安装中，作为用于确保接合部分的连接可靠性的方法，作为通常的方法采用以下方法：使环氧树脂类粘合剂介于形成于半导体芯片上的凸块电极(bump electrode)和电路基板的焊盘电极(padelectrode)之间。其中，含有聚酰亚胺树脂、环氧树脂及无机粒子的粘合剂利用聚酰亚胺树脂的耐热性和绝缘特性、环氧树脂的粘合性和耐水性、及无机粒子的低吸水性和低热线膨胀性，多用于电气、电子、建筑、汽车、航空器等各种用途(例如，参见专利文献1～3)。
此外，将半导体芯片及电路基板等的金属电极进行焊接时，使用助焊剂(fluxmaterial)。助焊剂的主要功能在于使焊接部洁净、防止金属的氧化、并提高焊料的润湿性。作为助焊剂，已知有松香系材料(例如，专利文献4、5)。
专利文献1：日本特开2004-319823号公报
专利文献2：日本专利3995022号公报
专利文献3：日本特开2009-277818号公报
专利文献4：日本特开2001-219294号公报
专利文献5：日本特开2005-059028号公报
发明内容
倒装芯片的安装中，为了除去所吸湿的水分而进行加热、或在半导体芯片安装工艺中进行加热，由于这些加热，以往的粘合剂缓慢地进行固化反应，半导体芯片的凸块电极变得难以贯通粘合剂，所以有时电连接变得不稳定，或者混入气泡而使连接可靠性变差。此外，有时上述加热导致粘合剂流动，厚度产生不均，连接可靠性变差。进而，对于使用以往的粘合剂而制作的半导体器件而言，还存在以下课题：进行吸湿回流焊处理(absorption-reflow process)及热循环处理之类需要更强耐久性的处理时，有时难以确保足够的连接可靠性。
为了解决这些问题，本发明的目的在于提供一种在热干燥处理及安装工艺的加热条件下、保存性优异的粘合剂。
本发明是一种含有(a)聚酰亚胺、(b)环氧化合物及(c)酸改性松香的粘合剂。
根据本发明，可得到一种对热干燥处理及安装工艺中的加热处理的稳定性优异的粘合剂。
具体实施方式
本发明的粘合剂是一种含有(a)聚酰亚胺、(b)环氧化合物及(c)酸改性松香的粘合剂。
本发明的粘合剂由于含有(a)聚酰亚胺，所以耐热性及耐药品性优异。特别是通过使用在聚酰亚胺的侧链上具有至少一个具有高极性的官能团(选自由酚羟基、磺酸基及硫醇基组成的组)的化合物，可以提高聚酰亚胺的有机溶剂可溶性及与环氧树脂的相容性，而且在热处理时可以促进环氧化合物的开环反应、及对其他有机溶剂可溶性聚酰亚胺的加成反应，由此能够得到具有更高密度网状结构的固化物。作为这样的聚酰亚胺的合成方法，例如可以举出以下方法：首先，使具有酚羟基、磺酸基、硫醇基等具高极性的官能团的二胺与酸二酐反应，合成聚酰亚胺前体，然后，使用伯单胺作为封端剂，进行该聚酰亚胺前体的末端修饰，接下来，在150℃以上进行热处理，使聚酰亚胺闭环。除此之外，还可以举出下述方法：预先使酸二酐与作为封端剂的伯单胺反应后，添加具有官能团的二胺，从而合成经末端修饰的聚酰亚胺前体，进而在150℃以上的高温下使聚酰亚胺闭环。但，并不限于上述例示的方法。
需要说明的是，本发明所使用的(a)聚酰亚胺，如果为在选自以下的至少1种的溶剂中于23℃溶解20质量％以上的有机溶剂可溶性聚酰亚胺，则得到的粘合剂清漆的涂布性提高，故优选。作为溶剂，可举出为酮系溶剂的丙酮、甲基乙基酮、甲基异丁基酮、环戊酮、环己酮；为醚系溶剂的1，4-二氧杂环己烷、四氢呋喃、二乙二醇二甲醚(Diglyme)；为二醇醚系溶剂的甲基溶纤剂、乙基溶纤剂、丙二醇单甲醚、丙二醇单***、丙二醇单丁醚、二乙二醇甲***；为其他溶剂的苄醇、N-甲基吡咯烷酮、γ-丁内酯、乙酸乙酯、N，N-二甲基甲酰胺。
(a)聚酰亚胺的优选之一例为：具有通式(2)或通式(3)表示的结构，并且含有相对于聚合物总量为5～15质量％的通式(1)表示的结构作为通式(2)或通式(3)中的R4。通过使通式(1)表示的结构的含量为5质量％以上，可以对聚酰亚胺赋予向有机溶剂的可溶性及适度的柔软性。通过使该含量为15质量％以下，可以维持聚酰亚胺的刚直性，并确保耐热性及绝缘性。
需要说明的是，此处的通过聚酰亚胺的合成而得到的聚合物(聚酰亚胺)的总量，是指通过由二胺和酸二酐及封端剂构成的构成成分进行聚合而得到的聚合物的质量。该合成时过量投入的、经聚合未成为聚合物的二胺、酸二酐及封端剂不包含在聚酰亚胺的质量中。
式中，R1表示2价的烃基，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同。R2表示1价的烃基，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同。n表示1～10的整数。
R1优选为碳原子数1～5的亚烷基或亚苯基。R2优选为碳原子数1～5的烷基或苯基。此外，n优选为1～2。使n为1以上时，可以抑制固化时粘合剂的收缩。使n为10以下时，可以不使聚酰亚胺骨架中的酰亚胺基团含有率减少，并提高粘合剂的绝缘性及耐热性。
式中，R3表示4～14价的有机基团，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同。此外，R4表示2～12价的有机基团，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同。此外，R3及R4中的至少一个为芳香族基团，所述芳香族基团含有至少一个选自由1，1，1，3，3，3-六氟丙基、异丙基、醚基、硫醚基及SO2基组成的组中的1个以上的基团。R5及R6表示选自由酚羟基、磺酸基及硫醇基组成的组中的1个以上的基团，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同。X表示1价的有机基团。m表示8～200的整数。α及β分别表示0～10的整数，并且，α+β为0～10的范围。其中，在式中的重复单元中，重复数m中、20～90摩尔％的重复单元中α+β＝1～10的范围。
需要说明的是，以下将上述选自由1，1，1，3，3，3-六氟丙基、异丙基、醚基、硫醚基及SO2基组成的组中的基团称为“特定基团”。
通式(2)、(3)中，R3表示酸二酐的结构成分，其中，优选碳原子数5～40的4～14价的有机基团。此外，R4表示二胺的结构成分，其中，优选为碳原子数5～40的2～12价的有机基团。此外，R3、R4两者优选含有至少一个上述特定基团。
R5为R3的取代基，选自由酚羟基、磺酸基及硫醇基组成的组。R5源自成为原料的酸二酐的取代基。R6为R4的取代基，选自由酚羟基、磺酸基及硫醇基组成的组。R6源自成为原料的二胺的取代基。
对使用的酸二酐进行说明。作为含有至少一个上述特定基团的酸二酐，具体而言，可以举出2，2-双(3，4-二羧基苯基)丙烷二酐、2，2-双(2，3-二羧基苯基)丙烷二酐、双(3，4-二羧基苯基)砜二酐、双(3，4-二羧基苯基)醚二酐、2，2-双(3，4-二羧基苯基)六氟丙烷二酐或者它们的芳香族环被烷基、卤原子取代而得到的化合物等。
作为具有至少一个上述特定基团、且具有至少一个选自由酚羟基、磺酸基及硫醇基组成的组中的基团的酸二酐的例子，具体而言，可以举出下述所示结构的芳香族酸二酐。
R9表示C(CF3)2、C(CH3)2、SO2、S或O。R10、R11表示氢原子、羟基、硫醇基或磺酸基。其中，R10及R11不同时为氢原子。
作为不具有上述特定基团、且具有至少一个选自由酚羟基、磺酸基及硫醇基组成的组中的基团的酸二酐的例子，具体而言，可以举出下述所示结构的芳香族酸二酐。
R7、R8表示氢原子、羟基、硫醇基或磺酸基。其中，R7及R8不同时为氢原子。
作为不具有上述特定基团、也不具有酚羟基、磺酸基或硫醇基的酸二酐，具体可举出均苯四甲酸二酐、3，3’，4，4’-联苯四甲酸二酐、2，3，3’，4’-联苯四甲酸二酐、2，2’，3，3’-联苯四甲酸二酐、3，3’，4，4’-二苯甲酮四甲酸二酐、2，2’，3，3’-二苯甲酮四甲酸二酐、1，1-双(3，4-二羧基苯基)乙烷二酐、1，1-双(2，3-二羧基苯基)乙烷二酐、双(3，4-二羧基苯基)甲烷二酐、双(2，3-二羧基苯基)甲烷二酐、1，2，5，6-萘四甲酸二酐、2，3，6，7-萘四甲酸二酐、2，3，5，6-吡啶四甲酸二酐、3，4，9，10-苝四甲酸二酐等芳香族四羧酸二酐或者它们的芳香族环被烷基、卤原子取代而得到的化合物。
本发明中，可以将这些酸二酐单独使用或者2种以上组合使用。
接下来，对二胺进行说明。作为具有至少一个上述特定基团的二胺，具体而言，可以举出3，4’-二氨基二苯硫醚、4，4’-二氨基二苯硫醚、3，4’-二氨基二苯醚、4，4’-二氨基二苯醚、3，4’-二氨基二苯砜、4，4’-二氨基二苯砜、双(4-氨基苯氧基苯基)砜、双(3-氨基苯氧基苯基)砜、双(4-氨基苯氧基)联苯、双{4-(4-氨基苯氧基)苯基}醚、1，4-双(4-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯、2，2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、2，2-双[4-(4-氨基苯氧基)苯基]丙烷、或者它们的芳香族环被烷基、卤原子取代而得到的化合物等。
作为具有至少一个上述特定基团、且具有至少一个选自由酚羟基、磺酸基及硫醇基组成的组中的基团的二胺，具体而言，可以举出2，2-双(3-氨基-4-羟基苯基)六氟丙烷、2，2-双(3-羟基-4-氨基苯基)六氟丙烷、2，2-双(3-氨基-4-羟基苯基)丙烷、2，2-双(3-羟基-4-氨基苯基)丙烷、3，3’-二氨基-4，4’-二羟基二苯醚、3，3’-二氨基-4，4’-二羟基二苯砜、3，3’-二氨基-4，4’-二羟基二苯硫醚、或者它们的芳香族环被烷基、卤原子取代而得到的化合物等、或下述所示结构的二胺等。
R16表示C(CF3)2、C(CH3)2、SO2、S或O。R17、R18表示氢原子、羟基、硫醇基或磺酸基。其中，R17及R18不同时为氢原子。
作为不具有上述特定基团、具有至少一个选自由酚羟基、磺酸基及硫醇基组成的组中的基团的二胺，具体而言，可以举出3，3’-二氨基-4，4’-二羟基联苯、2，4-二氨基-苯酚、2，5-二氨基苯酚、1，4-二氨基-2，5-二羟基苯、二氨基二羟基嘧啶、二氨基二羟基吡啶、羟基二氨基嘧啶、9，9-双(3-氨基-4-羟基苯基)芴、或它们的芳香族环上经烷基、卤原子取代而得到的化合物等、或下述所示结构的二胺等。
R12～R15表示氢原子、羟基、硫醇基或磺酸基。其中，R12及R13不同时为氢原子。
作为不具有上述特定基团、也不具有酚羟基、磺酸基、硫醇基的二胺，具体而言，可以举出3，4’-二氨基二苯基甲烷、4，4’-二氨基二苯基甲烷、联苯胺、间苯二胺、对苯二胺、1，5-萘二胺、2，6-萘二胺、2，2’-二甲基-4，4’-二氨基联苯、2，2’-二乙基-4，4’-二氨基联苯、3，3’-二甲基-4，4’-二氨基联苯、3，3’-二乙基-4，4’-二氨基联苯、2，2’，3，3’-四甲基-4，4’-二氨基联苯、3，3’，4，4’-四甲基-4，4’-二氨基联苯、2，2’-二(三氟甲基)-4，4’-二氨基联苯、或它们的芳香族环被烷基或卤原子取代而得到的化合物，对苯二甲酰肼、间苯二甲酰肼、邻苯二甲酰肼、2，6-萘二甲酸二酰肼、4，4’-联苯二碳酰肼(4，4’-bisphenyldicarbonohydrazine)、4，4’-环己烷二碳酰肼(4，4’-cyclohexane dicarbonohydrazine)、或它们的芳香族环被烷基或卤原子取代而得到的酰肼化合物等。二胺可以单独使用或2种以上组合使用。
此外，由于通式(1)表示的结构作为通式(2)和(3)中的R4被含有，所以成为二胺的构成成分。作为含有通式(1)表示的结构的二胺，可以举出双(3-氨基丙基)四甲基二硅氧烷、双(对氨基苯基)八甲基五硅氧烷等。
通过选择通式(2)及(3)中的R5及R6，可以调节将粘合剂进行热处理时的聚酰亚胺与环氧化合物的反应率，调节粘合剂的固化物的交联密度。由此能赋予粘合剂的固化物所需的耐热性、耐化学品性。α及β分别表示0～10的整数，并且，α+β为0～10的范围。其中，在式中的重复单元中，重复数m中的20～90摩尔％的重复单元中，α+β＝1～10的范围。此外，优选R5及R6的总计的20～90摩尔％为选自由酚羟基、磺酸基及硫醇基组成的组中的基团。通过使这些基团为R5及R6的总计的20摩尔％以上，可以提高固化前的粘合剂的有机溶剂可溶性、粘合剂的固化物的耐药品性及耐热性，通过使其为90％摩尔以下，可以将粘合剂的固化物的交联密度抑制在适当的范围内，保持固化后的粘合剂膜的伸长率及韧性。
通式(2)及(3)中，X表示1价的有机基团，为作为封端剂的伯单胺的残基。此处，作为伯单胺，可举出脂肪族单胺、脂环族单胺、芳香族单胺等。其中，从提高聚酰亚胺的耐热性的观点考虑，优选为芳香族单胺。它们单独或2种以上的组合均可。作为伯单胺，具体而言，可举出5-氨基喹啉、4-氨基喹啉、3-氨基萘、2-氨基萘、1-氨基萘、苯胺等。其中，优选使用苯胺。
此外，作为该伯单胺，优选使用另外不具有与环氧化合物反应的取代基的伯单胺。由此，可以得到在分子运动性高的聚酰亚胺的末端部不具有与环氧化合物反应的取代基的有机溶剂可溶性聚酰亚胺。通过使用上述伯单胺，有机溶剂可溶性聚酰亚胺与环氧化合物在室温下的反应变得难以进行，可以提高粘合剂的保存性。
关于通式(2)及(3)的X成分的导入比例，如果以其原成分即封端剂的伯单胺成分进行换算，则相对于聚酰亚胺所含有的全部二胺残基100摩尔，优选在0.1～60摩尔的范围内，特别优选为5～50摩尔。
通式(2)及(3)的m表示聚合物的重复数，其表示8～200的整数。优选为10～150的整数。就分子量而言，利用凝胶过滤色谱法测定的重均分子量(以聚苯乙烯换算)优选为4000～80000，特别优选为8000～60000。通过使m为8以上，可以增加得到的粘合剂清漆的粘度从而能进行厚膜涂布，通过使m为200以下，可以提高聚酰亚胺对溶剂的溶解性。将聚酰亚胺的重均分子量的测定方法例示如下。使用将聚酰亚胺溶解在N-甲基吡咯烷酮(NMP)中而得到的固态成分浓度为0.1质量％的聚酰亚胺溶液，利用GPC装置Waters2690(Waters(株)制)算出聚苯乙烯换算的重均分子量。对于GPC测定条件，流动相为分别以浓度0.05mol/L溶解有LiCl和磷酸的NMP，展开速度为0.4ml/分钟。作为使用的GPC装置，例如可举出：
检测器：Waters996
***控制器：Waters2690
柱温箱：Waters HTR-B
热控制器：Waters TCM
柱：TOSOH guard column
柱：TOSOH TSK-GELα-4000
柱：TOSOH TSK-GELα-2500等。
本发明所使用的(a)聚酰亚胺可以仅仅是由通式(2)及(3)表示的结构构成的物质，也可以为除通式(2)及(3)表示的结构以外也具有其他结构作为共聚成分的共聚物，还可以为它们的混合体。进而，除了这些聚酰亚胺，还可以混合具有其他结构的聚酰亚胺。此时，相对于全部聚酰亚胺，优选含有50摩尔％以上的具有通式(2)及(3)表示的结构的聚酰亚胺。关于共聚或混合中使用的结构的种类及量，优选在不破坏通过加热处理而得到的耐热性树脂的耐热性的范围内进行选择。
对于(a)聚酰亚胺而言，可以将二胺的一部分置换成作为单胺的封端剂，或者将酸二酐的一部分置换成作为单羧酸、酸酐、单酰氯化合物、单活性酯化合物的封端剂，利用已知的方法合成。例如，可以利用以下方法得到聚酰亚胺前体，所述方法包括：在低温下使四羧酸二酐与二胺化合物(将一部分置换成作为单胺的封端剂)反应的方法；在低温下使四羧酸二酐(将一部分置换成作为酸酐、单酰氯化合物或单活性酯化合物的封端剂)与二胺化合物反应的方法；通过四羧酸二酐与醇的反应得到二酯，之后在二胺(将一部分置换成作为单胺的封端剂)和缩合剂的存在下使其反应的方法；通过四羧酸二酐与醇的反应得到二酯，之后将残留的二羧酸进行酰氯化，然后使其与二胺(将一部分置换成作为单胺的封端剂)进行反应的方法等。然后，可以利用已知的方法将聚酰亚胺前体进行酰亚胺闭环，由此来合成聚酰亚胺。
此外，导入至聚合物中的通式(1)的结构及来自封端剂的结构可以利用以下方法容易地进行检测和定量。例如，将导入有通式(1)的结构及封端剂的聚合物溶解在酸性溶液或碱性溶液中，将其分解成聚合物的构成单元即二胺成分和酸酐成分，然后使用气相色谱(GC)、NMR对得到的分解物进行测定，由此能够容易地检测和定量通式(1)的结构及使用的封端剂。此外，也可以通过对导入有封端剂的聚酰亚胺直接进行热裂解气相色谱(PGC)、红外光谱及13CNMR光谱测定，从而容易地检测和定量通式(1)的结构及所使用的封端剂。
相对于(b)环氧化合物100质量份，粘合剂中的(a)聚酰亚胺的含量优选为15～90质量份，为了与环氧化合物反应而形成高密度网状结构，更优选为30～70质量份。(a)聚酰亚胺的含量为15质量份以上时，耐热性进一步提高。此外，(a)聚酰亚胺的含量为90质量份以下时，由于粘合剂的吸水进一步变少，所以可以进一步抑制使粘合剂加热固化时的发泡，例如，电路基板与半导体芯片之间的粘合力的降低进一步变少，连接可靠性进一步提高。
本发明的粘合剂含有(b)环氧化合物。由于(b)环氧化合物与(c)酸改性松香或聚酰亚胺侧链的酚羟基、磺酸基或硫醇基反应，构成具有高密度网状结构的固化物，所以得到的固化物对各种药品显示出耐性。由此，可以提高粘合剂对各种溶剂(特别是N-甲基吡咯烷酮)的耐性。此外，由于环氧化合物一般通过不伴有收缩的开环反应而进行固化，所以能够降低粘合剂固化时的收缩。作为(b)环氧化合物，优选为具有2个以上的环氧基的环氧化合物、环氧当量为100～500的环氧化合物。通过使环氧当量为100以上，可以增大固化后的粘合剂的韧性。通过使环氧当量为500以下，可以使固化后的粘合剂形成高密度网状结构，可以使固化后的粘合剂成为高绝缘性。
此外，(b)环氧化合物含有液态环氧化合物和固态环氧化合物两者，相对于环氧化合物总量，液态环氧化合物的含有比率优选为20质量％以上、70质量％以下，更优选为30质量％以上、60质量％以下。通过使粘合剂含有上述范围的量的液态环氧化合物，可以具备作为半导体用粘合剂的适当的可塑性及可挠性。
此处，液态环氧化合物是指在25℃、1.013×105N/m2下显示150Pa·s以下的粘度的物质，固态环氧化合物是指在25℃下粘度大于150Pa·s的物质。作为液态环氧化合物，例如，可举出JER(注册商标)828、JER(注册商标)1750、JER(注册商标)152、JER(注册商标)630、YL980(以上为商品名，三菱化学(株)制)、EPICLON(注册商标)HP-4032(以上为商品名，DIC(株)制)等，但并不限定于此。此外，还可以将它们中的2种以上组合使用。此外，作为固态环氧化合物，可举出JER(注册商标)1002、JER(注册商标)1001、YX4000H、JER(注册商标)4004P、JER(注册商标)5050、JER(注册商标)154、JER(注册商标)157S70、JER180S70(以上为商品名，三菱化学(株)制)、TEPIC(注册商标)S、TEPIC(注册商标)G、TEPIC(注册商标)P(以上为商品名，日产化学工业(株)制)、EPOTOTE(注册商标)YH-434L(商品名，新日铁化学(株)制)、EPPN502H、NC3000(以上为商品名，日本化药(株)制)、EPICLON(注册商标)N695、EPICLON(注册商标)N865、EPICLON(注册商标)HP-7200(以上为商品名，DIC(株)制)等，但并不限定于此。此外，还可以将它们中的2种以上组合使用。
本发明的粘合剂含有(c)酸改性松香。酸改性松香是使脂松香(gum rosin)、木松香、妥尔油松香(tall oil rosin)等原料松香类与(甲基)丙烯酸、马来酸(酐)、富马酸、柠康酸(酐)、衣康酸(酐)等不饱和羧酸进行迪尔斯·阿尔德反应(Diels-Alder reaction)(加成反应)而得到的。原料松香优选使用为了除去金属等杂质及提高树脂色调而利用蒸馏、重结晶、提取等进行纯化的松香。此外，酸改性松香可以通过氢化形成透明色调的酸改性松香。作为这样的酸改性松香，可举出Pinecrystal(注册商标)KE-604、Pinecrystal(注册商标)KR-120、MALKYD(注册商标)No.33(以上为商品名，荒川化学工业株式会社)。
这些酸改性松香具有2个以上的羧基。因此，酸改性松香与(a)有机溶剂可溶性聚酰亚胺及(b)环氧化合物的相容性优异。此外，酸改性松香可以与环氧化合物反应，形成高密度网状结构。需要说明的是，认为酸改性松香具有松香自身的体积大的结构和经酸改性而生成的体积大的环己烷环，这会立体地阻碍环氧基对羧基的反应，提高粘合剂的热干燥处理及安装工艺的加热条件下的稳定性。另一方面，在粘合剂的固化温度、例如200℃到250℃的温度下，酸改性松香的分子运动性提高，与环氧化合物的反应快速地进行，可在短时间内完成粘合剂的固化。
相对于100质量份的(b)环氧化合物，粘合剂中的(c)酸改性松香的含量优选为5质量份以上、30质量份以下。通过使酸改性松香的含量在该范围内，可使保存性优异，并且能在短时间内进行粘合剂的固化。相对于100质量份的(b)环氧化合物，(c)酸改性松香的含量更优选为20质量份以下。此外，该含量更优选为10质量份以上。
此外，通过使用酸改性松香，也有使粘合剂与电极等金属材料的粘合性提高、对粘合剂赋予助焊剂功能(flux function)的效果。即，通过使用本发明的粘合剂将电路构件进行电连接，可以使接合部洁净，防止作为粘合剂成分的树脂、无机粒子等混入接合部的电路构件间，并且能够提高焊料的润湿性。如此，(c)酸改性松香在粘合性的提高和电连接的可靠性提高这两方面有效果。而且，如上所述，由于酸改性松香的酸性基团在固化反应时与环氧化合物反应而被消耗，并且酸改性松香具有体积大的结构，所以在粘合后可以防止腐蚀电极等金属部分。
除此之外，还可以并用酸改性松香以外的其他已知潜在性固化剂。特别是碱性的潜在性固化剂显示出与酸改性松香的相互作用力，因此可以进一步提高潜在性。作为这样的碱性的潜在性固化剂，可以优选使用咪唑系潜在性固化剂。具体而言，优选使用Curezol(注册商标)2PZCNS、Curezol(注册商标)2PZCNS-PW、Curezol(注册商标)C11Z-CNS、Curezol(注册商标)2MZ-A、Curezol(注册商标)C11-A、Curezol(注册商标)2E4MZ-A、Curezol(注册商标)2MZA-PW、Curezol(注册商标)2MAOK-PW、CurezoI(注册商标)2PHZ-PW(以上为商品名，四国化成工业(株)制)、利用异氰酸酯处理咪唑系潜在性固化剂而得到的微囊型固化剂即Novacure(注册商标)HX-3941HP、Novacure(注册商标)HXA3922HP、Novacure(注册商标)HXA3932HP、Novacure(注册商标)HXA3042HP(以上为商品名，ASAHI KASEI E-MATERIALSCORPORATION制)等。
本发明的粘合剂可以进一步含有(d)无机粒子。作为(d)无机粒子的材质，可以将二氧化硅、氧化铝、二氧化钛、氮化硅、氮化硼、氮化铝、氧化铁、玻璃、其他金属氧化物、金属氮化物、金属碳酸盐、硫酸钡等金属硫酸盐等单独使用或混合使用2种以上。其中，从低热膨胀性、散热性、低吸湿率及粘合剂中的分散稳定性的观点考虑，可优选使用二氧化硅和氧化铝。
相对于前述(a)～(d)成分的总量，粘合剂中的(d)无机粒子的含量优选为30～80质量％，更优选为50～70质量％。通过使(d)无机粒子的含量为30～80质量％，可以在使粘合剂加热干燥时更难以产生由流动变形导致的厚度不均，与之相伴，使用该粘合剂所制作的半导体器件的连接可靠性进一步提高。特别是在进行吸湿回流焊处理及热循环处理之类的需要更强耐久性的处理的情况下，可以进一步保持连接可靠性。此外，在粘合剂中无机粒子的分散性变得更充分，无机粒子彼此之间的凝集进一步减少。此外，在将粘合剂形成于脱模性塑料膜上制成粘合膜、并卷绕成卷状时，粘合片材的破裂、从脱模性塑料膜脱落的问题更不易产生。
(d)无机粒子的形状可以为球状、破碎状、片状等非球状的任一种，由于球状的无机粒子在粘合剂中易均匀分散，所以可以优选使用。另外，球状无机粒子的平均粒径优选为3μm以下。该平均粒径更优选为10nm以上、1μm以下。通过使该平均粒径为10nm以上，从而分散性进一步提高，可以更高浓度地填充到粘合剂中。通过使该平均粒径为3μm以下，从而无机粒子的表面积变得足够大，因此，(d)无机粒子与上述(a)～(c)成分及根据需要而混合的成分之间的相互作用力变得足够大，在加热干燥时，更难以产生流动变形。
另外，粘合剂需要透明性时，无机粒子的粒径优选为100nm以下，更优选为60nm以下。例如，在基板上形成粘合剂后，存在出于对准(alignment)等目的、需要通过粘合剂识别位于基板表面的标记的情况等。
需要说明的是，无机粒子的平均粒径表示无机粒子单独存在时的粒径，其表示频率最高的粒径。所谓无机粒子的粒径，当无机粒子的形状为球状时表示其直径，为椭圆状及扁平状时表示形状的最大长度。进而，无机粒子的形状为棒状或纤维状时，无机粒子的粒径表示长度方向的最大长度。作为测定粘合剂中无机粒子的平均粒径的方法，可以利用SEM(扫描型电子显微镜)直接观察粒子，测定100个粒子的粒径。由基于测定而得到的粒径的分布，以个数基准选择频率最高的粒径，作为平均粒径。
为了使固化后的膜低应力化，本发明的粘合剂可以进一步含有热塑性树脂。作为热塑性树脂，例如可以举出苯氧基树脂、聚酯、聚氨酯、聚酰胺、聚丙烯、丙烯腈-丁二烯共聚物(NBR)、苯乙烯-丁二烯共聚物(SBR)、丙烯腈-丁二烯-甲基丙烯酸共聚物、丙烯腈-丁二烯-丙烯酸共聚物等，但并不限定于此。还可以进一步含有离子捕获剂、表面活性剂、硅烷偶联剂、有机染料、无机颜料等。
对于本发明的粘合剂而言，可以在溶剂中混合各构成材料而作为清漆使用。此外，还可以将粘合剂成型为片状制成粘合剂膜使用。作为将粘合剂成型为片状的方法，可以举出将上述粘合剂清漆涂布于剥离性基材上、然后进行脱溶剂的方法。
作为溶剂，可以将酮系溶剂的丙酮、甲基乙基酮、甲基异丁基酮、环戊酮、环己酮；醚系溶剂的1，4-二氧杂环己烷、四氢呋喃、二乙二醇二甲醚；二醇醚系溶剂的甲基溶纤剂、乙基溶纤剂、丙二醇单甲醚、丙二醇单***、丙二醇单丁醚、二乙二醇甲***；其他苄醇、N-甲基吡咯烷酮、γ-丁内酯、乙酸乙酯、N，N-二甲基甲酰胺等单独使用或者2种以上混合使用，但并不限定于此。
作为剥离性基材，可以举出聚丙烯膜、聚对苯二甲酸乙二醇酯膜、聚萘二甲酸乙二醇酯膜、聚酯膜、聚氯乙烯膜、聚碳酸酯膜、聚酰亚胺膜、聚四氟乙烯膜等氟类树脂膜、聚苯硫醚膜、聚丙烯膜、聚乙烯膜等，但并不限定于此。此外，剥离性基材可以使用硅系脱模剂、长链烷基系脱模剂、氟系脱模剂、脂肪族酰胺系脱模剂等施行脱模处理。剥离性基材的厚度没有特别限定，通常优选为5～75μm。从能减少对粘合剂的残留应力的方面考虑，优选使剥离性基材的厚度为粘合剂的厚度以上。此外，优选在粘合剂膜的与具有脱模性基材的面为相反侧的面上进一步层合其他剥离性基材，制成用剥离性基材夹持上下的粘合剂膜。作为其他剥离性基材的材质及厚度，可以使用与前面说明相同的材质及厚度。两种剥离性基材可以相同。
在用剥离性基材从粘合剂膜的两面层合的情况下，优选各剥离性基材与粘合剂膜之间的粘合力不同。特别地，粘合力的差优选为5N/m以上，更优选为47N/m以下。通过使粘合力的差为5N/m以上，可以在剥离粘合力较小的一方的剥离性基材时，不使粘合剂膜从另一方的剥离性基材上脱落或浮动。此外，通过使粘合力的差为47N/m以下，从而不易在剥离后的各剥离性基材的表面上残留粘合剂。
此外，在溶剂中混合各构成材料而制成清漆状的粘合剂，也可以在半导体晶片、电路基板等上进行涂布及脱溶剂而使用。
本发明的粘合剂的最低熔融粘度优选在100Pa·s以上、10000Pa·s以下的范围内。更优选的最低熔融粘度的范围为600Pa·s以上、5000Pa·s以下。通过使最低熔融粘度在上述范围内，从而在用作粘合剂膜时，可以进行粘合剂膜对半导体晶片、电路基板的层合而不引入皱褶、气泡。并且可以减少半导体芯片粘合时的粘合剂的溢出。需要说明的是，粘合剂的最低熔融粘度例如可以如下测定：使用动态粘弹性测定装置，在升温速度2℃/分钟、测定频率1Hz、测定应变9％、测定温度范围0℃到150℃的条件下，对尺寸为直径15mm、厚0.8mm的试样进行测定。随着测定温度从0℃开始升高，粘合剂的粘度降低，但如果温度超过某个值，则由于固化反应，粘合剂的粘度反而升高。将此时的粘度的极小值作为最低熔融粘度。
此外，对于本发明的粘合剂而言，在23℃、55％RH的环境下保存1个月后的最低熔融粘度优选在100～10000Pa·s的范围内。由此，即使将由本发明的粘合剂形成的粘合剂膜长时间保存后对半导体晶片、电路基板进行层合时，也可以不引入皱褶、气泡地进行层合。并且可以减少半导体芯片粘合时的粘合剂的溢出。
在本发明中，作为粘合剂的固化剂可以使用酸改性松香。对于所述酸改性松香而言，除了松香自身具有体积大的结构外，还具有经酸改性而生成的体积大的环己烷环，这会立体地阻碍环氧基对羧基的反应，因此，可以将在上述条件下保存后的最低熔融粘度控制在100～10000Pa·s的范围内。
本发明的粘合剂可以适合用作半导体用粘合剂，所述半导体用粘合剂用于半导体器件中使用的半导体元件、电路基板、金属布线材料等电路构件彼此之间的粘合或固定、半导体元件的密封。
本发明的半导体器件包含上述粘合剂的固化物或上述粘合剂膜的固化物。本发明中所述的半导体器件是指通过利用半导体元件的特性而能够发挥功能的全部装置。将半导体元件连接到基板上形成的装置、将半导体元件之间或基板之间连接形成的装置、电光学装置、半导体电路基板及电子仪器全部包含在半导体器件中。
本发明的半导体器件的制造方法的特征在于，使上述粘合剂或上述粘合剂膜介于第一电路构件和第二电路构件之间，利用加热加压将所述第一电路构件和所述第二电路构件进行电连接。
使用了本发明的粘合剂的半导体器件的制造方法的一例如下所述。首先，准备具有第一连接端子的第一电路构件和具有第二连接端子的第二电路构件。此处，作为电路构件，可举出半导体芯片、电阻器芯片、电容器芯片等芯片部件，具有TSV(硅通孔)电极的半导体芯片、硅中介层、玻璃环氧树脂电路基板、膜电路基板、玻璃基板、附贯通电极的玻璃中介层(glass interposer)等基板等。此外，作为连接端子，可举出由金、铜等形成的电镀凸块、附有焊料帽的铜柱凸块(通过在铜柱的前端将焊料形成半球状而得到)、柱形凸块(studbump)等凸块电极、焊料球、焊盘电极等。此外，可以在第一电路构件和/或第二电路构件形成有贯通电极，在构件的一面和/或两面形成有连接端子。
配置第一电路构件和第二电路构件，使第一连接端子与第二连接端子对置。接着，使本发明的粘合剂介于上述对置配置的第一连接端子与第二连接端子之间。然后，对第一电路构件和第二电路构件进行加热加压，使上述对置配置的第一连接端子与第二连接端子电连接。通过上述工序，第一电路构件和第二电路构件被牢固地电连接，同时，粘合剂固化，第一电路构件和第二电路构件被物理固定。
此处，可以将粘合剂仅赋予到之前任一个电路构件的连接端子侧的表面，还可以将粘合剂赋予到第一及第二电路构件的连接端子侧两者的表面。
作为更详细的实施方式的例子，针对以下方法进行说明：使用具有凸块的半导体芯片作为第一电路构件，并且使用具有布线图案的电路基板或半导体芯片作为第二电路构件，将两者经由本发明的粘合剂膜连接，用粘合剂密封第一电路构件与第二电路构件之间的空隙，制作半导体器件。
首先，在作为第二电路构件的形成有布线图案的电路基板或半导体芯片上粘贴粘合剂膜。此时，粘合剂膜可以在切成规定的大小后，粘贴在形成有布线图案的电路基板的布线图案面或半导体芯片的凸起形成面上。此外，可以在半导体晶片的凸起形成面上粘贴粘合剂膜后，切割半导体晶片使其单片化，由此制作粘贴有粘合剂膜的半导体芯片。
接着，配置作为第一电路构件的半导体芯片，使第一电路构件的凸块与第二电路构件的布线图案对置，使用粘合装置对两者进行加热加压。加热加压条件只要在能良好地获得电连接的范围内即可，没有特别限定，但为了进行粘合剂的固化，需要温度为100℃以上、压力为1mN/凸块以上、时间为0.1秒以上的加热加压。在下述粘合条件下进行：温度优选为120℃以上、300℃以下，更优选为150℃以上、250℃以下，压力优选为5mN/凸块以上、50000mN/凸块以下，更优选为10mN/凸块以上、10000mN/凸块以下，时间优选为1秒以上、60秒以下，更优选为2秒以上、30秒以下。此外，粘合时，作为临时压接，可以通过温度为50℃以上、压力为1mN/凸起以上、时间为0.1秒以上的加热加压，使半导体芯片上的凸块与电路基板上的布线图案接触后，在上述条件下进行粘合。根据需要，可以在进行粘合后，将附半导体芯片的电路基板在50℃以上、200℃以下的温度下加热10秒以上、24小时以下。
除此之外，本发明的粘合剂还可以用作粘合性树脂材料，所述粘合性树脂材料用于制作芯片粘接膜(die attach film)、切割芯片粘接膜(dicing die attach film)、导线架固定胶带(lead frame fixing tape)、放热板、增强板、屏蔽材料的粘合剂、阻焊剂(solder resist)等。
随着近年来半导体器件制造作业自动化的显著进步，对于半导体用粘合剂及粘贴有半导体用粘合剂的电路基板或半导体芯片而言，作为进行固化之前的保存期，要求优选能够室温放置30天以上，更优选能够室温放置60天以上。使用本发明的粘合剂时，可以得到下述连接可靠性优异的半导体器件：即使在室温下也能保存60天以上，在粘合时不起泡，短时间的加热加压下能初始导通，即使在吸湿回流焊后进行一40℃～125℃的热冲击试验也能导通。
实施例
以下举出实施例等对本发明进行说明，但本发明并不限定于这些例子。
合成例1 聚酰亚胺A的合成
干燥氮气流下，将1，3-双(3-氨基苯氧基)苯(以下称为APB-N)4.82g(0.0165摩尔)、3，3’-二氨基-4，4’-二羟基二苯基砜(以下称为ABPS)3.08g(0.011摩尔)、1，3-双(3-氨基丙基)四甲基二硅氧烷(以下称为SiDA)4.97g(0.02摩尔)及作为封端剂的3-氨基苯酚0.55g(0.005摩尔)溶解在N-甲基吡咯烷酮(以下称为NMP)130g中。向其中加入2，2-双{4-(3，4-二羧基苯氧基)苯基}丙烷二酐(以下称为BSAA)26.02g(0.05摩尔)和20g NMP，使其于25℃反应1小时，然后在50℃下搅拌4小时。之后，在180℃下搅拌5小时。搅拌结束后，将溶液倾入到3L水中，过滤并回收沉淀，用水清洗3次后，使用真空干燥机于80℃干燥20小时。测定所得的聚合物固体的红外吸收光谱，结果在1780cm-1附近、1377cm-1附近检测到来自聚酰亚胺的酰亚胺结构的吸收峰。由此获得在末端及侧链上具有酚羟基、含有11.5质量％的通式(1)所示结构的聚酰亚胺A。在4g聚酰亚胺A中加入6g四氢呋喃，在23℃下进行搅拌，结果溶解。
合成例2 聚酰亚胺B的合成
干燥氮气流下，将4.82g(0.0165摩尔)APB-N、3.08g(0.011摩尔)ABPS、4.97g(0.02摩尔)SiDA及作为封端剂的苯胺0.47g(0.005摩尔)溶解在130g NMP中。向其中加入26.02g(0.05摩尔)BSAA和20g NMP，使其于25℃反应1小时，然后在50℃下搅拌4小时。之后，在180℃下搅拌5小时。搅拌结束后，将溶液投入3L水中，过滤并回收沉淀，用水清洗3次后，使用真空干燥机于80℃干燥20小时。测定所得的聚合物固体的红外吸收光谱，结果在1780cm-1附近、1377cm-1附近检测到来自聚酰亚胺的酰亚胺结构的吸收峰。由此获得在侧链上具有酚羟基、含有11.6质量％的通式(1)所示结构的聚酰亚胺B。在4g聚酰亚胺B中加入6g四氢呋喃，在23℃下进行搅拌，结果溶解。
合成例3 聚酰亚胺C的合成
干燥氮气流下，使2，2-双(3-氨基-4-羟基苯基)六氟丙烷(以下称为BAHF)24.54g(0.067摩尔)、4.97g(0.02摩尔)SiDA及作为封端剂的苯胺1.86g(0.02摩尔)溶解在80g NMP中。向其中加入双(3，4-二羧基苯基)醚二酐(以下称为ODPA)31.02g(0.1摩尔)和20g NMP，使其于20℃反应1小时，然后在50℃下搅拌4小时。之后，添加二甲苯15g，使水与二甲苯共沸，同时在180℃下搅拌5小时。搅拌结束后，将溶液投入3L水中得到白色沉淀的聚合物。将该沉淀过滤回收，用水清洗3次后，使用真空干燥机在80℃下干燥20小时。测定所得的聚合物固体的红外吸收光谱，结果在1780cm-1附近、1377cm-1附近检测到来自聚酰亚胺的酰亚胺结构的吸收峰。由此获得在例链上具有酚羟基、含有7.5质量％的通式(1)所示结构的聚酰亚胺C。在4g聚酰亚胺C中加入6g四氢呋喃，在23℃下进行搅拌，结果溶解。
合成例4 聚酰亚胺D的合成
干燥氮气流下，将8.03g(0.0275摩尔)APB-N、4.97g(0.02摩尔)SiDA及作为封端剂的苯胺0.47g(0.005摩尔)溶解在130g NMP中。向其中加入26.02g(0.05摩尔)BSAA和20gNMP，使其于25℃反应1小时，然后在50℃下搅拌4小、时。之后，在180℃下搅拌5小时。搅拌结束后，将溶液投入3L水中，过滤并回收沉淀，用水清洗3次后，使用真空干燥机于80℃干燥20小时。测定所得的聚合物固体的红外吸收光谱，结果在1780cm-1附近、1377cm-1附近检测到来自聚酰亚胺的酰亚胺结构的吸收峰。由此获得含有11.6质量％的通式(1)所示结构的聚酰亚胺D。在4g聚酰亚胺D中加入6g四氢呋喃，在23℃下进行搅拌，结果溶解。
此外，实施例、比较例中使用的各材料如下所示。
(b)环氧化合物
固态环氧化合物
N865(商品名，环氧当量：200g/eq，DIC Corporation制)
液态环氧化合物
YL980(商品名，185g/eq，三菱化学(株)制)。
(c)酸改性松香
KE-604(商品名，酸值240(KOHmg/g)，软化点130℃，色调150hazen，丙烯酸改性松香，荒川化学工业(株)制)。
KR-120(商品名，酸值320(KOHmg/g)，软化点120℃，色调150hazen，荒川化学工业(株)制)。
(c’)其他的潜在性固化剂
Novacure(注册商标)HXA-3941HP(商品名，ASAHI KASEI E-MATERIALSCORPORATION制)中所含有的液态环氧化合物。Novacure(注册商标)HXA-3941HP中微囊型固化剂/液态环氧化合物为1/2，所含有的液态环氧化合物中双酚A型环氧化合物/双酚F型环氧化合物＝1/4。表中的Novacure(注册商标)HXA-3941HP记载的质量份中，括号内所记载的量表示以微囊计的质量份。
(d)无机粒子
SO-E2(商品名，Admatechs Co.，Ltd.制，球形二氧化硅粒子，平均粒径0.5μm)
(f)溶剂：甲基异丁基酮(以下称为MIBK)
(g)松香
KR-85(商品名，酸值175(KOHmg/g)，软化点85℃，色调60hazen，荒川化学工业(株)制)。
实施例1～30及比较例1～8
(1)粘合剂膜的制作方法
将表1～4所示的(a)～(f)成分按照表中记载的组成比进行混合，制作粘合剂清漆。使用狭缝模式涂布机(涂布机)将制作的粘合剂清漆涂布于剥离性基材即厚50μm的聚酯对苯二甲酸酯膜(商品名，Cerapeel(注册商标)HP2(U))的表面处理面上，在80℃下进行干燥10分钟。在由此得到的干燥后的厚度为50μm的粘合剂膜上，作为另外的剥离性基材层合厚10μm的聚丙烯膜(商品名，Torayfan(注册商标)BO型号YK57，一面电晕放电处理品)的未处理面，然后在外径为9.6cm的纸管上将其卷绕成卷状，使剥离性基材HP2(U)为外侧，得到在粘合剂膜的两面具有剥离性基材的片材原材料。接下来，使用膜分切机将该片材原材料分切成宽7.5mm，在外径为5.0cm的卷轴上将其卷绕成卷状，使剥离性基材HP2(U)为外侧，得到在两面具有剥离性基材的粘合剂膜的卷绕体。将得到的卷绕体分成：立即进行(2)以后的工序的卷绕体；和在23℃、55％RH的环境下分别保存1个月及3个月后再进行(2)以后的工序的卷绕体，并对保存条件不同的卷绕体进行评价。
(2)胶带粘贴工序
使用胶带贴合装置(Toray Engineering Co.，Ltd制，DA2000)向电路基板粘贴粘合剂膜。首先，从由(1)工序得到的、在两面具有剥离性基材的粘合剂膜的卷绕体上除去剥离性基材YK57，使粘合剂膜露出。然后，在温度80℃、1秒的条件下，在固定于载物台上的电路基板(实心铜焊盘电极、能搭载300个7.5mm见方的半导体芯片的带有电路的玻璃环氧树脂基板)上贴合将剥离性基材YK57剥离后的粘合剂膜的粘合剂膜面，之后除去剥离性基材HP2(U)。重复进行上述粘贴工序，得到在300处粘贴有7.5mm见方大小的粘合剂膜的电路基板。
(3)倒装芯片粘合及制作的液晶面板的显示试验
将(2)中制作的附粘合剂的电路基板在80℃下进行干燥处理1小时。然后，使用倒装芯片粘合装置(Toray Engineering Co.，Ltd.制，FC-2000)，在附粘合剂的电路基板上进行半导体芯片的倒装芯片粘合。将半导体芯片(附有由铜30μm+无铅焊料15μm形成的凸块电极、448凸块/芯片、间距60μm、***配置(peripheral arrangement)、7.5mm见方的芯片)固定在已加热到80℃的粘合载物台上，在温度80℃、压力15N/芯片、时间5秒的条件下，临时压接于上述附粘合剂的电路基板上，然后在温度250℃、压力200N/芯片的条件下进行正式压接，时间为10秒。1处的粘合结束后，进行下一个粘合，通过重复进行，在共计300个的位置进行半导体芯片的粘合。需要说明的是，从粘合开始至结束所花费的时间为60分钟。用基板切断装置将完成了粘合的电路基板分割，从而制作出300个带有半导体的电路基板。需要说明的是，得到的带有半导体的电路基板中，半导体芯片与电路基板经两者连接而构成雏菊链(daisy chain)。将制作的各个带有半导体的电路基板组入液晶基板，由此制作液晶面板(半导体器件)，进行显示试验。将能显示的液晶面板判定为合格，将因芯片与电路基板间产生连接不良而不能显示的液晶面板判定为不合格。对300个液晶面板进行显示试验，将合格的比例为99.5％以上表示为A、95.0％以上～小于99.5％表示为B、小于95.0％表示为C。结果示于表1～表4(可靠性试验前)。
(4)连接可靠性试验后的液晶面板的显示试验
将20个在(3)液晶显示试验中合格的带有半导体的电路基板在85℃、60％RH的条件的恒温恒湿槽中放置168小时，使其吸湿。之后，在260℃、5秒的回流条件下进行锡焊回流(吸湿回流焊处理)。接着，将带有半导体的电路基板在-40℃下维持5分钟、然后在125℃下维持5分钟，以此作为1个循环，分别对10个试样重复进行1000个循环，对剩下的10个试样重复进行2000个循环。进行这些处理后，将带有半导体的电路基板组入液晶基板，从而制作液晶面板，进行显示试验。对于进行1000个循环后、2000个循环后的各个试样而言，10个全部显示的为A，由于产生连接不良而1个也不显示的为C。结果示于表1～表4(可靠性试验后/1000个循环、2000个循环)。
(5)在23℃、55％RH下放置1个月及3个月后的粘合剂的熔融粘度测定
对于在(1)工序中在23℃、55％RH的环境下分别保存1个月及3个月的粘合剂膜，在以下条件下测定熔融粘度。将最低熔融粘度为100Pa·s以上、10000Pa·s以下的情形评价为A，将除此以外的情形评价为C。
动态粘弹性测定装置：MCR-302(Anton Paar Japan K.K.制)，
试样尺寸：直径15mm、厚度0.8mm，
升温速度：2℃/分钟，
测定频率：1Hz，
测定应变：9％，
测定温度范围：0℃到150℃。
由实施例1～30与比较例1～8的对比可知，不含酸改性松香的粘合剂的保存性差，在使用将卷绕体在23℃、55％RH的环境下保存1个月及3个月后的粘合剂膜的情况下，完全不能获得连接可靠性。此外可知，在粘合剂含有无机粒子的情况下，即使进行吸湿回流焊处理及热循环处理，也可保持连接可靠性。
实施例31～46及比较例9～12
将有机溶剂可溶性聚酰亚胺B变更为有机溶剂可溶性聚酰亚胺C，除此之外，与实施例8～14、22～30、比较例3、4、7、8同样地制作粘合剂并进行评价，结果分别得到与实施例8～14、22～30、比较例3、4、7、8的液晶显示试验的评价结果同样的结果。
实施例47～76
将潜在性固化剂的酸改性松香KE-604变更为酸改性松香KR-120，除此之外，与实施例1～30同样地制作半导体用粘合剂并进行评价，结果分别得到与实施例1～30的液晶显示试验的评价结果同样的结果。
实施例77～83及比较例13、14
对于表5所示的(a)～(f)成分而言，以成为表5所示的配合比进行调配，与实施例1同样地制作粘合剂并进行评价，结果得到表5的液晶显示试验的评价结果。
产业上的可利用性
本发明的粘合剂可以用作在个人计算机、便携终端中使用的电子部件或散热器与印刷电路板或挠性基板的粘合、及基板之间的粘合中使用的粘合剂，而且，可适合用作将LSI、LED、激光二极管等半导体芯片粘合或直接电接合于挠性基板、玻璃环氧树脂基板、玻璃基板、陶瓷基板等电路基板上时使用的半导体用粘合剂。

Claims (7)

1.一种粘合剂，含有(a)聚酰亚胺、(b)环氧化合物、(c)酸改性松香及碱性的潜在性固化剂，其中，相对于100质量份的(b)环氧化合物，(c)酸改性松香的含量为5质量份以上且为30质量份以下。
2.如权利要求1所述的粘合剂，其中，(a)聚酰亚胺为下述聚合物，所述聚合物具有通式(2)或通式(3)表示的结构，并且含有相对于聚合物总量为5～15质量％的通式(1)表示的结构作为通式(2)或通式(3)中的R4；
式中，R1表示2价的烃基，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同，R2表示1价的烃基，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同，n表示1～10的整数；
式中，R3表示4～14价的有机基团，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同；此外，R4表示2～12价的有机基团，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同；此外，R3、R4中的至少一个为芳香族基团，所述芳香族基团含有至少一个选自由1,1,1,3,3,3－六氟丙基、异丙基、醚基、硫醚基及SO2基组成的组中的1个以上的基团；R5、R6表示选自由酚羟基、磺酸基及硫醇基组成的组中的1个以上的基团，在1分子内可以相同也可以不同，另外在不同的分子中可以相同也可以不同；X表示1价的有机基团；m表示8～200的整数；α、β分别表示0～10的整数，α+β表示0～10的整数；其中，重复数m中，20～90％表示α+β＝1～10。
3.如权利要求1或2所述的粘合剂，其中，还含有(d)无机粒子，相对于(a)～(d)的总量，(d)无机粒子的含量为30～80质量％。
4.一种粘合剂膜，包含权利要求1～3中任一项所述的粘合剂。
5.如权利要求4所述的粘合剂膜，其中，在23℃、55％RH的环境下保存1个月后的最低熔融粘度在100～10000Pa·s的范围内。
6.一种半导体器件，包含权利要求1～3中任一项所述的粘合剂的固化物或者权利要求4或5所述的粘合剂膜的固化物。
7.一种半导体器件的制造方法，使权利要求1～3中任一项所述的粘合剂或者权利要求4或5所述的粘合剂膜介于第一电路构件与第二电路构件之间，经加热加压将所述第一电路构件与所述第二电路构件电连接。
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