CN107533991A - 焊料电极的制造方法及其用途 - Google Patents

焊料电极的制造方法及其用途 Download PDF

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Publication number
CN107533991A
CN107533991A CN201680026329.2A CN201680026329A CN107533991A CN 107533991 A CN107533991 A CN 107533991A CN 201680026329 A CN201680026329 A CN 201680026329A CN 107533991 A CN107533991 A CN 107533991A
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China
Prior art keywords
manufacture method
solder electrode
electronic pads
substrate
resist
Prior art date
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Pending
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CN201680026329.2A
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English (en)
Inventor
武川纯
高桥诚郎
高桥诚一郎
长谷川公
长谷川公一
楠本士朗
山口佳
山口佳一
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JSR Corp
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JSR Corp
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Publication of CN107533991A publication Critical patent/CN107533991A/zh
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
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    • H05K3/3468—Applying molten solder
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Abstract

本发明是一种焊料电极的制造方法，其包括：步骤(1)，在具有电极垫的基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，在所述开口部填充熔融焊料；且所述感光性树脂组合物至少含有苯并噁唑前体。本发明的焊料电极的制造方法如IMS法等那样，即便在焊料填充时抗蚀剂受到高热的情况下，也可防止抗蚀剂表面的龟裂产生，并可提高焊料填充能力，因此可恰当地制造适合于目的的焊料电极。

Description

焊料电极的制造方法及其用途
技术领域
本发明涉及一种焊料电极的制造方法、焊料电极、层叠体的制造方法、层叠体、电子零件、及感光性树脂组合物。
背景技术
注射成型焊料(Injection Molded Solder，IMS)法是用以形成焊料图案(焊料凸块)的方法之一。至今为止，作为在晶片等基板上形成焊料图案的方法，使用焊膏法、镀敷法等。然而，在这些方法中，存在不但焊料凸块的高度控制困难，而且无法自由选择焊料组成等的制约。相对于此，在IMS法中，已知并无这些制约的优点。
IMS法如专利文献1～专利文献4所示那样，是特征在于一边使可将熔融的焊料注射成型的喷嘴与抗蚀剂密接，一边在抗蚀剂图案间流入焊料的方法。
现有技术文献
专利文献
专利文献1：日本专利特开平06-055260号公报
专利文献2：日本专利特开2007-294954号公报
专利文献3：日本专利特开2007-294959号公报
专利文献4：日本专利特表2013-520011号公报
发明内容
发明所要解决的问题
关于IMS法，为了填充熔融焊料，而将加热至高温、通常为250℃以上的IMS头推抵至抗蚀剂表面而进行。因此，存在因高热引起的负载作用于抗蚀剂表面，在抗蚀剂表面产生龟裂、或产生抗蚀剂的溃烂，而焊料嵌入性降低的问题。
本发明的目的是提供一种如IMS法等那样，在焊料填充时抗蚀剂受到高热的情况下，也可防止抗蚀剂表面的龟裂产生，并谋求焊料填充能力的提高的技术。
解决问题的技术手段
本发明的焊料电极的制造方法包括：步骤(1)，在具有电极垫的基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，在所述开口部填充熔融焊料；且所述焊料电极的制造方法的特征在于：
所述感光性树脂组合物至少含有苯并噁唑前体。
在所述焊料电极的制造方法中，所述苯并噁唑前体优选具有以二羧酸为来源的结构及以二羟基二胺为来源的结构，进而所述二羧酸优选为芳香族系二羧酸，所述二羟基二胺优选为芳香族系二胺。
在所述焊料电极的制造方法中，所述感光性树脂组合物可进一步含有感光剂，可将所述感光剂设为萘醌二叠氮化合物。
所述焊料电极的制造方法可进一步包括：步骤(4)，将所述抗蚀剂剥离。
本发明的焊料电极是利用所述焊料电极的制造方法而制造的焊料电极。
本发明的第1层叠体的制造方法包括：步骤(1)，在具有电极垫的第1基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，一边加热一边将熔融焊料填充至所述开口部，而形成焊料电极；步骤(5)，经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构；且所述层叠体的制造方法的特征在于：
所述感光性树脂组合物至少含有苯并噁唑前体。
本发明的第2层叠体的制造方法包括：步骤(1)，在具有电极垫的第1基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，一边加热一边将熔融焊料填充至所述开口部，而形成焊料电极；步骤(4)，在步骤(3)之后，将所述抗蚀剂剥离；步骤(5)，在步骤(4)之后，经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构；且所述层叠体的制造方法的特征在于：
所述感光性树脂组合物至少含有苯并噁唑前体。
本发明的层叠体是利用所述第1层叠体的制造方法或第2层叠体的制造方法而制造的层叠体。
本发明的电子零件是具有所述层叠体的电子零件。
本发明的注射成型焊料用感光性树脂组合物至少含有苯并噁唑前体。
发明的效果
本发明的焊料电极的制造方法如IMS法等那样，在焊料填充时抗蚀剂受到高热的情况下，也可防止抗蚀剂表面的龟裂产生，并可提高焊料填充能力，因此可恰当地制造适合于目的的焊料电极。
本发明的层叠体的制造方法利用IMS法可恰当地制造适合于目的的焊料电极，因此可恰当地制造具有电性连接结构的层叠体。
附图说明
图1中的图1(1)～(4)是本发明的焊料电极的制造方法的各步骤中的包含基板的结构体的示意剖面图。
图2中的图2(5-1)及(5-2)是本发明的层叠体的示意剖面图。
具体实施方式
<焊料电极的制造方法>
本发明的焊料电极的制造方法包括：步骤(1)，在具有电极垫的基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，在所述开口部填充熔融焊料；且所述焊料电极的制造方法的特征在于：所述感光性树脂组合物至少含有苯并噁唑(benzoxazole)前体。
本发明的焊料电极的制造方法中，所述步骤(1)中所用的感光性树脂组合物含有苯并噁唑前体的方面与现有法不同。所述步骤(1)～步骤(3)中的操作可与现有法同样地进行。
以下，一边参照图1，一边对本发明的焊料电极的制造方法进行说明。
(步骤(1))
步骤(1)中，如图1(1)所示那样，在具有电极垫2的基板1上形成感光性树脂组合物的涂膜3。
基板1例如为半导体基板、玻璃基板、硅基板、以及在半导体板、玻璃板及硅板的表面设置各种金属膜等而形成的基板等。基板1具有大量的电极垫2。
涂膜3是通过在基板1上将感光性树脂组合物进行涂布等而形成。作为感光性树脂组合物的涂布方法，并无特别限定，例如可列举：喷雾法、辊涂法、旋涂法、狭缝模涂法、棒涂法、喷墨法。涂膜3的膜厚通常为1μm～500μm，优选为5μm～200μm，更优选为10μm～100μm。
所述感光性树脂组合物至少含有苯并噁唑前体。苯并噁唑前体受热后在分子内反应，急速地变为具有耐热性的结构。因此，由所述感光性树脂组合物形成的抗蚀剂当在IMS法等的焊料填充时加热至高温时，抗蚀剂所含的苯并噁唑前体急速地变为具有耐热性的结构，因此耐热性提高，其结果认为可防止抗蚀剂表面的龟裂产生，焊料嵌入性提高。
由感光性树脂组合物形成的涂膜在后述的步骤(2)中通过曝光而交联。但是，通常仅通过曝光，感光性树脂组合物中所含的交联剂不会完全消耗，未消耗的交联剂残存于抗蚀剂中。因此，仅通过进行曝光，抗蚀剂的交联不完全，抗蚀剂的强度不会充分提高。如现有法那样认为，在所述状态下利用IMS法而将高温的头推抵至抗蚀剂的表面来填充熔融焊料时，抗蚀剂不耐受自IMS头受到的热，而产生龟裂或溃烂。相对于此，在本发明的焊料电极的制造方法中，如所述那样，抗蚀剂通过加热而耐热性急速地提高，因此不会产生龟裂或溃烂。
另外，在使用不含苯并噁唑前体的感光性树脂组合物的现有的IMS法中，认为在正填充熔融焊料的过程中利用热而会进行由残存在抗蚀剂内的交联剂引起的交联反应，而强化抗蚀剂，但感光性树脂组合物所使用的多官能丙烯酸酯等交联剂由于交联反应速度慢，因此认为在交联反应充分进行之前，因自IMS头受到的热而产生龟裂或溃烂。
作为苯并噁唑前体，例如可适宜地列举：将二羧酸及二羟基二胺作为原料而得的聚苯并噁唑前体。这种苯并噁唑前体是使二羧酸及二羟基二胺反应而得，具有以二羧酸为来源的结构及以二羟基二胺为来源的结构、即二羧酸残基及二羟基二胺残基。这种苯并噁唑前体在受到热时成为耐热性特别高的结构，因此由包含所述苯并噁唑前体的本发明的感光性树脂组合物而得的抗蚀剂在受到高热时，可更有效地防止表面的龟裂产生。
作为所述二羧酸，可列举：间苯二甲酸、对苯二甲酸、2、2-双(4-羧基苯基)六氟丙烷、4，4’-联苯二甲酸、4，4’-二羧基二苯醚、4，4’-二羧基四苯基硅烷、双(4-羧基苯基)砜、2，2-双(对羧基苯基)丙烷、5-叔丁基间苯二甲酸、5-溴间苯二甲酸、5-氟间苯二甲酸、5-氯间苯二甲酸、2，6-萘二甲酸等芳香族系二羧酸，1，2-环丁二羧酸、1，4-环己二羧酸、1，3-环戊二羧酸、草酸、丙二酸、丁二酸等脂肪族系二羧酸等。这些可单独使用或组合两种以上而使用。这些中，就耐热性的方面而言，优选为芳香族系二羧酸。
作为所述二羟基二胺，可列举：3，3’-二氨基-4，4’-二羟基联苯、4，4’-二氨基-3，3’-二羟基联苯、双(3-氨基-4-羟基苯基)丙烷、双(4-氨基-3-羟基苯基)丙烷、双(3-氨基-4-羟基苯基)砜、双(4-氨基-3-羟基苯基)砜、双(3-氨基-4-羟基苯基)六氟丙烷、双(4-氨基-3-羟基苯基)六氟丙烷、双(3-氨基-4-羟基苯基)丙烷、双(4-氨基-3-羟基苯基)丙烷、4，6-二氨基间苯二酚、4，5-二氨基间苯二酚、双(4-氨基-3-羧基苯基)甲烷等芳香族系二胺。通过使用芳香族系二胺，而可获得耐热性良好的聚苯并噁唑前体。
作为苯并噁唑前体的利用凝胶渗透色谱(Gel Permeation Chromatography，GPC)法测定的聚苯乙烯换算的重量平均分子量(Mw)，优选为3,000～200,000，更优选为5,000～100,000。
关于所述感光性树脂组合物中的苯并噁唑前体的含量，若将所述组合物中所含的全部固体成分设为100质量％，则通常为50质量％以上，优选为60质量％～95质量％，更优选为70质量％～90质量％。
所述感光性树脂组合物除了苯并噁唑前体以外，还可含有在现有法中所用的感光性树脂组合物中通常含有的成分。
所述感光性树脂组合物可为正型也可为负型。所述感光性树脂组合物是正型还是负型，由感光性树脂组合物中所含的感光剂的种类决定。在所述感光性树脂组合物为正型时，感光剂包含萘醌二叠氮(naphthoquinone diazide)作为必须成分，在为负型时，感光剂包含光酸产生剂及阳离子系交联剂作为必须成分。
含有所述萘醌二叠氮化合物的涂膜对碱性显影液为难溶，但萘醌二叠氮化合物通过光照射，醌二叠氮基分解产生羧基，而变为碱易溶。因此，含有萘醌二叠氮化合物的涂膜通过光照射而自碱难溶性变为碱易溶性。
所述萘醌二叠氮化合物是具有1个以上酚性羟基的化合物与1，2-萘醌二叠氮-4-磺酸或1，2-萘醌二叠氮-5-磺酸的酯化合物。
作为萘醌二叠氮化合物，例如可列举：4，4’-二羟基二苯基甲烷、4，4’-二羟基二苯醚、2，3，4-三羟基二苯甲酮、2，3，4，4’-四羟基二苯甲酮、2，3，4，2’，4’-五羟基二苯甲酮、三(4-羟基苯基)甲烷、三(4-羟基苯基)乙烷、1，1-双(4-羟基苯基)-1-苯基乙烷、1，3-双[1-(4-羟基苯基)-1-甲基乙基]苯、1，4-双[1-(4-羟基苯基)-1-甲基乙基]苯、4，6-双[1-(4-羟基苯基)-1-甲基乙基]-1，3-二羟基苯、1，1-双(4-羟基苯基)-1-[4-[1-(4-羟基苯基)-1-甲基乙基]苯基]乙烷等与1，2-萘醌二叠氮-4-磺酸或1，2-萘醌二叠氮-5-磺酸的酯化合物。
萘醌二叠氮化合物可单独使用一种，也可并用两种以上。
所述光酸产生剂是通过光照射而形成酸的化合物。通过所述酸作用于阳离子系交联剂的阳离子反应性基而形成交联结构，因此包含光酸产生剂及阳离子系交联剂的涂膜通过光照射而对碱性显影液变为难溶。
作为光酸产生剂，例如可列举：鎓盐化合物、含有卤素的化合物、砜化合物、磺酸化合物、磺酰亚胺化合物、重氮甲烷化合物。这些中，就可形成伸长物性优异的硬化膜而言，优选为鎓盐化合物、含有卤素的化合物。
作为鎓盐化合物，例如可列举：錪盐、锍盐、鏻盐、重氮鎓盐、吡啶鎓盐。作为优选的鎓盐的具体例，可列举：二苯基錪三氟甲磺酸盐、二苯基錪对甲苯磺酸盐、二苯基錪六氟锑酸盐、二苯基錪六氟磷酸盐、二苯基錪四氟硼酸盐、三苯基锍三氟甲磺酸盐、三苯基锍对甲苯磺酸盐、三苯基锍六氟锑酸盐、4-叔丁基苯基·二苯基锍三氟甲磺酸盐、4-叔丁基苯基·二苯基锍对甲苯磺酸盐、4，7-二-正丁氧基萘基四氢噻吩嗡三氟甲磺酸盐、4-(苯硫基)苯基二苯基锍三(五氟乙基)三氟磷酸盐。
作为含有卤素的化合物，例如可列举：含有卤化烷基的烃化合物、含有卤化烷基的杂环式化合物。作为优选的含有卤素的化合物的具体例，可列举：1，10-二溴-正癸烷、1，1-双(4氯苯基)-2，2，2-三氯乙烷、苯基-双(三氯甲基)-均三嗪、4-甲氧基苯基-双(三氯甲基)-均三嗪、苯乙烯基-双(三氯甲基)-均三嗪、萘基-双(三氯甲基)-均三嗪等均三嗪衍生物。
作为砜化合物，例如可列举：β-酮砜化合物、β-磺酰基砜化合物及这些化合物的α-重氮化合物。作为优选的砜化合物的具体例，可列举：4-三苯甲酰甲基砜、均三甲苯基苯甲酰甲基砜、双(苯甲酰甲磺酰基)甲烷。
作为磺酸化合物，例如可列举：烷基磺酸酯类、卤化烷基磺酸酯类、芳基磺酸酯类、亚氨基磺酸酯类。作为优选的磺酸化合物的具体例，可列举：安息香甲苯磺酸酯、连苯三酚三-三氟甲磺酸酯、邻硝基苄基三氟甲磺酸酯、邻硝基苄基对甲苯磺酸酯。
作为磺酰亚胺化合物，例如可列举：N-(三氟甲基磺酰氧基)丁二酰亚胺、N-(三氟甲基磺酰氧基)邻苯二甲酰亚胺、N-(三氟甲基磺酰氧基)二苯基顺丁烯二酰亚胺、N-(三氟甲基磺酰氧基)双环[2.2.1]庚-5-烯-2，3-二甲酰亚胺、N-(三氟甲基磺酰氧基)萘基酰亚胺。
作为重氮甲烷化合物，例如可列举：双(三氟甲基磺酰基)重氮甲烷、双(环己基磺酰基)重氮甲烷、双(苯基磺酰基)重氮甲烷。
光酸产生剂可单独使用一种，也可并用两种以上。
所述阳离子系交联剂发挥出作为交联成分(硬化成分)的作用。作为阳离子系交联剂，例如可列举：具有2个以上经烷基醚化的氨基的化合物(以下也称为“含有氨基的化合物”)、含有氧杂环丙烷环的化合物、含有氧杂环丁烷环的化合物、含有异氰酸酯基的化合物(包括经嵌段化者)、含有醛基的酚化合物、含有羟甲基的酚化合物。但是具有环氧基的硅烷偶合剂自含有氧杂环丙烷环的化合物除外，具有异氰酸酯基的硅烷偶合剂自含有异氰酸酯基的化合物除外。
作为经烷基醚化的氨基，例如可列举：下述式所示的基团。
[化1]
(式中，R11表示亚甲基或亚烷基，R12表示烷基。)
作为含有氨基的化合物，例如可列举：(聚)羟甲基化三聚氰胺、(聚)羟甲基化甘脲、(聚)羟甲基化苯代三聚氰胺、(聚)羟甲基化脲等氮化合物中的活性羟甲基(CH2OH基)的一部分或全部(至少两个)经烷基醚化的化合物。此处，作为构成烷基醚的烷基，例如可列举：甲基、乙基、丁基，这些可彼此相同，也可不同。此外，未经烷基醚化的羟甲基可在一分子内自缩合，也可在二分子间缩合，其结果可形成寡聚物成分。具体可使用：六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、四甲氧基甲基甘脲、四丁氧基甲基甘脲等。
作为含有氧杂环丙烷环的化合物，只要在分子内含有氧杂环丙烷环即可，并无特别限定，例如可列举：苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚型环氧树脂、三酚型环氧树脂、四酚型环氧树脂、苯酚-亚二甲苯基型环氧树脂、萘酚-亚二甲苯基型环氧树脂、苯酚-萘酚型环氧树脂、苯酚-二环戊二烯型环氧树脂、脂环式环氧树脂、脂肪族环氧树脂。
作为含有氧杂环丙烷环的化合物的具体例，例如可列举：间苯二酚二缩水甘油醚、季戊四醇缩水甘油醚、三羟甲基丙烷聚缩水甘油醚、甘油聚缩水甘油醚、苯基缩水甘油醚、新戊二醇二缩水甘油醚、乙二醇/聚乙二醇二缩水甘油醚、丙二醇/聚丙二醇二缩水甘油醚、1，6-己二醇二缩水甘油醚、山梨糖醇聚缩水甘油醚、丙二醇二缩水甘油醚、三羟甲基丙烷三缩水甘油醚。
作为含有氧杂环丁烷环的化合物，只要在分子内含有氧杂环丁烷环即可，并无特别限定，例如可列举：式(d-1)～式(d-3)所示的化合物。
[化2]
式(d-1)～式(d-3)中，A表示直接键、或亚甲基、亚乙基、亚丙基等亚烷基；R表示甲基、乙基、丙基等烷基；R1表示亚甲基、亚乙基、亚丙基等亚烷基；R2表示甲基、乙基、丙基、己基等烷基，苯基、亚二甲苯基等芳基，下述式所示的基团(式中，R及R1分别与式(d-1)～式(d-3)中的R及R1同义)，
[化3]
下述式(i)所示的二甲基硅氧烷残基，亚甲基、亚乙基、亚丙基等亚烷基，亚苯基，下述式(ii)～式(vi)所示的基团；i与R2的价数相等，为1～4的整数。另外，下述式(i)～式(vi)中的“*”表示键结部位。
[化4]
式(i)及式(ii)中，x及y分别独立地为0～50的整数。式(iii)中，Z为直接键、或以-O-、-CH2-、-C(CH3)2-、-C(CF3)2-、-CO-或-SO2-表示的2价基。
作为式(d-1)～式(d-3)所示的化合物的具体例，例如可列举：1，4-双{[(3-乙基氧杂环丁烷-3-基)甲氧基]甲基}苯(商品名“OXT-121”、东亚合成公司制造)、3-乙基-3-{[(3-乙基氧杂环丁烷-3-基)甲氧基]甲基}氧杂环丁烷(商品名“OXT-221”、东亚合成公司制造)、4，4’-双[(3-乙基-3-氧杂环丁基)甲氧基甲基]联苯(宇部兴产制造、商品名“艾塔纳科(ETERNACOLL)OXBP”)、双[(3-乙基-3-氧杂环丁基甲氧基)甲基-苯基]醚、双[(3-乙基-3-氧杂环丁基甲氧基)甲基-苯基]丙烷、双[(3-乙基-3-氧杂环丁基甲氧基)甲基-苯基]砜、双[(3-乙基-3-氧杂环丁基甲氧基)甲基-苯基]酮、双[(3-乙基-3-氧杂环丁基甲氧基)甲基-苯基]六氟丙烷、三[(3-乙基-3-氧杂环丁基甲氧基)甲基]苯、四[(3-乙基-3-氧杂环丁基甲氧基)甲基]苯、下述式(d-a)～式(d-d)所示的化合物。
[化5]
此外，除了这些化合物以外，还可使用高分子量的具有多价氧杂环丁烷环的化合物。例如可列举：氧杂环丁烷寡聚物(商品名“欧力多(Oligo)-OXT”、东亚合成公司制造)、式(d-e)～式(d-g)所示的化合物。
[化6]
式(d-e)～式(d-g)中，p、q及s分别独立地为0～10000的整数，优选为1～10的整数。式(d-f)中，Y为亚乙基、亚丙基等亚烷基、或以-CH2-Ph-CH2-表示的基团(式中，Ph表示亚苯基)。
阳离子系交联剂可单独使用一种，也可并用两种以上。
(步骤(2))
在步骤(2)中，如图1(2)所示那样，通过将涂膜3选择性曝光，进而进行显影，而在与各电极垫2对应的区域形成具有开口部4的抗蚀剂5。
即，以形成容纳各电极垫2的开口部4的方式，对涂膜3进行部分曝光，然后进行显影，而形成容纳各电极垫2的开口部4。其结果在与各电极垫2对应的区域获得具有开口部4的抗蚀剂5。开口部4是贯通抗蚀剂5的孔。关于曝光及显影，可根据现有法进行。开口部4的最大宽度通常为涂膜3的膜厚的0.1倍～10倍、优选为0.5倍～2倍。
(步骤(3))
在步骤(3)中，一边加热一边将熔融焊料填充至开口部4。冷却后，如图1(3)所示那样，在各开口部4形成焊料电极6。
一边加热一边将熔融焊料填充至开口部4的方法并无特别限制，可采用IMS法的通常的填充方法。在IMS法中，通常一边将熔融焊料加热至250℃以上一边进行填充。
如所述那样，在本发明的焊料电极的制造方法中，由于所述感光性树脂组合物含有通过热而变为耐热性高的结构的苯并噁唑前体，因此如IMS法那样在将高温的头推抵至抗蚀剂5的表面而填充熔融焊料时，也可抑制抗蚀剂5表面的龟裂的产生及溃烂的产生。
利用本发明的焊料电极的制造方法以所述的方式制造的焊料电极，在不会在抗蚀剂产生龟裂或溃烂的状态下形成，因此无形状等的混乱，而成为适合于目的的电极。
所述焊料电极的制造方法在步骤(3)之后可进一步具有步骤(4)：将抗蚀剂5自基板1剥离。图1(4)表示在步骤(3)之后将抗蚀剂5自基板1剥离的状态。
利用本发明的焊料电极的制造方法而制造的焊料电极，既可如图1(3)所示那样与抗蚀剂5一起利用，也可如图1(4)所示那样在无抗蚀剂5的状态下利用。
<层叠体的制造方法>
本发明的第1层叠体的制造方法包括：步骤(1)，在具有电极垫的第1基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，一边加热一边将熔融焊料填充至所述开口部，而形成焊料电极；步骤(5)，经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构；且所述感光性树脂组合物至少含有苯并噁唑前体。
本发明的第2层叠体的制造方法包括：步骤(1)，在具有电极垫的第1基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，一边加热一边将熔融焊料填充至所述开口部，而形成焊料电极；步骤(4)，在步骤(3)之后，将所述抗蚀剂剥离；步骤(5)，在步骤(4)之后，经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构；且所述感光性树脂组合物至少含有苯并噁唑前体。
第1层叠体的制造方法及第2层叠体的制造方法中的步骤(1)～步骤(3)、及第2层叠体的制造方法中的步骤(4)，与所述焊料电极的制造方法中的步骤(1)～步骤(5)分别实质相同。即，第1层叠体的制造方法是在所述焊料电极的制造方法中的步骤(1)～步骤(3)之后进行步骤(5)的方法，第2层叠体的制造方法是在所述焊料电极的制造方法中的步骤(1)～步骤(4)之后进行步骤(5)的方法。
在第1层叠体的制造方法及第2层叠体的制造方法中，所述焊料电极的制造方法中的基板相当于第1基板。
第1层叠体的制造方法是在所述步骤(1)～步骤(3)之后进行步骤(5)：经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构。
图2(5-1)表示利用第1层叠体的制造方法而制造的层叠体10。层叠体10具有以如下方式形成的电性连接结构：经由通过所述步骤(1)～步骤(3)而制造的图1(3)所示的状态的焊料电极6，将所述第1基板1的电极垫2、与具有电极垫12的第2基板11的电极垫12连接。
在将第1基板1与第2基板11以形成有电极垫的面相对的方式相对放置时，第2基板11所具有的电极垫12设置于与第1基板1的电极垫2对向的位置。使第2基板11的电极垫12与图1(3)所示的状态的焊料电极6接触，进行加热和/或压接，由此经由焊料电极6使第1基板1的电极垫2与第2基板11的电极垫12电性连接，而形成电性连接结构，获得层叠体10。所述加热温度通常为100℃～300℃，所述压接时的力通常为0.1MPa～10MPa。
在图1(3)所示的状态下，在第1基板1上载置抗蚀剂5，因此层叠体10具有：第1基板1、焊料电极6、第2基板11、被第1基板1及第2基板11夹持的抗蚀剂5。
第2层叠体的制造方法是在所述步骤(1)～步骤(4)之后进行步骤(5)：经由所述焊料电极，形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构。
图2(5-2)表示利用第2层叠体的制造方法而制造的层叠体20。层叠体20具有以如下方式形成的电性连接结构：经由通过所述步骤(1)～步骤(4)而制造的图1(4)所示的状态的焊料电极6，将所述第1基板1的电极垫2、与具有电极垫12的第2基板11的电极垫12连接。
使第2基板11的电极垫12与图1(4)所示的状态的焊料电极6接触，进行加热和/或压接，由此经由焊料电极6使第1基板1的电极垫2与第2基板11的电极垫12电性连接，而形成电性连接结构，获得层叠体20。
在图1(4)所示的状态下，由于在第1基板1上未载置抗蚀剂5，因此层叠体20由第1基板1、焊料电极6、及第2基板11形成。
如所述那样，利用本发明的层叠体的制造方法而制造的层叠体，可在第1基板与第2基板之间具备抗蚀剂，也可不具备抗蚀剂。在如层叠体10那样具备抗蚀剂时，所述抗蚀剂用作底层填充。
利用本发明的层叠体的制造方法而制造的层叠体，利用IMS法而具有适合于目的的电性连接结构，因此由于焊料组成的选择性扩大，而能够应用于半导体元件、显示元件、及功率器件等各种电子零件。
利用本发明的层叠体的制造方法而制造的层叠体，可应用于半导体元件、显示元件、及功率器件等电子零件。
[实施例]
以下，根据实施例对本发明进行更具体地说明，但本发明并不限定于这些实施例。在以下的实施例等的记载中，“份”以“质量份”的含义而使用。
1.物性的测定方法
(聚苯并噁唑前体及碱可溶性树脂的重量平均分子量(Mw)的测定方法)
在下述条件下利用凝胶渗透色谱法测定聚苯并噁唑前体及碱可溶性树脂的重量平均分子量(Mw)。
·管柱：将东曹(Tosoh)公司制造的管柱TSK-M及TSK2500串列连接
·溶剂：四氢呋喃
·温度：40℃
·检测方法：折射率法
·标准物质：聚苯乙烯
·GPC装置：东曹制造、装置名“HLC-8220-GPC”
2.抗蚀剂形成用组合物的准备
[合成例1]聚苯并噁唑前体的合成
在烧瓶中加入间苯二甲酸20g及N-甲基吡咯烷酮100g，将烧瓶内容物冷却至5℃后，滴加亚硫酰氯29g，反应30分钟，而获得间苯二甲酰氯的溶液。
继而，在烧瓶中加入N-甲基吡咯烷酮100g，添加双(3-氨基-4-羟基苯基)六氟丙烷26g及1，3-双(4-氨基苯氧基)苯9g，搅拌溶解后，添加吡啶20g。将溶液的温度保持为5℃，在所述溶液中历时30分钟滴加所述间苯二甲酰氯的溶液后，继续搅拌60分钟进行反应。将反应液投入至3升水中，将所产生的析出物过滤分离后，利用纯水清洗所述析出物，而获得聚苯并噁唑前体。聚苯并噁唑前体的重量平均分子量为20,000。
[合成例2]碱可溶性树脂的合成
在经氮气置换的带有干冰/甲醇回流器的烧瓶中，加入作为聚合引发剂的2，2’-偶氮双异丁腈5.0g、及作为聚合溶剂的二乙二醇乙基甲醚90g，进行搅拌。在所得的溶液中，添加甲基丙烯酸10g、对异丙烯基苯酚15g、甲基丙烯酸三环[5.2.1.02，6]癸酯25g、丙烯酸异冰片酯20g、及丙烯酸正丁酯30g，开始搅拌，升温至80℃为止。然后，在80℃下加热6小时进行反应。
在加热结束后，将反应液滴加至大量的环己烷中，使反应产物凝固。将所述凝固物水洗，将所述凝固物再溶解于与凝固物相同质量的四氢呋喃中后，将所得的溶液滴加至大量的环己烷中再次进行凝固。进行合计3次所述再溶解及凝固作业后，将所得的凝固物在40℃下真空干燥48小时，而获得碱可溶性树脂。碱可溶性树脂的重量平均分子量为10,000。
[实施例1]感光性树脂组合物1的制备
使用所述合成例1中合成的聚苯并噁唑前体100份、1，1-双(4-羟基苯基)-1-[4-[1-(4-羟基苯基)-1-甲基乙基]苯基]乙烷与1，2-萘醌二叠氮-5-磺酸的缩合物(后者相对于前者的摩尔比：2.0)10份、N-甲基-2-吡咯烷酮100份，将它们混合、搅拌，而获得均匀的溶液。利用孔径为10μm的胶囊过滤器对所述溶液进行过滤，而制备感光性树脂组合物1。
[制备例1]感光性树脂组合物2的制备
使用所述合成例2中合成的碱可溶性树脂100份、聚酯丙烯酸酯(商品名“亚罗尼斯(Aronix)M-8060”、东亚合成(股)制造)50份、二苯基(2，4，6-三甲基苯甲酰基)氧化膦(商品名“路西林(LUCIRIN)TPO”、巴斯夫(BASF)(股)制造)4份、2，2-二甲氧基-1，2-二苯基乙烷-1-酮(商品名“艳佳固(IRGACURE)651”、巴斯夫(股)制造)19份、丙二醇单甲醚乙酸酯80份，将它们混合、搅拌，而获得均匀的溶液。利用孔径为10μm的胶囊过滤器对所述溶液进行过滤，而制备感光性树脂组合物2。
[实施例2]
使用旋涂机将实施例1中所制备的感光性树脂组合物1涂布于在硅板上具有大量铜电极垫的基板上，利用热板以120℃加热5分钟，而形成厚度为20μm的涂膜。继而，使用对准器(苏斯(Suss)公司制造、型号“MA-200”)，隔着图案掩模以照射强度300mJ/cm2对所述涂膜进行波长为420nm的光的曝光。曝光后，使涂膜与2.38质量％氢氧化四甲基铵水溶液接触240秒，利用流水清洗涂膜并显影，而形成在与电极垫对应的部分具有开口部的抗蚀剂保持基板。利用电子显微镜进行观察，结果各开口部的开口是直径为30μm的圆形，各开口部的深度为20μm。此外，开口部的最大宽度为30μm。
将具有所述开口部的抗蚀剂保持基板在1质量％硫酸水溶液中在23℃下浸渍1分钟后，进行水洗、干燥。在干燥后的基板的开口部，一边将在250℃下使SAC305(制品名、无铅焊料、千住金属工业(股))熔融而得的熔融焊料加热至250℃，一边历时10分钟进行填充。利用电子显微镜观察熔融焊料填充后的抗蚀剂保持基板，结果确认到抗蚀剂无龟裂，并且熔融焊料良好地填充，焊料电极良好地形成。
然后，在混合二甲基亚砜90份、氢氧化四甲基铵3份及水7份而得的溶液中，在50℃下将形成有焊料电极的抗蚀剂保持基板浸渍20分钟，而自基板剥离抗蚀剂。将所得的具备焊料电极的基板进行水洗并干燥。
对于另外的具有铜电极垫的基板，在所述具有铜电极垫的基板上，经由所述焊料电极，以两者取得电性连接结构的方式，载置另外的具有铜电极垫的基板。在所述2片具有铜电极垫的基板上，使用粘晶机装置，以两者压接的方式，在250℃下施加30秒的0.3MPa的压力，而制造依序包含具有铜电极垫的基板、焊料电极、具有铜电极垫的基板的层叠体。利用电子显微镜观察所述层叠体，结果确认到为具有合格的电性连接结构的层叠体。
[比较例1]
使用旋涂机将制备例1中所制备的感光性树脂组合物2涂布于在硅板上具有大量铜电极垫的基板上，利用热板以120℃加热5分钟，而形成厚度为20μm的涂膜。继而使用对准器(苏斯公司制造、型号“MA-200”)，经由图案掩模以照射强度300mJ/cm2对所述涂膜进行波长为420nm的光的曝光。曝光后，使涂膜与2.38质量％氢氧化四甲基铵水溶液接触240秒，利用流水清洗涂膜并显影，而形成在与电极垫对应的部分具有开口部的抗蚀剂保持基板。利用电子显微镜进行观察，结果各开口部的开口是直径为30μm的圆形，各开口部的深度为20μm。此外，开口部的最大宽度为30μm。
将具有所述开口部的抗蚀剂保持基板在1质量％硫酸水溶液中在23℃下浸渍1分钟后，进行水洗、干燥。在干燥后的基板的开口部，一边将在250℃下使SAC305(制品名、无铅焊料、千住金属工业(股))熔融而得的熔融焊料加热至250℃，一边历时10分钟进行填充。利用电子显微镜观察熔融焊料填充后的抗蚀剂保持基板，结果确认到抗蚀剂产生龟裂。此外，熔融焊料无法良好地填充。
符号的说明
1、11：基板
2、12：电极垫
3：涂膜
4：开口部
5：抗蚀剂
6：焊料电极
10、20：层叠体

Claims (13)

1.一种焊料电极的制造方法，其包括：步骤(1)，在具有电极垫的基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，在所述开口部填充熔融焊料；且所述焊料电极的制造方法的特征在于：
所述感光性树脂组合物至少含有苯并噁唑前体。
2.根据权利要求1所述的焊料电极的制造方法，其中所述苯并噁唑前体具有以二羧酸为来源的结构及以二羟基二胺为来源的结构。
3.根据权利要求2所述的焊料电极的制造方法，其中所述二羧酸为芳香族系二羧酸。
4.根据权利要求2或3所述的焊料电极的制造方法，其中所述二羟基二胺为芳香族系二胺。
5.根据权利要求1至4中任一项所述的焊料电极的制造方法，其中所述感光性树脂组合物进一步含有感光剂。
6.根据权利要求5所述的焊料电极的制造方法，其中所述感光剂为萘醌二叠氮化合物。
7.根据权利要求1至6中任一项所述的焊料电极的制造方法，其进一步包括：步骤(4)，将所述抗蚀剂剥离。
8.一种焊料电极，其是通过根据权利要求1～7中任一项所述的焊料电极的制造方法而制造。
9.一种层叠体的制造方法，其包括：步骤(1)，在具有电极垫的第1基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，一边加热一边将熔融焊料填充至所述开口部，而形成焊料电极；步骤(5)，经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构，且所述层叠体的制造方法的特征在于：
所述感光性树脂组合物至少含有苯并噁唑前体。
10.一种层叠体的制造方法，其包括：步骤(1)，在具有电极垫的第1基板上形成感光性树脂组合物的涂膜；步骤(2)，通过将所述涂膜选择性曝光，进而进行显影，而在与电极垫对应的区域形成具有开口部的抗蚀剂；步骤(3)，一边加热一边将熔融焊料填充至所述开口部，而形成焊料电极；步骤(4)，在步骤(3)之后，将所述抗蚀剂剥离；步骤(5)，在步骤(4)之后，经由所述焊料电极，而形成所述第1基板的电极垫与具有电极垫的第2基板的电极垫的电性连接结构，且所述层叠体的制造方法的特征在于：
所述感光性树脂组合物至少含有苯并噁唑前体。
11.一种层叠体，其是利用根据权利要求9或10中任一项所述的层叠体的制造方法而制造。
12.一种电子零件，其具有根据权利要求11所述的层叠体。
13.一种注射成型焊料用感光性树脂组合物，其至少含有苯并噁唑前体。
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